Rehabilitation of contaminated soils and water using “tailor-made” Technosols

INTERNATIONAL DOCTORAL
SCHOOL OF THE USC
Ma ia João
Ce ei a Fe nandes
PhD Thesis
Rehabili a ion o con amina ed
soils and wa e using “ ailo -
made” Technosols
San iago de Compos ela, 2023
Doc o al P og amme in Chemical and En i onmen al Enginee ing
TESIS DE DOCTORADO
REHABILITATION OF
CONTAMINATED SOILS AND
WATER USING “TAILOR-
MADE” TECHNOSOLS
Ma ia João Ce ei a Fe nandes
ESCUELA DE DOCTORADO INTERNACIONAL DE LA UNIVERSIDAD DE SANTIAGO DE
COMPOSTELA
PROGRAMA DE DOCTORADO EN INGENIERÍA QUÍMICA Y AMBIENTAL
SANTIAGO DE COMPOSTELA / LUGO
2023
ii
DECLARACIÓN DO AUTOR/A DA TESE
D./Dna.
Ma ia João Ce ei a Fe nandes
Tí ulo da ese:
Rehabili a ion o con amina ed soils and wa e using “ ailo -made” Technosols
P esen o a miña ese, seguindo o p ocedemen o axei ado ao Regulamen o, e decla o que:
1) A ese aba ca os esul ados da elabo ación do meu aballo.
2) De se o caso, na ese aise e e encia ás colabo acións que i o es e aballo.
3) Con i mo que a ese non inco e en ningún ipo de plaxio dou os au o es nin de aballos
p esen ados po min pa a a ob ención dou os í ulos.
4) A ese é a e sión de ini i a p esen ada pa a a súa de ensa e coincide a e sión imp esa coa
p esen ada en o ma o elec ónico
E comp omé ome a p esen a o Comp omiso Documen al de Supe isión no caso de que o o ixinal non
es ea na Escola.
En San iago de Compos ela, 03 de Ab il de 2023.
Sina u a elec ónica
AUTORIZACIÓN
DEL
TUTOR DE LA TESIS
Rehabili a ion o con amina ed soils and wa e using “ ailo -
made” Technosols
D.
Juan Manuel Lema Rodicio
INFORMA:
Que la p esen e esis, se co esponde con el abajo ealizado po Dª. Ma ia João Ce ei a
Fe nandes, bajo mi u o ización, y a
u o izo
su
p esen ación
, conside ando
que eúne os
equisi os
exigidos en el R
eglamen o
de Es udios de
Doc o ado de la USC,
y
que
como di ec o de es a
no incu e en las causas de
abs ención es ablecidas
en la Ley
40/2015.
De acue do con lo indicado en el Reglamen o de Es udios de Doc o ado, decla a ambién
que la p esen e esis doc o al es idónea pa a se de endida en base a la modalidad
Monog á ica con ep oducción de publicaciones, en los que la pa icipación del doc o ando/a
ue decisi a pa a su elabo ación y las publicaciones se ajus an al Plan de In es igación.
En San iago de Compos ela, 30 de mayo de 2023

AUTORIZACIÓN
DO
DIRECTOR
/
TITOR DA TESE
Rehabili a ion o con amina ed soils and wa e using “ ailo -
made” Technosols
D./Dna.
Felipe Macias Vazquez
D./Dna.
Ma ia C is ina Fe nandes Dele ue Al im de Ma os
INFORMA/N:
Que a p esen e ese, co espóndese co aballo ealizado po D/Dna. Ma ia João Ce ei a
Fe nandes, baixo a miña di ección/ i o ización, e a
u o izo
a súa
p esen ación
, conside ando
que eúne os
equisi os
esixidos no R
egulamen o
de Es udos de
Dou o amen o da
USC,
e
que
como di ec o des a
non inco e nas causas de
abs ención es ablecidas
na Lei
40/2015.
De aco do co indicado no Regulamen o de Es udos de Dou o amen o, decla a amén que a
p esen e ese de dou o amen o é idónea pa a se de endida en base á modalidade de
Monog á ica con ep oducción de publicaciones
, nos que a pa icipación do/a
dou o ando/a oi decisi a pa a a súa elabo ación e as publicacións se axus an ao
Plan de In es igación.
En San iago de Compos ela, 3 de Ab il de 2023
Ma ia João Ce ei a Fe nandes
iii
ACKNOWLEDGMENTS
I would like o exp ess my since e g a i ude o Doc o P o esso C is ina Dele ue-Ma os,
my supe iso , o he in aluable guidance, suppo , and encou agemen h oughou my
esea ch jou ney. He expe ise and eedback we e c ucial in shaping his hesis, and I am
deeply g a e ul o he men o ship. In addi ion, I would like o hank he o he ca e and
conce n she has shown o he pe sonal side o his long, di icul bu beau i ul jou ney.
I am also deeply g a e ul o Doc o P o esso Felipe Macías Vásquez, also my supe iso ,
o his wide knowledge, insigh ul and cons uc i e commen s, sugges ions, and eedback ha
ha e helped me e ine my esea ch and b ing i o comple ion. Addi ionally, and in spi e o all
di icul ies, I hank him o he kindness and iendly smile ha he has always gi en me, in
good and no so good momen s.
I am also g a e ul o Doc o Sonia Figuei edo, who ha e played a signi ican ole in he
de elopmen o my scien i ic pape s, always wi h a good ad ice.
I would also like o hank Doc o Manuela Ca alho o he kindness and iendship, along
wi h he sugges ions and eedback. They we e p ecious o me in he de elopmen o his ip.
I ex end my app ecia ion o all my colleagues om GRAQ/REQUIMTE and IIT-LTA, o hei
aluable con ibu ions o my esea ch. Thei help, expe ience, and iendship made my ime
in he lab enjoyable and ewa ding.
In pa icula , I would like o ex end a hea el hanks o:
Diana and Ma ia, o hei in aluable help and suppo du ing e e y s ep o his jou ney,
making i always ligh e . Thei iendship, ad ice, and encou agemen ha e been a cons an
sou ce o inspi a ion and mo i a ion, as well as hei p o essional and pe sonal suppo .
Paula, i s in aluable help, ellowship, and suppo ha e made his challenging p ocess
much mo e manageable and enjoyable.
Sa a and Luz, o hey iendship and suppo du ing his jou ney.
I would like o hank my amily and iends o hei suppo , encou agemen , and lo e
h oughou my academic jou ney. Thei belie in me and my abili ies has been a cons an
sou ce o mo i a ion and inspi a ion.
Acknowledgmen s
i
Finally, I would like o exp ess my deep g a i ude o my pa en s and b o he o hei
unwa e ing suppo , lo e, and encou agemen h oughou all my li e. They ha e always been
a solid basis o me, and hei suppo has been ins umen al o me o achie e my goals and
be whe e I am oday. I am also g a e ul o my husband, Paulo, o his lo e, suppo , and
e e yday encou agemen . His kindness, posi i i y, and capaci y o ans o m om husband
o a he , and some imes mo he , ha e been a cons an sou ce o inspi a ion and mo i a ion.
I mus also hank my son, F ancisco, o coming o ans o m ou li es in o some hing much
mo e meaning ul and o eaching me new hings e e y day.
Ma ia João Ce ei a Fe nandes
RESUMO
A con aminación ambien al, a al e ación dos p ocesos ambien ais na u ais que a ec an
an o aos compoñen es ísicos como biolóxicos do sis ema Te a/a mos e a, ep esen a un
p oblema g a e e ac ual pa a a sociedade mode na. O no able c ecemen o da poboación
p o ocou cambios p o undos nos pa óns de consumo, incluíndo as necesidades alimen a ias
e sani a ias, e o conseguin e uso excesi o de subs ancias como pes icidas (p odución de
alimen os) e a macéu icos (saúde humana e animal). Tan o os p odu os a macéu icos como
os pes icidas considé anse cada ez máis p odu os químicos de p eocupación eme xen e, con
e ec os nega i os coñecidos sob e as especies do solo e acuá icas e os seus espec i os
ecosis emas, así como e ec os po enciais sob e a saúde humana.
A luoxe ina é un an idep esi o moi u ilizado pa a a a a dep esión. Como oco e con
ou os p odu os a macéu icos, só unha pa e des e compos o é me abolizada polo co po
humano, men es que o es o, así como os seus me aboli os, son exc e ados, chegando
inalmen e aos sis emas de augas esiduais e po encialmen e ao medio ambien e.
O gli osa o e o glu osina o, dous he bicidas o gano os o ados non selec i os de amplo
espec o, e o ácido aminome il os ónico (AMPA), o p incipal me aboli o do gli osa o, amén
son es compos os de in e ese. O ni el de exposición de humanos e animais e os e ec os
noci os des es compos os es án amplamen e documen ados.
Ademais dou os con aminan es eme xen es, a con aminación ambien al po luoxe ina,
gli osa o, glu osina o e AMPA equi e de medidas co ec o as, impoñendo o
desen ol emen o de ecnoloxías de emediación pa a a ehabili ación das zonas a ec adas.
Es udá onse e desen ol é onse di e sas ecnoloxías de emediación pa a ace on e ás
con aminacións ambien ais. Unha des as ecnoloxías de emediación é a adso ción, un
mé odo no que as moléculas ou pa ículas dunha subs ancia son e idas na supe icie dun
ma e ial sólido ou líquido a a és de di e sos mecanismos, como a a acción elec os á ica,
o zas de Van de Waals ou enlaces químicos. Úsase habi ualmen e en p ocesos indus iais
pa a elimina impu ezas de líquidos ou gases, así como na ehabili ación de solos, a amen o
de augas esiduais e depu ación de auga po able. Ademais, é un p oceso que se p oduce de
o ma espon ánea en di e sos sis emas na u ais, como no solo, bene iciando a abso ción de
nu ien es po pa e das plan as ou a adso ción de gases da a mos e a polas pa ículas do
solo. A adso ción in lúe signi ica i amen e na ans e encia e dispoñibilidade de pes icidas no
solo, sendo un dos p incipais p ocesos pa a con ola a lixi iación dos pes icidas e educi a
Resumo
xii
de óxidos de aluminio e e o, a xila e ma e ia o gánica. O desen ol emen o de Tecnosoles “a
la ca a” o ece unha solución inno ado a e in eg ada que con ibúe a mello a a calidade dos
ecu sos na u ais, p omo endo a sus en abilidade, educindo a p odución de esiduos e
es au ando zonas con aminadas.
En xe al, os coñecemen os adqui idos pe mi en coñece mello o es ado ac ual de
con aminación ambien al po p odu os a macéu icos e p aguicidas, xa que demos a que a
con aminación non só chega aos cu sos de auga, senón que amén a ec a aos sedimen os e
ás augas sub e áneas. Es a in es igación p opo ciona da os aliosos sob e a adso ción de
luoxe ina, gli osa o, AMPA e glu osina o en di e en es ma e iais. Os es udos de adso ción
mos a on, en e ou os esul ados, que os ma e iais biocha p obados xu di on como
excelen es ma e iais adso ben es de luoxe ina pe o, pola con a, non eñen unha boa
capacidade de e ención de compos os como o gli osa o, o AMPA e, especialmen e, o
glu osina o. Po ou a banda, os solos e Tecnosoles mos a on unha al a capacidade de
e ención de gli osa o e AMPA. O glu osina o non endeu a adso bi se a ningún dos ma e iais
ensaiados.
Os esul ados apoian o desen ol emen o de ecnoloxías de emediación des inadas a
mi iga o impac o ambien al des es compos os, p e i a con aminación e sal aga da a saúde
pública. Ademais, p opoñen o uso do biocha como compoñen e dos ecnosoles p oducidos
pa a e e a luoxe ina. Tamén des aca algunhas das ca ac e ís icas undamen ais que se
equi en dos cons i uín es do ecnosol pa a a co ec a adso ción do gli osa o e do AMPA.

Ma ia João Ce ei a Fe nandes
xiii
RESUMEN
La con aminación ambien al, la al e ación de los p ocesos ambien ales na u ales que a ec an
an o a los componen es ísicos como biológicos del sis ema Tie a/a mós e a, ep esen a un
p oblema g a e y ac ual pa a la sociedad mode na. El no able c ecimien o demog á ico ha
p o ocado p o undas al e aciones en los pa ones de consumo, incluyendo las necesidades
alimen a ias y sani a ias, y el consiguien e uso excesi o de sus ancias como los plaguicidas
(p oducción de alimen os) y los p oduc os a macéu icos (salud humana y animal). Tan o los
p oduc os a macéu icos como los plaguicidas se conside an cada ez más sus ancias químicas
de p eocupación eme gen e, con e ec os nega i os conocidos sob e el suelo y las especies
acuá icas y sus espec i os ecosis emas, así como e ec os po enciales sob e la salud humana.
La luoxe ina es un an idep esi o ampliamen e u ilizado pa a a a la dep esión. Como
ocu e con o os p oduc os a macéu icos, sólo una pa e de es e compues o es me abolizada
po el cue po humano, mien as que el es o, así como sus me aboli os, son exc e ados,
alcanzando e en ualmen e los sis emas de aguas esiduales y po encialmen e el medio
ambien e.
El gli osa o y el glu osina o, dos he bicidas o gano os o ados no selec i os de amplio
espec o, y el ácido aminome il os ónico (AMPA), me aboli o p incipal del gli osa o, son
ambién es compues os de in e és. El ni el de exposición de humanos y animales y los
e ec os noci os de es os compues os es án ampliamen e documen ados.
Así como o os con aminan es eme gen es, la con aminación ambien al po luoxe ina,
gli osa o, glu osina o y AMPA, equie e medidas co ec o as, imponiéndose el desa ollo de
ecnologías de emediación pa a la ehabili ación de las zonas a ec adas.
Se han es udiado y desa ollado a ias ecnologías de emediación pa a a a las
con aminaciones medioambien ales. Una de es as ecnologías de emediación es la adso ción,
un mé odo en el que las moléculas o pa ículas de una sus ancia son e enidas en la supe icie
de un ma e ial sólido o líquido a a és de dis in os mecanismos, como la a acción
elec os á ica, las ue zas de Van de Waals o los enlaces químicos. Se u iliza habi ualmen e
en p ocesos indus iales pa a elimina impu ezas de líquidos o gases, así como en la
ehabili ación de suelos, en el a amien o de aguas esiduales y en la pu i icación de agua
po able. Además, es un p oceso que ocu e espon áneamen e en di e sos sis emas na u ales,
como en el suelo, bene iciando la abso ción de nu ien es po las plan as o la adso ción de
gases de la a mós e a po las pa ículas del suelo. La adso ción in luye signi ica i amen e en
Resumen
xi
la ans e encia y disponibilidad de los plaguicidas en el suelo, siendo uno de los p incipales
p ocesos de con ol de la lixi iación de plaguicidas y educiendo su mig ación y el po encial de
con aminación de las aguas supe iciales o sub e áneas. Dado que se u iliza ampliamen e en
a amien os de aguas esiduales a la ga escala, debido a su sencilla es uc u a, su al a
e iciencia y la posibilidad de u iliza adso ben es de bajo cos e y no óxicos, puede op imiza se
y aplica se a la eliminación de p oduc os a macéu icos y plaguicidas. Pa a es udia la
adso ción de di e en es ipos de sus ancias como la luoxe ina, el gli osa o, el AMPA y el
glu osina o, es esencial e alua el uso de una amplia a iedad de ma e iales adso ben es y sus
p opiedades isicoquímicas. Su selección es de g an impo ancia, y ca ac e ís icas como el bajo
cos e, la sos enibilidad, la no oxicidad y la al a capacidad de so ción son a ibu os
signi ica i os a ene en cuen a.
El biocha es un ma e ial po oso sólido y es able con al o con enido en ca bono,
p oducido a a és de la pi ólisis/ca bonización de biomasa en un en o no de oxígeno limi ado
o ausen e y en condiciones de empe a u a mode ada. Es un ma e ial a ac i o pa a se
implemen ado como adso ben e pa a e ene y elimina con aminan es de ambien es sólidos
y acuosos. Su uso se p esen a como una he amien a pa a la ges ión medioambien al,
ac uando en la mejo a de la calidad de los suelos, en el a amien o de esiduos, en la
mi igación del cambio climá ico y en la p oducción de ene gía. Además de se
económicamen e a ac i os, los biocha se u ilizan en g an medida como adso ben es debido
a su al a capacidad de e ención de dis in os con aminan es asociada a su ele ada supe icie
especí ica y po osidad, capacidad de in e cambio iónico y pH. La selección de la ma e ia p ima
puede in luencia ampliamen e sus p opiedades, así como las condiciones del p oceso de
p oducción, es deci , la empe a u a, la apidez de calen amien o, la p esión y el iempo de
esidencia.
O a ecnología inno ado a de emediación es el uso de Tecnosoles “a la ca a”. Los
Tecnosoles son un g upo de suelos de e e encia de inido en la Wo ld Re e ence Base pa a los
ecu sos edá icos (de la O ganización de las Naciones Unidas pa a la Ag icul u a y la
Alimen ación y la Unión In e nacional de Ciencias del Suelo) como una combinación de suelos
"cuyas p opiedades y pedogénesis es án dominadas po su o igen écnico". Es os suelos,
dominados o ue emen e a ec ados po ma e iales ab icados po el homb e y ue emen e
modi icados (denominados a e ac os, como esiduos de ma e iales como lad illos, id io,
esiduos domés icos, esiduos de minas, lodos, en e o os) o ex aídos de g andes
p o undidades, se encuen an con ecuencia en zonas u banas e indus iales. Los Tecnosoles
"a la ca a" son suelos a i iciales c eados median e la combinación de suelo na u al con
Ma ia João Ce ei a Fe nandes
x
ma e iales an opogénicos, de i ados de ac i idades humanas, con o os adi i os pa a
ob ene las ca ac e ís icas deseadas. Replican las unciones del suelo na u al y pueden
u iliza se pa a p opo ciona a ias unciones del suelo y se icios ecosis émicos, como
condiciones adecuadas pa a el c ecimien o/p oducción de plan as (alimen os y biomasa), la
ecupe ación del suelo, el secues o de ca bono, la es au ación de masas de agua y zonas
deg adadas o con aminadas, la eposición de aguas sub e áneas y la biodi e sidad de los
ecosis emas. El biocha es uno de los ma e iales que pueden inco po a se en la p oducción de
Tecnosoles "a la ca a".
Así, como una p ime a ap oximación a los p oblemas abo dados en es e abajo, se lle ó
a cabo el moni o eo de an ibió icos y an idep esi os en las aguas y sedimen os de dos íos del
no e de Po ugal. Se ecogie on mues as de sedimen os de dos camadas, la camada
supe io , en e 0 y 2 cm de p o undidad, y la camada in e io , en e 2 y 10 cm. El p esen e
es udio incluyó la ca ac e ización y el análisis de mues as pa a diecisie e an ibió icos y diez
an idep esi os. La compa ación de las concen aciones de á macos en las mues as del ío
Leça y del ío Dou o e eló ni eles más ele ados en el ío Leça. Sólo se de ec a on
ca bamazepina y luoxe ina en las mues as de agua del Dou o, mien as que las mues as de
agua de Leça con enían ece de los ein isie e p oduc os a macéu icos, incluidos seis
an ibió icos y sie e á macos psiquiá icos. En pa icula , la azi omicina se encon ó en la
concen ación más al a (2.82 µg/L) en las mues as del ío Leça, especialmen e ce ca de un
pun o de desca ga de e luen es de una plan a de a amien o de aguas esiduales. La
luoxe ina p esen ó la mayo ecuencia de de ección en las mues as de agua. La p esencia
de ca bamazepina y enla axina en el agua del ío Leça ue e elado a de iesgos po enciales
pa a las algas. En las mues as de sedimen os, se encon ó sul ame oxipi idazina en el
sedimen o del Dou o, mien as que se de ec ó azi omicina en el sedimen o de Leça, ambas
p incipalmen e en la camada supe io del sedimen o. También se de ec a on á macos
psiquiá icos, cua o en el sedimen o de Dou o y seis en el de Leça. Una compa ación en e
las camadas supe io e in e io del sedimen o en cada pun o de mues eo mos ó que la
enla axina, el único á maco cuan i icado en el ío Dou o, p esen aba una mayo
concen ación en la zona in e io , po encialmen e elacionada con la mig ación del suelo. En
los sedimen os de Leça, se obse a on concen aciones más ele adas en la camada supe io ,
p obablemen e asociadas a episodios ecien es de con aminación en la zona. Una e isión de
los es udios de moni o ización epo ados en la li e a u a e eló una inclusión educida de
análisis de sedimen os, cen ándose la mayo ía de los es udios únicamen e en mues as de
agua (especialmen e pa a d ogas psiquiá icas). Po lo an o, no ue posible iden i ica un
pa ón de con aminación consis en e ni es ablece un ínculo cla o en e la con aminación de
Resumen
x i
los sedimen os y la mig ación de con aminan es del agua, basándose en los esul ados
ob enidos y en las compa aciones bibliog á icas. Sin emba go, se obse a on
sis emá icamen e concen aciones más ele adas de con aminan es en los luga es de
mues eo si uados aguas abajo de los e idos de las plan as de a amien o de aguas
esiduales.
Además, se ealizó una e isión bibliog á ica de la con aminación del agua y los
sedimen os po gli osa o, AMPA y glu osina o en odo el mundo. El obje i o ue in es iga la
con aminación y la mo ilidad de las sus ancias e e idas en los medios acuá icos, con especial
a ención a las mues as de agua y sedimen os. La in es igación incluyó una exhaus i a e isión
bibliog á ica pa a analiza los es udios publicados en los úl imos cinco años que moni o iza on
las concen aciones de es os compues os en agua ( an o supe icial como sub e ánea) y
sedimen os. El análisis de la legislación aplicable e eló a iaciones signi ica i as en los alo es
lími e de es os con aminan es en los dis in os países. Po ejemplo, la Unión Eu opea
es ableció el lími e legal más bajo pa a los esiduos de gli osa o en el agua des inada al
consumo humano, con un lími e de 0.1 μg/L, mien as que Japón es ableció el lími e más al o
en 2 000 μg/L. Los mé odos de de ección más u ilizados en los es udios analizados ue on la
c oma og a ía líquida de al a esolución (HPLC) en ándem con la espec ome ía de masas
(MS/MS). Sin emba go, se encon ó que sólo el 40% de los es udios e isados epo a on
lími es de de ección po debajo del alo máximo pe misible de la Unión Eu opea pa a la
con aminación del agua po plaguicidas indi iduales (0.1 μg/L). La in es igación del moni o eo
del gli osa o en el agua y los sedimen os e eló endencias in e esan es. F ancia esul ó se el
país con la mayo elación mues as/publicaciones, seguido de Japón e I alia. A gen ina, po
su pa e, p esen ó una mayo ecuencia de publicaciones de es udios, pe o una meno
elación mues as/publicaciones. En pa icula , los países eu opeos que ealiza on un mayo
núme o de análisis del ni el de gli osa o endie on a co esponde se con una mayo asa de
aplicación de gli osa o. En cuan o al seguimien o de AMPA, A gen ina p esen ó una mayo
ecuencia de es udios, mien as que F ancia man u o su posición como país con la mayo
elación mues as/publicación, seguida de Es ados Unidos, Suecia e I alia. China se des acó
con un núme o signi ica i amen e mayo de mues as moni o eadas pa a glu osina o en
compa ación con o os países con publicaciones sob e es e compues o. Las concen aciones
máximas de con aminan es a ia on en unción de la ma iz ambien al. En aguas supe iciales,
las concen aciones más al as se encon a on pa a el AMPA (6 872 μg/L), seguido del gli osa o
(5 750 μg/L) y el glu osina o (13.15 μg/L). En las aguas sub e áneas, los alo es máximos
ue on de 8 700 μg/L pa a el gli osa o, 233 μg/L pa a el AMPA y 0.03 μg/L pa a el glu osina o.
Los sedimen os mos a on las mayo es concen aciones de ec adas de glu osina o (14.9
Ma ia João Ce ei a Fe nandes
x ii
μg/kg), mien as que el gli osa o y el AMPA alcanza on concen aciones máximas de 1 882
μg/kg y 4 033 μg/kg, espec i amen e. Con a iamen e a lo espe ado, la concen ación
máxima de gli osa o ue mayo en las aguas sub e áneas que en las supe iciales. Sin
emba go, la ecuencia de de ección ue signi ica i amen e mayo en las aguas supe iciales
(70%) en compa ación con las sub e áneas (18%). En cuan o al AMPA y al glu osina o, la
ecuencia de de ección en las aguas supe iciales ue del 87% y del 6%, espec i amen e,
mien as que en las aguas sub e áneas ue del 16% y del 0.7%. Los países sudame icanos
p esen a on los alo es más al os de concen ación máxima de ec ada pa a el gli osa o y el
AMPA, mien as que los sedimen os ue on la ma iz ambien al con mayo concen ación de
glu osina o. F ancia p esen ó las mayo es concen aciones máximas de gli osa o en aguas
supe iciales, seguida de I alia y Alemania. En las aguas sub e áneas, Suecia p esen ó las
concen aciones máximas de gli osa o, seguida de I alia. Alemania y C oacia p esen a on los
ni eles máximos de concen ación en sedimen os. Se iden i ica on a ios ac o es como
impulso es de la dispe sión de es os compues os en aguas supe iciales, sedimen os y aguas
sub e áneas. Es os ac o es incluían el exceso de pul e ización, la de i a de la pul e ización,
las esco en ías supe iciales, los ni eles eá icos poco p o undos, la baja conduc i idad
hid áulica de los acuí e os, el bajo g adien e hid áulico, la elocidad muy baja del lujo, el ipo
de suelo y la cons i ución química. La aplicación pe sis en e y c ecien e de es os compues os
en ac i idades ag ícolas y domés icas, el uso inadecuado y las plan as de a amien o de aguas
esiduales se iden i ica on como uen es po enciales de con aminación. Es a e isión acla ó el
p oblema de la con aminación y la mo ilidad del gli osa o, el AMPA y el glu osina o en el agua
y los sedimen os. Los esul ados sub aya on la necesidad de lle a a cabo un seguimien o
con inuo y de desa olla es a egias de emediación pa a mi iga el impac o ambien al de
es os compues os. Los esul ados ambién pusie on en elie e la impo ancia de una
legislación a monizada y unos alo es lími e uni icados en odos los países pa a ga an iza una
p o ección e icaz de los ecu sos híd icos.
A la is a de la con aminación documen ada asociada a los compues os in es igados, es
c ucial iden i ica ecnologías de emediación que no sólo se ocupen de los luga es
con aminados, sino que ambién eduzcan la mo ilidad de es os compues os. Es as
ecnologías pueden e i a la con aminación del agua y del suelo y minimiza los p oblemas de
salud asociados a la inges ión de es os compues os. En consecuencia, es a in es igación se
cen ó en el es udio de la adso ción de luoxe ina, gli osa o, AMPA y glu osina o sob e
di e sos ma e iales, con di e en es ca ac e ís icas, con el in de comp ende y op imiza su
adso ción. Con es e in, se desa olla on es udios de adso ción, a sabe , ensayos de equilib io,
ciné icos y de in luencia del pH, pa a es udia la adso ción de los cua o compues os

Resumen
x iii
analizados. Se ensaya on di e en es adso ben es con ca ac e ís icas dis in as pa a encon a
los ma e iales y ca ac e ís icas más adecuados pa a in eg a la composición de un Technosol
"a la ca a". Si se aplican a la p oducción de un Technosol "a la ca a”, los esul ados pe mi i án
desa olla una solución inno ado a e in eg ada que con ibuya a mejo a la calidad de los
ecu sos na u ales, la sos enibilidad, la educción de la p oducción de esiduos y la
es au ación de zonas con aminadas.
En la p ime a ase del es udio se ensaya on doce biocha s de i ados de di e en es
esiduos o es ales y ag oalimen a ios (podas de Que cus ilex, Eucalyp us g andis, Pinus
pinas e , Que cus sube , Malus pumila, P unus spinosa, Cydonia oblonga, E iobo ya japonica,
Juglans egia, Ac inidia deliciosa, Ci us sinensis y Vi is ini e a) como adso ben es po enciales,
de bajo cos e y eno ables, pa a la eliminación de la luoxe ina del agua. Los expe imen os
p elimina es de adso ción pe mi ie on selecciona los adso ben es más p ome edo es,
Que cus ilex (encina), Cydonia oblonga (memb illo), Eucalyp us, Juglans egia (nogal) y
ma e ial de poda de Vi is ini e a ( id). Se ca ac e iza on median e análisis p oximal,
elemen al y mine al, análisis e mog a imé ico, espec oscopia in a oja po ans o mada
de Fou ie , de e minación de la supe icie especí ica y pH en el pun o de ca ga ce o (pHPZC).
Se ealiza on es udios po ba ch y de equilib io, y se e aluó la in luencia del pH. Se
de e mina on las capacidades de adso ción de los biocha s seleccionados, con alo es que
oscilaban en e 2.21 y 6.41 mg/g según el modelo de Langmui . En e los biocha s ensayados,
el biocha de eucalip o mos ó la mayo capacidad de adso ción, seguido de los biocha s de
encina, id, nogal y memb illo. La ciné ica de adso ción ue ápida, p oduciéndose la adso ción
comple a en menos de 15 minu os. Los expe imen os de adso ción en columna ealizados con
biocha de eucalip o demos a on su e icacia en modo con inuo, p esen ando un a ance del
50% de eliminación a los 90 minu os, lo que sugie e su po encial como al e na i a eno able
pa a la eliminación de luoxe ina.
La siguien e ase de la in es igación se cen ó en in es iga la adso ción de gli osa o,
AMPA y glu osina o en cua en a y un ma e iales di e en es, incluidos biocha s, suelos y
Tecnosoles "a la ca a" (TMT). Los biocha s ensayados se p oduje on a pa i de oncos de
acacia (Acacia melanoxylon) di ididos en albu a (BAcSw-3) y du amen (BAcHw-2), amas de
eucalip o (BEu-2), se ín de pino (BSd-1), co eza de pino (BPb), compos de o ujo de oli a
(BOpc), casca illa de a oz (BRh), mazo ca de maíz (BCc1 y BCc-2), y as illas de made a
i u adas alemanas (BSdG). Las ocho mues as de suelo analizadas e an Umb isoles
alumínicos (S4A, 11B, 13A), Fe asoles de i ados de an iboli as (S9B), Umb isoles Háplicos
(1Ah y 2Ah) y Lep osoles Ándicos y Fe álicos. En elación con el TMT, los ma e iales ensayados
Ma ia João Ce ei a Fe nandes
xix
se clasi ica on como Tecnosoles a énicos cálcicos (TMT 1), Tecnosoles aluándicos (TMT 2),
Tecnosoles ándicos eú icos (TMT 3, G, I, J, K, L, M, Q, R y S), Tecnosoles eú ico educ o es
(TMT 4 y A), Tecnosoles dís icos (TMT B y D), Tecnosoles cálcicos (TMT C), Tecnosoles ándicos
(TMT E y F), Tecnosoles eú icos (TMT H y O), Tecnosol é ico (TMT N) y Tecnosoles ándicos
educ o es (TMT P). Es os TMT se p oduje on a pa i de esiduos indus iales y
ag oindus iales, a sabe , sedimen os de mina, biomasa de se ín, lodos del a amien o de
aguas esiduales, compos o gánico, cenizas y a ena. Los esul ados indica on que los es
compues os ue on pob emen e adso bidos po la mayo ía de las mues as de biocha , con
asas máximas de eliminación del 25% pa a el gli osa o, 12% pa a el AMPA, y 4% pa a el
glu osina o. Es os esul ados se a ibuye on p incipalmen e a la empe a u a de p oducción
de los biocha . Po el con a io, los suelos ensayados mos a on al as capacidades de
adso ción pa a gli osa o y AMPA, con asas máximas de eliminación del 94% y 91% en los
ensayos p elimina es, espec i amen e. Sin emba go, la adso ción de glu osina o ue limi ada,
con asas de eliminación que no supe a on el 6%. Los TMT ambién mos a on capacidades
de adso ción signi ica i as du an e los ensayos p elimina es, con asas de eliminación
máximas del 79% pa a el gli osa o y del 83% pa a el AMPA. Una ez más, el glu osina o mos ó
alo es de adso ción bajos, con una asa de eliminación máxima de sólo el 3%. Además, se
obse ó que los amaños de g ano más pequeños mejo aban el endimien o de la adso ción
en compa ación con los suelos o TMT con amaños de g ano más g andes. El iempo de
equilib io pa a la adso ción a ió, p oduciéndose la adso ción o al en 14 ho as en el caso de
los suelos y en 72 ho as en el de los TMT, lo que concue da con hallazgos an e io es en la
bibliog a ía. Las capacidades máximas de adso ción, según el modelo de Langmui , se
de e mina on en 10.84 mg/g pa a el gli osa o (suelo S9B) y 15.08 mg/g pa a el AMPA (TMT 1).
En cuan o a la in luencia del pH en el p oceso de adso ción, el gli osa o y el ácido
aminome il os ónico (AMPA) p esen an compo amien os de ca ga dis in os. Analizando el
impac o del pH en el p oceso de adso ción con los adso ben es ensayados, que ienen un
pHPZC de ap oximadamen e 4.9, la adso ción de gli osa o y AMPA exhibió un
compo amien o dependien e del pH. La adso ción aumen ó en e pH 1 y pH 3,
co espondiendo a la pé dida de p o ones asociada al g upo ca boxilo del gli osa o (pKa2) y al
g upo os ónico del AMPA (pKa1) en p esencia de una supe icie adso ben e
p edominan emen e ca gada posi i amen e. Pos e io men e, se p odujo una disminución
g adual de la adso ción en e pH 3 y pH 6, más p onunciada pa a el gli osa o que pa a el AMPA.
En e pH 6 y 10, la adso ción de gli osa o en los adso ben es ensayados disminuyó
signi ica i amen e, excep o en el caso de TMT 1, que sólo mos ó una adso ción educida a
pH supe io es a 10, ace cándose a alo es p óximos a ce o. En el caso del AMPA, la educción
Resumen
xx
de la adso ción po los TMT se p odujo de o ma más des acada a pa i de alo es de pH
supe io es a 9, obse ándose una adso ción ela i amen e cons an e en e pH 6 y 10 pa a el
es o de adso ben es. Pa a odos los adso ben es, se p odujo una no able disminución de la
adso ción has a alo es ce canos a ce o en e pH 10 y 12, excep o pa a la adso ción de
gli osa o en el suelo S4A, que mos ó una adso ción lige amen e supe io a pH 12 en
compa ación con los o os adso ben es. En gene al, la mayo adso ción de gli osa o y AMPA
en suelos y TMTs ocu ió den o del ango de pH de 2 a 5, con las supe icies de los
adso ben es p edominan emen e ca gadas posi i amen e, y aunque la p incipal o ma iónica
del AMPA den o de es e ango de pH es neu a. Es os hallazgos demues an que los suelos
na u ales y los TMT pueden se i como adso ben es e icaces, de bajo cos e y sos enibles pa a
elimina el gli osa o y el AMPA de soluciones acuosas. Además, pa a la p oducción de TMT
debe ían selecciona se ma e iales con pH ela i amen e bajo y al o con enido en óxidos de
aluminio y hie o, a cilla y ma e ia o gánica. El desa ollo de Tecnosoles a medida o ece una
solución inno ado a e in eg ada que con ibuye a mejo a la calidad de los ecu sos na u ales,
p omo e la sos enibilidad, educi la p oducción de esiduos y es au a las zonas
con aminadas.
En gene al, los conocimien os adqui idos pe mi en comp ende mejo el es ado ac ual de
la con aminación ambien al po p oduc os a macéu icos y plaguicidas, pues demues an que
la con aminación no sólo llega a los cu sos de agua, sino que ambién a ec a a los sedimen os
y las aguas sub e áneas. Es a in es igación apo a aliosos da os sob e la adso ción de
luoxe ina, gli osa o, AMPA y glu osina o en dis in os ma e iales. Los es udios de adso ción
mos a on, en e o os esul ados, que los ma e iales de biocha ensayados se e igie on como
excelen es ma e iales adso ben es de luoxe ina pe o, po el con a io, no p esen an una
buena capacidad de e ención a compues os como gli osa o, AMPA y, especialmen e,
glu osina o. Po o o lado, los suelos y los Technosols han mos ado una al a capacidad de
e ención pa a el gli osa o y el AMPA. El glu osina o no endió a adso be se en ninguno de los
ma e iales ensayados.
Los esul ados apoyan el desa ollo de ecnologías de emediación des inadas a mi iga el
impac o ambien al de es os compues os, p e eni la con aminación y sal agua da la salud
pública. Además, p oponen el uso de biocha como componen e de Tecnosoles p oducidos
pa a e ene la luoxe ina. También des aca algunas de las ca ac e ís icas cla e que se
equie en de los cons i uyen es del Tecnosol pa a una adso ción adecuada del gli osa o y el
AMPA.
Ma ia João Ce ei a Fe nandes
xxi
ABSTRACT
En i onmen al pollu ion, he dis u bance o na u al en i onmen al p ocesses ha a ec
bo h he physical and biological componen s o he ea h/a mosphe e sys em, ep esen s a
se ious and cu en p oblem o mode n socie y. The subs an ial popula ion g ow h has led o
ema kable al e a ions in consump ion pa e ns, including ood and heal h necessi ies and
consequen o e use o subs ances such as pes icides ( ood p oduc ion) and pha maceu icals
(human and animal heal h). Bo h pha maceu icals and pes icides a e inc easingly
acknowledged as chemicals o eme ging conce n, wi h known nega i e impac s on soil and
aqua ic species and espec i e ecosys ems and po en ial e ec s on human heal h.
Fluoxe ine is an an i-dep essan pha maceu ical widely used o ea dep ession. As wi h
o he pha maceu icals, only a pa o his compound is me abolized by he human body, while
he es , as well as i s me aboli es, a e exc e ed, e en ually eaching he was ewa e sys ems
and po en ially he en i onmen .
Glyphosa e and glu osina e, wo b oad-spec um, non-selec i e, o ganophospho us
he bicides, and aminome hylphosphonic acid (AMPA), he p ima y me aboli e o glyphosa e,
a e also h ee compounds o conce n. The exposu e le el o humans and animals and he
ha m ul e ec s o hese compounds is la gely documen ed.
As well as o he eme ging pollu an s, en i onmen al con amina ion by luoxe ine,
glyphosa e, glu osina e, and AMPA, equi e co ec i e measu es, imposing he de elopmen
o emedia ion echniques o he ehabili a ion o he a ec ed a eas.
Se e al emedia ion echnologies ha e been s udied and de eloped o ea
en i onmen al con amina ions. One o hese emedia ion echnologies is adso p ion, a
me hod in which molecules o pa icles o a subs ance a e e ained on he su ace o a solid
o liquid ma e ial h ough a ious mechanisms, such as elec os a ic a ac ion, an de Waals
o ces, o chemical bonding. I is commonly used in indus ial p ocesses o emo e impu i ies
om liquids o gases, as well as in soil emedia ion, was ewa e ea men , and d inking wa e
pu i ica ion. Also, i is a p ocess ha spon aneously occu s in many na u al sys ems, such as
in soil, bene i ing he up ake o nu ien s by plan s o he adso p ion o gases in he
a mosphe e by soil pa icles. Adso p ion signi ican ly a ec s he ans e and a ailabili y o
pes icides in soil, being one o he main p ocesses o con olling pes icide leaching and
educing hei mig a ion and he po en ial o con amina e su ace wa e s o g oundwa e . As
i is ex ensi ely used in la ge-scale was ewa e ea men s, due o i s simple layou , high
Abs ac
xx iii
o e ain luoxe ine. I also highligh s some o he key cha ac e is ics equi ed om he
Technosol cons i uen s o adequa e adso p ion o glyphosa e and AMPA.

Ma ia João Ce ei a Fe nandes
xxix
INDICE
LIST OF ABBREVIATIONS ........................................................................................... XXXIII
CHAPTER 1 INTRODUCTION .......................................................................................... 1
1.1 Gene al backg ound .................................................................................................................... 1
1.2 Objec i es and s uc u e ............................................................................................................. 2
1.2.1 Main objec i e ............................................................................................................................... 2
1.2.2 Speci ic objec i es ......................................................................................................................... 3
1.2.3 Thesis ou line ................................................................................................................................ 4
CHAPTER 2 LITERATURE REVIEW ................................................................................... 7
2.1 En i onmen al Pollu ion ............................................................................................................. 7
2.2 Pha maceu ical p oduc s ............................................................................................................ 9
2.2.1 Fluoxe ine an idep essan use .................................................................................................... 16
2.2.2 An idep essan Fluoxe ine - chemical and physical p ope ies .................................................. 18
2.2.3 An idep essan Fluoxe ine - deg ada ion and dissipa ion pa hs ................................................ 20
2.2.4 Analy ical me hodologies o Fluoxe ine de ec ion in en i onmen al ma ixes ......................... 21
2.3 Pes icides en i onmen al con amina ion ...................................................................................22
2.3.1 The use o glyphosa e and glu osina e‐based he bicides ........................................................... 28
2.3.2 Chemical and physical p ope ies o glyphosa e and glu osina e ............................................... 33
2.3.3 Glyphosa e and Glu osina e - deg ada ion and dissipa ion pa hs .............................................. 35
2.3.4 Analy ical me hodologies o Glyphosa e, AMPA and Glu osina e de ec ion in en i onmen al
ma ixes 40
2.4 Inno a i e echnologies o mi iga ion o new con aminan s ....................................................43
2.4.1 Adso p ion ................................................................................................................................... 48
2.4.2 P ospec i e use o biocha o emedia e con amina ed si es .................................................... 49
2.4.3 P ospec i e use o ailo -made Technosols o emedia e con amina ed si es ........................... 52
2.4.4 Selec ion o he emedia ion echnologies o glyphosa e, AMPA, glu osina e, and luoxe ine
con amina ion in soil and wa e ....................................................................................................................... 55
Indice
xxx
CHAPTER 3 ANTIBIOTICS AND ANTIDEPRESSANTS OCCURRENCE IN SURFACE WATERS
AND SEDIMENTS COLLECTED IN THE NORTH OF PORTUGAL ................................................. 57
3.1 In oduc ion ...............................................................................................................................59
3.2 Ma e ials and me hods ..............................................................................................................61
3.2.1 Physical cha ac e is ics and poin s o pollu ion o he Dou o and Leça i e s............................ 61
3.2.2 Ri e wa e s and sedimen s sampling ......................................................................................... 62
3.2.3 Ri e wa e s and sedimen s cha ac e iza ion ............................................................................. 63
3.2.4 Reagen s and chemicals .............................................................................................................. 64
3.2.5 SPE ca idges and QuEChERS ube ............................................................................................. 65
3.2.6 Ri e wa e s and sedimen s ex ac ion p ocedu es ................................................................... 65
3.2.7 UHPLC-MS/MS analysis ............................................................................................................... 65
3.2.8 Valida ion .................................................................................................................................... 66
3.2.9 S a is ical analysis ....................................................................................................................... 66
3.2.10 Risk assessmen ...................................................................................................................... 66
3.3 Resul s and discussion ...............................................................................................................66
3.3.1 Pa ame e s .................................................................................................................................. 66
3.3.2 Me hod pe o mance o pha maceu ical moni o ing ............................................................... 68
3.3.3 Ri e wa e s and sedimen s moni o ing ..................................................................................... 72
3.3.4 S a is ical analysis ....................................................................................................................... 76
3.3.5 Concen a ion ound in li e a u e ............................................................................................... 78
3.4 Conclusions ................................................................................................................................80
CHAPTER 4 GLYPHOSATE, AMPA AND GLUFOSINATE OCCURRENCE IN WATERS AND
SEDIMENTS – WORLD ASSESSMENT ................................................................................... 111
4.1 Limi s and h eshold o Glyphosa e, AMPA, and Glu osina e in wa e .................................... 112
4.2 P e- ea men , ex ac ion, and analysis ................................................................................... 115
4.3 En i onmen al moni o ing ....................................................................................................... 118
4.4 Glyphosa e, AMPA and glu osina e in wa e and sedimen s .................................................... 122
4.5 P esence o glyphosa e, AMPA and glu osina e in o he ma ixes ........................................... 128
Ma ia João Ce ei a Fe nandes
xxxi
4.6 S udy and analysis o highe mobili y pa hways ...................................................................... 129
4.7 Glyphosa e, AMPA and glu osina e con amina ion sou ces ..................................................... 132
CHAPTER 5 EVALUATION OF THE ADSORPTION POTENTIAL OF BIOCHARS PREPARED
FROM FOREST AND AGRI-FOOD WASTES FOR THE REMOVAL OF FLUOXETINE .................... 135
Abs ac ................................................................................................................................................ 137
5.1 In oduc ion ............................................................................................................................. 137
5.2 Ma e ials and me hods ............................................................................................................ 139
5.2.1 Chemicals .................................................................................................................................. 139
5.2.2 Biocha p epa a ion .................................................................................................................. 139
5.2.3 Biocha cha ac e iza ion ........................................................................................................... 140
5.2.4 P elimina y adso p ion assays................................................................................................... 141
5.2.5 Kine ic assays ............................................................................................................................ 142
5.2.6 E ec o pH ................................................................................................................................ 142
5.2.7 Equilib ium assays ..................................................................................................................... 143
5.2.8 Column assays ........................................................................................................................... 144
5.2.9 De e mina ion o luoxe ine concen a ion .............................................................................. 145
5.3 Resul s and discussion ............................................................................................................. 145
5.3.1 P elimina y adso p ion assays................................................................................................... 145
5.3.2 Biocha cha ac e iza ion ........................................................................................................... 146
5.3.3 Kine ic assays ............................................................................................................................ 148
5.3.4 pH s udies .................................................................................................................................. 150
5.3.5 Adso p ion iso he ms ................................................................................................................ 152
5.3.6 Column adso p ion assay .......................................................................................................... 154
5.4 Conclusions .............................................................................................................................. 155
CHAPTER 6 INFLUENCE OF ADSORBENT MATERIAL AND ITS CHARACTERISTICS ON THE
GLYPHOSATE, AMPA AND GLUFOSINATE REMOVAL ............................................................ 161
Abs ac ................................................................................................................................................ 163
Indice
xxxii
6.1 In oduc ion ............................................................................................................................. 163
6.2 Ma e ials and me hods ............................................................................................................ 168
6.2.1 Chemicals and eagen s ............................................................................................................ 168
6.2.2 Adso ben Ma e ials P epa a ion/Sou ce ................................................................................. 168
6.2.3 Adso ben Ma e ials Cha ac e iza ion ...................................................................................... 169
6.2.4 Ba ch adso p ion assays ............................................................................................................ 170
6.2.5 pH in luence .............................................................................................................................. 172
6.2.6 De e mina ion o glyphosa e, AMPA, and glu osina e .............................................................. 172
6.3 Resul s and discussion ............................................................................................................. 173
6.3.1 Adso ben Ma e ials Cha ac e iza ion ...................................................................................... 173
6.3.2 Ba ch adso p ion assays ............................................................................................................ 175
6.3.3 pH in luence .............................................................................................................................. 186
6.3.4 Discussion .................................................................................................................................. 190
6.4 Conclusions .............................................................................................................................. 191
CHAPTER 7 GENERAL CONCLUSIONS ......................................................................... 201
7.1 Main ou comes o he hesis .................................................................................................... 201
7.2 Fu u e esea ch ecommenda ions .......................................................................................... 205
REFERENCES ................................................................................................................ 207
LIST OF PUBLICATIONS ................................................................................................ 250
ANNEX - AUTHORIZATION FOR USE AND ADAPTATION OF FIGURES ............................. 255
Lis o Abb e ia ions
xxxiii
LIST OF ABBREVIATIONS
AA
Ace icacidanhyd ide
ACN
Ace oni ile
AOP
Ad anced oxida ion p ocess
EC
Elec ical conduc i i y
CEC
Chemicals o eme ging conce n
CE-MS
Capilla y elec opho esis-mass spec ome y
DAD
Diode a ay de ec o
EBS
e ec i e base sa u a ion
ECD
Elec ochemical de ec ion
EFSA
Eu opean Food Sa e y Au ho i y
ELISA
Enzyme-linked immunoso ben assay
ESI-MS/MS
Elec osp ay ionisa ion andem mass spec ome y
FAO
Food and Ag icul u e O ganiza ion o he Uni ed Na ions
FLD
Fluo escence de ec ion
FLX
Fluoxe ine
FMOC-Cl
9- luo enylme hylchlo o o ma e
GBH
Glyphosa e based he bicides
GC
Gas ch oma og aphy
HFB
Hep a luo obu anol
HPAEC
High-pe o mance anion-exchange ch oma og aphy
IC
Ion ch oma og aphy wi h supp essed conduc i i y de ec ion
IC-HESI-MS/MS
Ion ch oma og aphy hyphena ed o elec osp ay andem mass
spec ome y
ICP-MS/MS
Induc i ely coupled plasma andem mass spec ome y
LC
Liquid Ch oma og aphy

Lis o Abb e ia ions
xxxi
LOD
Limi o de ec ion
LOQ
Limi o quan i ica ion
MDL
Me hod de ec ion limi
MKP, KH2PO4
Monopo assium phospha e
MQL
Me hod quan i ica ion limi
MS
Mass spec ome y
NSAIDs
Non-S e oidal An i-In lamma o y D ugs
NBD-Cl
4-chlo o-7-ni obenzo u azan
NPD
Ni ogen-phospho ous de ec ion
OM
O ganic ma e
OPA-MCE
o-ph halaldehyde-2-me cap oe hanol
PAD
Pulsed ampe ome ic de ec ion
PFAS
Pe - luo oalkyl and poly luo oalkyl subs ances
PTFE
Poly e a luo oe hylene
Q-TOF-MS
Quad upole Time-o -Fligh Mass Spec ome y
RP-HPLC
Re e se phase high-pe o mance liquid ch oma og aphy
SIC
Sequen ial injec ion ch oma og aphy
SIM
Selec ed ion moni o ing
SM-FIA
Spec opho ome ic me hod - s anda d low injec ion analysis
SSRI
Selec i e se o onin eup ake inhibi o
SWV
Squa e-wa e ol amme y
UHPLC-HRMS
Ul a-pe o mance liquid ch oma og aphy high- esolu ion mass
spec ome y
UPLC-MS/MS
Ul a-pe o mance liquid ch oma og aphy Mass spec ome e
UV
Ul a iole de ec ion
UV-Vis
Ul a iole – isible spec opho ome y
VDP
Di e en ial pulse ol amme y
WHO
Wo ld Heal h O ganiza ion
1
CHAPTER 1 INTRODUCTION
1.1 Gene al backg ound
En i onmen al con amina ion is an issue o g owing conce n wo ldwide. Due o he known
and unknown possible impac on he en i onmen , Human and wildli e heal h, eme ging
con aminan s ha e aised ala ms among he scien i ic communi y and o icial en i onmen al
agencies. Eme ging con aminan s a e newly de eloped o ca ego ized as con aminan s o
known compounds eshly iden i ied in he en i onmen ( equen ly associa ed wi h analy ical
de elopmen s) and cause known o suspec ed ad e se ecological and/o human heal h
e ec s. They inco po a e a wide a ie y o subs ances such as pe sonal ca e p oduc s,
pha maceu ical p oduc s, pes icides, e e ina y p oduc s, hea y me als, mic oplas ics,
indus ial by-p oduc s, enginee ed nanoma e ials, ood addi i es, and na u al and syn he ic
ho mones. Thei me aboli es and ans o ma ion p oduc s a e also included (X. Li e al., 2022;
Pu i e al., 2023). A e hei en ance in o he en i onmen , hey p esen se e al possible
biogeochemical beha io s. The mos common and impac ing a e ans o ma ion, ans e , and
accumula ion along he ood chain, al e ing some p ope ies and possibly u ning hei
de ec ion in o a challenging p ocess. Addi ionally, hese changes and wide-sp ead can esul
in dis inc and unknown impac s on en i onmen al heal h (X. Li e al., 2022).
An h opogenic ac i i ies a e he majo sou ces o eme ging con aminan s’ in oduc ion
in o he en i onmen . Was ewa e ea men plan s (WWTPs) a e one o he main en y
channels o hese compounds in he soil and wa e en i onmen al compa men , as hey
ecei e was ewa e om se e al sou ces (e.g. households, hospi als, indus ies) and a e
unable o en i ely deg ade eme ging con aminan ’s using con en ional ea men s (e.g.
ac i a ed sludge, il a ion, and disin ec ion) (Mukhopadhyay e al., 2022; Pu i e al., 2023;
Te penning & Öbe g, 2017). Addi ionally, acco ding o Wo ld Heal h O ganiza ion (WHO), in
2020, nea ly 22% o he global popula ion (1.7 billion people) s ill did no ha e basic sani a ion
se ices, and 45% o he household was ewa e globally gene a ed was discha ged wi hou
sa e ea men , inc easing he po en ial o e luen s wi h high concen a ions o hese
con aminan s o be eleased in o wa e bodies (Wo ld Heal h O ganiza ion & Uni ed Na ions
Child en’s Fund, 2020).
Pes icides a e chemicals used o con ol plagues and diseases in ag icul u e, while
pha maceu icals a e d ugs used o ea o p e en diseases in humans and animals. E en
hough hese subs ances ha e b ough signi ican bene i s o socie y, hei widesp ead use
In oduc ion
2
has also led o unin ended consequences, such as soil, wa e , and ai pollu ion (Sousa e al.,
2018). Bo h pes icides and pha maceu icals a e conside ed eme ging con aminan s o
conce n because hei impac on he en i onmen is complex and mul i ace ed, and hei
e ec s on ecosys ems can be sub le and challenging o p edic , leading o long- e m ecological
and economic consequences.
Due o he con inuous in oduc ion o human-made and na u al o ganic subs ances in o
he en i onmen , i is c ucial o unde s and be e he chemical s a us o he Ea h's su ace
wa e and soils. To educe and p e en wa e and soil pollu ion, i is essen ial o in es in
in as uc u e and echnology o imp o e was ewa e ea men and educe he discha ge o
pollu an s in o wa e sou ces. P omo ing sus ainable p ac ices in ag icul u e and indus y is
also c ucial, as inc easing public awa eness o he impo ance o p o ec ing ou wa e
esou ces.
This wo k add ess and explo e he p esence, po en ial sou ces, pa hways, and impac s o
en i onmen al con amina ion by eme gen pollu an s, ocusing on ou signi ican subs ances:
glyphosa e and i s p ima y deg ada ion p oduc (AMPA) and glu osina e, pes icides om
he bicides amily and luoxe ine, a pha maceu ical belong o an idep essan g oup. Also,
examine some o he s a egies and echnologies used o mi iga e his p oblem p oposing and
assessing adso p ion as one o he echnologies applied o ea hese con aminan s in wa e
o di ec ly in soils, p e en ing hem om lowing in o wa e bodies.
1.2 Objec i es and s uc u e
1.2.1 Main objec i e
This wo k aimed, i s ly, o imp o e knowledge wi hin he scope o new con amina ion ends
as well as he p ima y sou ces o con amina ion and hei pa hways o each he
en i onmen al compa men s. Glyphosa e, i s majo deg ada ion p oduc AMPA, glu osina e
and luoxe ine we e selec ed o ep esen wo di e en amilies o compounds: he bicides
and pha maceu icals. Thus, also in end o ill in he gaps in he exis ing knowledge on
glyphosa e, AMPA, glu osina e and luoxe ine en i onmen al con amina ion and o p opose a
low-cos and sus ainable emedia ion echnique o p e en hei sp ead and consequen
con amina ion o soils, and wa e esou ces, namely he applica ion o ailo -made Technosol.
Secondly, i sough o sea ch o inexpensi e and sus ainable ma e ial wi h high glyphosa e,
AMPA, glu osina e and luoxe ine adso p ion capabili y ha could be inco po a ed as a ailo -
made Technosol componen .
Chap e 1
3
Figu e 1.1 p esen s a low cha o he se e al s eps h ough he subjec ’s app oach wi h
a ocus on he main objec i es o he wo k.
Figu e 1.1 - Flow cha o he opics app oached h oughou he hesis o each he objec i es.
1.2.2 Speci ic objec i es
1. To moni o si es con amina ed wi h pha maceu icals and pes icides, namely
luoxe ine, glyphosa e, AMPA and glu osina e in Po ugal and in he Wo ld;
2. To disco e sus ainable ma e ial o use as adso ben s. Addi ionally, o unde s and
he cha ac e is ics ha make hem mo e a o able o he adso p ion o he a ge
compounds;
An dep essan s
Fluoxe ne
e bicides
lyphosa e AMPA
lu osina e
Li e a u e Re iew
10
could be gene a ed by hei use by human and animal as well as by indus y. Exc e ion o
unme abolized pha maceu ical d ugs by he human/animal body a e consump ion, disposal
o lushing down he oile s o unused p oduc s, and ba hing, and washing o opically applied
medica ions a e h ee o he p ima y ou es ha p omo e he a i al o hese con aminan s
o wa e bodies h ough WWTPs o di ec discha ge (J. L. San os e al., 2022; Silo i e al., 2022).
Figu e 2.3 – The apeu ical classes o he mos ound pha maceu icals in en i onmen al ma ixes
(de eloped by he au ho ).
Mo eo e , hey con inuously mo e in o he en i onmen h ough di e en pa hways,
namely hei discha ge om household, hospi als, o indus y o was ewa e ea men
sys ems o di ec ly o he en i onmen . Addi ionally, he use o he sludges p oduced in
WWTPs as o ganic amendmen s and nu ien s sou ce o ag icul u al pu poses (highly
equen in Eu opean Union, wi h speci ic applica ion a es h oughou he Membe S a es),
and he i iga ion wi h ecycled wa e o was ewa e ea men discha ge, ep esen a
p obable pa hway o hese compounds o end up in soil o in he aqua ic en i onmen ,
inc easing he isk o soil and wa e con amina ion (J. L. San os e al., 2022).
Thus, con en ional WWTP ep esen s a signi ican sou ce o human pha maceu icals in
he en i onmen . Since hei ea men me hods we e no designed o emo e hese
chemicals, and due o he pha maceu ical’s complex s uc u e and physicochemical
p ope ies, hey a e ine ec i e in en i ely emo ing hem (J. L. San os e al., 2022; J. Sha ma

Chap e 2
11
e al., 2022; Silo i e al., 2022). Ne e heless, he con amina ion sou ces and he en y poin s
in o he en i onmen al compa men s can a y g ea ly depending on he ci cums ances o
each coun y. Fo example, in Eas A ican coun ies, imp ope pha maceu ical handling and
disposal is he main challenge (Ka ungamye e al., 2022).
Rega ding he emo al o pha maceu icals in WWTP, acco ding o se e al s udies, only in
occasional cases was he e a educ ion in he concen a ion o hese compounds in he
in luen compa ed o he e luen . This a iance was highly dependen on he applied
ea men le els and sys ems a he acili y. The concen a ion educ ion in wa e may no
ha e been exclusi ely due o he emo al o hese compounds bu a he o hei
concen a ion in he solid phase esul ing om he a ious ea men s (sludge). Addi ionally,
he ou pu concen a ion was highe o some pha maceu icals han he inpu concen a ion.
Conce ning psychia ic d ugs, no emo al in he WWTP was obse ed (Lopez e al., 2022; Paula
Paíga e al., 2016, 2019; Papageo giou e al., 2016).
In Eu ope, he Wa e F amewo k Di ec i e is he p ima y egula ion o wa e p o ec ion.
I applies on he quali y o he inland, ansi ional, and coas al su ace wa e s h ough he
“daugh e ” En i onmen al Quali y S anda ds Di ec i e de ined in he Di ec i e 2000/60/EC
(Eu opean Commission, 2000), and on he quali y and quan i y o g oundwa e , h ough he
G oundwa e Di ec i e 2006/118/EC (Eu opean Commission, 2006). One o he se e al
amending o Di ec i e 2000/60/EC, he Di ec i es 2008/105/EC o 16 Decembe (Eu opean
Commission, 2008) and 2013/39/EU o 12 Augus (Eu opean Commission, 2013) s ipula ed
ha he Eu opean Commission should es ablish a wa ch lis o subs ances o which Union-
wide moni o ing da a would be ga he ed o suppo u u e p io i iza ion exe cises in
ag eemen wi h he A icle 16 o he emended di ec i e, complemen ing i s a icles 5 and 8.
The con inuous moni o ing pe iod o any indi idual subs ance included in he lis mus be a
leas 12 mon hs and no exceed ou yea s. Addi ionally, his lis mus be upda ed e e y 24
mon hs a e ha , and any subs ance o which a isk-based assessmen , as e e ed o in
A icle 16 (2) o Di ec i e 2000/60/EC, can be concluded wi hou addi ional moni o ing da a
should be emo ed. Following he p e iously es ablished, a wa ch lis o subs ances o Union-
wide moni o ing in he ield o wa e policy was c ea ed, s a ing wi h 10 subs ances o g oups
o subs ances (as ecommended in he Di ec i e 2013/39/EU), i s ly de ined in he
Commission Implemen ing Decision (EU) 2015/495 o 20 Ma ch 2015 (Figu e 2.4) (Eu opean
Commission, 2015b). In i s annex a e included some indica i e analy ical me hod o each
subs ance o g oup o subs ances and he maximum accep able me hod de ec ion limi .
Subs ances included o added o he wa ch lis mus be ca e ully chosen om amongs hose
Li e a u e Re iew
12
ha exhibi signs o po en ially signi ican isks o o ia he aqua ic en i onmen a he
Eu opean Union le el bu o which he e is no su icien da a o make a conclusi e
de e mina ion. The wa ch lis was upda ed in 2018 (Eu opean Commission, 2018), 2020
(Eu opean Commission, 2020b), and 2022 (Eu opean Commission, 2022a). Cu en ly, his lis
includes 26 subs ances o g oups o subs ances, and o mos o hese compounds, he SPE
ex ac ion me hod and LC, HPLC, o UPLC in andem wi h MS/MS analysis me hod a e
sugges ed.
Figu e 2.4 - E olu ion o he wa ch lis h oughou he yea s (de eloped by he au ho ).
Thus, inc easing awa eness o he en i onmen 's nega i e impac s, oxici y, a e,
occu ences, and ans e s o pha maceu ical p oduc s is essen ial o enhance ou knowledge
and egula e hem. Hawash e al. (2023) execu ed a majo e iew ela i e o he global
occu ence o pha maceu icals and pe sonal ca e p oduc s esidues in aqua ic sys ems
(d inking/ ap wa e , su ace wa e , g oundwa e , and WWTPs) in he pe iod om 2012 o
2022. The highes concen a ions o pha maceu ical p oduc s in su ace wa e s we e obse ed
in A ica and Sou h Ame ica, wi h a maximum epo ed concen a ion o 272,2 μg/L
(amoxicillin - an ibio ic) in Nige ia, 25.4 μg/L (aspi in - NSAID), and 23.5 μg/L (nalidixic -
an ibio ics), bo h in Sou h A ica and 127.0 μg/L (ca eine - s imulan ) and 21.0 (aspi in) in
B azil. In China, a ca eine maximum concen a ion o 9.8 μg/L was de ec ed, ollowed by 2.8
μg/L o he an ibio ic’s e y h omycin and oxy e acycline. In Eu ope, he maximum
concen a ions obse ed we e 3.5 μg/L (ca eine), 3.0 μg/L (salicylic acid - NSAIDs/analgesics),
and 2.05 μg/L ( ime hop im - an ibio ic). F om he class o an idep essan compounds, and
al eady in a much lowe concen a ion ange, equen ly de ec ed enla axine was epo ed
Sul ame hoxazole
T ime hop im
enla axine
and O‐
desme hyl enla axine
Azole compounds
Clo imazole
Fluconazole
Imazalil
Ipconazole
Me conazole
Miconazole
Penconazole
P ochlo az
Tebuconazole
Te aconazole
Dimoxys obin
Azoxys obin
Famoxadone
Di u enican
Fip onil
Clindamycin
O oxacin
Me o min and uanylu ea
Sunsc een agen s
u yl me hoxydibenzoyl ‐me hane
Oc oc ylene
enzophenone‐3
17‐Alpha‐e hinyles adiol (EE2)
17
‐ e a‐es adiol (E2) and Es one
(E1)
Diclo enac
2,6‐Di e ‐bu yl‐4‐me hylphenol
2‐E hylhexyl 4‐me hoxycinnama e
Mac olide an bio cs
Me hioca b
Neonico noids
Oxadiazon
T i‐alla e
Me a umizone
Amoxicillin
Cip o oxacin
Sul ame hoxazole
T ime hop im
enla axine
and O‐
desme hyl enla axine
Azole compounds
Clo imazole
Fluconazole
Imazalil
Ipconazole
Me conazole
Miconazole
Penconazole
P ochlo az
Tebuconazole
Te aconazole
Dimoxys obin
Famoxadone
17‐Alpha‐e hinyles adiol (EE2)
17
‐ e a‐es adiol (E2) and Es one
(E1)
Mac olide an bio cs
Me hioca b
Neonico noids
Me a umizone
Amoxicillin
Cip o oxacin
Chap e 2
13
in a maximum concen a ion o 0.128 μg/L in Spain. Also luoxe ine was equen ly de ec ed,
wi h maximum concen a ions o 0.101 μg/L and 0.025 μg/L ound in China and USA,
espec i ely, and 0.017 μg/L in Spain (Hawash e al., 2023; Y. Xiang e al., 2021).
Conce ning supe icial wa e s in Po ugal (Lei ia, Lis i e ), he occu ence o 33
pha maceu icals and me aboli es be ween 2013 and 2014 was e alua ed in i e wa e ,
in luen s and e luen s o wo WWTPs loca ed along he i e (Paula Paíga e al., 2016). A
de ec ion equency o 100% was ob ained o ibup o en, ke op o en (bo h
NSAIDs/analgesics), ca bamazepine, and luoxe ine (bo h psychia ic d ugs), and he
me aboli e salicylic acid (NSAIDs/analgesics), e ealing he maximum le el o 1.3 μg/L o
ibup o en and 0.53 μg/L o ace aminophen (NSAIDs/analgesics) (Paula Paíga e al., 2016).
Acco dan ly, Acuña e al. de ec ed 50 o he 75 moni o ed pha maceu icals in he Ibe ian
Ri e s (Eb o basin) and spo ed a maximum concen a ion o 5.1 μg/L o Iop omide (β-
blocke s), 1.9 μg/L o gem ib ozil (lipid egula o ), 1.75 μg/L o lu as a in (s a in), 1.15 μg/L
o hyd ochlo o hiazide (diu e ics) and 1.8 μg/L o alsa an (an ihype ensi e d ugs) (Acuña
e al., 2015). Fluoxe ine, al hough no de ec ed in high concen a ions in su ace wa e , usually
has high de ec ion equencies (Paula Paíga e al., 2016; P. Zhang e al., 2017).
A e achie ing supe icial wa e s, o once in he soil, hese con aminan s a e pe sis en
and mobile, allowing hem o in il a e g oundwa e h ough pe cola ion (Mejías e al., 2021;
J. Sha ma e al., 2022; Silo i e al., 2022).
While g oundwa e is gene ally conside ed mo e esilien o con amina ion by eme ging
pollu an s compa ed o su ace wa e , aces o se e al con aminan s, including
pha maceu icals, ha e been ound in g oundwa e sys ems o se e al coun ies, namely China
(L. Chen e al., 2018; Ma e al., 2022), Nige ia (Ebele e al., 2020; Olai an e al., 2017), B azil
(Mon agne e al., 2019), Bangladesh, Kenya (K’o eje e al., 2016), India (B. M. Sha ma e al.,
2019), Spain (Gasco Ca e o e al., 2023), among many o he s. Remo ing hem om ma ices
such as ocks, soil, sedimen s, and he unsa u a ed zone p o es o be a challenging ask.
In 2012, Lapwo h e al. published a wide- anging e iew highligh ing he wo ld’s
widesp ead con amina ion o g oundwa e esou ces by a la ge a ie y o eme ging
con aminan s de ec ed a po en ially en i onmen ally signi ican concen a ions un il 2011
(excluding ag icul u al pes icides and hei deg ada ion p oduc s). Rega ding pha maceu icals,
he mos equen ly epo ed g oup o compounds in he analyzed s udies p esen ed a e age
(maximum) alues o 15.1 𝜇g/L (120 𝜇g/L) o pa ace amol, 9.77 𝜇g/L (110 𝜇g/L) o ca eine
and 5.31 𝜇g/L (99,2 𝜇g/L) o ca bamazepine.
Li e a u e Re iew
14
A e he publica ion o he Eu opean Commission’s oundwa e Di ec i e 2006/118/EC
(Eu opean Commission, 2006), aiming o ‘p e en and con ol g oundwa e pollu ion’ by
se e al con aminan s, in 2014, an amendmen o i s Annex II was published, highligh ed ha
he lack o in o ma ion made i impossible o c ea e new g oundwa e quali y s anda ds o
any pollu an s (Eu opean Commission, 2014). I also emphasized he need o inc ease he
a ailabili y o moni o ing da a on subs ances posing a isk o po en ial isk o g oundwa e
bodies by de e mining backg ound le els and es ablishing a “wa ch lis o pollu an s o
g oundwa e ”. In 2019, a olun a y G oundwa e Wa ch Lis (GWWL) was implemen ed,
anking as compounds o cu en conce n nine pha maceu ical and wo pe - luo oalkyl and
poly luo oalkyl subs ances (PFAS). Fou addi ional PFAS we e sho lis ed o inclusion. The
goal o he GWWL was o cen e a en ion on hese p io i y compounds un il de ailed
in o ma ion is a ailable o se egula o y le els. This lis is ac i e and cons an ly e ol ing. As
new esul s a e collec ed, o he s will be added o o eplace lis ed ones possibly egula ed.
Following he wo k o Lapwo h e al., and aiming o unde s and he e olu ion o
g oundwa e con amina ion in Eu ope due o imp o emen s o he Di ec i e 2006/118/EC
(Eu opean Commission, 2006), in 2021, Bun ing e al., e iewed he p esence o eme ging
o ganic compounds, his ime ocusing in Eu opean g oundwa e , h ough he analysis o 39
published s udies be ween 2012 and 2020. Once again, he mos equen ly epo ed ca ego y
o compounds was ‘Pha maceu icals’. In his e iew, he mos equen ly de ec ed compounds
we e he an i-epilepsy d ug ca bamazepine, he an ibio ic sul ame hoxazole, he an i-
in lamma o ies diclo enac, and ibup o en (included in he 11 compounds o cu en conce n
o he GWWL), and he lipid egula o beza ib a e.
Recen ly, Silo i e al., (2022) also pe o med a sys ema ic li e a u e e iew conce ning he
occu ence o pha maceu icals (among o he CEC) in g oundwa e epo ed om o he
second decade o 21s cen u y in he wo ld. Figu e 2.5 highligh s he con amina ion
concen a ion ange o six pha maceu ical classes in eigh o he coun ies included in he
e iewed esea ch.
Chap e 2
15
Figu e 2.5 - Range o PPCPs' g oundwa e con amina ion (𝜇g/L) o all he he apeu ic classes -
Analgesics/An ipy e ics/NSAIDs (AG), an iepilep ics (AP), β-blocke s (β-B), an ibio ics (AB), lipid
egula o s (LR) and s imulan s (ST) – sample si e. * Only he maximum concen a ion o he gi en
he apeu ic class (Adap ed wi h pe mission om (Silo i e al., 2022). Copy igh 2022, Jou nal o
En i onmen al Managemen ).
The highes concen a ion was ound in India, o 1 390 𝜇g/L o diclo enac (NSAID),
ollowed by o loxacin (an ibio ic) ha p esen ed a maximum concen a ion o 122.7 𝜇g/L, by
nap oxen (NSAID) o 98.39 𝜇g/L, and by sul ame hoxazole (an ibio ic) o 32.00 𝜇g/L, bo h in
USA. Sul ame hoxazole was, also, he pha maceu ical compound wi h he maximum
concen a ion epo ed in China (20.06 𝜇g/L). In addi ion, Singapo e p esen ed a maximum
concen a ion o ca eine (s imulan s) o 16.25 𝜇g/L (no included in he igu e).
Moni o iza ion s udies in sedimen s con amina ion a e less equen . Xiang e al. (2021)
e iewed he occu ence o pha maceu icals in he aqua ic en i onmen in China, including
sedimen s. The de ec ion le el in li e a u e a ies bu se e al pha maceu icals we e ound in
concen a ions highe han 100 μg/kg (103.0 - 384.59 μg/kg), including he an ibio ics
o loxacin, en o loxacin, oxy e acycline, e acycline, ime hop im, azi h omycin,
oxi h omycin, and e y h omycin. The highes de ec ed concen a ion was ound o
azi h omycin (1 179 μg/kg) and no loxacin (1 140 μg/kg). An i-in lamma o y diclo enac (278.1
μg/kg) and Ibup o en (227.1 μg/kg), an ipy e ic ace aminophen (320.7 μg/kg) and s imulan
ca eine (482 μg/kg) we e also de ec ed (Y. Xiang e al., 2021). Lowe alues ha e been
epo ed in Kenya (maximum concen a ions anged 1.8 μg/kg – 47.4 μg/kg o ime hop im,
and cip o loxacin, espec i ely) (Kai igo e al., 2020), as well as in B azil (maximum

Li e a u e Re iew
16
concen a ions anged 0.9 μg/kg – 15.5 μg/kg o diclo enac and nap oxen, espec i ely) (de
Oli ei a San os e al., 2022).
The consump ion o psychia ic d ugs (in which an idep essan s a e included) has seen a
signi ican ise in ecen yea s, p obably due o he inancial c isis in Eu ope, ollowed by he
COVID-19 pandemic, which p omo ed ad e se psychological e ec s and nume ous psychia ic
diso de s and, consequen ly, inc eased hei usage (Bo o a e al., 2014; Pazzagli e al., 2022).
Conside ing he p e iously epo ed high equency o an ibio ic de ec ion and he
inc easing use o an idep essan s, i is essen ial o con inue o moni o he a ious
en i onmen al compa men s o con amina ion by hese p oduc s so ha egula o s and
go e nmen s can unde s and how se ious he cu en si ua ion is and wha measu es will be
mos app op ia e o add ess i .
Pha maceu ical manu ac u e s, egula o y agencies, and was ewa e ea men plan s
manage s a e wo king o add ess he issue o pha maceu ical con amina ion in he
en i onmen . S a egies include imp o ing he design o d ugs o make hem less pe sis en
in he en i onmen , inc easing he e ec i eness o was ewa e ea men sys ems o emo e
pha maceu icals, and p omo ing p ope disposal o medica ions by pa ien s (Ko wani e al.,
2021). Indi iduals can also play and impo an ole in educing en i onmen pha maceu ical
con amina ion by p ope ly disposing o unused medica ions h ough designa ed ake-back
p og ams o pa icipa ing in a -home medica ion disposal me hods ecommended by he
En i onmen al P o ec ion Agency. Moni o iza ions is essen ial o measu e he le el o
con amina ion and lead o s udies o oxici y and new con amina ion ea men s.
2.2.1 Fluoxe ine an idep essan use
The consump ion o an idep essan s has been on he ise in ecen decades,
p edominan ly due o an inc ease in men al heal h issues such as dep ession and anxie y
(Figu e 2.6). The COVID-19 pandemic u he exace ba ed his end, as i led o a heigh ened
p e alence o psychological diso de s. Consequen ly, he e has been a signi ican ise in he
use o an idep essan s, including selec i e se o onin eup ake inhibi o s (SSRIs).
An idep essan d ugs, in 2020, accoun ed o 4% o pha maceu ical sales in Po ugal, 2.7% in
Spain, 2.2% in Aus ia, and 1.7% in I aly, sugges ing a signi ican cos in some Eu opean
coun ies (OECD.S a , 2022). This g owing consump ion o an idep essan s may pose a
po en ial con amina ion isk o he en i onmen . When indi iduals exc e e hese compounds
Chap e 2
17
and hei me aboli es, hey can en e wa e bodies due o he insu icien emo al a es in
wa e ea men plan s.
Figu e 2.6 – De ined daily dosage pe 1 000 inhabi an s pe day o an idep essan in 2017 and 2020 by
he O ganiza ion o Economic Co-ope a ion and De elopmen (OECD) coun ies (Da a sou ce: (OECD.S a ,
2022) - de eloped by he au ho ).
As a esul , hese subs ances a e eleased in o he en i onmen a a ying
concen a ions, which can ha e mul iple and di e se e ec s on bo h e es ial and aqua ic
species. Exposu e o hese subs ances can lead o consequences such as changes in gene ic
ansc ip ion, ep oduc i e de iciencies, and impai ed mo ili y. Addi ionally, hey can cause
al e a ions in he beha io o o ganisms du ing mig a ion and when de ending agains
p eda o s. O e all, he inc eased use o an idep essan s is no only a e lec ion o he g owing
men al heal h challenges aced by socie y bu also a po en ial en i onmen al conce n ha
needs o be add essed (Diaz-Camal e al., 2022; Mole & B ooks, 2019).
Fluoxe ine is a 2nd gene a ion an idep essan ca ego ized as a SSRI, ac ing on he cen al
ne ous sys em by blocking he se o onin anspo e in he neu on memb ane. Se o onin, is
a p ominen neu omodula o p esen in he ne ous sys ems o bo h e eb a es and
in e eb a es, playing a signi ican ole in a ious physiological p ocesses encompassing
beha io , g ow h, and ep oduc ion (Co eia e al., 2023; Na ional Cen e o Bio echnology
0
20
40
60
80
100
120
140
160
Iceland
Po ugal
Aus alia
Canada
Sweden
Spain
elgium
Finland
Denma k
Chile
eece
Czech Republic
Slo enia
Aus ia
e many
No way
Is ael
Luxembou g
F ance
T kiye
Slo ak Republic
Ne he lands
I aly
Cos a Rica
Es onia
Li huania
unga y
Ko ea
La ia
De ned daily dosage pe 1 000 inhabi an s pe day
2020
2017
Li e a u e Re iew
18
In o ma ion, 2023b). Is cu en ly app o ed by he U.S. Food and D ugs Adminis a ion (FDA)
indica ed o bo h acu e and main enance ea men o majo dep essi e diso de in pa ien s
aged eigh yea s and olde , including obsessi e-compulsi e diso de , panic diso de , and
bulimia (Co eia e al., 2023; Sohel e al., 2023). I is usually sold as Fluoxe ine Hyd ochlo ide
unde he ade name P ozac© (Na ional Cen e o Bio echnology In o ma ion, 2023b). This
an idep essan was disco e ed in 1974 by chemis s a he pha maceu ical company Eli Lilly
and au ho ized o comme cializa ion by he FDA o he i s ime in 1987 (Co eia e al.,
2023). Fluoxe ine is a well-es ablished medica ion, he ou h mos used SSRI an idep essan s
in he USA, wi h app oxima ely 23 million o al p esc ip ions in 2020 and anking 25 h on he
lis o he 200 mos p esc ibed d ugs (no accessible da a ound o Eu ope in ecen yea s)
(ClinCalc D ugS a s Da abase, 2023).
Fluoxe ine has ecei ed subs an ial a en ion because o i s equen de ec ion in su ace
wa e s and municipal e luen s (Biel-Maeso e al., 2018; M. P. Gomes e al., 2022; Mejías e
al., 2021; Paula Paíga e al., 2019). Gi en i s ubiqui y in he en i onmen and hese ype o
compounds mode o ac ion in low doses, conce ns ha e eme ged ega ding he po en ial
impac s o luoxe ine, on aqua ic o ganisms and hei associa ed beha io al pa e ns,
highligh ing he impo ance o he applicable egula ion (Be am e al., 2018; Co eia e al.,
2023; de Fa ias e al., 2019). Fu he in es iga ion is essen ial o: (i) cla i y he ex en o which
luoxe ine exposu e may al e he no mal unc ioning o se o onin-media ed p ocesses in
aqua ic species, be ween o he al e a ions, consequen ly a ec ing hei su i al and o e all
ecosys em heal h and: (ii) o p opose new ea men echnologies.
2.2.2 An idep essan Fluoxe ine - chemical and physical p ope ies
In addi ion o he amoun consumed and exc e ed, same pha maceu ical p ope ies could
de ine hei endency o con amina e and accumula e in wa e o e ime. These p ope ies
include hei solubili y, pe sis ence, and bioaccumula ion po en ial. Pha maceu icals a e o en
designed o be soluble in wa e o ensu e ha hey can be easily abso bed by he body and
each hei a ge si es. This high solubili y allows hem o be anspo ed by wa e and be
eadily abso bed by aqua ic o ganisms. Many pha maceu icals a e ca ego ized as
en i onmen ally pe sis en , since s abili y is o en conside ed o be a bene icial p ope y o
hei use by humans. Addi ionally, hei pe sis ence is also associa ed o hei con inuous low
in o he en i onmen (Pa el e al., 2019). Conce ning he bioaccumula ion po en ial, desc ibed
as he abili y o pha maceu icals o accumula e in he issues o o ganisms o e ime, i occu s
when o ganisms abso b he pha maceu icals a a as e a e han hey can elimina e hem. As
Chap e 2
19
a esul , he concen a ion o he pha maceu icals in he o ganism's issues and o gans
inc eases, po en ially leading o ha m ul e ec s on he o ganism i sel o p eda o s ha
consume i (de Oli ei a San os e al., 2022; Pa el e al., 2019).
The main luoxe ine physicochemical p ope ies a e esumed in Table 2.1.
Table 2.1 - Fluoxe ine physicochemical p ope ies (Da a sou ce: D ugBank and PubChem® 2022 da abase
(Na ional Cen e o Bio echnology In o ma ion, 2023d, 2023c))
Compound
Glyphosa e
CAS
54910-89-3
IUPAC name
N-me hyl-3-phenyl-3-[4-
( i luo ome hyl)phenoxy]p opan-1-amine
Chemical s uc u e
Fo mula
C17H18F3NO
Molecula weigh (g/mol)
309.33
Wa e solubili y a 25 ◦C (mg/L-1)
1.7 (almos insoluble)a
LogKow
4.05
pKa
9.8
a 14x103 mg/L as Fluoxe ine Hyd ochlo ide
The s abili y o pha maceu icals can be in luenced by he ype o molecula ac ions
connec ed o he a oma ic ings, such as ni o-, chlo o-, and luo o- unc ional g oups, which
ypically inc ease he pe sis ence o hese compounds in he en i onmen (Pa el e al., 2019).
Howe e , o he ac o s like pH and empe a u e, as well as bio ic ac o s such as mic o lo a
and auna, p esen in he wa e body can nega i ely impac he s abili y o pha maceu ical
compounds, leading o hei deg ada ion. Despi e his deg ada ion p ocess, he con inuous
elease o la ge quan i ies o pha maceu ical esidues and hei slowe a e o au o-
deg ada ion can cause con amina ion le els o inc ease. This build-up o con amina ion can
ha e ha m ul e ec s on human heal h, and aqua ic li e (Pa el e al., 2019; J. Sha ma e al.,
2022). Fluoxe ine hal -li e in na u al wa e s ange om 2 o 7 days acco ding wi h se e al
s udies (Kosma e al., 2020; Pan e al., 2022), and can each 183.2 days in ul apu e wa e (Yin
e al., 2017).
Li e a u e Re iew
26
Figu e 2.11 – Range o pes icides concen a ion (su ace wa e (SW) and g oundwa e (GW): 𝜇g/L;
sedimen s (SED) and soils: μg/kg) ound in se e al s udies (Da a sou ce: USA: Glinski e al., 2018; Spain:
Pos igo e al., 2021; Cos a Rica: (Ca azo-Rojas e al., 2018) A gen ina: Mac Loughlin e al., 2022;
U uguay: Rod íguez-Bolaña e al., 2023; Tanzania: Ma e u e al., 2021;India: (Ku akal a & A adhi,
2022);China: Xu e al., 2020; Ge many: Tauchni z e al., 2020; Malaysia: El ik ie e al., 2020) DF:
De ec ion F equency; ND: unde he de ec ion limi (de eloped by he au ho ).
Y. Chen e al. (2018) assessed 31 a ge pes icides in su ace wa e om wo impo an
i e s in China used as d inking wa e sou ce and ound, wi h almos 100% de ec ion
equency, 8 o ganochlo ine pes icides, 16 o ganophospha e pes icides and 7 syn he ic
py e h oids wi h maximum concen a ions anging om 0.02–0.09 μg/L, 0.01–0.3 μg/L, and
om 0.02–0.1 μg/L, espec i ely. The maximum summed pes icide concen a ion was ound
o be 1.7 μg/L (Y. Chen e al., 2018). Addi ionally, in a nea by i e , Xu e al., (2020) de ec ed
29 pes icides, wi h a maximum concen a ion o 0.60 μg/L o he ungicide ca bendazim and
he o al summed concen a ion o 1.04 μg/L in win e and 0.79 μg/L in summe (L. Xu e al.,
2020).
In A gen ina, su ace wa e and sedimen s om a small ho icul u al s eam conce ning
he p esence o 40 compounds we e s udied by Mac Loughlin e al., (2022), ha ound
he bicide glyphosa e and i s deg ada ion p oduc AMPA as he mos equen ly de ec ed
pes icides, wi h maximum concen a ions in wa e o 20.0 μg/L and 4.9 μg/L, and in sedimen
o 1 146.5 μg/kg and 4 032.7 μg/kg. Pes icides we e ound in all ma ices analyzed a e e y
si e sampled in 5 ou o 6 sampling campaigns (Mac Loughlin e al., 2022b). In Geo gia, USA,
he concen a ions ound in su ace wa e we e wi hin he same o de o magni ude, wi h a
maximum alue o 10.5 μg/L o he he bicide me olachlo a (also he mos equen ly

Chap e 2
27
de ec ed). The highes summed pes icide concen a ion was 39.67 μg/L, in summe (Glinski e
al., 2018).
In U uguay, a moni o ing su ey was pe o med o in es iga e he p esence o 88
pes icides in su ace wa e (d inking wa e sou ces). 25 o he 88 analyzed pes icides we e
de ec ed in su ace wa e , wi h highe occu ences in sp ing and summe han in au umn and
win e . He bicide glyphosa e, AMPA, and he insec icide chlo an anilip ole we e he mos
equen ly de ec ed and p esen ed alues anging 0.23-1.05 μg/L, 0.58-0.89 μg/L and 0.008-
0.063 μg/L, espec i ely (Rod íguez-Bolaña e al., 2023).
Ca azo-Rojas e al. (2018) s udied he Tempisque i e basin, in Cos a Rica, and epo ed
he p esence, wi h he highes concen a ions de ec ed in he wa e samples among o he
pes icides, o he insec icide dime hoa e (0.4-61.2 μg/L), and he he bicides p opanil
(30.6 μg/L), diu on (0.1-22.8 μg/L) and e bu yn (0.05-4.8 μg/L). The ungicide ca bendazim
was he mos equen ly de ec ed pes icide. In sedimen s, he mos equen ly de ec ed
pes icide was he insec icide endosul an, and he highes le els we e ound o be o he
insec icides iazophos (0.04-491 μg/kg), cype me h in (0.8-71.5 μg/kg) and pe me h in
(47.8 μg/kg), ollowed by he bicide e bu yn (3.0-38.7 μg/kg) (Ca azo-Rojas e al., 2018). The
au ho s also e e , as Tauchni z e al. (2020) in Ge many, ha he ag icul u al p ac ices nea
he s udied wa e body, which in ol e high applica ion a es and equen use o some
pes icides, do no appea o ha e a di ec co ela ion wi h highe de ec ion equencies o
concen a ions ound. This implies ha o he aspec s, such as mobiliza ion/ anspo , maybe
mo e signi ican in de e mining he occu ence o pes icides in he egion.
Also, in Tanzania, Ma e u e al., (2021) ound maximum le els o 3.9 μg/L (he bicide
monu on) in wa e s, 1 830 μg/kg (insec icide chlo py i os) in sedimen s and 550 μg/kg
(he bicide glyphosa e) in soils and in Malaysia, El ik ie e al., (2020) has de ec ed ungicide
p opiconazole as he pes icide wi h he highe concen a ion in he s udied i e wa e , wi h
a alue o 4.5 μg/L. In gene al, in he analyzed s udies, and as expec ed, he le els o pes icides
ound in su ace wa e s exhibi seasonal pa e ns, wi h g ea e concen a ions de ec ed
du ing pe iods o in ensi e usage (such as sp ing and summe , du ing he p epa a ions o
cul i a ion), and lowe le els du ing he win e and a e he ha es ing o c ops.
Some o he de ec ed compounds a e banned compounds acco ding o he coun y
legisla ion (e.g. banned in U uguayan: p,p′-DDT, p,p′-DDD, p,p′-DDE, a azine, alpha-BHC and
e hion; no app o ed o use in he Eu opean Union: ace ochlo , bi en h in, chlo py i os,
diazinon, me alaxyl, pe me h in, and simazine). This embodies a key challenge as hese
Li e a u e Re iew
28
subs ances ha e been banned o hei ad e se e ec s on he ecosys em and human heal h
(Rod íguez-Bolaña e al., 2023).
2.3.1 The use o glyphosa e and glu osina e‐based he bicides
Glyphosa e o N-(phosphonome hyl) glycine, is a b oad-spec um he bicide widely used
h oughou he wo ld. Compa able in s uc u e o o he o ganophospha e pes icides, his
compound di e s in e ms o i s oxicology, as i does no inhibi cholines e ase ac i i y (IARC,
2017). I is used o con ol a wide a ie y o annual and pe ennial weeds in many c ops,
including co n, soybeans, co on, and whea . Ag icul u e, o es y, landscaping, and managing
oadside ege a ion also ep esen some o he glyphosa e applica ions. When abso bed by
he g een pa s o he plan and i s oo sys em (mino i y), i supp esses he unc ion o he
enzyme 5-enolpy u ylshikima e-3-phospha e syn hase (EPSPS), which is an in e media y in
he syn hesis o a oma ic amino acids ia he shikimic acid pa hway. These amino acids a e
i al o syn hesizing p o eins and p oducing seconda y plan p oduc s including phenolic
compounds, lignin, and a ious g ow h p omo e s and inhibi o s. Besides pho osyn hesizing
o ganisms, essen ially plan s and algae, and some mic oo ganisms in he soil (bac e ia and
ungi), EPSPS is no exp essed in mammals and o he e eb a es, appa en ly keeping hem
sa e om unin en ional damage (Foglia o e al., 2020; Padilla & Selim, 2020; Solomon, 2020).
Acciden ly disco e ed by D . Hen i Ma in in 1950 as a po en ial pha maceu ical,
glyphosa e’s po en ial o use in ag icul u e was only ecognized a ound 20 yea s la e , when
D . John F anz, he ounde o Monsan o Company, e ealed i s capabili ies as an he bicide
( imeline p esen ed in Figu e 2.12). The pa en o glyphosa e was illed in 1972, and i was
i s in oduced o he ma ke in 1974 by Monsan o Company unde he ade name
Roundup®. Though, despi e i s e iciency as a nonselec i e, b oad-spec um he bicide, he
global use o glyphosa e has, i s ly, inc eased slowly o e ime. Due o i s ini ial limi ed
applica ions, since i can only be applied o kill all ege a ion in non-c op a eas such as public
o p i a e pa ks, ceme e ies, ga dens, and along oads and ailway acks, and i s use in
ag icul u e was es ic ed o pos -ha es o la e-season applica ions, no mally applied when
o he con ol measu es ha e ailed (Benb ook, 2016; Mesnage & An oniou, 2017). In 1996,
he Roundup Ready c op’s in oduc ion, a a ie y o c ops gene ically enginee ed o su i e
glyphosa e-based he bicides applica ion, led o a signi ican inc ease in he sales and usage o
glyphosa e, simpli ying weed managemen p ocesses (Benb ook, 2016; IARC, 2017; Mesnage
& An oniou, 2017).
Chap e 2
29
Figu e 2.12 – Timeline displaying he highligh s o glyphosa e his o y; GE: gene ically enginee ed; GBH:
glyphosa e-based he bicide; GRG: Glyphosa e Renewal G oup; WHO: Wo ld Heal h O ganiza ion (Da a
sou ce: (EFSA, 2023; Eu opean Commission, 2023; Kudsk & Ma hiassen, 2020) - de eloped by he au ho ).
Subsequen o he in oduc ion and sp ead o Roundup Ready c ops use, he expi a ion
o Monsan o’s pa en and he consequen de elopmen o new glyphosa e o mula ions by
o he companies, led o an exponen ial g ow h in glyphosa e ag icul u al applica ion, and
consequen inc eases o i s esidues p esence in ood (J. Xu e al., 2019), eed (Zhao e al.,
2018), and en i onmen al ma ix as ai (Rami ez-Habe kon, Aima , e al., 2021), soil (V. Sil a
e al., 2018, 2019), and wa e (Suciu e al., 2023).
Following he Wo ld Heal h O ganiza ion's eclassi ica ion o glyphosa e as p obably
ca cinogenic (G oup 2A) o humans in 2015 by he IARC (EFSA, 2015; IARC, 2017), he amoun
o published a icles ela ed o se e al glyphosa e app oaches has been g owing, and
nume ous e iew a icles ha e been published on a ious glyphosa e- ela ed opics and i s
con en iousness (Gillezeau e al., 2019; Muñoz e al., 2021; Ri as-Ga cia e al., 2022; Solomon,
2020; J. Xu e al., 2019).
In 2017, he Appeal Commi ee on Plan P o ec ion P oduc s legisla ion, in ol ing
ep esen a i es om EU membe s a es, o ed in a o o he EU Commission's p oposal o
e-app o e he use o he he bicide glyphosa e o a pe iod o i e yea s. Howe e , due o
in ense discussions du ing he e-app o al p ocess, he esponsibili y o any u he
es ic ions on glyphosa e's use was delega ed by he EU o indi idual Membe S a es,
con a y o he common ha moniza ion s a egy (Eu opean Commission, 2017; Huhn, 2018).
lyphosa e was app o ed s me
a he EU le el
R applies o
license enewal
EFSA announced a signi can delay in
he elease o i s conclusions leading
o an ex ended o ano he yea
Eu opean Commission
p oposes a 15‐yea
enewal o glyphosa e
lyphosa e s EU ma ke
license is enewed o 5 yea s
Disco e y o glyphosa e
N‐(phosphonome hyl)
glycine by he Swiss
chemis , D . en i Ma n.
lyphosa e was
pa en ed as an
he bicide by Monsan o
In oduced in o he
pes cides ma ke in 1974 as
a pes cide ac e p inciple ‐
ade name
In oduc on and
legaliza on o se e al E
he bicide‐ ole an c ops ‐
Monsan o s s pa en expi ed
P ice dec ease and in ensi ca on o
he gene ic p epa a ons sales Reclassi ed as p obably ca cinogenic ( oup
2A) o humans by W O/IARC
1950 1974
2015
20172023
1972 1991 1996
2022 2016
2019
2002
Li e a u e Re iew
30
While se e al coun ies acknowledge he po en ial haza ds o glyphosa e, hey cu en ly lack
sa e al e na i es and o he weed managemen echnologies ha could p o ide an
economically iable subs i u e o weed con ol (Alcán a a-de la C uz e al., 2021; Foglia o e
al., 2020). Known al e na i es o glyphosa e a e cu en ly limi ed, less e ec i e, and mo e
expensi e. As a esul , success ul and p o i able weed managemen in majo ag onomic c ops
wi hou glyphosa e ep esen s a signi ican challenge and equi es he acquisi ion o new
knowledge and skills o a success ul ansi ion (Alcán a a-de la C uz e al., 2021; Beckie e al.,
2020). These disc epancies ha e spa ked widesp ead con o e sy and led o di e en
egula ions wo ldwide, anging om comple e bans o pe missi e policies (Ri as-Ga cia e al.,
2022).
The e-app o al o glyphosa e p oduced an in ense deba e ega ding i s p obably
ca cinogenic e ec s. Howe e , his IARC classi ica ion was opposed by o he na ional agencies
and o ganiza ions associa ed wi h he WHO, as well as he EU. This disc epancy caused a g ea
deal o con o e sy su ounding he e-app o al p ocess, wi h he sa e y o glyphosa e being
a majo poin o disag eemen (Huhn, 2018; Ri as-Ga cia e al., 2022).
Aminome hylphosphonic acid (AMPA), a weak o ganic acid wi h a phosphonic acid g oup,
is he p ima y deg ada ion p oduc o glyphosa e. In addi ion, AMPA is also used in he
p oduc ion o amino-me hylene-polyphosphona es, which a e a ype o phosphona es widely
u ilized in bo h household and indus ial applica ions as de e gen s, lame e a dan s,
an ico osi e, an i-scaling agen s, and complexing agen s (mainly in he ex ile indus y),
be ween o he indus ial applica ions. Ne e heless, he domes ic con ibu ion o u ban loads
o AMPA is negligible (G andcoin e al., 2017).
Glu osina e (2-amino-4-(hyd oxyme hylphosphinyl)bu anoic acid o D,L-
phosphino h icin), also used as glu osina e-ammonium, is a non-selec i e he bicide wi h a
b oad weed con ol spec um, also, an o ganophospho us he bicide, used mos ly o
con olling weeds and unwan ed plan g ow h. I is abso bed h ough he lea es and can cause
lea chlo osis and nec osis by inhibi ing he enzyme glu amine syn he ase (Takano & Dayan,
2020; C. Zhou e al., 2020). In oduced in he ea ly 1990s, and ound as a na u al p oduc ,
glu osina e was e e ed o as “a na u al amino acid wi h unexpec ed he bicidal p ope ies”
(Hoe lein, 1994) and i s use has a signi ican inc ease in he Uni ed S a es (US) o e he pas
decade associa ed o he g owing numbe o glyphosa e- esis an weeds, wi h glu osina e
se ing as an al e na i e he bicide o glyphosa e. Al hough glu osina e- esis an c ops we e
a ailable while glyphosa e- esis an c ops, hey we e less applied due o glu osina e’s lowe
e icacy and consis ency in compa ison o glyphosa e. Ne e heless, he use o glu osina e is
Chap e 2
31
widesp ead in some egions such as No h Ame ica, pa icula ly in he Midwes and Sou he n
US whe e glu osina e- esis an soybean and co on a e commonly g own. In Sou h Ame ica,
i is also widely used, especially in no- ill c opping sys ems whe e glu osina e- esis an co on
is popula in no heas B azil. O he c ops such as ice, o cha ds, ineya ds, and mino c ops,
as well as non-ag icul u al a eas, also accoun o a signi ican po ion o glu osina e use in he
wes e n Uni ed S a es and o he pa s o he wo ld (Takano & Dayan, 2020). Conce ning
Eu opean coun ies, glu osina e is no longe applied because i s ma ke license expi ed in
2018 and i s use was no e-app o ed by he Eu opean Commission due o conce ns abou i s
oxicology, being legally banned in Eu ope in 2020 (Eu opean Commission, 2020a, 2022a; C.
Zhou e al., 2020). Addi ionally, i s use and selling had al eady been p ohibi ed in F ance since
he end o 2017, due o i s po en ial oxici y o human ep oduc ion (C. Zhou e al., 2020).
Al hough glyphosa e and glu osina e ha e been widely discussed in e ms o hei impac ,
he lack o publicly accessible da a on hei global use has esul ed in inc eased unce ain y in
he global es ima es epo ed. Only a limi ed numbe o coun ies, including Po ugal and
Spain, make annual epo s publicly a ailable con aining in o ma ion abou na ional he bicide
and glyphosa e/glu osina e use. Mo eo e , he e is a iabili y in he le el o de ail p o ided,
wi h some epo s only e e ing o o al he bicides consumed o sold, wi hou speci ying he
ac i e ing edien s. I has been obse ed ha mos o he inc ease in global glyphosa e use can
be associa ed wi h he adop ion o gene ically enginee ed he bicide- ole an c ops p o iding
o be a solid basis o p ojec o al glyphosa e use wi h g ea e con idence, in he coun ies
whe e hey a e used. Benb ook, (2016) use his me hodology o p e iew ends in glyphosa e
use in he U.S. om 1997 and 2014, being one o he mos ci ed sou ces o in o ma ion
conce ning he quan i ies used and, consequen ly, he po en ial o con amina ion.
Conce ning Eu ope, in 2019 Eu opean Ne wo k o he Du able Exploi a ion o c op p o ec ion
s a egies (ENDURE) ne wo k s a ed a su ey on he uses o glyphosa e and he exis ing
al e na i es in 32 coun ies: he EU-28 coun ies plus No way, Se bia, Swi ze land, and Tu key
(EU 28+4) (C. An ie e al., 2020). The main conclusions we e ha glyphosa e sales we e
highes in F ance, Poland, Ge many, I aly, and Spain (wi h Po ugal in 10 h place), ha , on he
o he hand, conside ing he use o glyphosa e pe hec a e o ag icul u al a ea, Denma k,
Poland, Ne he lands, Po ugal, and F ance p esen ed he highes alues in 2017, and ha
glyphosa e is essen ially consumed by he ag icul u al sec o (90% o o al na ional glyphosa e
sales in he 13 coun ies whe e his in o ma ion was a ailable) (C. An ie e al., 2020).
Figu e 2.13A shows he annual o al alues, conce ning he yea s 2017 and 2019, o he
ag icul u al use o glyphosa e in some Eu opean coun ies (some o he coun ies wi h he

Li e a u e Re iew
32
highes exp ession in he use o glyphosa e acco ding o he ENDURE epo (C. An ie e al.,
2020)) as well as he amoun o all he o he he bicides used in each coun y and in each yea .
Addi ionally, da a on he use o glyphosa e and o he he bicides in he same yea s in B azil
and he USA, as well as in a o al o 28 Eu opean coun ies plus No way, Swi ze land, and
Tu key a e shown in Figu e 4B (in o ma ion sou ces shown in he igu e legend).
Figu e 2.13 – E olu ion o he bicides sales o ag icul u al use wi h a highligh on glyphosa e om 2017
o 2019: A) in some EU coun ies (2017 da a sou ce: (C. An ie e al., 2020); 2019 da a sou ce: Spain:
(Minis e io de Ag icul u a Alimen ación y Medio Ambien e, 2021); Po ugal: (DGAV, 2021); F ance:
(Ch is ine Vey ac, 2021); Ge many: (Fede al O ice o Consume P o ec ion and Food Sa e y, 2021)) and
B) sum o 28 EU plus No way, Swi ze land, and Tu key (2017 – da a sou ce: (C. An ie e al., 2020);
2019:(FAO, 2022)) compa ed wi h B azil (IBAMA, 2022) and USA (IBAMA, 2022) (bo h 2017 and 2019) (EU
28+3 da a abou 2019 glyphosa e use was no ound) - de eloped by he au ho .
As shown in Figu e 2.13A, in Eu opean coun ies he e was a decline in he use o
he bicides om 2017 o 2019, excep o Po ugal whe e a sligh inc ease occu ed (17%).
Spain p esen ed he mos signi ican dec ease, showing a educ ion o abou 62% in he bicide
sales, assis ed by a 10% educ ion in glyphosa e sales, ollowed by F ance, wi h a 26%
educ ion (35% in glyphosa e sales), and inally Ge many, wi h 17% o e all educ ion and 35%
in glyphosa e sales. In Figu e 2.13B i can be seen ha he global end in he EU was a
dec ease o 11% in he bicide sales (da a o glyphosa e sales in 2019 o he EU28+3 we e no
a ailable), in con as wi h B azil, which showed an inc ease in global sales o 17% and 21% in
he case o glyphosa e sales. The U.S. showed he same amoun s o he bicides used in bo h
yea s, wi h a 3% dec ease in glyphosa e sales.
Fo he use o glu osina e, access o in o ma ion is e en mo e di icul . Wi h ega d o he
amoun used, his ac i e subs ance ep esen ed less han 0.05% o he o al he bicides applied
in Spain, F ance, and Ge many. In B azil, i ep esen ed 0.5% in 2017 and 0.3% in 2019, and
o he U.S. 2.8% in 2017, he es ima e o 2019 is no ye a ailable o he la e .
Bo h glyphosa e and glu osina e ha e been he subjec o con o e sy and egula o y
sc u iny in ecen yea s due o conce ns abou hei po en ial impac on human heal h and
0
50
100
150
200
250
300
350
400
2017 2019 2017 2019 2017 2019
Eu 28 3 azil USA
0
5
10
15
20
25
30
35
2017 2019 2017 2019 2017 2019 2017 2019
Spain Po ugal F ance e many
Thousand onnes o glyphosa e
lyphosa e O he he bicides
Chap e 2
33
he en i onmen . Howe e , bo h he bicides a e s ill widely used a ound he wo ld, and hei
sa e y and e icacy con inue o be e alua ed by egula o y agencies and scien i ic esea che s
(Z. Li & Fan ke, 2022; No o ny, 2022).
2.3.2 Chemical and physical p ope ies o glyphosa e and glu osina e
To asce ain he en i onmen al a e and beha io o ag ochemicals, i is impe a i e o
conside hei physicochemical p ope ies. Key pa ame e s in his e alua ion include he
o ganic ca bon-soil pa i ion coe icien (KOC), oc anol-wa e pa i ion coe icien (KOW), apo
p essu e, solubili y, and pe sis ence, as ep esen ed by he ime equi ed o 50% o he
pa en compound o unde go ans o ma ion and dissipa e om soil, wa e , o ai (DT50) ( on
Mé ey e al., 2016).
Glyphosa e and AMPA sha e simila physicochemical p ope ies as i s low apo p essu e,
making i s ola iliza ion om soil insigni ican , pola i y and i s mode a e o high solubili y in
wa e (see Table 2.2) (EFSA, 2005, 2015). Glyphosa e is a colo less, odo less, c ys alline solid
chemical wi h a h ee-pola unc ional g oup s uc u e namely, amine, ca boxyla e and
phosphona e, ampho e ic and cha ac e ized by a linea a anged con igu a ion (Ojelade e al.,
2022; Spengle e al., 2021). Being a zwi e ion, wi h ou cha ac e is ic pKa alues, ha e an
ionic o m, a highly pola i y and solubili y due o he exis ence o his unc ional g oups in i s
s uc u e. Despi e hei wa e solubili y, glyphosa e and AMPA show a high a ini y o soil
pa icles, pa icula ly in clay- ich soils. Nume ous labo a o y expe imen s ha e demons a ed
a signi ican abso p ion capaci y o he glyphosa e molecule in soil, wi h abso p ion cons an s
anging om 8 o 377 dm3/kg (López-Vázquez e al., 2023; Ojelade e al., 2022).
Glu osina e is a phosphinic acid belonging o he o ganophospho us chemical amily,
unlike any o he chemical class o he bicides. Glu osina e is a hyd ophilic he bicide (logKow:
−4.0), also highly wa e soluble, wi h a low apo p essu e and wi h h ee di e en ioniza ion
cons an (pKa) alues associa ed wi h he p esence o he amine and hyd oxyl g oups in i s
s uc u e (see Table 2.2).
Li e a u e Re iew
34
Table 2.2 – Physical-chemical p ope ies o glyphosa e, AMPA and glu osina e (Da a sou ce FAO and
PubChem® 2022 da abase (Na ional Cen e o Bio echnology In o ma ion, 2023d, 2023c))
Compound
Glyphosa e
AMPA
Glu osina e
CAS
1071-83-6
77521-29-0
51276-47-2
IUPAC name
N-(phosphonome hyl)glycine
(Aminome hyl)phosphonic
acid
2-amino-4-
[hyd oxy(me hyl)phospho yl]
bu anoic acid
Chemical
s uc u e
Fo mula
C3H8NO5P
C7H10N2O4
C5H12NO4P
Molecula weigh
(g/mol)
169.07
111.04
181.13
Wa e solubili y a
25 ◦C (mg/L)
1.0 × 106
1.0 × 106
1370
O ganic sol en
solubili y a 25 ◦C
(mg/L)
P ac ically insoluble
P ac ically insoluble
≈1×10-6
LogKow
-3.4
-2.17
-4.0
pKa
pKa1=0.8, pKa2=2.3, pKa3=5.6,
pKa4=11.0
pKa1=1.8, pKa2=5.4, pKa3=10.0
pKa1=2, pKa2=2.9, pKa3=9.8
Koc
2600-4900
1.937
9.6-1229
Vapo p essu e a
25 ◦C (a m)
1.29 × 10-10
(No ola ili y)
1.66 × 10−7
1.16 × 10−12
(No ola ili y)
Usually is p esen as an ammonium sal (Figu e 2.14) in he exis ing p epa a ions, which,
in aqueous solu ion, ends o dissocia e.
Figu e 2.14 - Glu osina e (ammonium sal ) molecula s uc u e.
Chap e 2
35
2.3.3 Glyphosa e and Glu osina e - deg ada ion and dissipa ion pa hs
Gi en he cu en unde s anding o glyphosa e, glu osina e and AMPA pe sis ence,
mobili y, leaching, and a el ime i 's possible o accoun o hei p esence in g oundwa e
h ough a ious pa hways, including poin sou ce con amina ion, a o able soil
physicochemical p ope ies, shallow g oundwa e , highe wa e sheds dimension, mac opo e
low, and he in low o su ace wa e o bank il a e. Also, he exis ence o subsu ace ile o
s o m d ains, o sewe s, and he occu ence o o e land low om de eloped and a id
landscapes ha e been associa ed wi h si es wi h highe concen a ions o hese compounds
(Medalie e al., 2020; Suciu e al., 2023).
The p olonged u iliza ion o hese he bicides o e he pas 45 yea s has aised
app ehension ega ding i s po en ial impac on heal h and he en i onmen . The p ocess o
manu ac u ing, anspo ing, and applying a e belie ed o be he majo weaknesses, being
mos ly associa ed o such conce n (Me aul e al., 2020).
As p e iously men ioned, he pe asi eness o glyphosa e and AMPA ac oss a ious
subs a es such as soil, su ace/g oundwa e , and ai has been ex ensi ely eco ded.
Mo eo e , i was e en de ec ed in human u ine in se e al coun ies (Campbell e al., 2022;
No a e al., 2020; Suciu e al., 2023), indica ing he ex en o exposu e ha bo h humans and
animals a e subjec o.
The exceedingly low apo p essu e o glyphosa e and AMPA ende s i esis ance o
signi ican ola iliza ion, e en in he e en o p ocesses as mine aliza ion/deg ada ion,
immobiliza ion, o leaching occu ed ollowing i s applica ion. In soils hese wo compounds
a e mos ly deg aded by mic oo ganisms, which use hese as nu ien sou ces. Glyphosa e
could be also subjec , in mino ex en and in speci ic en i onmen s, o pho ooxida ion and
abio ic deg ada ion(Samson-B ais e al., 2022). Upon mine aliza ion /deg ada ion, he
b eakdown p oduc s include AMPA, he p ima y and majo me aboli e o glyphosa e
deg ada ion, sa cosine, and glycine (Figu e 2.15). The mos equen pa hway occu s h ough
he C-N bond oxida ion, in which mic oo ganisms deg ade glyphosa e using i as ca bon
sou ce, p oducing AMPA and glyoxyla e (an easily assimilable ene gy sou ce). Subsequen ly,
AMPA also could unde goes mine aliza ion, p oducing me hylamine o o maldehyde and
phospha e (Cas ejón-Godínez e al., 2021; Espinoza-Mon e o e al., 2020; Ojelade e al.,
2022).
Li e a u e Re iew
42
equen ly used echnique, applied o se e al sample ma ix ypes, including aqueous
samples, biological and clean-up o solid samples, al hough SPE ca idge a e expensi e and
he me hod uses o ganic sol en du ing p epa a ion and elu ion (Cheng e al., 2011; Pi es e
al., 2020). To wa e sample p e-concen a ion, lyophiliza ion can also be applied (Pi es e al.,
2020, 2023).
A e he use o hese p ocedu es, i i was necessa y, wo ypes o me hodologies a e
commonly used: di ec me hods and hose in ol ing a de i a iza ion s ep. Di ec me hods a e
ad an ageous due o hei educed sample p epa a ion s eps. Howe e , he highly pola i y o
glyphosa e, glu osina e, and AMPA make i impossible o di ec ly sepa a e hese compounds
h ough e e se-phase ch oma og aphy. Some analy ical columns can p o ide be e
e en ion o analy es wi h his s ongly anionic phosphona e s uc u e. Recen ly, se e al
ch oma og aphic columns ha e been de eloped o measu e hese pes icides, seeking g ea e
sensi i i y, ep oducibili y and educing he wo k associa ed wi h sample p epa a ion. Among
he indi ec me hods used, h ee ypes o de i a iza ion s eps a e mos commonly applied.
The i s is p e-column de i a iza ion using FMOC-Cl in ACN eagen o diminish hei pola
cha ac e , acili a ing ch oma og aphic e en ion, and allowing analysis by liquid
ch oma og aphy wi h mass spec ome y (Figu e 2.18).
Figu e 2.18 – Example o a p e-column de i a iza ion o glyphosa e, AMPA and glu osina e wi h FMOC
(adap ed wi h pe mission om (Campanale e al., 2022). Copy igh 2022, Jou nal o Ch oma og aphy A).
The second is pos -column de i a iza ion, p omo ing he con e sion o glyphosa e in o
glycine and subsequen de i a iza ion wi h o-ph halaldehyde, ollowed by a luo escen
de ec o . De i a iza ion wi h i luo oace ic acid anhyd ide and hep a luo obu anol, is also
OO
PN
O O O
O
PN 2
O O
p 9
Cl
O
OCl
O
O
O
O
P
N
O
O
O
OO
P
O
O N 2
O
O
O
O
P
O
O
N
O
O
O
PN
O O

Chap e 2
43
applied o ob ain ola ile and s able molecules equi ed o gas ch oma og aphy analysis
(IARC, 2017; Ma a Małysiak and Tomasz Kiljanek, 2022).
2.4 Inno a i e echnologies o mi iga ion o new con aminan s
Gi en he high equency and pe sis ence o he compounds unde s udy in he
en i onmen and hei po en ial impac on human and animal heal h, i has become essen ial
o de elop ea men p ocesses o emedia e en i onmen al pollu ed ma ixes. Soil and wa e
emedia ion echnologies a e he me hods used o clean up con amina ed a eas con ained in
hese wo en i onmen compa men s. These echnologies can di e o dis inc
con aminan s and ypes o con amina ed ma ix (soil o wa e ).
Va ious echniques including physical, chemical, he mal, and biological me hods could
be u ilized o he emedia ion o pha maceu ical and pes icide con amina ions in wa e
and/o soil (Na imani & Sil a, 2020). Physical me hods mainly ocus on ans e ing he
compounds om he aqueous phase o he solid phase. On he o he hand, biological and
chemical ea men s in ol e chemical eac ions wi h he compounds, leading o he o ma ion
o new me aboli es o deg ada ion p oduc s, wi h comple e mine aliza ion being a po en ial
ou come (Na imani & Sil a, 2020; Pa el e al., 2019; Samal e al., 2022). Some o hose
echnologies applied o emedia e pha maceu icals and pes icides con amina ed soil, wa e ,
o bo h a e p esen ed in Figu e 2.19.
Li e a u e Re iew
44
Figu e 2.19 – Resume o some emedia ion echnologies applied o pha maceu icals and pes icides
con amina ed soils, wa e , o bo h (de eloped by he au ho ).
Adso p ion, elec odialysis, e apo a ion, dialysis, il a ion, loccula ion, e e se osmosis,
sedimen a ion, and s eam s ipping a e some o he a ailable physical ea men s, being
adso p ion and memb ane sepa a ion he mos used echnologies o pha maceu ical and
pes icides emo al (Logana han e al., 2023; Pa el e al., 2019). Chemical me hods include ion-
exchange, neu aliza ion, educ ion, p ecipi a ion, calcina ion, and ad anced oxida ion
p ocesses (AOPs), his las one b oadly used in e ia y ea men s in WWTP (Logana han e
al., 2023; Pa el e al., 2019). The mal me hods essen ially include incine a ion and py olysis.
Conce ning biological me hods, ac i a ed sludge, ae a ed lagoons, anae obic diges ion,
ickling il e s, and was e s abiliza ion ponds a e used (Pa el e al., 2019). The ac i a ed sludge
p ocess, based on mic obial deg ada ion, is he p ima y applied biological p ocess, la gely
used as a seconda y ea men p ocess in WWTPs (Logana han e al., 2023). Many o he
adi ional me hods ha e been employed o emo e o ganic subs ances and suspended solids
om was ewa e . Howe e , some p o ed o be inadequa e o elimina ing pha maceu icals,
pa icula ly i hey a e hyd ophilic, and pes icides. The need o an addi ional e ia y
ea men p ocess a ises o e ec i ely educe he concen a ion o pha maceu icals and
Chap e 2
45
pes icides in o de o mi iga e hei po en ial en y and accumula ion in su ace wa e and
g oundwa e esou ces (P adhan e al., 2023).
Memb anes a e widely used as pe meable o semi-pe meable ba ie ha selec i ely
allows ce ain subs ances o pass h ough while es ic ing o he s based on hei p ope ies
such as size and cha ge and in a d i ing o ce. The d i ing o ces equi ed o p omo e he
mo emen o subs ances ac oss he memb ane can include p essu e di e ence,
concen a ion g adien , and a po en ial ield ha ini ia es ions mo emen (O hman e al.,
2022; Pa el e al., 2019). Re e se osmosis, mic o il a ion, nano il a ion, and ul a il a ion
a e e ec i e me hods using memb anes o emo ing an idep essan pha maceu icals and
syn he ic o ganic con aminan s such as o ganophospha e he bicides. Conce ning e e se
osmosis, he d i ing o ce is he p essu e di e ence be ween he il a e and eed si es o he
sepa a ion memb ane. On he o he hand, he p ima y ope a ional d i ing o ce o nano- and
ul a il a ion is ion epulsion, since he memb anes used a e cha ged. Dalbosco e al. (2023)
es ed e e se osmosis and nano il a ion in luoxe ine emo al om wa e . Nano il a ion
p esen ed a emo al a e be ween 50 and 60%, and e e se osmosis demons a ed a a e o
98.8% (Dalbosco e al., 2023). The same wo echnologies we e also es ed in Non-s e oidal
an i-in lamma o y d ugs (NSAIDs) om g oundwa e demons a ing success ul emo al a es
o o e 85% (Pa el e al., 2019). Al hough i s e iciency, e e se osmosis can be expensi e and
equi es egula main enance. This physical ea men p esen s he ad an age o does no
lead o he de elopmen o con aminan byp oduc s (me aboli es), as echnologies such as
AOPs o biological-based ea men s, whe e hese ans o ma ion p oduc s could also be o
en i onmen al conce n (Rod iguez-Mozaz e al., 2015).
The employmen o phy o emedia ion (i.e., he use o plan s o abso b and de oxi y
chemical con aminan s), phyco emedia ion (i.e., he use o algae o emo e con aminan s
such as hea y me als, o ganic compounds, and nu ien s, om con amina ed wa e o soil),
and mic obial emedia ion echnologies (i.e., he use o mic oo ganisms such as bac e ia,
ungi, and cyanobac e ia) a e achie ing p ominence as a mo e cos -e ec i e and
en i onmen ally sus ainable al e na i e o adi ional physical and chemical me hods o
emo ing hea y me als and o ganic con aminan s, al hough i is a slowe me hodology (Bha
e al., 2020). Phyco emedia ion was es ed using li ing and non-li ing mic oalgae o he
emo al o luoxe ine om aqueous solu ions ob aining 100% o emo al in six days (And eia
Sil a e al., 2022).
Adso p ion echniques ha e been a key me hodology in wa e and was ewa e ea men
o a p olonged pe iod, and hei g owing popula i y co esponds, besides o hei simple
Li e a u e Re iew
46
design, low cos , lexibili y, easy o use, and insensi i i y o oxic con aminan s, wi h he
ongoing eme gence o no el mic opollu an s in aqua ic en i onmen s as well as he disco e y
o sus ainable and cos -e ec i e adso ben s (A zal Husain Khan e al., 2022; Mo one e al.,
2019; Samal e al., 2022).
Se e al AOPs ha e been implemen ed o elimina e pes icides, including glyphosa e,
namely Fen on and Pho o-Fen on p ocesses, ozona ion (O3), pho oca alysis, pho olysis wi h
hyd ogen pe oxide and UV ligh (H2O2-UV), elec ochemical oxida ion, and
pho oelec ochemical p ocesses (Espinoza-Mon e o e al., 2020; Feng e al., 2020; Kudzin e
al., 2019). Ozona ion is a p omising AOP ha applies ozone o he ea men o was ewa e
and soil. Ozone is a highly po en oxidan , possessing one o he highes oxida ion po en ials
o any known subs ance. This e sa ile agen can be applied in ei he a gas o aqueous phase
o acili a e a wide ange o chemical eac ions and is capable o oxidizing pes icides, and o he
con aminan s. Fu he mo e, he in-si u gene a ion o ozone is a no able ad an age, as i can
apidly decay and be con e ed in o oxygen ia chemical decomposi ion, he eby minimizing
he buildup o oxic byp oduc s and p omo ing ae obic biodeg ada ion. (Ma ínez e al., 2022).
T ea men o concen a es con amina ed wi h glyphosa e and AMPA (ob ained om a
memb ane sys em in a d inking wa e p oduc ion plan ) was es ed applying h ee
me hodologies: ozona ion, adso p ion, and he combina ion o bo h. Comple e deg ada ion
o bo h glyphosa e and AMPA was obse ed o he highes applied ozone concen a ions,
mos ly by di ec ozona ion. Adso p ion on o ac i a ed ca bon, on he o he hand, was
signi ican ly low. These esul s we e associa ed wi h glyphosa e and AMPA high solubili ies,
he pH o he concen a e (8), and high na u al o ganic ma e concen a ions. Adso p ion
ollowed by ozona ion allowed he elimina ion o glyphosa e and AMPA ha canno be
emo ed by ca bon adso p ion. Addi ionally, o he impo an ad an ages o his combina ion
we e lowe ope a ional cos s due o educed con ac ime (10 min e sus 25 min) and
equipmen needs (Bozkaya-Sch o e e al., 2008).
(Rezaei Kalan a y e al., 2022) es ed he emo al capaci y o a con en ional d inking
wa e ea men plan (WTP) wi h p ima y sedimen a ion, coagula ion, loccula ion, cla i ie ,
apid il a ion (wi h sand and g anula ac i a ed ca bon), ollowed by chlo ine disin ec ion.
This s udy concluded ha mos o he pes icide’s emo al occu ed in coagula ion- loccula ion
and apid sand il a ion uni s (87%), ou comes associa ed wi h he hyd ophobic na u e, and
in a il a ion uni using g anula ed ac i a ed ca bon. A good pe o mance o he o al
pes icides emo al om he wa e was achie ed (50%), bu he emo ed pes icides du ing he
coagula ion- loccula ion p ocess we e accumula ed in o he sludge ha , possibly, will be
Chap e 2
47
discha ged in o he en i onmen wi hou any ea men , ending up being eleased in o he
soil (Rezaei Kalan a y e al., 2022).
In he en i onmen , he main dissipa ion p ocess o glyphosa e om he soil is h ough
biological b eakdown, p ima ily d i en by mic obial ac i i y, including ac inomyce es,
bac e ia, ungi, and mic ocy es, in which bac e ia play a dominan ole. The mic obial
deg ading capaci y has been ex ensi ely s udied and e iewed, and i is well es ablished ha
bac e ia can use i as a sou ce o ino ganic phospho us, as well as ni ogen and ca bon sou ces
unde ce ain condi ions (Singh e al., 2020; Zabaloy e al., 2022; Zhan e al., 2018). The e o e,
i is impe a i e o conside soil habi a s as a c ucial ac o ha egula es no only he
biodeg ada ion o glyphosa e bu also i s adso p ion and dissipa ion, he eby con ibu ing o
i s o e all p esence in he en i onmen (Zabaloy e al., 2022; Zhan e al., 2018).
Soil apo ex ac ion is a soil emedia ion echnique ha emo es ola ile con aminan s,
using a acuum pump, bu i can be cos ly and ime-consuming (Baldissa elli e al., 2019). On
he o he hand, enhanced bio emedia ion is a ea men ha implies adding nu ien s o he
soil o inc ease speci ic mic oo ganisms’ g ow h capable o deg ade con aminan s. This is a
cos -e ec i e and en i onmen ally iendly echnology, bu ime-consuming un il he desi ed
esul s a e achie ed (Pa hak e al., 2022). Conce ning elec okine ic emedia ion, in which an
elec ic ield is applied o he soil o p omo e he con aminan s emo al, is mo e e ec i e o
emo ing hea y me als and o ganic con aminan s (as some pes icides), bu i can be expensi e
and ene gy-in ensi e (Baldissa elli e al., 2019; F. L. Souza e al., 2016). Fo chemical oxida ion
ea men s, he addi ion o an oxidizing agen is pe o med ( o con amina ed soil o wa e )
esul ing in he con aminan ’s oxida ion. E ec i e o ea ing a wide ange o con aminan s,
bu i can be expensi e and equi es ca e ul moni o ing o a oid seconda y con amina ion.
Adso p ion can also be applied o soil and wa e and is a p ocess by which a solid ma e ial
cap u es and holds molecules o a dissol ed o suspended subs ance om a liquid o gas
(Samal e al., 2022). This echnology is widely used o emedia e con amina ed si es, as i can
e ec i ely emo e a a ie y o pollu an s.
The ques o no el me hods o elimina e di e en pollu an s in was ewa e is an ongoing
endea o . Howe e , i is equally impo an o es ablish ha he ea ed ma ices a e
en i onmen ally sa e, as any compound can pose a h ea as a pollu an , depending on i s
concen a ion and he si e whe e i occu s. The e o e, nons op esea ch and de elopmen o
no el me hods hold signi ican impo ance o he u u e elimina ion o a ange o eme ging
con aminan s (Diaz-Camal e al., 2022).

Li e a u e Re iew
48
2.4.1 Adso p ion
Adso p ion is a p ocess by which a solid ma e ial, called an adso ben , cap u es, and holds
on o molecules o a dissol ed o suspended subs ance, called an adso ba e, om a liquid o
gas. This is an in e ace p ocess ha in ol es physical in e ac ions, such as elec os a ic o ces,
and/o chemical bonds o a ach species (adso ba es) om he gas o liquid phase o a solid
ma e ial (adso ben ) (Sidoli e al., 2016). This p ocess is widely used as a means o emedia e
con amina ed si es o ea con amina ed e luen s, as i can e ec i ely emo e a a ie y o
pollu an s om wa e o soil (Espinoza-Mon e o e al., 2020; Mo one e al., 2019).
Adso p ion has se e al ad an ages o he emedia ion o he con amina ed ma ix. I can
e ec i ely emo e a a ie y o pollu an s, including hea y me als, o ganic compounds, as well
as nu ien s. I can, also, be used o ea g oundwa e , su ace wa e , e luen s, and soils. I
is ela i ely simple o ope a e, wi h high emo al a es o mos pollu an s and a cos -e ec i e
me hod compa ed o o he emedia ion echniques (Espinoza-Mon e o e al., 2020; Sidoli e
al., 2016).
Con aminan s ha can be emo ed by adso p ion include pes icides, he bicides, and
indus ial chemicals (J. Chen e al., 2017; McGinley e al., 2022; Moji i e al., 2020). Adso p ion
is also e ec i e in emo ing lead, me cu y, and a senic (Guo e al., 2020). The e ec i eness o
adso p ion depends on se e al ac o s, such as he ype o adso ben used, he concen a ion
and ype o con aminan , and he con ac ime be ween he adso ben and he con amina ed
liquid o gas (Goldan e al., 2022).
In he case o wa e ea men , adso p ion can be used as an indi idual echnique o as
pa o a mul i-s ep ea men p ocess, such as in combina ion wi h biological o chemical
ea men me hods (Mukhopadhyay e al., 2022).
The mos used adso ben s o he emedia ion o con amina ed si es a e ac i a ed
ca bon, biocha , zeoli es, and clays. These ma e ials ha e high su ace a eas and po e
olumes, which allows hem o adso b many pollu an s om he su ounding en i onmen
(Amalina e al., 2023; McGinley e al., 2022; Rissouli e al., 2017; asilje ić e al., 2019). In
addi ion, hey can be easily modi ied o imp o e hei adso p ion capaci y o speci ic
pollu an s (Tee e al., 2022).
The e ec i eness o adso p ion o emedia ion o con amina ed si es depends on se e al
ac o s, including he ype and concen a ion o pollu an s, he p ope ies o he adso ben ,
and he si e condi ions. In addi ion, he adso p ion capaci y o he adso ben can be a ec ed
Chap e 2
49
by ac o s such as empe a u e, pH, and he p esence o compe ing ions (G. Oli ei a e al.,
2018).
Adso p ion can be used in se e al ways o emedia ion o con amina ed si es, including
in-si u and ex-si u ea men . In-si u ea men in ol es ea ing he con amina ed soil o
wa e on-si e, while ex-si u ea men in ol es emo ing he con amina ed soil o wa e om
he si e o ea men . In-si u ea men is gene ally p e e ed, as i is mo e cos -e ec i e and
less dis up i e o he su ounding en i onmen . I could also be applied as a WWTP ea men ,
being included in he de eloped ea men p ocess (Espinoza-Mon e o e al., 2020;
Mukhopadhyay e al., 2022).
The ex en o adso p ion signi ican ly in luences he ans e and a ailabili y o
con aminan s as pes icides in soil and is one o he main mechanisms ha con ol pes icide
leaching. This p ocess educes he abili y o pes icides o mig a e and limi s hei po en ial o
con amina e su ace wa e s o g oundwa e , making i a c ucial ac o in p e en ing
en i onmen al pollu ion (Sidoli e al., 2016).
In summa y, adso p ion is a p omising echnique o emedia ion o con amina ed si es.
I is a simple and cos -e ec i e me hod ha can emo e a wide ange o pollu an s om wa e
and soil. Howe e , ca e ul conside a ion o si e condi ions and he selec ion o app op ia e
adso ben s a e necessa y o achie e success ul esul s.
2.4.2 P ospec i e use o biocha o emedia e con amina ed si es
Biocha is a ype o ca bonaceous ma e ial p oduced h u he py olysis o o ganic
ma e ials, such as ag icul u al was e o o es y esidues in an oxygen-limi ed en i onmen .
The he mal b eakdown o lignin, cellulose, hemicellulose, a , and s a ch con ained in he
eeds ock occu s du ing py olysis and p oduces h ee dis inc esul s: biocha (solid ac ion),
pa ly condensed ola ile ma e known as bio-oil (liquid ac ion), and non-condensable gases
(gaseous ac ion) as CO2, CO, CH4, and H2. These gases and bio-oil can be cap u ed o gene a e
ene gy and c ea e wo hwhile byp oduc s, such as ood la o ing, biochemical compounds,
adhesi e, and wood p ese a i es, based on he eeds used (Goldan e al., 2022; Pokha el e
al., 2020).
I has gained inc easing a en ion as a po en ial ool o emedia ing con amina ed soil
o wa e due o i s abili y o adso b and immobilize con aminan s (Lehmann & S ephen, 2009;
Z. Li & Fan ke, 2022; McGinley e al., 2022).
Li e a u e Re iew
50
The use o biocha o emedia ion echnology, as adso p ion, has se e al ad an ages.
Fi s ly, biocha can be p oduced om a wide ange o was e o ganic ma e ials ha a e eadily
a ailable, and ac ing as a ecycling p ocess, which makes i a cos -e ec i e and sus ainable
solu ion (Rubio, 2018). Second, biocha has a high su ace a ea, allowing i o adso b se e al
subs ances as hea y me als, o ganic compounds, and nu ien s. Thi d, biocha is s able and
can emain in he soil o hund eds o yea s, which makes i a long- e m solu ion o
con amina ed si es. The las is ha i is an o ganic ca bon- ich ma e ial capable o imp o e
soil condi ions as: inc eases soil o ganic ca bon con en , po osi y, wa e , and nu ien
e en ion capaci y, and de elops mic obial popula ion and ac i i y, inclusi ely s imula ing he
g ow h o bene icial mic oo ganisms ha comba plan diseases and acqui e esis ance o
pes s and diseases (K. Webe & Quicke , 2018). The e o e, biocha can be applied o
con amina ed soils h ough di ec mixing wi h soil, inco po a ion in o soil amendmen s, o
applica ion as a op laye . When biocha is mixed wi h soil, i can imp o e soil e ili y, and
wa e -holding capaci y, p omo e ca bon seques a ion, and mic obial ac i i y, po en ially
enhancing plan g ow h (Ahmad e al., 2014; McGinley e al., 2022).
Se e al s udies ha e shown ha biocha can be e ec i e in emedia ing con amina ed
soils and wa e and applica ed in dis inc app oaches as di ec ly in he con amina ed si e o
used as adso ben s in wa e ea men acili ies (Aghababaei e al., 2023; Bilias e al., 2021;
Guo e al., 2020; McGinley e al., 2022; L. Xiang e al., 2022). Acco ding o exis ing li e a u e,
he addi ion o biocha o con amina ed soils can e ec i ely immobilize hea y me als and
se e al pe sis en o ganic pollu an s, educing hei bioa ailabili y. P ecipi a ion, elec os a ic
in e ac ion, su ace adso p ion, and s uc u al seques a ion, a e some o he immobiliza ion
mechanisms e e ed o as mos p edominan , leading o a acili a ed decomposi ion.
Howe e , he ex en o decon amina ion e icacy is dependen on se e al ac o s such as he
biocha sou ce, amendmen a e, soil ype, and pollu an species (Guo e al., 2020).
Xiang e al. (2022) e iewed he use o biocha , bac e ia, and plan s in he sus ainable
emedia ion o soils con amina ed wi h o ganic pollu an s. As shown in Figu e 2.20 illus a e
he po en ial mechanisms in ol ed in his in eg a ed app oach, including plan up ake,
bac e ial deg ada ion, and biocha adso p ion, he in eg a ion o hese h ee componen s can
signi ican ly enhance he emo al e iciency o o ganic pollu an s om soil. The use o such a
comp ehensi e s a egy p o ides a p omising solu ion o he complex challenge o o ganic
pollu an con amina ion in soil (L. Xiang e al., 2022).
Chap e 2
51
Figu e 2.20 - P oposed mechanisms by which biocha media es he emedia ion o o ganic pollu an s in
soil. (adap ed wi h pe mission om: (L. Xiang e al., 2022). Copy igh 2022, En i onmen al Science and
Technology).
As highligh ed in Figu e 2.20, biocha acili a es o ganic pollu an oxida ion/deg ada ion
ia he p oduc ion o eac i e oxygen species, such as •O , SO4•-, and O2•-, h ough ee adical
eac ions wi h O2, S2O82-, o H2O2 (Figu e 2.20a). O ganic pollu an s can also be immobilized in
soil ia di e en biocha in e ac ions, a p ocess in which ca bonized ac ion o biocha
in e media es adso p ion (elec os a ic a ac ion and nonpola biocha –pollu an
in e ac ions), and unca bonized ac ion in e media es pa i ion (Figu e 2.20b). Fu he mo e,
biocha 's po ous su ace can hos soil mic obial communi ies, es ain and elease enzymes,
and eloca e elec ons o mic oo ganisms and pollu an s, in luencing o ganic pollu an s
me abolism o plan and mic obial communi ies in soil (Figu e 2.20c) (L. Xiang e al., 2022).
Howe e , he use o biocha o he emedia ion o con amina ed si es has some
limi a ions. Fi s , he e ec i eness o biocha depends on he ype and concen a ion o
con aminan s in he con amina ed ma ix. Second, he op imal applica ion a e and me hod
o biocha applica ion depend on he speci ic si e condi ions (when he applica ion is in-si e).
Finally, he long- e m e ec s o biocha applica ion on soil p ope ies and plan g ow h a e
no well unde s ood and equi e u he esea ch (Bilias e al., 2021).
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
58

Chap e 3
59
Abs ac
To ou knowledge, his is he i s s udy in Po ugal o he analysis o bo h an ibio ics and
psychia ic d ugs in i e wa e s om Dou o and Leça i e s and i s sedimen s. Samples we e
ex ac ed using solid phase ex ac ion and QuEChERS p ocedu es and he analysis was
pe o med using liquid ch oma og aphy wi h andem mass spec ome y.
Highe numbe o pha maceu icals and highe concen a ions we e ound in he Leça i e
o he wo ma ices unde s udy. The highes de ec ion equency o he wen y-se en
pha maceu icals was obse ed o luoxe ine wi h 83.3% in bo h ma ices. None o he s udied
an ibio ics we e de ec ed in wa e collec ed in he Dou o i e howe e six an ibio ics
(azi h omycin, cip o loxacin, cla i h omycin, moxi loxacin, o loxacin, and ime hop im) we e
ound in he Leça i e . Fu he , he analysis o sedimen s exhibi s he occu ence o
sul ame hoxypy idazine in he Dou o i e and azi h omycin in he Leça i e . The highes
concen a ion was obse ed in Leça i e o azi h omycin in he i e wa e (2,819 ng/L) and
sedimen s (43.2 ng/g). Ca bamazepine, ci alop am, luoxe ine, se aline, azodone, and
enla axine we e he psychia ic d ugs de ec ed in i e wa e s and sedimen s wi h mo e
diazepam as wa e i e con amina ion. Concen a ions anged om <me hod de ec ion limi
(MDL)) o 2.0 ng/L ( i e wa e s) and <MDL o 0.251 ng/g (sedimen s) in Dou o i e and
be ween <MDL o 354 ng/L ( i e wa e s) and <MDL o 6.35 ng/g (sedimen s) in Leça i e . To
iden i y he possible sou ces o pollu ion mo e moni o ing s udies should be pe o med along
he s udied i e s.
Keywo ds: Pha maceu icals, QuEChERS, Moni o ing, Su ace wa e s, Sedimen s, Solid
Phase Ex ac ion
3.1 In oduc ion
The p esence o pha maceu icals and i s me aboli es and deg ada ion p oduc s in he
en i onmen equi es con inuous esea ch and moni o ing s udies o assess hei po en ial
isks o he human and ecosys em’s heal h (Paula Paíga e al., 2019). These s udies need o be
pe o med o he assessmen o pha maceu icals in he di e en en i onmen al
compa men s o e alua e hei dis ibu ion, o iden i y con amina ion sou ces, and o
con ibu e o es ablishing limi alues o p o ec he en i onmen and human heal h. The
end in sample p epa a ion in ace analysis emphasized he op imiza ion o ex ac ion
p ocedu es o being simple , as e , less expensi e, and mo e en i onmen ally iendly han
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
60
adi ional echniques. The analy ical me hodologies a e be e es ablished and nowadays,
he scien i ic communi y ocuses mo e on moni o ing s udies.
The pha maceu icals p e alence in he en i onmen is cu en ly a well-es ablished and
well-quan i ied p oblem and has become a ma e o bo h scien i ic and public conce n (Lolić
e al., 2015; Paula Paíga e al., 2019) due o i s en i onmen al isk. Mo eo e , se e al s udies
ha e examined he bioaccumula ion o pha maceu icals and hei oxici y on non- a ge
o ganisms as ish, algae, c us aceans, mussels, snails, be ween o he animals, p esen ing
bioaccumula ion ac o s om 1.4 o 32000 (Ebele e al., 2017).
The e a e se e al possible sou ces and ou es o pha maceu icals o each he
en i onmen , bu was ewa e ea men plan s (WWTP) ha e been iden i ied as he main ail
(Jelić e al., 2012) Sou ces o was ewa e include domes ic, bu also hospi al was ewa e s,
medicine manu ac u es, land ill leacha es and di ec disposal o unused d ugs in he
en i onmen (Nikolaou e al., 2007; O iz de Ga cía e al., 2013). A e he ea men
pe o med in WWTP, he ea ed e luen s a e discha ged in o i e s, and he p oduced
sludges a e elimina ed o eused in ag icul u al as a e ilize p oduc . As a consequence o
he incomple e elimina ion o he pha maceu icals and me aboli es in he WWTP, hese
compounds each all en i onmen al compa men s (Nikolaou e al., 2007). The incidence o
pha maceu icals in he aqua ic en i onmen is con med a was ewa e , su ace wa e ,
g oundwa e , and d inking wa e (O iz de Ga cía e al., 2013). Howe e , since hese
compounds ha e he abili y o pa i ion o en i onmen al solid phases (Min en e al., 2011),
inc easing a en ion has been paid, in ecen yea s, o he con amina ion o pha maceu icals
in soils all o e he wo ld. None heless, sedimen s a e na u al eposi o ies o many chemical
subs ances p esen in he wa e (Be e a e al., 2014) and sedimen s p o ides a wide a ie y
o binding si es and ac as majo sinks o he deposi ion o pollu an s (O ega-Cal o e al.,
2013; Saka i e al., 2014).
In ecen yea s, an ibio ic and psychia ics pha maceu icals consump ion has a ac ed
a en ion wo ldwide. As a esul o he s a egic plans o he educ ion o an ibio ic
consump ion in he Eu opean Union including Po ugal (i.e. P og am o P e en ion and
Con ol o In ec ions and Resis ance o An imic obials), o e all consump ion o an ibac e ials
has been declining in ecen yea s, emaining a a s ill high le el (21.6 daily doses de ined pe
housand inhabi an s pe day in 2016) o Po ugal wi h simila alue obse ed in Eu ope (21.9
daily doses de ined pe housand inhabi an s pe day) (Rod igues e al., 2018). Conce ning o
he psychia ic d ugs and despi e he implemen a ion o he Na ional P og am o Men al
Heal h ha ocus on he a ionaliza ion o i s p esc ip ion and on he p e en ion o men al
Chap e 3
61
heal h p oblems, he e has been an in ensi ica ion o i s consump ion, wi h an inc ease o 15.2
M o 30.0 M consumed packages om 2013 o 2016 (P og ama Nacional pa a a Saúde Men al,
2017).
Human su i al depends on sus ainable linkages wi h he en i onmen . Howe e , he
"p esen " shows a di e en eali y. The deg ada ion o he en i onmen is cons an by he
s ong ac i i ies o he human being. Thus, s opping pollu ion is he mos p oblema ic subjec
o he plane . In he las decades, a new opic has a ac ed a en ion, he issue o
pha maceu icals and hei po en ial en i onmen al isk. O e he las yea s, he assessmen
o pha maceu icals in su ace wa e s has inc eased bu ewe s udies a e being pe o med in
soils and sedimen s. Thus, in he p esen s udy, he assessmen o pha maceu icals belonging
o an ibio ics and psychia ic d ugs in su ace wa e and sedimen s o wo i e s (Dou o and
Leça) loca ed in he No h o Po ugal was pe o med. Published s udies pe o med by he
scien i ic communi y in he Dou o i e showed ha i s pollu ion by pha maceu icals is
consis en and i s occu ence is equen , co e ing a wide a ea and displaying ho -spo s (Lolić
e al., 2015; Madu ei a e al., 2010). In he Leça i e , da a ega ding he occu ence o
pha maceu icals in i s basin is sca ce, howe e , he exis en ial pollu ion in he Leça i e mus
no be neglec . Thus, solid phase ex ac ion (SPE) o i e wa e s collec ed along he Dou o
and Leça i e s and quick, easy, cheap, e ec i e, ugged, and sa e me hodology (QuEChERS)
used o in he sedimen s om he same i e s bank we e he p ocedu es used o he
ex ac ion o wen y-se en pha maceu icals belonging o an ibio ics and psychia ic d ugs.
The analysis was pe o med using liquid ch oma og aphy wi h andem mass spec ome y
(U PLC−MS/MS) and he ob ained esul s in i e wa e s and sedimen s ( op and bo om)
we e analyzed. The en i onmen isk coe icien was pe o med as also he co ela ion
be ween he pa ame e s and he ob ained concen a ion o he s udied pha maceu icals. To
ou knowledge, his is he i s wo k in Po ugal ha simul aneously analyses i e wa e s and
sedimen s o he se o pha maceu icals unde s udy.
3.2 Ma e ials and me hods
3.2.1 Physical cha ac e is ics and poin s o pollu ion o he Dou o and Leça
i e s
D aining o he A lan ic Ocean, Dou o and Leça i e s a e wo o he i e s ha c oss he
ci y o Po o in Po ugal. Dou o i e , wi h i s sou ce in U bion (Spain), co e s an a ea o abou
98 000 km2 sha ed among Po ugal and Spain, wi h a o al leng h o 927 km and an a e age
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
62
low o 700 m3/s. In he o he hand, Leça i e ha ises in Mon e Co do a, San o Ti so
(Po ugal), co e s an a ea o only 190 km2, wi h a o al leng h o 45 km and an a e age low
o 3.4 m3/s. I s main in o ma ion’s a e p esen in Table SM2 (Supplemen a y Ma e ial).
The Dou o Ri e ecei es e luen s om se e al WWTPs. Two o hem, loca ed in he
lowe and medium s e ch o he es ua y, belonging o he me opoli an a ea o he Po o ci y
a e Sob ei as and F eixo WWTP, which oge he se e an equi alen popula ion o abou 370
000 inhabi an s, achie ing an a e age daily low o abou 90 000 m3 (C uzei o e al., 2017;
Madu ei a e al., 2010; Mendes e al., 2017).
The wo mos impo an WWTP ha discha ge e luen s o Leça i e a e loca ed in Maia
(Pa ada and Pon e de Mo ei a WWTP). Those WWTP ea daily nea ly 23,000 m3 pe day o
u ban was ewa e s, om domes ic and indus ial e luen s (A. I. Gomes e al., 2014). The Leça
i e ecei es un ea ed and ea ed e luen s om nume ous indus ies, o qui e di e en
ypologies, namely: ex ile dyeing and p in ing, me allu gical, mechanical, and ag o- ood
plan s (A. I. Gomes e al., 2014).
3.2.2 Ri e wa e s and sedimen s sampling
Samples (wa e i e and sedimen s) we e collec ed in No embe o 2017. The sampling
poin s we e numbe ed om C es uma-Le e dam o he i e mou h in Dou o and om u al
a eas o he po o Leixões in Leça (Figu e 3.1). Sampling si es 4 and 5 om he Dou o Ri e
we e loca ed nea he i e mou h (app oxima ely 1.5 km in he igh i e bank), sho ly a e
he discha ge poin o Sob ei as WWTP. In he same i e side, poin s 2 and 3, abou 2 km
ups eam, we e se in Massa elos. The i s sampling poin , abou 4.5 km ups eam, in he
o he i e bank (Vila No a de Gaia), was loca ed in he A eínho i e beach. Conce ning o
Leça Ri e sampling poin s, one was loca ed in a ec ea ional pa k, downs eam he discha ge
o Pon e de Mo ei a WWTP (poin 6), and poin 7, in Pon e do Ca o ec ea ion a ea, also
inse ed in a e i alized zone, a e a s ongly indus ialized a ea. The cou se o he Leça i e
is ca ied ou be ween p i a e ag icul u al ields and loca ed in a eas wi h educed
accessibili y, limi ing he access o he i e . Thus, ewe sampling poin s we e made in he
Leça i e .
Chap e 3
63
Figu e 3.1 - Sampling loca ions o su ace wa e and sedimen samples in he Dou o and Leça i e s.
Ri e wa e s we e collec ed i e cen ime e s deep, nea he ma gin o each i e
(app oxima ely 50 cm), using a ma high-densi y polye hylene bo le p e-washed wi h
ul apu e wa e . Sedimen s we e collec ed in he same sampling poin s, a wo dep hs ( op:
0-2 cm and bo om: 2 o 10 cm), excep a he collec ion poin in he Pon e do Ca o ec ea ion
a ea (poin 7, Figu e 3.1), since hese sedimen s we e no accessible due o he i e bed
s uc u e. A o al o wel e samples ( op and bo om) we e collec ed. Subsequen ly, samples
we e kep a 4°C un il a i al o he labo a o y. Wa e samples we e acuum il e ed h ough
0.45 μm nylon memb ane il e s (Fio oni Fil e s, Ing é, F ance).
All he samples we e s o ed a -20°C un il ex ac ion (no mo e han one week).
3.2.3 Ri e wa e s and sedimen s cha ac e iza ion
Wa e empe a u e (T), pH, conduc i i y (CE), edox po en ial (Eh), and dissol ed oxygen
(DO) we e measu ed in si u, along he sampling campaign. Wa e quali y pa ame e s such as
elemen analysis (F-, Cl-, Ca, Mg, Na, K, Fe, Al, Si), hea y me als (As, B, Cd, Co, C , Cu, Mn, Ni,
Pb, Zn), and sulpha e (SO42−), ammonium (NH4+), ni a e (NO3-), and ni i e (NO2-) ions we e
de e mined acco ding o he p ocedu e desc ibed in Fe ei o e al. (2017).
Pa ame e s including pH (H2O, KCl, and CaCl2) (1:2.5 m:V), conduc i i y (CE), wa e
con en (WC), o ganic ma e (OM), phospha e (PO43−), and sulpha e (SO42−) (Mussa e al.,
2009) we e analyzed in sedimen , and he same elemen analyzed in i e wa e s and hea y

An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
64
me als analysis was pe o med (Fe ei o, 2017). To al Phospho us (P) and ex ac able P (Olsen
me hod) we e measu ed, in addi ion o o al ca bon, ni ogen, and sulphu de e mina ion
(analyzed by combus ion wi h a LECO analyze ). A pa icle size dis ibu ion cha ac e iza ion
was pe o med using a lase di ac ome e (Mas e size 2000, Mal e n, UK) coupled wi h a
dispe sion uni - Hyd o G, (Mal e n, UK), capable o analyze pa icle size be ween 0.02 o 2000
µm. The e ac i e index o he dispe sed phase was 1.65 and he abso bance was 0.1. The
used con inuous phase was wa e , wi h a e ac i e index o 1.330. The sample amoun placed
wi hin he measu emen sys em, wi h a eloci y o he s i e o 600 .p.m. and pump speed
se a 1250 .p.m., was such ha he alue o obscu e ell wi hin he ange o 10-20%.
3.2.4 Reagen s and chemicals
Fo he ex ac ion, ace oni ile (assay 99.99%) and me hanol (assay 100%) we e
pu chased om VWR Chemicals (Fon enay-sous-Bois, F ance), hyd ochlo ic acid (HCl) 37%
we e supplied by Ca lo E ba (Rodano, I aly), ammonium hyd oxide solu ion (NH3aq, 28.0–
30.0%) was ob ained om Sigma-Ald ich (S einheim, Ge many), and
e hylenediamine e aace ic acid disodium sal 2-hyd a e (Na2EDTA) (assay >99.0%) was
ob ained om Pan eac (Ba celona, Spain). Ace ic acid glacial (assay 100%) was pu chased
om VWR Chemicals (Fon enay-sous-Bois, F ance).
Fo he analysis in UHPLC-MS/MS, me hanol and ace oni ile, bo h LC-MS g ade, we e
supplied by Scha lau (Ba celona, Spain), p opanol LC-MS g ade was ob ained om Sigma-
Ald ich (S einheim, Ge many), and o mic acid (PA-ACS) was supplied by Ca lo E ba (Rodano,
I aly). A Simplici y 185 sys em (Millipo e, Molsheim, F ance) was used o p oducing ul a-pu e
wa e ( esis i i y o 18.2 MΩ.cm).
All ch oma og aphic sol en s we e il e ed h ough a 0.22 µm nylon memb ane il e
(Supelco, Belle on e, PA, USA) using a acuum pump (Dinko D-95, Ba celona, Spain) and
degassed o 15 min in an ul asonic ba h (Sono ex Digi al 10P, Bandelin DK 255P, Ge many).
All samples we e il e ed h ough a PTFE sy inge il e (0.20 μm) p io o he injec ion in he
UHPLC- MS/MS sys em.
All an ibio ics and psychia ic d ugs and iso opically-labelled in e nal s anda ds we e o
high pu i y g ade (≥98%). Lome loxacin, moxi loxacin, luoxe ine, no luoxe ine, pa oxe ine,
se aline, azodone, enla axine, cip o loxacin-d8, and luoxe ine-d5 we e ob ained in he
o m o he hyd ochlo ide sal . The chemical abs ac se ice (CAS), molecula weigh ,
Chap e 3
65
o mula, s uc u e, supplie company, and he solu ion used o p epa ed each s ock solu ion
a e lis ed in Table SM1 (Supplemen a y Ma e ial).
Indi idual s ock s anda d a a concen a ion o 1 g/L was p epa ed on a weigh basis in
sol en (See Table SM1, Supplemen a y ma e ial) and s o ed a -20ºC and an in e media e
solu ion (mix u e o all compounds), wi h a ixed concen a ion o 20 mg/L, was p epa ed by
adding an app op ia e amoun o each s ock solu ion. Wo king s anda d solu ions we e
p epa ed om he in e media e solu ion in ace oni ile:ul a-pu e wa e (30:70, / ) be o e
each analy ical un and o he o i ica ion es s.
3.2.5 SPE ca idges and QuEChERS ube
SPE ca idges S a a-X (200 mg, 3 mL) om Phenomenex (Cali o nia, USA) and o iginal
QuEChERS ex ac ubes (1 g NaCl and 4 g MgSO4) ob ained om Agilen Technologies (Lake
Fo es , CA, USA) we e used o he ex ac ion o wa e s and sedimen s, espec i ely. A e
QuEChERS ex ac ion, a dispe si e SPE (150 mg C18 and 900 mg MgSO4) was used o clean-
up s ep (Agilen Technologies (Lake Fo es , CA, USA)).
3.2.6 Ri e wa e s and sedimen s ex ac ion p ocedu es
SPE and QuEChERS ex ac ion me hodologies used we e adap ed om he wo k o P.
Paíga e al. (2017) o i e wa e s and San os e al. (2016) o sedimen s, espec i ely. The
s eps used in he wo ex ac ion me hods we e illus a ed in Figu e SM1 (Supplemen a y
ma e ial). A he end o each ex ac ion, he ex ac s we e e apo a ed unde a gen le s eam
o ni ogen o d yness and he esidues we e econs i u ed wi h 500 μL o ace oni ile:ul a-
pu e wa e (3:7, / ). Finally, 5 μL o a mix u e o iso opically-labelled in e nal s anda ds
solu ions was added.
3.2.7 UHPLC-MS/MS analysis
The ch oma og aphic and mass spec ome y (MS) condi ions used o he an ibio ics and
psychia ic d ugs unde s udy a e desc ibed in he a icle published by he au ho s (P. Paíga e
al., 2017). A ep esen a i e ch oma og am o a 500 µg/L s anda d mix u e o he selec ed
pha maceu icals is p esen in Figu e SM2 (Supplemen a y ma e ial). Re en ion ime and ion
a io o all compounds a e lis ed in Table SM4 (Supplemen a y Ma e ial). The concen a ion
o iso opically-labelled in e nal s anda ds in he s anda ds and in he ex ac s o i e wa e s
and in sedimen s a e shown in Table SM3 (Supplemen a y Ma e ial).
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
66
3.2.8 Valida ion
The quali y and consis ency o he analy ical esul s was check in me hod alida ion o
he wen y-se en pha maceu icals unde s udy. SPE and QuEChERS we e he me hodologies
used o he ex ac ion o he compounds in i e wa e s and in sedimen s and UHPLC-MS/MS
was used o he analysis. Linea i y, p ecision, ma ix e ec (ME), me hod de ec ion limi
(MDL), me hod quan i ica ion limi (MQL), and eco e y we e he pa ame e s analyzed o
bo h ma ices.
3.2.9 S a is ical analysis
Desc ip i e s a is ics was used o summa ize he esul s o pha maceu ical and
physicochemical con amina ion in wa e and sedimen s samples. Pai wise co ela ion
coe icien s be ween he a iables in he i e wa e and sedimen s we e done (Pea son
co ela ion coe icien ). P incipal Componen Analysis (PCA) was pe o med using XLSTAT
Ve sion 2019.3.1 o explo e possible ela ionships be ween he le els o pha maceu icals in
wa e and sedimen (bo h laye s) wi h he wa e and sedimen s p ope ies. S a is ical
signi icance was de ined a p < 0.05. O he wen y-se en pha maceu icals, only he de ec ed
we e conside ed in his analysis. When applicable, alues we e assumed o be equal o hal o
he limi o de ec ion/quan i ica ion.
3.2.10 Risk assessmen
The p o ec ion o he aqua ic ecosys em om pha maceu icals pollu ion is u mos
impo an and i s impac on he en i onmen should be e alua ed. Risk assessmen was
de e mined ollowing he wo k published by Paíga e al. (2019).
3.3 Resul s and discussion
3.3.1 Pa ame e s
The physical and chemical pa ame e s we e analyzed in i e wa e s and in sedimen s
om Dou o and Leça i e s (Table SM5 and SM6, Supplemen a y Ma e ial). Acco ding o he
pa icle size dis ibu ion esul s, all he sedimen s p esen ed a sandy ex u e. The analysis o
E.C., DO, chlo ide, ni a e and sulpha e show he same p o ile in he samples WsD3, WsL1,
and WsL2, s anding ou as he poin s wi h he lowes alues o hese pa ame e s.
Chap e 3
67
Figu e 3.2 p esen s he le els o elemen s con en in he sedimen s and i e wa e s. The
concen a ion le els and he pa e n o dis ibu ion o elemen s in bo h ma ices and di e en
sampling poin s we e di e en . The elemen quan i y le els ound in sedimen s we e ypically
highe han in he co esponding i e wa e s. The bo om sedimen sample SsD3 p esen a
highe concen a ion o almos all he analyzed elemen s. The main highligh s o he i e
wa e we e he sodium (64.85-67.65 mg/L in Leça and 69.62-4,863 mg/L in Dou o), chlo ide
(76-79 mg/L in Leça and 63-11 552 mg/L in Dou o) and sulpha e (38-71 mg/L in Leça and 51-
1,548 mg/L in Dou o) which, oge he wi h he elec ical conduc i i y, show an inc ease on
he Dou o Ri e as i app oaches he sea. This salini y inc emen in he i e cou se nea o
ocean is coinciden wi h o he s udies (Liu e al., 2019). This cha ac e is ic shows he sligh es
in luence ha he sea p esen s on he Leça i e , since i s mou h is loca ed a Po o Leixões
basin.
Figu e 3.2 - Elemen concen a ion in i e wa e and sedimen samples (Si in g/Kg).
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
74
highes de ec ion equency was obse ed o luoxe ine wi h 83.3% ollowed by
ca bamazepine wi h 66.7%.
In Dou o, only ca bamazepine and luoxe ine we e de ec ed, ca bamazepine wi h alues
lowe han MDL in wo samples and luoxe ine wi h a simila concen a ion (be ween 1.87 o
1.94 ng/L) in h ee o he ou collec ed samples. In Leça, hi een pha maceu icals
(azi h omycin, cip o loxacin, cla i h omycin, moxi loxacin, o loxacin, ime hop im,
ca bamazepine, ci alop am, diazepam, luoxe ine, se aline, azodone, and enla axine)
we e de ec ed. Concen a ion anged om <MDL ( azodone) o 2,819 ng/L (azi h omycin) in
WsL1 and be ween <MDL (ci alop am and azodone) o 235 ng/L ( enla axine) in WsL2. The
highes concen a ion was achie ed o azi h omycin in µg/L le els in sample WsL1 o
an ibio ics and ca bamazepine and enla axine o psychia ic d ugs in ng/L le els. Fo all
pha maceu icals highe le els we e achie ed in sample WsL1 when compa ed wi h sample
WsL2. This can be explained by he loca ion o he sampling poin . Sample WsL1 was collec ed
nea he WWTP e luen discha ge. The g ea es di e ence be ween samples WsL1 and WsL2
was obse ed o azi h omycin since he concen a ion ound in sample WsL1 is app oxima ely
12 imes highe han he concen a ion ound in sample WsL2.
Re e ing o he Dou o wa e sampling poin s and o he de ec ed compounds, a sligh
educ ion o concen a ions along he i e can be obse ed, excep o poin WsD3, in which
no compound was de ec ed. The p esence o a wa e discha ge poin (o unknown o igin)
be ween he poin WsD2 and WsD3 may ha e p omo ed he dilu ion o he pollu an s a his
poin .
The po en ial en i onmen al isk posed by he de ec ed pha maceu icals in he Dou o and
Leça i e s was assessed in h ee di e en ophic le els ( ish, Daphnia magna, and algae).
Azi h omycin, cip o loxacin, cla i h omycin, o loxacin, ime hop im, ca bamazepine,
ci alop am, luoxe ine, se aline, azodone, and enla axine we e he pha maceu icals wi h
measu ed concen a ions in Leça i e and ca bamazepine and luoxe ine in Dou o Ri e . The
isk quo ien was calcula ed using he highes concen a ion de ec ed in bo h i e s (Table 1).
The esul s a e p esen ed in Figu e SM3 (Supplemen a y Ma e ial). Ca bamazepine exceeds
he h eshold alue o one, showing a po en ial isk o algae and enla axine is oo close o
each he en i onmen po en ial isk also o algae, in Leça i e .

Chap e 3
75
3.3.3.2 Sedimen s
Many pollu an s, o iginally in oduced in o wa e , ha e a ini y o sedimen s pa icles
due o hei hyd ophobic/lipophilic p ope ies (Pe elo, 2010; Reid e al., 2000). The e o e, ou
s udy was ex ended o he ex ac ion and analysis o pha maceu icals in sedimen s and six
sampling poin s we e selec ed along Dou o and Leça o collec sedimen s samples. Then, wo
samples we e collec ed a each sampling poin . One sample was collec ed a he op (0-2 cm
dep h) and he second sample was collec ed a he bo om (2-10 cm) zone (see sec ion 2.6).
Concen a ions we e compa ed no only be ween he di e en sampling poin s bu also
be ween di e en dep hs o he same sampling poin ( op, bo om) (Table 3.2).
Table 3.2 - Concen a ion o de ec ed an ibio ics and psychia ic d ugs exp essed ng/g o sedimen
samples and ela i e s anda d de ia ion (%RSD).
Pha maceu icals o ganized by alphabe ic o de and by i s he apeu ic g oup.
De en ion equency was calcula ed aking in o accoun o all samples.
Conc-Concen a ion; n.d.- No de ec ed; MDL-Me hod de ec ion limi ; RSD- Rela i e S anda d De ia ion
Two an ibio ics (azi h omycin and sul ame hoxypy idazine) and six psychia ic d ugs
(ca bamazepine, ci alop am, luoxe ine, se aline, azodone, and enla axine) we e
de ec ed in he sedimen s. Concen a ions we e below he MDL wi h excep ion o enla axine
(0.251 ng/g) o sedimen s collec ed in Dou o and om <MDL (ca bamazepine and azodone)
o 43.2 ng/g (azi h omycin) in Leça sedimen s. Fluoxe ine had he highes de ec ion equency.
Only one an ibio ic was de ec ed ei he in he Dou o sedimen s (sul ame hoxypy idazine,
<MDL, SsD4 op) ei he in he Leça sedimen s (azi h omycin, 43.2 ng/g, SsL1 op).
When op and bo om zones we e compa ed, i mus be aken in o accoun ha soils wi h
sandy ex u e do no ha e su icien o ganic ma e ha slows he mig a ion o
pha maceu icals, inc easing he isk o i s in il a ion h ough he soil (Fehsen eld, 2015). In
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
76
he p esen s udy, sul ame hoxypy idazine, ci alop am, luoxe ine, and azodone de ec ed in
Dou o sedimen s had insigni ican di e ences be ween he op and he bo om zones due o
he lowe le els (<MDL) ound. In he o he hand, enla axine in sample SsD1 was no de ec ed
a he op and de ec ed a he bo om zone, showing i s mig a ion h ough he SsD1 sedimen
sample. In Leça, esul s e ealed lowe concen a ions in he bo om when compa ed wi h he
op zone o azi h omycin, ci alop am, luoxe ine, se aline, and enla axine. The de ec ion
o hese pha maceu icals in bo om zone also demons a es he mig a ion o he
pha maceu icals h ough sedimen . Fo he au ho s, he highe concen a ion a he op zone,
could be an e idence o ecen con amina ion. Fo ca bamazepine and azodone, simila
concen a ion in he wo zones wi h alues below he MDL was obse ed.
3.3.4 S a is ical analysis
O he wen y-se en pha maceu icals, only he de ec ed we e conside ed in PCA. In he
gene al analysis, pe o med wi h all he wa e and sedimen samples o bo h s udied i e s,
PCA exp esses 42.46% o o al a iance, highligh ing he opposi ion among he wa e samples
WsL1 and WsL2, bo h om Leça Ri e , wi h WsD4, om Dou o Ri e . SsD3 and SsD2 bo om
and SsL1 and SsD1 op, a e cha ac e izes by he highe elemen concen a ion (excep o B
and Na). WsL1 and WsL2 we e he mos con amina ed wa e samples and mos associa ed
wi h NO2, NH4+, Cl- and Eh (Figu e 3.5.A).
Acco ding o he Pea son ma ix (da a no shown), no signi ican co ela ions among
le els o pha maceu icals in wa e and sedimen s samples and i s cha ac e iza ion we e ound
excep o he NH4+ and he pha maceu icals moxi loxacin and diazepam.
Chap e 3
77
Figu e 3.5 - PCA analysis o pha maceu ical le els and cha ac e is ics o he wa e and sedimen s
samples om Dou o and Leça Ri e (A); F om Leça Ri e (B) and om Dou o Ri e (C and D) (AZM –
Azi h omycin; SMP – Sul ame hoxypy idazine; CIP - Cip o loxacin; CTM – Cla i h omycin; MXF –
Moxi loxacin; OFL – O loxacin; TMP - T ime hop im; CBZ – Ca bamazepine; CIT- Ci alop am; DZ –
Diazepam; FLU – Fluoxe ine; SER – Se aline; TRZ – T azodone; VEN – Venla axine; Temp –
Tempe a u e).
Be ween he sedimen s and wa e samples cha ac e is ics, some o he signi ican
co ela ions ound we e he OM wi h he Sil and Clay pe cen age, Pb and Ca wi h he PO43-
concen a ion and P o al wi h C and N pe cen age, Cd and Polsen concen a ion.
In he Leça Ri e samples, he i s wo p incipal componen s explained 45.49% and
32.56% o he o al a iance, espec i ely. Signi ican di e ences can be obse ed in he
dis ibu ion o pha maceu ical subs ances in bo h wa e and sedimen s. High le els o
pha maceu ical we e ound in he sample WsL1, as well as highe alues o EC, pH H2O, SO42-
and empe a u e. I is, also, accen ua ed he opposi ion among he sedimen samples SsL1
bo om and op. PO43-, Sand and S we e mo e associa ed wi h he bo om laye and he ace
elemen s Hg, Mg, As, Cd, Co, C , Ni, and Pb wi h he op laye , as well as se aline (SER) highe
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
78
concen a ion. pH (KCl and CaCl2), Polsen and P o al, OM and he pe cen age o Sil and G a el
we e, also, mo e associa ed wi h he op laye sample (Figu e 3.5.B). In addi ion, he
signi ican co ela ions among pha maceu icals concen a ion in wa e and sedimen s, and i s
cha ac e iza ion we e ound among he azodone (TRZ) concen a ion, he E.C., and he
concen a ion o Si, Ca, K, Fe and Mn. Also, SO42- p esen s a signi ican co ela ion wi h he
concen a ion o cla i h omycin (CTM), ca bamazepine (CBZ) and enla axine (VEN). A s ong
co ela ion also can be obse ed be ween concen a ion o ca bamazepine (CBZ) and E.C.
In Dou o Ri e , he i s wo p incipal componen s explained 27,21% and 15.37% o he
o al a iance, espec i ely. The samples WsD1, WsD2 and WsD4 we e s ongly associa ed
wi h highe ca bamazepine (CBZ) and luoxe ine (FLU) concen a ions, and he samples SsD2
op and bo om be ween each o he and wi h he SsD4 bo om and SsD1 op. The samples
SsD3 bo om showed opposi ion ela i ely o he samples SsD1 bo om, SsD3 and SsD4 op
and SsD5 op and bo om, p esen ing highe concen a ion o , PO43-, P o al, Polsen, NO3-, NO2-,
Hg, Ca, Mg, Na, Co, Pb and pe cen age o Wa e con en , OM, C, N, S and G a el (Figu e 5.C).
Including he hi d componen s explaining, in accumula ed, 55,93% o he o al a iance,
some o he associa ions we e emphasized, as he s ong ela ion be ween SsD2 bo om and
op and be ween WsD2 and WsD4 (Figu e 5.D). Also, he opposi ion be ween he samples
WsD3, SsD5 op and bo om and SsD1 bo om and SsD2 bo om, and op is highligh ed. In
addi ion, no signi ican co ela ions among pha maceu icals concen a ion in he Dou o
samples and i s cha ac e is ics we e ound excep be ween luoxe ine (FLU) and Si
concen a ion and wi h EC.
3.3.5 Concen a ion ound in li e a u e
Resea ch was ca ied ou in he li e a u e conside ing he ma ix, he pha maceu icals
included in ou s udy, and he wo ks published in he las decade. The measu ed
concen a ion ob ained in hese s udies is lis ed in Table SM10 (Supplemen a y Ma e ial) o
i e wa e s (ng/L) and sedimen s (ng/g).
Se e al moni o ing s udies we e ound o i e wa e s howe e ew s udies we e
published wi h esul s om he moni o ing o pha maceu icals in sedimen s and e en less in
sedimen s and i e wa e s om he same si e. Mo eo e , using he keywo ds
“pha maceu icals”, “sedimen s”, and “Po ugal”, hi y wo ks we e achie ed, al hough hese
s udies we e ocus on issues such as biodeg ada ion, emedia ion, and bio emedia ion. A ou
knowledge and o ou se o pha maceu icals, no wo ks we e ounded in moni o ing s udies
Chap e 3
79
in Po ugal o sedimen s. The pha maceu icals de ec ed and i s concen a ions wo ldwide
a e showed in Table SM10 (Supplemen a y Ma e ial) and discussed in he ollowing
pa ag aphs.
The highes concen a ions ound o an ibio ics in he li e a u e s and ou o
sul onamide an ibio ics ime hop im (13 600 ng/L) in Laizhou Bayin in China (R. Zhang e al.,
2012) and o sul ame hazine (1 090 ng/L) and sul ame hoxazole (5 320 ng/L) in Msunduzi
Ri e in Sou h A ica (Ma ongo e al., 2015) in i e wa e and o luo oquinolone
cip o loxacin (1 290 ng/g) in Hai Ri e (L. J. Zhou e al., 2011) in sedimen s. The µg/L and µg/g
le els ound in hese s udies could be ei he an indica ion ha poin sou ce pollu ion occu ed
in he s udied a ea a he ime o sampling as also a esul o cons an and agg essi e pollu ion.
Fo he emain s udies, he concen a ion o an ibio ics anged om <MDL o ng/L o ng/g
le els. P uli loxacin and moxi loxacin we e no de ec ed in any wo k.
In Pea l, Ba, and Huangpu i e s in China and Msunduzi i e in Sou h A ica,
pha maceu icals we e assessed in bo h ma ices (S. Li e al., 2018; Liang e al., 2013; Ma ongo
e al., 2015) bu mo e an ibio ics we e de ec ed in Pea l i e (S. Li e al., 2018; Liang e al.,
2013). These s udies we e compa ed be ween hemsel es o each pha maceu ical and
gene ally, when a concen a ion is highe in he i e wa e is also highe in i s sedimen s o
ice e sa. Howe e , his pa e n was no always e i ied. The unexpec ed p o ile can esul
in a poin -sou ce pollu ion ha occu s in he a ea as also mus be conside he mig a ion o
he pollu an s h ough soils. Ou esul s, in i e wa e we e in acco dance wi h he esul s
ound in Pea l Ri e bu wi h lowe concen a ion o ime hop im (WsL1 sample). The wo
an ibio ics ound in ou s udy o sedimen s collec ed in Dou o and Leça i e s we e no a
a ge o s udies in he li e a u e.
In Po ugal, pha maceu icals we e analyzed in hi een i e s (An uã, A ade, A e, Cé ima,
Guadiana, Leça, Lis, Mondego, Tagus, Tâmega, T ancão, Tua, and Xa ama i e s) bu no
s udies we e pe o med in sedimen s. Concen a ions o an ibio ics ound in Leça Ri e we e
highe han he concen a ions ound in he o he s udies conduc ed in Po ugal.
Fo psychia ic d ugs, all s udies we e ca ied ou in i e wa e s excep o he s udy
pe o med in Sou h A ica in which bo h ma ices we e assessed. Ma ongo e al. in 2015 ound
o ca bamazepine concen a ion be ween 130 o 3 240 ng/L in Msunduzi Ri e and be ween
<0.535 o 6.07 ng/g in sedimen s (Ma ongo e al., 2015). The highes concen a ion o
psychia ic d ugs (ca bamazepine) was ound in he s udy o Ma ongo e al. The le els ound
in ou s udy we e in acco dance wi h he emain esul s in Po ugal, howe e o sample WsL1
(Leça i e ) enla axine ha e highe concen a ion.

An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
80
3.4 Conclusions
In mul i esidue me hod, good esul s o all compounds a e no always ound in one single
ex ac ion, namely: sul onamides and luo oquinolones. The di e ences o he
physicochemical p ope ies o hese compounds and he ex ac ion condi ions used o en do
no allow highe eco e ies o all a ge analy es. Op imizing single ex ac ion o each
compound is no accep able since he cos s, ex ac ion ime, sol en s, and he p oduced
was es would be inc eased, and he p inciples o G een Chemis y a e se aside. In ou s udy,
he adop ed ex ac ion p ocedu es, SPE and QuEChERS me hodologies, yielded good
eco e ies o mos o he s udy pha maceu icals.
Ri e wa e s and sedimen s ( op and bo om) we e collec ed along Dou o and Leça i e s.
All samples we e cha ac e ized, and pha maceu icals we e analyzed in bo h ma ices. Highe
concen a ion was ound in samples ( i e wa e and sedimen s) collec ed in Leça when
compa ed wi h samples collec ed in Dou o. In i e wa e , only wo psychia ic d ugs we e
ound (ca bamazepine and luoxe ine). In he o he hand, hi een (six an ibio ics and se ens
psychia ic d ugs) o he wen y-se en pha maceu icals we e de ec ed in Leça i e wa e s. I
mus be highligh ed he highes concen a ion ound o azi h omycin in µg/L le el. Sampling
poin WsL1 is loca ed nea o he WWTP e luen discha ge, his can jus i y he alues ound.
Ca bamazepine and enla axine showed a po en ial isk o algae in Leça i e .
In he case o sedimen s, sul ame hoxypy idazine was ound in Dou o sedimen and
azi h omycin in Leça sedimen . Psychia ic d ugs we e ound in he collec ed samples: ou in
Dou o sedimen ) and six in Leça sedimen s. The concen a ion ound in he op and a he
bo om in each sample we e compa ed: in Dou o sedimen enla axine had a highe
concen a ion in he bo om zone which could be co ela ed wi h he mig a ion o he
pha maceu ical h ough he soil. In Leça sedimen s highe concen a ion was ound in op
zone, which could be a ibu ed o ecen pollu ion in he s udied a ea.
Compa ing he wo ks epo ed in li e a u e he e is no pa e n o he concen a ion ound
in bo h ma ices due o he poin -sou ce pollu ions in he i e wa e and mig a ion o he
pollu an s in he sedimen s. F om he esul s ob ained in ou s udy, mo e moni o ing s udies
need o be pe o med in all cou ses o he i e s. Sou ce o pollu ion need o be iden i ied;
hus samples need o be collec ed in he u al a ea, in he indus ialized a ea, and nea o he
ha bo .
As ew s udies we e ound in li e a u e in sedimen s as also emb acing oge he i e
wa e s and sedimen s, he con ibu ion o his a icle is impo an o u he moni o ing
Chap e 3
81
s udies. Pha maceu ical pollu ion no only eaches he wa e cou ses, because also sedimen s,
soil, and g oundwa e a e a ec ed.
CRediT au ho ship con ibu ion s a emen
Ma ia Joao Fe nandes: ~ W i ing - o iginal d a , In es iga ion, Da a cu a ion. Paula Paíga:
W i ing - o iginal d a , In es iga ion, Valida ion, Da a cu a ion. Ana Sil a: W i ing - o iginal
d a , Resou ces. Ca men Pe ez Llaguno: In es iga ion, Valida ion. Manuela Ca alho: Fo mal
analysis, Resou ces, W i ing - e iew & edi ing. Felipe Macías Vazquez: Concep ualiza ion,
Fo mal analysis, Resou ces, W i ing - e iew & edi ing, Supe ision. C is ina Dele ue-Ma os:
Concep ualiza ion, Fo mal analysis, Resou ces, W i ing - e iew & edi ing, P ojec
adminis a ion, Supe ision.
Acknowledgmen
This wo k was also suppo ed by UID/QUI/50006/2019 wi h unding om FCT/MCTES
h ough na ional unds. The au ho s would like o hank also he EU and FCT / UEFISCDI
/FORMAS o unding, in he ame o he collabo a i e in e na ional conso ium REWATER
inanced unde he ERA-NET Co und Wa e Wo ks2015 Call. This ERA-NET is an in eg al pa o
he 2016 Join Ac i i ies de eloped by he Wa e Challenges o a Changing Wo ld Join
P og amme Ini ia i e (Wa e JPI)
Appendix A. Supplemen a y da a
Supplemen a y da a o his a icle can be ound online a
h ps://doi.o g/10.1016/j.chemosphe e.2019.124729.
Chap e 3
82
Appendix A. Supplemen a y da a
Table SM1. Pha maceu icals, me aboli es, iso opically-labelled in e nal s anda ds, Chemical Abs ac s Se ice (CAS), molecula weigh , o mula, s uc u e, sol en
used, and supplie company.
Pha maceu icals and Iso opically-Labelled
In e nal S anda ds
CAS*, ¥
Molecula Weigh ¥
(g/mol)
Fo mula and S uc u e¥
pka
Sol en used o he
p epa a ion o he s ock
solu ion
Supplie Company
An ibio ics
Azi h omycin
83905-01-5
748.996
C38H72N2O12
S onges acidic pKa: 12.43
S onges basic pKa: 9.57
Me hanol
Sigma-Ald ich
(Mad id, Spain)
Cip o loxacin
85721-33-1
331.347
C17H18FN3O3
5.76; 8.68
Milli-Q Wa e -10% ace ic
acid in Milli-Q wa e
(1:1, / )
Sigma-Ald ich
(Mad id, Spain)
Cla i h omycin
81103-11-9
747.964
C38H69NO13
S onges acidic pKa: 12.46
S onges basic pKa: 8.38
Me hanol
Sigma-Ald ich
(Mad id, Spain)
En o loxacin
93106-60-6
359.401
C19H22FN3O3
5.69: 6.68
Milli-Q Wa e -10% ace ic
acid in Milli-Q wa e (1:1,
/ )
Sigma-Ald ich
(Mad id, Spain)
E y h omycin
643-22-1
733.937
C37H67NO13
S onges acidic pKa: 12.45
S onges basic pKa: 8.38
Me hanol
Sigma-Ald ich
(Mad id, Spain)
Chap e 3
83
Lome loxacin
98079-51-7
351.354
C17H19F2N3O3
S onges acidic pKa: 5.45
S onges basic pKa: 8.7
Milli-Q Wa e -10% ace ic
acid in Milli-Q wa e
(1:1, / )
Moxi loxacin
151096-09-2
401.438
C21H24FN3O4
S onges acidic pKa: 5.49
S onges basic pKa: 9.42
Milli-Q Wa e -10% ace ic
acid in Milli-Q wa e
(1:1, / )
No loxacin
70458-96-7
319.33
C16H18FN3O3
S onges acidic pKa: 5.58
S onges basic pKa: 8.68
Milli-Q Wa e -10% ace ic
acid in Milli-Q wa e
(1:1, / )
Sigma-Ald ich
(Mad id, Spain)
O loxacin
82419-36-1
361.373
C18H20FN3O4
5.45; 6.20
Milli-Q Wa e -10% ace ic
acid in Milli-Q wa e
(1:1, / )
Sigma-Ald ich
(Mad id, Spain)
P uli loxacin
123447-62-1
461.464
C21H20FN3O6S
S onges acidic pKa: 5.93
S onges basic pKa: 5.27
Milli-Q Wa e -10% ace ic
acid in Milli-Q wa e
(1:1, / )
To on o Resea ch
Chemicals Inc.
(On a io, Canada)
Sul adiazine
68-35-9
250.276
C10H10N4O2S
2.01; 6.99
Me hanol
Sigma-Ald ich
(Mad id, Spain)
Sul adime hoxine
122-11-2
310.328
C12H14N4O4S
1.95; 6.91
Me hanol
Sigma-Ald ich
(Mad id, Spain)
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed
in he no h o Po ugal
90
Table SM4. Re en ion ime and ion a io o an ibio ic, psychia ic d ugs, and iso opically-labelled
in e nal s anda ds.
Pha maceu icals
(min)
Ion Ra io (%)
a e age
(min)
RSD
(%)
n
-20%
Ion Ra io
A e age
(%)
+20%
RSD
(%)
n
An ibio ics
Azi h omycin
2.317
0.234
30
1.36
1.71
2.05
4.37
18
Cip o loxacin
2.265
0.321
30
0.942
1.18
1.41
3.30
13
Cla i h omycin
2.751
0.140
30
0.968
1.21
1.45
1.87
20
En o loxacin
2.302
0.313
30
4.50
5.62
6.75
3.74
17
E y h omycin
2.606
0.100
30
3.29
4.11
4.93
2.37
16
Lome loxacin
2.279
0.236
30
0.814
1.02
1.22
4.90
17
Moxi loxacin
2.403
0.356
30
0.897
1.12
1.35
3.44
27
No loxacin
2.250
0.219
30
0.964
1.21
1.45
3.80
26
O loxacin
2.249
0.326
30
1.22
1.52
1.83
2.92
25
P uli loxacin
2.701
0.165
30
0.993
1.24
1.49
4.05
27
Sul adiazine
2.435
0.307
30
1.13
1.42
1.70
2.55
28
Sul adime hoxine
2.989
0.0946
30
1.60
2.00
2.40
1.92
27
Sul ame hazine
2.629
0.214
30
1.00
1.25
1.50
2.90
22
Sul ame hoxazole
2.856
0.114
30
0.955
1.19
1.43
2.47
28
Sul ame hoxypy idazine
2.634
0.110
30
1.53
1.92
2.30
3.10
23
Sul apy idine
2.482
0.164
30
0.777
0.97
1.16
2.54
23
T ime hop im
2.217
0.199
30
2.18
2.72
3.27
3.85
18
Psychia ic d ugs
Ca bamazepine
3.095
0.0843
30
3.81
4.76
5.72
2.86
28
Ci alop am
2.631
0.118
30
27.9
34.8
41.8
4.94
21
Diazepam
3.529
0.110
30
1.01
1.26
1.51
2.51
25
10,11-Epoxyca bamazepine
2.869
0.108
30
1.12
1.40
1.68
2.99
26
Fluoxe ine
2.789
0.0991
30
2.22
2.78
3.33
2.85
25
No luoxe ine
2.763
0.389
30
2.60
3.25
3.90
2.03
24
Pa oxe ine
2.694
0.0770
30
0.833
1.04
1.25
3.60
28
Se aline
2.811
0.160
30
1.16
1.45
1.74
2.35
24
T azodone
2.501
0.0702
30
0.923
1.15
1.39
4.07
25
Venla axine
2.462
0.116
30
0.888
1.11
1.33
2.36
27
Iso opically-labelled
in e nal s anda ds
Azi h omycin-d3
2.315
0.152
30
Ca bamazepine-d10
3.080
0.101
30
Cip o loxacin-d8
2.262
0.132
30
Diazepam-d5
3.515
0.0500
30
Fluoxe ine-d5
2.785
0.0974
30
Sul ame hoxazole-d4
2.851
0.0664
30
Venla axine-d6
2.462
0.0878
30
Pha maceu icals o ganized by alphabe ic o de and by i s he apeu ic g oup.

Chap e 3
91
Table SM5. Analyzed pa ame e s in sedimen samples om Dou o and Leça i e s.
Pa ame e s
SsD1
op
SsD1
bo om
SsD2
op
SsD2
bo om
SsD3
op
SsD3
bo om
SsD4
op
SsD4
bo om
SsD5
op
SsD5
bo om
SsL1
op
SsL1
bo om
pH H2O
8.10
7.55
8.06
7.15
8.31
7.21
7.85
7.58
7.62
7.56
6.74
6.36
pH KCl
7.90
7.15
8.07
7.00
8.55
6.87
7.89
7.55
7.91
7.18
6.42
5.91
pH CaCl2
7.32
6.97
7.45
6.96
n.a.
6.79
7.31
n.a.
7.08
6.97
6.07
6.06
C.E. (mS cm-1)
3.01
1.49
5.72
7.29
n.a.
4.21
5.70
n.a.
2.57
1.50
0.44
0.36
Wa e Con en (%)
9.4
14.9
33.7
39.0
n.a.
18.8
21.2
n.a.
7.0
4.4
74.4
22.25
OM (%)
2.03
1.02
3.12
5.65
n.a.
2.21
1.30
n.a.
1.45
0.29
1.88
1.00
SO42- (g L-1)
n.d.
0.22
n.d.
1.89
n.a.
n.d.
n.d.
n.a.
0.29
0.23
n.d.
0.28
PO43- (mg L-1)
n.d.
0.06
0.18
n.d.
n.a.
1.22
n.d.
n.a.
n.d.
0.01
n.d.
0.01
P o al (mg/Kg)
395.50
218.19
n.a.
432.72
251.37
614.24
371.38
345.31
185.54
156.30
1,115.25
n.d.
Polsen (mg/Kg)
30.63
4.55
n.a.
13.32
6.96
40.18
16.79
15.92
5.31
3.40
54.71
n.d.
C (%)
0.99
0.26
n.a.
0.57
0.28
2.10
0.44
0.59
0.28
0.21
2.30
n.d.
N (%)
0.17
0.03
n.a.
0.04
0.03
0.14
0.04
0.08
0.02
0.03
0.27
n.d.
S (%)
0.051
0.004
0.320
0.053
0.020
0.168
0.055
0.060
0.014
0.01
0.137
0.195
G a el (%)
65.37
48.71
9.61
7.21
n.a.
62.74
22.96
n.a.
12.05
34.62
30.20
4.40
Sand (%)
32.61
51.03
81.92
80.51
n.a.
36.93
76.02
n.a.
87.95
65.38
69.32
95.60
Sil (%)
1.97
0.26
8.06
11.30
n.a.
0.33
1.02
n.a.
0.00 b
0.00 b
0.48
0.00b
Clay (%)
0.05
0.00a
0.41
0.98
n.a.
0.00 a
0.00 a
n.a.
0.00 a
0.00 a
0.00 a
0.00 a
Tex u e
Sandy
Sandy
Sandy
Sandy
n.a.
Sandy
Sandy
-
Sandy
Sandy
Sandy
Sandy
n.a. – no analysed
a – he esul o he sum o all he g anulome ic ac ions unde 0.002 mm was 0.00.
b – he esul o he sum o all he g anulome ic ac ions be ween 0.002-0.02 mm was 0.00.
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed
in he no h o Po ugal
92
Table SM6. Analysed pa ame e s in wa e samples om Dou o and Leça i e s.
Pa ame e s
WsD 1
WsD 2
WsD 3
WsD 4
WsL 1
WsL 2
Tempe a u e (ºC)
19.8
18.5
19.4
19.0
18.9
14.6
pH
7.24
6.09
7.38
7.20
7.15
7.05
E.C. (μS/cm)
11,490
15,770
578
20,600
932
818
Eh (mV)
456
403
383
360
438
483
DO (mg/L)
11.0
11.6
n.a.
11.8
n.a.
n.a.
F- (mg/L)
0.39
0.54
1.01
0.67
0.09
0.10
Cl- (mg/L)
5,658
8,713
63
11,552
76
79
SO42- (mg/L)
705
1,040
51
1,548
71
38
NH4+ (mg/L)
< 0.03
< 0.03
1.16
0.22
6.70
22.21
NO3- (mg/L)
10
12
1
38
n.a.
3
NO2- (mg/L)
0.10
0.64
0.13
1.65
2.62
3.07
n.a. – no analysed
Chap e 3
93
Sec ion 1. Me hod alida ion
Calib a ion cu e
Linea i y was s udied using s anda ds p epa ed in he sol en , in i e wa e s, and in
sedimen s ex ac s. Thus, o all pha maceu icals, en concen a ion le els o calib a ion cu e in
sol en be ween 5.0 and 1,000 µg/L and six concen a ion le els o a ma ix-ma ched calib a ion
cu e be ween 5.0 and 500 µg/L we e used. Calib a ion cu es we e made in bo h MRM
ansi ions. Th ee eplica ions (wi h an injec ion olume o 5 μL) we e made o each s anda d
solu ion o check he epea abili y a each concen a ion le el.
Me hod Limi s o de ec ion (MDL) and quan i ica ion (MQL)
MDL and MQL we e de e mined as he minimum amoun de ec able o he analy e wi h a
signal- o-noise a io o 3 and 10, espec i ely. The limi s we e de e mined in i e wa e s and in
sedimen s bu only i he pha maceu ical was de ec ed in hese samples, o he wise limi s we e
de e mined in he ma ix-ma ched calib a ion cu e.
Repea abili y
Repea abili y analysis exp essed as he ela i e s anda d de ia ion (RSD (%)). Th ee
concen a ion o s anda ds (100, 250, 500 µg/L) we e epea ed six- ime sequen ial and epea ed
along he ba ch (n=6).
Ma ix e ec
The in luence o he ME was e alua ed compa ing one s anda d p epa ed in sol en and one
s anda d p epa ed in he ma ix (Jelić e al., 2012). Fo each compound eco e y was calcula ed
by compa ing i s a ea in he samples spiked p io o SPE ex ac ion (p e-spiked sample) wi h he
a ea in he samples spiked a e SPE ex ac ion (pos -spiked sample) (Paíga and Dele ue-Ma os,
2016). Thus, o i e wa e s and sedimen s, a blank and o i ied sample we e ca ied ou o he
p e- and pos -spiked samples. A posi i e alue o ME is an indica i e o ion enhancemen signal
and a nega i e alue ep esen s an ion supp ession signal (Jelić e al., 2012).
Re e ences
Jelić, A., G os, M., Pe o ic, M., Gineb eda, A., Ba celó, D., 2012. Occu ence and Elimina ion o
Pha maceu icals Du ing Con en ional Was ewa e T ea men . Eme g. P io . Pollu . Ri e s.
Handb. En i on. Chem. 19, 1–24. h ps://doi.o g/10.1007/978-3-642-25722-3
Paíga, P., Dele ue-Ma os, C., 2016. A h oughpu me hod using he quick easy cheap e ec i e
ugged sa e me hod o he quan i ica ion o ibup o en and i s main me aboli es in soils. J. Sep.
Sci. 39, 3436–3444. h ps://doi.o g/10.1002/jssc.201600412
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed
in he no h o Po ugal
94
Table SM7. Me hod de ec ion and me hod quan i ica ion limi s (MDL, MQL) in i e wa e (ng/L)
and sedimen samples (ng/g).
Pha maceu icals
Ri e wa e
Decision 2018/840
o 5 June 2018*
MDL (ng/L)
Sedimen **
MDL
(ng/L)
MQL
(ng/L)
MDL
(ng/g)
MQL
(ng/g)
An ibio ics
n.a.
*
Azi h omycin
3.98
13.3
19
0.00200
0.00667
*
Cip o loxacin
41.1
137
89
1.04
3.46
*
Cla i h omycin
0.0750
0.225
19
0.00200
0.00667
En o loxacin
1.55
5.18
n.a.
1.31
4.38
*
E y h omycin
9.20
30.7
19
0.00400
0.0150
Lome loxacin
37.8
126
n.a.
5.43
18.1
Moxi loxacin
39.6
132
n.a.
1.16
3.85
No loxacin
23.5
78.3
n.a.
3.39
11.3
O loxacin
0.450
1.53
n.a.
0.0170
0.0560
P uli loxacin
12.1
40.4
n.a.
0.294
0.979
Sul adiazine
7.50
25.0
n.a.
0.0430
0.144
Sul adime hoxine
65.2
217
n.a.
0.0300
0.0990
Sul ame hazine
2.35
7.80
n.a.
0.114
0.379
Sul ame hoxazole
0.150
0.475
n.a.
0.225
0.752
Sul ame hoxypy idazine
55.5
185
n.a.
0.0490
0.163
Sul apy idine
9.33
31.1
n.a.
0.0660
0.219
T ime hop im
9.45
31.5
n.a.
0.0810
0.272
Psychia icd ugs
Ca bamazepine
1.05
3.48
n.a.
0.00643
0.0257
Ci alop am
0.500
1.63
n.a.
0.00429
0.0143
Diazepam
3.70
12.35
n.a.
0.00400
0.0133
10,11-Epoxyca bamazepine
2.28
7.60
n.a.
0.00900
0.0300
Fluoxe ine
0.225
0.750
n.a.
0.00214
0.00710
No luoxe ine
8.25
27.5
n.a.
0.189
0.630
Pa oxe ine
0.0500
0.150
n.a.
0.369
1.23
Se aline
0.125
0.425
n.a.
0.00214
0.00710
T azodone
0.850
2.85
n.a.
0.00900
0.0300
Venla axine
0.575
1.93
n.a.
0.0364
0.120
Pha maceu icals o ganized by alphabe ic o de and by i s he apeu ic g oup.
*Pha maceu icals wi h maximum accep able me hod de ec ion limi (ng/l) in he Commission Implemen ing Decision (EU)
2018/840 o 5 June 2018 (O icial Jou nal o he Eu opean Union, L 141/9. COMMISSION IMPLEMENTING DECISION
(EU) 2018/840 o 5 June 2018 es ablishing a wa ch lis o subs ances o Union-wide moni o ing in he ield o wa e
policy pu suan o Di ec i e 2008/105/EC o he Eu opean Pa liamen and o he Council and epealing Commission
Implemen ing Decision (EU) 2015/495. A ailable a : h ps://eu -lex.eu opa.eu/legal-
con en /EN/TXT/PDF/?u i=CELEX:32018D0840& om=EN, Accessed da a: No embe 2018)
n.a. - No Limi was applicable in he wa e samples
** - No Limi was applicable in he sedimen s samples
Chap e 3
95
Table SM8. Reco e ies (%) a h ee le els o o i ica ion o i e sample ma ix.
Pha maceu icals
Le el I
Le el II
Le el III
A e age
eco e y*
Reco e y
(%)
RSD
(%)
Reco e y
(%)
RSD
(%)
Reco e y
(%)
RSD
(%)
An ibio ics
Azi h omycin
66.5
3.7
73.7
6.1
No e
No e
70.1
Cip o loxacin
102
5.1
95.6
6.7
96.5
2.7
98.0
Cla i h omycin
74.0
2.0
67.0
4.1
70.5
1.1
70.5
En o loxacin
83.6
2.3
78.9
2.3
83.8
3.7
82.1
E y h omycin
82.3
4.6
78.7
4.1
80.8
6.7
80.6
Lome loxacin
107.9
4.1
102
5.4
94.6
3.4
101.5
Moxi loxacin
87.4
1.2
88.8
4.7
79.6
1.4
85.3
No loxacin
92.4
4.3
96.2
4.6
98.8
5.3
95.8
O loxacin
71.1
2.7
70.3
3.7
64.6
2.5
68.7
P uli loxacin
86.8
2.1
94.3
0.57
102
1.8
94.3
Sul adiazine
52.1
3.4
49.1
5.7
56.5
3.1
52.6
Sul adime hoxine
56.6
5.8
61.5
3.8
55.2
4.1
57.8
Sul ame hazine
51.2
3.9
52.4
6.6
54.7
2.3
52.8
Sul ame hoxazole
47.8
1.8
50.5
3.2
53.4
5.3
50.6
Sul ame hoxypi idazine
58.1
4.1
53.7
2.0
51.4
3.4
54.4
Sul apy idine
55.5
2.1
52.6
4.1
52.9
2.7
53.7
T ime hop im
91.3
2.1
95.6
3.8
97.5
3.5
94.8
Psychia ic d ugs
Ca bamazepine
103
3.1
95.1
2.9
98.6
1.8
98.9
Ci alop am
89.5
9.3
89.5
2.7
85.5
2.8
88.2
Diazepam
97.0
3.9
94.4
1.1
94.8
6.6
95.4
10,11-Epoxyca bamazepine
63.7
2.6
64.9
4.4
69.1
0.59
65.9
Fluoxe ine
90.5
2.5
88.3
1.6
85.1
1.6
88.0
No luoxe ine
80.6
4.3
77.8
3.8
81.4
2.5
79.9
Pa oxe ine
83.5
4.8
84.2
1.2
85.8
5.4
84.5
Se aline
85.7
1.6
91.3
1.5
86.1
1.9
87.7
T azodone
89.1
1.7
93.2
3.7
81.7
2.5
88.0
Venla axine
91.1
5.4
98.2
3.6
93.4
5.4
94.2
Pha maceu icals o ganized by alphabe ic o de and by i s he apeu ic g oup.
* A e age eco e y emb acing he h ee o i ied le els.
No e: in spiking le el III azi h omycin was no de ec . Some p oblem mus ha e occu ed du ing he ex ac ion and his le el was
discha ged.

An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
96
Table SM9. Reco e ies (%) a h ee le els o o i ica ion o sedimen sample ma ix.
Pha maceu icals
Le el I
Le el II
Le el III
A e age
eco e y*
Reco e y
(%)
RSD
(%)
Reco e y
(%)
RSD
(%)
Reco e y
(%)
RSD
(%)
An ibio ics
Azi h omycin
66.9
2.8
74.4
4.5
87.8
2.4
76.4
Cip o loxacin
2.15
49
0.89
41
0.340
33
1.13
Cla i h omycin
76.9
2.0
80.9
5.6
83.7
7.6
80.5
En o loxacin
10.2
6.3
13.1
34
7.39
49
10.2
E y h omycin
86.4
0.66
63.5
7.4
64.3
12
71.4
Lome loxacin
3.16
35
5.8
58
2.52
60
3.82
Moxi loxacin
3.11
65
3.3
40
1.92
96
2.76
No loxacin
2.86
53
0.75
48
0.512
16
1.37
O loxacin
2.29
37
1.9
61
1.20
65
1.80
P uli loxacin
16.0
20
18.8
3.5
18.2
12
17.7
Sul adiazine
13.3
18
17.2
29
15.9
1.0
15.4
Sul adime hoxine
29.1
17
31.5
25
30.1
19
30.2
Sul ame hazine
18.7
8.8
26.2
4.1
29.5
4.3
24.8
Sul ame hoxazole
28.1
21
29.5
22
31.2
19
29.6
Sul ame hoxypi idazine
13.9
22
21.4
28
21.2
4.7
18.8
Sul apy idine
18.0
11
27.8
31
24.9
12
23.6
T ime hop im
74.8
7.0
92.8
7.7
78.2
6.2
81.9
Psychia ic d ugs
Ca bamazepine
91.4
6.1
103
3.6
91.9
5.1
95.6
Ci alop am
71.0
7.4
74.3
4.6
68.6
3.0
71.3
Diazepam
100
6.1
108
5.0
106
5.0
104.3
10,11-Epoxyca bamazepine
73.9
2.9
81.9
6.8
73.2
2.6
76.3
Fluoxe ine
68.7
2.6
75.7
1.2
67.2
6.7
70.5
No luoxe ine
63.6
10
67.9
8.2
57.8
4.8
63.1
Pa oxe ine
56.8
3.3
64.2
1.9
54.8
2.9
58.6
Se aline
46.6
11
50.7
3.8
44.2
6.0
47.2
T azodone
59.9
10
66.6
6.4
62.7
6.0
63.1
Venla axine
70.4
6.0
75.9
3.6
72.4
5.0
72.9
Pha maceu icals o ganized by alphabe ic o de and by i s he apeu ic g oup.
* A e age eco e y emb acing he h ee o i ied le els.
Chap e 3
97
Table SM10. Measu ed concen a ions (ng/L) o he a ge analy es i e wa e and sedimen om he esea ch conduc ed by he scien i ic communi y in he las yea s.
Pha maceu icals
Con inen
Ri e (Coun y)
Wa e Concen a ion
(ng/L)
Sedimen Concen a ion
(ng/g)
Re e ence
An ibio ics
Cip o loxacin
Asia
China (Xiangjiang Ri e )
n.d.
(Lin e al., 2018)
Asia
Pea l Ri e Es ua y (Zhuhai Ci y, China)
24.6-365
0.09-104
(Li e al., 2018)
Asia
Ba Ri e (Lan ian Coun y, Shannxi P o ince)
2.66-28.6
2.40-62.5
(Jia e al., 2018)
Asia
Yellow Ri e (China)
n.d.-32.8
(Zhou e al., 2011)
Asia
Hai Ri e (China)
2.05 - 1,290
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d.-28.7
(Zhou e al., 2011)
Asia
Huangpu Ri e (Shangai, China)
n.d. - <LOQ (9.33)
(Jiang e al., 2011)
Asia
Huangpu Ri e (Shanghai, China)
n.d.-34.2
(Chen and Zhou, 2014)
Asia
Laizhou Bay- i e discha ge poin s (China)
n.d. - 346
(Zhang e al., 2012)
Asia
Chao Ph aya Ri e (Thailand)
48 (max.)
(Tewa i e al., 2013)
Eu ope
Seine Ri e (Pa is, F ance)
n.d.
(Tam am e al., 2008)
Eu ope
Tâmega Ri e (Cha es, Po ugal)
n.d.
(Pe ei a e al., 2017)
Eu ope
Tua Ri e (Mi andela, Po ugal)
n.d.
(Pe ei a e al., 2017)
Eu ope
Mondego Ri e (Po ugal)
n.d.
(Pe ei a e al., 2017)
Eu ope
T ancão Ri e (Lisbon, Po ugal)
n.d.
(Pe ei a e al., 2017)
Eu ope
Tagus Ri e (Lisbon, Po ugal)
n.d.
(Pe ei a e al., 2017)
Eu ope
Xa ama Ri e (É o a, Po ugal)
n.d.
(Pe ei a e al., 2017)
Eu ope
Guadiana Ri e (Vila Real de San o An ónio, Po ugal)
n.d.
(Pe ei a e al., 2017)
Eu ope
Lis Ri e (Lei ia, Po ugal)
n.d.-88.7
(Paíga e al., 2016)
En o loxacin
Asia
China (Xiangjiang Ri e )
n.d.
(Lin e al., 2018)
Asia
Huangpu Ri e (Shangai, China)
n.d. - <LOQ (11.34)
(Jiang e al., 2011)
Asia
Laizhou Bay- i e discha ge poin s (China)
n.d.-24.6
(Zhang e al., 2012)
Asia
Pea l Ri e (China)
n.d.
1.43*
(Liang e al., 2013)
Asia
Huangpu Ri e (Shanghai, China)
n.d.-14.6
n.d.-8.9
(Chen and Zhou, 2014)
Eu ope
Seine Ri e (Pa is, F ance)
n.d.
(Tam am e al., 2008)
Eu ope
A e Ri e (No h o Po ugal)
n.d.
(Ba bosa e al., 2018)
Eu ope
Leça Ri e (No h o Po ugal)
n.d.-44.99
(Ba bosa e al., 2018)
Eu ope
An uã Ri e (No h o Po ugal)
n.d.-343.28
(Ba bosa e al., 2018)
Eu ope
Cé ima Ri e (No h-Cen al Po ugal)
n.d.-45.53
(Ba bosa e al., 2018)
O loxacin
Asia
China (Xiangjiang Ri e )
n.d.-23
(Lin e al., 2018)
Asia
Pea l Ri e Es ua y (Zhuhai Ci y, China)
0.80–195
n.d.-157
(Li e al., 2018)
Asia
Qian ang Ri e basin (China)
40 62
(Chen e al., 2012)
Asia
Yellow Ri e (China)
n.d.-124
(Zhou e al., 2011)
Asia
Hai Ri e (China)
1.96-653
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d.-50.5
(Zhou e al., 2011)
Asia
Laizhou Bay- i e discha ge poin s (China)
n.d.-45.4
(Zhang e al., 2012)
Asia
Pea l Ri e (China)
15.8*
13.7*
(Liang e al., 2013)
Asia
Huangpu Ri e (Shangai, China)
<LOQ (8.34)
(Jiang e al., 2011)
Asia
Huangpu Ri e (Shanghai, China)
n.d.-28.5
n.d.-12.4
(Chen and Zhou, 2014)
Eu ope
Seine Ri e (Pa is, F ance)
n.d.-30
(Tam am e al., 2008)
Eu ope
A e Ri e (No h o Po ugal)
n.d.
(Ba bosa e al., 2018)
Eu ope
Leça Ri e (No h o Po ugal)
n.d.
(Ba bosa e al., 2018)
Eu ope
An uã Ri e (No h o Po ugal)
n.d.
(Ba bosa e al., 2018)
Eu ope
Cé ima Ri e (No h-Cen al Po ugal)
n.d.
(Ba bosa e al., 2018)
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he no h o Po ugal
98
No loxacin
Asia
China (Xiangjiang Ri e )
n.d.
(Lin e al., 2018)
Asia
Pea l Ri e Es ua y (Zhuhai Ci y, China)
32.8-381
3.38-444
(Li e al., 2018)
Asia
Ba Ri e (Lan ian Coun y, Shannxi P o ince)
5.33-122
6.04-680
(Jia e al., 2018)
Asia
Qian ang Ri e basin (China)
n.d.-500
(Chen e al., 2012)
Asia
Yellow Ri e (China)
n.d.-142
(Zhou e al., 2011)
Asia
Hai Ri e (China)
n.d.-5770
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d.-177
(Zhou e al., 2011)
Asia
Laizhou Bay- i e discha ge poin s (China)
n.d. - 572
(Zhang e al., 2012)
Asia
Pea l Ri e (China)
136*
20.5*
(Liang e al., 2013)
Asia
Huangpu Ri e (Shangai, China)
n.d.
(Jiang e al., 2011)
Asia
Huangpu Ri e (Shanghai, China)
n.d.-0.2
(Chen and Zhou, 2014)
Eu ope
Seine Ri e (Pa is, F ance)
n.d.-46
(Tam am e al., 2008)
Moxi loxacin
Lome loxacin
Asia
Yellow Ri e (China)
n.d.
(Zhou e al., 2011)
Asia
Hai Ri e (China)
1.67
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d.
(Zhou e al., 2011)
Eu ope
Seine Ri e (Pa is, F ance)
n.d.
(Tam am e al., 2008)
P uli loxacin
T ime hop im
Asia
China (Xiangjiang Ri e )
n.d.-93
(Lin e al., 2018)
Asia
Pea l Ri e Es ua y (Zhuhai Ci y, China)
n.d.-492
n.d.-210
(Li e al., 2018)
Asia
Ba Ri e (Lan ian Coun y, Shannxi P o ince, China)
11.3-106
0.79-31.4
(Jia e al., 2018)
Asia
Qian ang Ri e basin (China)
n.d.
(Chen e al., 2012)
Asia
Yellow Ri e (China)
n.d.-2.86
(Zhou e al., 2011)
Asia
Hai Ri e (China)
n.d.-5.63
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d.-9.84
(Zhou e al., 2011)
Asia
B ahmapu a Ri e (Bangladesh)
< 0.08-17.20
(Hossain e al., 2018)
Asia
Chao Ph aya Ri e (Thailand)
3*
(Tewa i e al., 2013)
Asia
Laizhou Bay- i e discha ge poin s (China)
n.d.-13,600
(Zhang e al., 2012)
A ica
Msunduzi Ri e , KwaZulu-Na al, Sou h A ica
n.d.-290
<MDL (0.246)-87.55
(Ma ongo e al., 2015)
Ame ica
Hudson Ri e (New Yo k)
n.d.-350
(Can well e al., 2018)
Eu ope
Danube Ri e (Se bia, Belg ade)
n.d.-25
(G ujić e al., 2009)
Eu ope
Sa a Ri e (Se bia, Belg ade)
n.d.
(G ujić e al., 2009)
Eu ope
Tamis Ri e (Se bia)
24
(G ujić e al., 2009)
Eu ope
Seine Ri e (Pa is, F ance)
12-27
(Tam am e al., 2008)
Eu ope
Ri e Foss (Uni ed Kingdom)
n.d.-76
(Bu ns e al., 2018)
Eu ope
Ri e Ouse (Uni ed Kingdom)
n.d.-22.9
(Bu ns e al., 2018)
Eu ope
Lis Ri e (Lei ia, Po ugal)
n.d.
(Paíga e al., 2016)
Eu ope
A e Ri e (No h o Po ugal)
n.d.
(Ba bosa e al., 2018)
Eu ope
Leça Ri e (No h o Po ugal)
n.d.-15.63
(Ba bosa e al., 2018)
Eu ope
An uã Ri e (No h o Po ugal)
n.d.-64.14
(Ba bosa e al., 2018)
Eu ope
Cé ima Ri e (No h-Cen al Po ugal)
n.d.-12.68
(Ba bosa e al., 2018)
Sul ame hoxypy idazine
Asia
Luan Ri e (No h China)
0.16-3.1
(Li e al., 2014)
Eu ope
Eb o Ri e (No heas Spain)
0.6-18.1
(Ga cía-Galán e al., 2011)
Sul apy idine
Asia
Pea l Ri e Es ua y (Zhuhai Ci y, China)
n.d.-58.3
n.d.-126
(Li e al., 2018)
Asia
Yellow Ri e (China)
n.d.
(Zhou e al., 2011)
Asia
Hai Ri e (China)
n.d.
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d.
(Zhou e al., 2011)
Asia
Huangpu Ri e (Shanghai, China)
2.54-16.6
(Jiang e al., 2011)
Asia
Huangpu Ri e (Shanghai, China)
n.d.-103.1
n.d.-6.6
(Chen and Zhou, 2014)
Chap e 3
99
Asia
Luan Ri e (No h China)
<0.1-3.4
(Li e al., 2014)
Eu ope
Eb o Ri e (No heas Spain)
0.1-42.5
(Ga cía-Galán e al., 2011)
Eu ope
Lis Ri e (Lei ia, Po ugal)
n.d.
(Paíga e al., 2016)
Sul ame hazine
Asia
Xiangjiang Ri e (China)
n.d.-60
(Lin e al., 2018)
Asia
Pea l Ri e Es ua y (Zhuhai Ci y, China)
n.d.-226
n.d.-72.3
(Li e al., 2018)
Asia
Ba Ri e (Lan ian Coun y, Shannxi P o ince)
8.64-464
7.80-690
(Jia e al., 2018)
Asia
Yellow Ri e (China)
n.d.
(Zhou e al., 2011)
Asia
Hai Ri e (China)
n.d.-5.69
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d.
(Zhou e al., 2011)
Asia
B ahmapu a Ri e (Bangladesh)
< 0.01-11.35
(Hossain e al., 2018)
Asia
Luan Ri e (No h China)
0.21-3.7
(Li e al., 2014)
Asia
Huangpu Ri e (Shangai, China)
5.45-313.44
(Jiang e al., 2011)
Asia
Huangpu Ri e (Shanghai, China)
19.9-389.4
0.2-2.7
(Chen and Zhou, 2014)
Asia
Laizhou Bay- i e discha ge poin s (China)
<LOQ - 108
(Zhang e al., 2012)
A ica
Msunduzi Ri e , KwaZulu-Na al, Sou h A ica
n.d.-1,090
n.d.
(Ma ongo e al., 2015)
Asia
Pea l Ri e (China)
218*
3.24*
(Liang e al., 2013)
Asia
Chao Ph aya Ri e (Thailand)
5*
(Tewa i e al., 2013)
Eu ope
Eb o Ri e (No heas Spain)
2.5-65.2
(Ga cía-Galán e al., 2011)
Eu ope
Seine Ri e (Pa is, F ance)
n.d.
(Tam am e al., 2008)
Eu ope
Lis Ri e (Lei ia, Po ugal)
n.d.-123
(Paíga e al., 2016)
Eu ope
Mess Ri e (Luxembou g)
19 (max)
(Meye e al., 2011)
Sul adime hoxine
Asia
B ahmapu a Ri e (Bangladesh)
n.d.
(Hossain e al., 2018)
Asia
Luan Ri e (No h China)
0.95-3.56
(Li e al., 2014)
Eu ope
Eb o Ri e (No heas Spain)
1-23.1
(Ga cía-Galán e al., 2011)
Eu ope
Mess Ri e (Luxembou g)
n.d.
(Meye e al., 2011)
Sul adiazine
Asia
China (Xiangjiang Ri e )
n.d.-68
(Lin e al., 2018)
Asia
Pea l Ri e Es ua y (Zhuhai Ci y, China)
n.d.-50.7
n.d.-198
(Li e al., 2018)
Asia
Ba Ri e (Lan ian Coun y, Shannxi P o ince)
1.69-36.8
0.59-7.10
(Jia e al., 2018)
Asia
China, Hanjiang Ri e ( h ough Hubei and Shaanxi)
1.9-6.3
0.35-0.54
(Hu e al., 2018)
Asia
Yellow Ri e (China)
n.d.-22.0
(Zhou e al., 2011)
Asia
Hai Ri e (China)
n.d.-1.71
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d.-11
(Zhou e al., 2011)
Asia
Huangpu Ri e (Shangai, China)
2.66-22.33
(Jiang e al., 2011)
Asia
Huangpu Ri e (Shanghai, China)
4.9-112.5
0.07-0.71
(Chen and Zhou, 2014)
Asia
Pea l Ri e (China)
18.0*
n.d.*
(Liang e al., 2013)
Asia
Laizhou Bay- i e discha ge poin s (China)
n.d.-18.7
(Zhang e al., 2012)
Asia
B ahmapu a Ri e (Bangladesh)
< 0.01-0.58
(Hossain e al., 2018)
Asia
Luan Ri e (No h China)
0.35-10.86
(Li e al., 2014)
Eu ope
Eb o Ri e (No heas Spain)
0.7-6.4
(Ga cía-Galán e al., 2011)
Eu ope
Lis Ri e (Lei ia, Po ugal)
n.d.
(Paíga e al., 2016)
Sul ame hoxazole
Asia
Pea l Ri e Es ua y (Zhuhai Ci y, China)
n.d.-195
0.37–219
(Li e al., 2018)
Asia
Yellow Ri e (China)
n.d.
(Zhou e al., 2011)
Asia
Hai Ri e (China)
n.d.
(Zhou e al., 2011)
Asia
Liao Ri e (China)
n.d. - <LOQ
(Zhou e al., 2011)
Asia
Huangpu Ri e (Shangai, China)
6.78-28.34
(Jiang e al., 2011)
Asia
Huangpu Ri e (Shanghai, China)
2.2-764.9
0.05-0.6
(Chen and Zhou, 2014)
Asia
Laizhou Bay- i e discha ge poin s (China)
0.36 - 527
(Zhang e al., 2012)
Asia
Pea l Ri e (China)
37.6*
n.d.
(Liang e al., 2013)
Asia
Chao Ph aya Ri e (Thailand)
2*
(Tewa i e al., 2013)
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed
in he no h o Po ugal
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was ewa e ea men plan s and ecei ing wa e s in Bangkok, Thailand, and associa ed
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pha maceu icals in he u ban wa e sys em o Shanghai, China. Chemosphe e 138, 486–493.
h ps://doi.o g/10.1016/j.chemosphe e.2015.07.002
Zhang, R., Zhang, G., Zheng, Q., Tang, J., Chen, Y., Xu, W., Zou, Y., Chen, X., 2012. Occu ence and
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Chap e 3
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pea l i e sys em, Sou h China. En i on. Toxicol. Chem. 29, 1377–1384.
h ps://doi.o g/10.1002/e c.161
Zhou, L.J., Ying, G.G., Zhao, J.L., Yang, J.F., Wang, L., Yang, B., Liu, S., 2011. T ends in he
occu ence o human and e e ina y an ibio ics in he sedimen s o he Yellow Ri e , Hai Ri e
and Liao Ri e in no he n China. En i on. Pollu . 159, 1877–1885.
h ps://doi.o g/10.1016/j.en pol.2011.03.034
Chap e 3
108
Figu e SM1. Schema ic SPE and QuEChERS me hodologies o he ex ac ion o he pha maceu icals unde s udy in i e wa e and sedimen samples.
SPE ex ac ion (Paíga e al., 2017)
QuEChERS me hodology (San os e al., 2016)
Chap e 3
109
a) An ibio ics
b) Psychia ic d ugs
No e: The o e lap o he wen y-se en pha maceu icals would be ba ely pe cep ible in he ch oma og am, so he pha maceu icals
we e di ided in o wo ch oma og ams sepa a ing hem by he he apeu ic class.
Figu e SM2. O e lay ch oma og am o a) an ibio ics and b) psychia ic d ugs in a s anda d mix u e wi h
a concen a ion o 500 µg/L in each pha maceu ical.
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 min
0
25000
50000
75000
100000
125000
150000
175000
200000
225000
250000
275000
300000
325000
350000
375000
400000
17:E y h omycin 734,50>158,00(+) CE: -35,0
16:Azi h omycin 749,30>83,20(+) CE: -55,0
15:Cla i h omycin 748,20>158,10(+) CE: -33,0
14:Sul ame hoxazole 254,00>156,00(+) CE: -17,0
13:Sul adiazine 250,90>156,00(+) CE: -18,0
11:Sul ame hazine 278,80>186,05(+) CE: -20,0
10:sul apy idine 249,80>92,05(+) CE: -30,0
9:Sul ame hoxypy idazine 280,80>156,00(+) CE: -19,0
8:T ime hop im 290,80>230,10(+) CE: -26,0
7:P uli loxacin 461,90>443,95(+) CE: -23,0
6:Lome loxacin 352,00>334,10(+) CE: -22,0
5:Moxi loxacin 401,95>384,10(+) CE: -24,0
4:No loxacin 320,00>302,05(+) CE: -23,0
3:O loxacin 362,00>318,15(+) CE: -20,0
2:En o loxacin 359,90>342,15(+) CE: -23,0
1:Cip o loxacin 331,90>314,10(+) CE: -23,0
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 min
0
250000
500000
750000
1000000
1250000
1500000
1750000
2000000
2250000
28:10,11-epoxi ca bamazepine 253,00>180,05(+) CE: -27,0
27:Diazepam 284,95>154,10(+) CE: -29,0
26:T azodone 371,95>176,00(+) CE: -25,0
25:Pa oxe ine 330,00>44,05(+) CE: -28,0
24:Venla axine 278,00>58,00(+) CE: -20,0
23:ci alop am 324,95>109,10(+) CE: -30,0
22:Se aline 305,95>274,90(+) CE: -15,0
21:Fluoxe ine 310,05>44,00(+) CE: -15,0
20:Ca bamazepine 236,95>194,10(+) CE: -20,0
19:no luoxe ine 296,00>134,10(+) CE: -9,0
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
110
Figu e SM3. The isk quo ien s (RQ) o di e en ophic le els (algae, Daphnia magna, and ish) o
an ibio ics and psychia ic d ugs in he su ace wa e s. Bold line ma ks isk quo ien equal o one.
Chap e 4
111
CHAPTER 4 GLYPHOSATE, AMPA AND GLUFOSINATE
OCCURRENCE IN WATERS AND SEDIMENTS – WORLD
ASSESSMENT
As p e iously men ioned in Chap e 2, glyphosa e has been he subjec o legal
con o e sy in ecen yea s conce ning i s sa e y and po en ial link o cance (No o ny, 2022).
In 2015, he In e na ional Agency o Resea ch on Cance (IARC), o he Wo ld Heal h
O ganiza ion (WHO), classi ied glyphosa e as "p obably ca cinogenic o humans" based on
s udies ha showed an associa ion be ween glyphosa e exposu e and an inc eased isk o
non-Hodgkin's lymphoma. This classi ica ion led o a se ies o lawsui s agains he
manu ac u e s o glyphosa e-based he bicides, mos no ably Monsan o (now owned by
Baye ). Howe e , he US En i onmen al P o ec ion Agency (EPA) and o he egula o y
agencies ha e gene ally a i med ha glyphosa e is sa e when used acco ding o label
ins uc ions and ha e no es ic ed i s use. Despi e he possibili y o posing a isk o he
en i onmen and o human and animals heal h, he Eu opean Commission (EC) ecen ly
enewed he use o glyphosa e-based he bicides un il Decembe 15 o , 2023, app o ing a one-
yea ex ension on he p e ious i e-yea au ho iza ion (Eu opean Commission, 2017).
On he o he hand, he use o glu osina e is al eady banned in Eu ope since 2020
(Eu opean Commission, 2020a, 2022a). Conside ing he alleged ep o oxici y, among o he
es ed isks o human heal h ela ed o he exposu e o glu osina e, in 2017, he F ench Heal h
and En i onmen Regula o (ANSES) had al eady wi hd awn he selling au ho iza ion o his
p oduc in he F ench ma ke , ha included all he plan p o ec ion p oduc s con aining
glu osina e (ANSES, 2017).
A e hei applica ion o he soil/plan , hey end o deg ade apidly in o hei
deg ada ion p oduc s. Glyphosa e is deg aded, mos ly by mic obial ac ion, aking he o m o
sa cosine acid and aminome hylphosphonic acid (AMPA), he las being i s main me aboli e
and highly pe sis en in he en i onmen (S ephen O. Duke, 2020).
The i s published s udy on glyphosa e moni o ing in g oundwa e da es back o 1996
(Smi h e al., 1996) and in su ace wa e o 1998 (Ska k e al., 1998), his las epo ing also
AMPA’s con amina ion. Since hen, conce n abou con amina ion by hese compounds has
been g owing o e he yea s, coupled wi h an inc ease o en i onmen al sampling s udies.
To assess and e alua e glyphosa e, AMPA, and glu osina e wo ld’s en i onmen al
con amina ion, he published s udies be ween Janua y 1, 2018, and Ma ch 30, 2023, including
glyphosa e, AMPA, and glu osina e moni o ing in wa e (su ace and g oundwa e ) and

Glyphosa e, AMPA and Glu osina e occu ence in wa e s and sedimen s – wo ld assessmen
112
sedimen s we e analyzed. An ex ensi e sea ch on academic da abases, such as Scopus, Web
o Science, Science Di ec , PubMed, Resea ch Ga e, and Google Schola , was conduc ed using
he combina ion o he ollowing keywo ds: “glyphosa e”, “glu osina e”,
“aminome hylphosphonic acid”, o “AMPA” wi h “ i e ”, "wa e esou ce", “ i e side”,
"hyd og aphic basin", “wa e cou se”, “ eshwa e ”, “ i e basin”, “s eam”, “ ibu a y”,
“lake”, “pond”, “g oundwa e ”, “su ace wa e ”, “c eeks”, “we land”. A e emo ing
duplica es, he publica ions sc eening was pe o med by examining he en i e con en o he
a icles and ga he ing he ele an in o ma ion (e.g., concen a ions, analy ical me hods,
numbe o samples, de ec ion equency) o he h ee compounds unde s udy. A icles
p esen ing model-based p edic ions o con amina ions wi hou in o ma ion on he measu ed
occu ences o compounds we e excluded.
Nine y- ou publica ions we e selec ed h ough mo e han 1 000 analyzed a icles; he
in o ma ion con ained he ein is e iewed below.
4.1 Limi s and h eshold o Glyphosa e, AMPA, and Glu osina e in wa e
In o de o analyze he concen a ions o glyphosa e, AMPA, and glu osina e ound in
wa e s and sedimen s a ound he wo ld, a summa y o he ele an legisla ion is o u mos
impo ance. The applicable legisla ion o con amina ions associa ed o hese pollu an s di e s
widely om coun y o coun y. Addi ionally, he same coun y may ha e di e en limi alues
depending on he ype o wa e (d inking wa e , su ace wa e , o g oundwa e ). The
es ic ions can be a ge ed o indi idual and speci ied compounds, any pes icide indi idually,
o e en he sum o all pes icides ound.
The Figu e 4.1 shows he maximum glyphosa e concen a ion alues allowed in wa e
in ended o human consump ion es ablished o some coun ies by cu en legisla ion.
In Eu ope, he Council Di ec i e 98/83/EC on he quali y o wa e in ended o human
consump ion p o ides a limi o 0.1 𝜇g L-1 (maximum indi idual alue) o g oundwa e
con amina ion by “pes icides and hei ele an me aboli es, deg ada ion and eac ion
p oduc s” and o 0.5 𝜇g L-1 o he sum o all indi idual pes icides. Addi ionally, he di ec i e
s a es ha “only hose pes icides which a e likely o be p esen in a gi en supply need be
moni o ed“, lea ing i unclea which compounds need o be moni o ed (Eu opean
Commission, 1998). The Eu opean Union (EU) coun ies apply his di ec i e and i s
amendmen s. Addi ionally, some EU coun ies ha e adap ed hei legisla ion based on
Eu opean di ec i es, as is he case o F ance, whe e in addi ion o he 0.1 𝜇g L-1 de ined o
Chap e 4
113
g oundwa e , i also de ines en i onmen al quali y s anda ds (EQS) o be aken in o accoun
in he assessmen o he ecological s a us o con inen al su ace wa e s (no in ended o
d inking wa e p oduc ion) o 28 𝜇g L-1 o glyphosa e and 452 𝜇g L-1 o AMPA. Also, p opose
a maximum accep able alue o 70 𝜇g L-1 o glyphosa e and 45200 𝜇g L-1 o AMPA. Fo ma ine
wa e es ablish an en i onmen al guide alue o 5.6 𝜇g L-1 and 45 𝜇g L-1 o glyphosa e and
AMPA, espec i ely wi h a maximum accep able concen a ion alue o 14 𝜇g L-1 and 4520 𝜇g
L-1, espec i ely (Minis e de l’écologie du dé eloppemen du able e de l’éne gie, 2015;
Po ail Subs aces Chimiques, 2020).
Figu e 4.1 – Legal limi s o glyphosa e esidues in wa e in ended o human consump ion (de eloped by
he au ho ).
In he USA, En i onmen al P o ec ion Agency (EPA) na ional p ima y d inking wa e
egula ions also conside ed glyphosa e in he lis o o ganic con aminan s in d inking wa e
wi h a maximum con amina ion le el o 700 𝜇g L-1 (EPA, 2009).
Canada guidelines ixed he maximum accep able concen a ion o glyphosa e in d inking
wa e o 280  𝜇g L-1 (Heal h Canada, 2022). A gen ina es ablished simila d inking wa e quali y
guideline le els o glyphosa e, namely 300 𝜇g L-1 and a quali y guide le el o aqua ic bio a
p o ec ion o 240 𝜇g L-1, bo h exp essed as glyphosa e isop opylamine (Subsec e a ia de
Recu sos Híd icos de la Nación, 2003).
Rega ding Aus alian egula ion, ecommended maximum le el o glyphosa e p esence
in wa e is 1000 𝜇g/L. In his case, he legisla ed alues a e no gene alized o all pes icides
Glyphosa e, AMPA and Glu osina e occu ence in wa e s and sedimen s – wo ld assessmen
114
bu a e indi idualized conside ing hei cha ac e is ics and po en ial p esence in he
en i onmen (NHMRC & NRMMC, 2011).
In China, wa e bodies a e di ided in o i e classes acco ding o he u iliza ion pu poses
and p o ec ion objec i es: class I e e s o sp ing wa e and na ional na u e ese es; class II
and III a e he i s and second classes o p o ec ed a eas o cen alized sou ces o d inking
wa e , o aqua ic species and swimming a eas; class IV e e s o wa e a eas o indus ial and
non-di ec exposu e ec ea ion uses; and class V is mainly applicable o he wa e bodies o
ag icul u al use and landscape (Asian De elopmen Bank, 2016). Also, g oundwa e is simila ly
classi ied in he S anda d o g oundwa e quali y (Gene al Adminis a ion o Quali y
Supe ision, 2017). En i onmen al Quali y S anda ds o Su ace Wa e apply o he di e en
classes o su ace wa e . GB 5749-2006, he s anda ds o d inking Wa e Quali y conce ning
d inking wa e sou ces (class II and III), p esen s a limi especially o glyphosa e, o 700 𝜇g L-1
(Minis y o Heal h o China, 2006).
Japan legisla ion exhibi s one o he highes limi alues o glyphosa e concen a ion in
wa e , o 2 000 𝜇g L-1. This legal amewo k is he pa icula i y ha he indica ed limi e e s
o he sum o glyphosa e and AMPA’s concen a ion. Addi ionally, in 2014 a e iew o he
legisla ion included he addi ion o a maximum concen a ion alue o glu osina e
con amina ion o 20 𝜇g L-1 (Minis y o Heal h Labo and Wel a e o Japan, 2003).
In B azil, he e a e wo dis inc limi s o he con amina ion o wa e in ended o human
consump ion. The i s is p esen ed in he applicable legisla ion o su ace wa e s which,
simila ly o China, p esen s a i e-class ca ego iza ion aking in o accoun he su ace wa e
des ina ion: special class, wa e in ended o d inking wa e supply, wi h disin ec ion as well
as he p ese a ion o he na u al balance o aqua ic communi ies and en i onmen s; class 1,
in ended o d inking wa e supply, a e simpli ied ea men , as well as he p o ec ion o
aqua ic communi ies, ec ea ional ac i i ies o p ima y con ac (e.g. swimming, di ing) and
i iga ion o aw and di ec consump ion ege ables; class 2, des ined o he d inking wa e
supply, a e con en ional ea men as well as he p o ec ion o aqua ic communi ies,
ec ea ional ac i i ies o p ima y con ac and he i iga ion o ege ables, ui plan s among
o he s wi h which he public may ha e di ec con ac ; class 3, des ined o he d inking wa e
supply, a e con en ional o ad anced ea men , i iga ion and ec ea ional ac i i ies o
seconda y con ac ; and class 4, des ined o na iga ion; and o landscape ha mony. Fo
classes 1 and 2, he limi alue o glyphosa e concen a ion is 65 𝜇g L-1, and o class 3, 280
𝜇g L-1 (CONAMA, 2005). Fo wa e in ended o human consump ion supplied om an
al e na i e wa e supply sys em o solu ion, i is es ablished a di e en limi o 500 𝜇g L-1 no
Chap e 4
115
only o glyphosa e concen a ion in wa e bu o he sum o glyphosa e and AMPA’s
concen a ion (Minis é io da Saúde, 2017).
Gi en he e iden di e ences ound in he maximum limi s o glyphosa e and AMPA in
wa e in ended o human consump ion and, in some cases, he absence o any one o all
h ee in hei legal documen s associa ed wi h wa e quali y, se e al au ho s e e o he
impo ance and u gency o e ise he cu en legal limi s o glyphosa e, AMPA and glu osina e
in su ace and g oundwa e s o human and aqua ic bio a p o ec ion (Campanale e al., 2021;
D. M. de Oli ei a e al., 2023; Z. Li, 2018; Z. Li & Fan ke, 2022).
4.2 P e- ea men , ex ac ion, and analysis
Accu a e measu emen o glyphosa e, AMPA, and glu osina e concen a ions in
en i onmen al samples is essen ial o quan i a i e exposu e assessmen s. Howe e , he
unique chemical p ope ies o hese compounds, such as high-wa e solubili y, low solubili y
in o ganic sol en s and ola iliza ion, absence o ch omopho es o luo opho es, ionic
cha ac e and hei p e e ence o o ming complexes u ns ex ac ion and quan i ica ion in o
a challenging p ocess (EFSA, 2005, 2015; Valle e al., 2019).
Re iewing he analy ical me hods applied in he en i onmen al moni o ing o wa e s and
sedimen s con amina ion by glyphosa e, AMPA, and glu osina e published be ween Janua y
2018 and Ma ch 2023 wo ldwide, i can be seen ha he mos applied de ec ion me hods can
be di ided in o h ee main ca ego ies: high-pe o mance, ul a-pe o mance o Ul a-High-
Pe o mance liquid ch oma og aphy (HPLC, UPLC o UHPLC) (Alonso e al., 2022; Lajmano ich
e al., 2023; López-Vázquez e al., 2023; Raby e al., 2022; Rod íguez-Bolaña e al., 2023; Suciu
e al., 2023; Na alia Ve onica Van Ops al e al., 2023), gas-ch oma og aphy (GC) (Donald e al.,
2018; Rezaei Kalan a y e al., 2022; Tongo e al., 2022), and enzyme-linked immunoso ben
assay (ELISA) (Ho n e al., 2019; Melendez-Pas o e al., 2021; Reynoso e al., 2020; Welch e
al., 2019). Figu e 4.2 esumes all analy ical me hods used in he s udies and shows ha high-
pe o mance (HPLC – 38%) and ul a-pe o mance o Ul a-High-Pe o mance (UHPLC/UPLC-
36%) liquid ch oma og aphy we e he mos applied me hodologies, ollowed by LC (7%), ELISA
(4%) and gas ch oma og aphy (GC-3%).
Re e ences
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Lis o Publica ions
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LIST OF PUBLICATIONS
Published a icles used in his Thesis: igh s, con ibu ions and quali y indica o s
An ibio ics and an idep essan s occu ence in su ace wa e s and sedimen s collec ed in he
no h o Po ugal
Ma ia João Fe nandesa,b, Paula Paígaa, Ana Sil aa, Ca men Pé ez Llagunob, Manuela Ca alhoa,
Felipe Macías Vázquezb, C is ina Dele ue-Ma osa
aREQUIMTE/LAQV, Ins i u o Supe io de Engenha ia do Po o, Poli écnico do Po o, Rua D . An ónio
Be na dino de Almeida, 431, 4200-072 Po o, Po ugal;
bIIT/LTA - Ins i u o de In es igaciones Tecnológicas, Uni e sidad de San iago de Compos ela, E-15782
San iago de Compos ela, Spain
Chemosphe e, ISSN: 0045-6535, olume 239 (2020): 124729, pages 1-12
DOI: 10.1016/j.chemosphe e.2019.124729
Speci ic con ibu ion o he publica ion
Ma ia João Fe nandes con ibu es wi h sample collec ion and p e- ea men ,
expe imen al wo k, namely: ex ac ion and analysis, da a s a is ical analysis and o he w i ing
o he o iginal a icle d a .
Quali y indica o :
The jou nal Chemosphe e, published by Else ie L d., cu en ly p esen s an impac ac o
o 8.943 (2022 Jou nal Ci a ion Repo s), an H-index o 265 and a Ci eSco e index (2021) o
11.7 (consul ed in Scopus 31/03/2023). Is a jou nal co e ing he
echnologies/ ields/ca ego ies ela ed o Chemis y (miscellaneous) (Q1); En i onmen al

Ma ia João Ce ei a Fe nandes
251
Chemis y (Q1); En i onmen al Enginee ing (Q1); Heal h, Toxicology and Mu agenesis (Q1);
Medicine (miscellaneous) (Q1); Pollu ion (Q1); Public Heal h, En i onmen al and Occupa ional
Heal h (Q1).
The con en o his jou nal a icle was en i ely used in he sub-chap e 3.1.1. o his doc o al
hesis, unde he consen o he publishe (Else ie ).
E alua ion o he adso p ion po en ial o biocha s p epa ed om o es and ag i- ood
was es o he emo al o luoxe ine
Ma ia João Fe nandesa,b , Manuela M. Mo ei aa,⁎ , Paula Paígaa , Diogo Diasc , Ma ia Be na doc,
Manuela Ca alhoa , Nuno Lapac , Isabel Fonsecac , Simone Mo aisa , Sónia Figuei edoa , C is ina
Dele ue-Ma osa
aREQUIMTE/LAQV, Ins i u o Supe io de Engenha ia do Po o, Poli écnico do Po o, Rua D . An ónio
Be na dino de Almeida, 431, 4200-072 Po o, Po ugal;
Lis o Publica ions
252
bIIT/LTA - Ins i u o de In es igaciones Tecnológicas, Uni e sidad de San iago de Compos ela, E-15782
San iago de Compos ela, Spain
cLAQV/REQUIMTE, Faculdade de Ciências e Tecnologia (FCT), Uni e sidade No a de Lisboa (UNL),
2829-516 Capa ica, Po ugal
Bio esou ce Technology, ISSN: 0045-6535, olume 292 (2019): 121973, pages 1-10
DOI: 10.1016/j.bio ech.2019.121973
Speci ic con ibu ion o he publica ion
Ma ia João Fe nandes con ibu es wi h sample p e- ea men , expe imen al wo k,
namely: adso p ion (ba ch and column) assays, and luoxe ine analysis, esul discussion and
he w i ing o he o iginal a icle d a .
Quali y indica o :
The jou nal Bio esou ce Technology, published by Else ie L d., cu en ly p esen s an
impac ac o o 11.889 (2021 Jou nal Ci a ion Repo s), an H-index o 341 and a Ci eSco e
index (2021) o 17.4 (consul ed in Scopus 31/03/2023). Is a jou nal i s posi ions in he di e en
ca ego ies acco ding o Scimago a e Bioenginee ing (Q1); En i onmen al Enginee ing (Q1);
Was e Managemen and Disposal (Q1); Medicine (miscellaneous) and (Q1); Renewable
Ene gy, Sus ainabili y and he En i onmen (Q1).
The con en o his jou nal a icle was en i ely used in in he chap e 4 o his doc o al hesis,
unde he consen o he publishe (Else ie ).
Ma ia João Ce ei a Fe nandes
253
O he publica ions
Pee Re iewed Jou nals
Paula Paíga; Manuela Co eia; Ma ia João Fe nandes; Ana Sil a; Manuela Ca alho; Joana Viei a;
Sand a Jo ge; Jaime G. Sil a; C is ina Dele ue-Ma os. "Assessmen o 83 pha maceu icals in WWTP
in luen and e luen samples by UHPLC-MS/MS: Hou ly a ia ion". Science o The To al En i onmen
648 (2019): 582-600. h p://www.sciencedi ec .com/science/a icle/pii/S0048969718330936.
Cong ess P oceedings
O al con ibu ions
Ma ia J. Fe nandes, Paula Paíga, Sónia Figuei edo, Felipe Macías & C is ina Dele ue-Ma os.
“ lyphosa e and Aminome hylphosphonic acid adso p ion in soils”. P esen ed in Cong eso
In e nacional XXVI Encon o Galego Po ugês de Química, 2022
Ma ia J. Fe nandes, Felipe Macías & C is ina Dele ue-Ma os. “Tecnosolos a la ca e: Um mé odo
ino ado , ab angen e e sus en á el de emedição de con aminações de solos e águas”. P esen ed in
GEO em FOCO, 2019
Pos e con ibu ions
Ma ia João Fe nandes; Paula Paíga; Ana Sil a; Ca men Llaguno; Manuela Ca alho; Felipe
Macías Vázquez; C is ina Dele ue-Ma os. "Assessmen o an ibio ics and psychia ic d ugs in
sedimen s om Dou o and Leça Ri e s (Po ugal)". P esen ed in 4GEO| esou ces, ma e ials,
echnologies & en i onmen | 1s Con e ence 2019, 2019.
Ma ia João Fe nandes; Paula Paíga; Ana Sil a; C. P. Llaguno; Manuela Ca alho; Felipe Macías
Vázquez; Dele ue-Ma os, C is ina. "De e minación de á macos psiquiá icos y an ibió icos en
las aguas supe iciales de los íos Dou o y Leça (Po ugal)". P esen ed in 1º Simposio
"P esencia y eliminación de mic ocon aminan es en agua" de la Red_No eda , 2019.
Ma ia João Fe nandes; Manuela Mo ei a; Diogo Dias; Ma ia Be na do; Manuela Ca alho;
Nuno Lapa; Isabel Fonseca; e al. "Mic opollu an Remo al F om Wa e Th ough Biocha
Adso ben s". P esen ed in 1s In e na ional Con e ence on Ad anced P oduc ion and
P ocessing (ICAPP), pos e NP-P.52, No i Sad, Sé ia, No i Sad, 2019.
Ma ia João Fe nandes; Manuela M. Mo ei a; Paula Paíga; Sil ia Capelas; Manuela Ca alho;
Sónia Figuei edo; Simone Mo ais; C is ina Dele ue-Ma os. "E alua ion o he adso p ion
po en ial o biocha s p epa ed om ag o- ood was es o he emo al o luoxe ine".
P esen ed in XXIV Encon o Luso-Galego de Química, 2018.
Fe nandes, Ma ia; Sil a, A.; Paíga, P.; Ca alho, M. M.; Llaguno, C.; Vázquez, F. Macías;
Dele ue-Ma os, C.. "De e mina ion o Glyphosa e in Sedimen s: A New Analy ical App oach".
P esen ed in 40 h In e na ional Con e ence on En i onmen al & Food Moni o ing, San iago
de Compos ela, 2018.
Lis o Publica ions
254
Sil a, A.; Ma ia João Fe nandes; Paula Paíga; Ca alho, M. M.; Llaguno, C.; Vázquez, F. Macías;
Dele ue-Ma os, C.. "De elopmen o a QuEChERS Sample P epa a ion Me hod o Fluoxe ine
De e mina ion in Sedimen s". P esen ed in 40 h In e na ional Con e ence on En i onmen al
& Food Moni o ing, 2018.
Ma ia João Ce ei a Fe nandes
255
ANNEX - AUTHORIZATION FOR USE AND ADAPTATION OF
FIGURES
Figu e 2.1 and Figu e 2.2
F om he epo : WHO/UNICEF. (2021). P og ess on household d inking wa e , sani a ion and
hygiene 2000-2020: i e yea s in o he SDGs. Licence: CC BY-NC-SA 3.0 IGO.
h p://apps.who.in /booko de s.
Use and adap a ion au ho iza ion:

Annex - Au ho iza ion Fo Use And Adap a ion O Figu es
256
Figu e 2.5
F om: Silo i, R., Sh i as a a, V., Singh, A., Sha ma, P., Aouad, M., Mahlknech , J., & Kuma , M.
(2022). Global g oundwa e ulne abili y o Pha maceu ical and Pe sonal ca e p oduc s
(PPCPs): The scena io o second decade o 21s cen u y. Jou nal o En i onmen al
Managemen , 320(115703), 1–18. h ps://doi.o g/10.1016/j.jen man.2022.115703
Use and adap a ion au ho iza ion:
Ma ia João Ce ei a Fe nandes
257
Annex - Au ho iza ion Fo Use And Adap a ion O Figu es
258
Ma ia João Ce ei a Fe nandes
259
Figu e 2.15
F om: Espinoza-Mon e o, P. J., Vega-Ve duga, C., Alulema-Pullupaxi, P., Fe nández, L., & Paz,
J. L. (2020). Technologies employed in he ea men o wa e con amina ed wi h glyphosa e:
A e iew. Molecules, 25(23), 1–26. h ps://doi.o g/10.3390/molecules25235550, Licensee
MDPI, Basel, Swi ze land. This a icle is an open access a icle dis ibu ed unde he e ms and
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