CEST2013 – A hens, G eece Re no: 0624
Please do no use page numbe s
TEMPORAL EVOLUTION OF EMERGING CONTAMINANTS, PRIORITY
SUBSTANCES AND HEAVY METALS MOST FREQUENTLY DETECTED IN
RECLAIMED WATER AND GROUNDWATER IN A VOLCANIC AQUIFER
E. ESTÉVEZ1, M.C. CABRERA1, J.R. FERNÁNDEZ-VERA2, A. MOLINA-DÍAZ3, J.R.
ROBLES-MOLINA3 and M.P. PALACIOS-DÍAZ4
1 Uni e si y o Las Palmas de G an Cana ia, Depa men o Physics, 2 Labo a o io
Ag oalimen a io y Fi opa ológico (Cabildo de G an Cana ia) 3 Uni e si y o Jaén,
Analy ical Chemis y Resea ch G oup, Depa men o Physical and Analy ical Chemis y,4
Uni e si y o Las Palmas de G an Cana ia, Depa men o Animal Pa hology, 35017,
Cana y Islands, Spain, [email p o ec ed],
EXTENDED ABSTRACT
The p esence o eme ging con aminan s has been p e iously desc ibed in eclaimed
wa e and g oundwa e o G an Cana ia (Spain). Despi e o he en i onmen al isk
associa ed o i iga ion wi h eclaimed wa e (R), his p ac ice is necessa y conside ing
sus ainabili y o he hyd ological cycle in semia id zones, especially ega ding ag icul u al
ac i i y.
The aim o his s udy was: i) o analyse he e olu ion du ing wo yea s o con aminan s o
eme ging conce n, p io i y subs ances (2008/105/EC) and hea y me als in eclaimed
wa e (R) and in a olcanic aqui e in he NE o G an Cana ia whe e a gol cou se has
been i iga ed wi h R since 1976 and ii) o ela e his p esence wi h physicochemical
wa e p ope ies and hyd ogeological media.
Reclaimed wa e and g oundwa e (GW) we e moni o ing qua e ly om July 2009 o
Sep embe 2011. So p ion and deg ada ion p ocesses in soil accoun o mo e
compounds being de ec ed in R. Diazinon and chlo en inphos we e de ec ed always in
R and e bu hylazine, e bu yn and diu on a 90% o equency. Conside ing all he
samples, he mos equen compounds we e chlo py i os e hyl, luo ene, phenan h ene
and py ene. Al hough hei concen a ions we e equen ly below 50 ngL-1, some
con aminan s, we e occasionally de ec ed a highe concen a ions. Chlo py i os e hyl
and diu on a e p io i y subs ances de ec ed equen ly and a high concen a ions so hey
mus be included in moni o ing s udies. Geology and loca ion seem o be ela ed o he
eme ging compounds p esence due o occasional con amina ion e en s (no ela ed o R
i iga ion) and he e o e no o an exis ence o a dange ous di use con amina ion le el.
Thus, i is p e e able o selec wells wi h less s able chemical wa e quali y, in o de o
moni o he isk o eme ging compounds p esence. Conside ing he ela ionship be ween
con aminan p esence, chemical wa e quali y, seasonal a ia ion, hyd ogeological
cha ac e is ics and wells loca ion we can conclude ha chlo py i os e hyl and diu on we e
he mos dange ous p io i y subs ances in e ms o GW quali y so hey mus be included
in all o he moni o ing s udies, a leas in Cana y Islands.
Keywo ds: eme ging con aminan s, p io i y subs ances, hea y me als, eclaimed wa e ,
g oundwa e , i iga ion, olcanic zone.
1. INTRODUCTION
Reclaimed wa e euse o e s a gua an eed supply and con ibu es o mi iga e he
sho age o na u al wa e esou ces, especially, in semia id zones, whe e eclaimed wa e
cons i u es an impo an sou ce o i iga ion wa e (Kuma e al., 2005; Kinney e al.,
2006). In G an Cana ia (Spain), his p ac ice has been used o mo e han hi y yea s
(Ma e o and Palacios, 1996), and eclaimed wa e cu en ly ep esen s 8% o wa e
esou ces (Palacios e al., 2008). Nowadays, ad ances in ea men p ocesses esul in
accep able eclaimed wa e quali ies. In he s udy a ea, e luen quali y has been
imp o ed due o he ins alla ion o new in as uc u es, highligh ing a desalina ion sys em
o he seconda y e luen since 2002. Aqui e s in eg a e echa ge wa e (na u al o om
i iga ion e u ns) om di e en imes, especially in semia id zones and i g oundwa e
able head is deep.
The main sou ces o eme ging o ganic compounds in g oundwa e a e ela ed o
was ewa e e luen s o euse, sep ic anks, li es ock ac i i ies and hospi al e luen s
(Lapwo h e al., 2012). The main p ocesses con olling eme ging con aminan s du ing
mig a ion h ough he soil, unsa u a ed zone and aqui e a e so p ion mainly o o ganic
ma e and clay mine als, ion exchange, and mic obial deg ada ion o ans o ma ions.
Indeed, he con aminan p ope ies as well as ansi ime h ough he unsa u a ed zone
and g oundwa e esidence ime, edox condi ions and o al loading will be impo an in
de e mining p esence and pe sis ence in g oundwa e . In olcanic ma e ials, he
p esence o p e e en ial pa hs in he unsa u a ed zone can a ou a apid echa ge, so
eme gen con aminan s can each he aqui e in ela i e sho imes.
The p esence o eme ging con aminan s has been p e iously iden i ied and desc ibed in
eclaimed wa e used o i iga e a gol cou se and in g oundwa e o he NE o G an
Cana ia (Es é ez e al., 2012). This s udy moni o s 183 con aminan s o eme ging
conce n and p io i y subs ances (2008/105/EC) since July 2009 o May 2010. The mos
equen compounds we e ca eine, nico ine (s imulan s), chlo py i os e hyl
(o ganophospha e insec icide), luo ene, phenan h ene and py ene (PAHs).
Concen a ions we e always below 50 ngL-1, al hough some pha maceu icals and one
pes icide, chlo py i os e hyl, we e occasionally de ec ed a highe concen a ions. This
pape poin s o mo e en y ou es apa om eclaimed wa e i iga ion: ag icul u al
p ac ices, sep ic anks leaks and sewe age b eaks, and men ions he impo ance o
adso p ion, deg ada ion and p e e en ial lows phenomena. Howe e , empo al a ia ions
o he con aminan s concen a ion had no been obse ed and a longe sampling pe iod
was ecommended.
One o he aims o ou s udy was o analyse he empo al e olu ion 36 con aminan s o
he o al de ec ed by Es é ez e al. (2012), also including he esul s o an ex ended
pe iod un il Sep embe 2011 and he esul s o 20 compounds non de ec ed in he i s
s udy. A seconda y objec i e was o ela e hei p esence wi h chemical wa e p ope ies
and hyd ogeological condi ions. Resul s o analyses o hea y me als in he whole pe iod
a e also p esen ed.
2. MATERIAL AND METHODS
2.1. Loca ion and desc ip ion o he s udy a ea
The Bandama Gol Cou se is loca ed in he NE o he G an Cana ia Island in he cen al
pa o he Las Go e as basin, be ween 400 m and 500 m high. The Las Go e as basin is
included in he N4 zone o he G an Cana ia Wa e Adminis a ion Plan (CIAGC, 1999),
which is ep esen ed in Figu e 1. A e age p ecipi a ion in he a ea is 300 mm pe yea ,
he a e age annual empe a u e is 19°C, and he ange o humidi y is om 78% o 85%.
Since 1976, he Bandama Gol Cou se has been i iga ed wi h eclaimed wa e om he
Was ewa e T ea men Plan o Las Palmas de G an Cana ia, whe e e ia y ea men
ins alled since 2002, consis ed in desalina ion and disin ec ion (Es e ez e al., 2010).
Figu e 1. Loca ion and geology o he s udy a ea (modi ied om Balcells e al., 1990),
si ua ion o he main a ines, he Bandama Calde a, he gol cou se and moni o ing
poin s ( eclaimed wa e : R, wells: W0-W6 and he El Cula ón wa e galle y) and
piezome y o Janua y 2009 (Cab e a e al., 2009, modi ied).
The s udy a ea is nex o he qua e na y Bandama olcanic complex, and includes a
olcanic calde a. F esh basal ic and basani ic la as and py oclas ic ma e ials (2,000
yea s old) ou c op in he a ea (Hansen and Mo eno, 2008). These ma e ials o e lie
ac u ed basani ic la a lows and landslide b eccias, which co e Miocene phonoli es.
In e bedded allu ial conglome a es ou c op inside he Bandama Calde a (Fig. 1). The
island has a low pe meabili y “co e” wi h successi e co e s o younge , mo e pe meable
ma e ials whe e g oundwa e low concen a es (Cus odio, 2003; SPA-15, 1975).
P e ious hyd ogeological s udies in he a ea (Cab e a e al., 2009) ha e shown ha he
g oundwa e lows om summi s o coas ollow a p e e en ial low line h ough he Las
Go e as a ine and ha he e is a g oundwa e low om he gol cou se o he a ine.
The g oundwa e able head is loca ed 250 m below he Bandama Gol Cou se. The
aqui e sys em in he s udy a ea is exploi ed by sha wells o 2.5-3 m in diame e
(“cana ian” wells) and 15-300 m dep hs. These i iga ing wells, desc ibed in Table 1,
exploi mainly he ac u ed Miocene phonoli es wi h equi alen con inuous yields lowe
han 1 Ls-1 pe day. Cab e a e al. (2010) demos a ed ha g oundwa e salini y inc eases
om summi o sho e and ha hyd ogeochemis y changes om sodium bica bona e
(occasionally wi h an endogenous gas supply) o chlo ide sodium bica bona e in he
middle a ea and o sodium chlo ide on he coas al inge. Also, ni a e con en s inc ease
om summi o sho e (up o 180 mgL-1), exceeding no ma i e h esholds (Di ec i e
91/676 EEC) so i is designed as a ulne able zone by he Regional Cana y Islands
Go e nmen . The men ioned s udy concluded ha he wa e om he El Cula ón wa e
galle y: G (Figu e 1 and Table 1), abou 40 m long and loca ed 60 m below he gol
cou se, d ains a pe ched aqui e wi h a cons an low a e o 0.05 Ls-1 and ecei es wa e
om di e en sou ces, including gol cou se leacha es. The wa e galle y
hyd ogeochemis y di e s sligh ly om he g oundwa e sampled in he wells loca ed a
he bo om o he Las Go e as a ine (Cab e a e al., 2009).
Table 1. Desc ip ion o g oundwa e sampling s a ions (1: Dep h (m), 2: Bo om
ele a ion (m), 3: Exploi ed Fo ma ion, 4: Hyd ochemical g oundwa e ype) and chemical
pa ame e s o he moni o ing ne wo k poin s p esen ing mean (x) and s anda d de ia ion
(sd).
W0 W1 W2 W3 W4 W5 W6 G R
x sd x sd x sd x sd x sd x sd x sd x sd x sd
1 208 133 32 158 34 70 96 40**
2 504 168 183 27 76 205 57 430
3 Roque
Nublo Phonoli es Recen
Basal s
Recen
Basal s -
Phonoli es
Phonoli es Phonoli es
Recen
Basal s -
Phonoli es
Roque Nublo
Slipped
b eccia
4 HCO3-Na Cl-HCO3-
Na Cl-Na HCO3-Na Cl-Na Cl-SO4-Na Cl-Na Cl-Na
pH 7.8b 0.3 7.6b 0.2 7.9b 0.3 6.6a 0.2 7.7b 0.2 8.0b 0.2 7.7b 0.0 7.7b 0.2 7.7b 0.2
EC 0.5a 0.0 1.6b 0.1 2.4c 0.1 3.0d 0.2 3.5e 0.2 1.6b 0.2 3.0d 0.1 1.7b 0.1 0.4a 0.1
NO3
- 7.2a 2.5 38.6b 4.3 117.0d 5.8 64.6c 18.3 185.0e 12.0 76.2c 13.5 133.0d 1.4 59.3c 7.9 8.1a 3.1
Na+ 50a 1.0 200bc 2.9 252cd 22.4 590 57.7 468e 33.5 183b 10.1 436e 24.7 304d 5.7 49a 28.2
K+ 10.3bc 0.5 13.1c 0.7 17.8d 1.3 37.8 4.4 41.9g 2.5 12.3c 1.0 33.0e 1.4 7.6ab 0.7 3.8a 1.8
Ca2+ 22.8b 0.5 51.9cd 5.0 99.3e 11.5 39.4c 6.8 107.7e 7.2 56.6d 8.0 62.0d 5.7 8.0a 0.4 11.6ab 1.6
Mg2+ 15.7ab 0.5 43.8c 5.2 76.5d 9.6 23.8b 4.5 88.6e 7.0 51.4c 7.1 76.0d 5.7 9.4a 0.6 8.7a 1.8
Cl- 31.3a 2.9 236.6b 7.0 412.0e 54.5 324.1c 18.6 676.5e 65.8 224.9b 17.0 624.0e 32.5 328.9c 10.3 58.4a 27.5
SO4
2- 7.9a 1.9 155.2b 9.6 232.1c 24.5 371.0d 45.7 335.5d 14.7 233.6c 29.5 251.5c 6.4 130.0b 4.1 17.2a 6.9
HCO3- 246bc 14 310cd 14 275cd 15 839e 127 346d 21 181ab 11 303cd 29 132a 12 93a 19
SiO2 89.5d 0.6 66.4c 1.3 40.2b 2.5 67.3c 4.4 48.8b 2.0 69.1c 5.0 72.0c 4.2 64.8c 4.2 28.3a 5.7
P 0.09a 0.0 0.09a 0.1 0.24bc 0.1 0.12ab 0.1 0.11ab 0.1 0.10a 0.1 0.25c 0.1 0.42d 0.0 0.13abc 0.1
B 0.06a 0.0 0.23ab 0.0 0.46ab 0.1 1.07b 0.1 0.83ab 0.1 0.18a 0.0 0.56ab 0.0 0.53ab 0.0 0.34ab 0.2
Fe 0.00a 0.0 0.00a 0.0 0.00a 0.0 0.00a 0.0 0.00a 0.0 0.01a 0.0 0.00a 0.0 0.00a 0.0 0.09b 0.1
Mn 0.01a 0.0 0.00a 0.0 0.03a 0.1 0.32b 0.1 0.01a 0.0 0.01a 0.0 0.00a 0.0 0.00a 0.0 0.02a 0.0
W ep esen s he 3 m-diame e wells, G: wa e galle y and R: eclaimed i iga ion wa e . Elec ic conduc i i y (EC).
*: Da a wi h he same le e a e no signi ican ly di e en a 0.05.
**: Leng h o he wa e galle y. Dep h om he gol cou se o he wa e galle y: 60m
2.2. Moni o ing ne wo k
In he moni o ing ne wo k ca ied ou un il Sep embe 2011 we e sampled he gol cou se
i iga ion wa e (R), he El Cula ón wa e galle y (G) and he same wells conside ed in
Es é ez e al. (2012): W1, W2, W3 and W4, adding a con ol well loca ed a he highes
al i ude and wo wells: W5 (nea e he gol cou se) - W6 (be ween W3 and W4).
Samples we e aken in ambe glass bo les wi h Te lon caps (1L) o analyse o ganic
compounds and in PE-LD bo les (250 ml and 500 ml) o analyse hea y me als and
chemical pa ame e s espec i ely. All samples we e immedia ely s o ed in an insula ed
con aine chilled wi h ice packs o be dispa ched by exp ess deli e y o he labo a o y. All
he samples we e aken on he same da e and we e dispa ched wi hin 48h. I iga ion
wa e was sampled di ec ly om a wa e ou le loca ed in a ai way o he gol cou se,
wa e galle y samples we e aken om a pipe discha ging di ec ly om i , and well
samples we e aken a e pumping a minimum o 15 minu es.
This pape p esen s he esul s o he occu ence o 65 eme ging con aminan s and
p io i y subs ances (2008/105/EC) in nine qua e ly campaigns conduc ed om July 2009
o Sep embe 2011. Only R and G we e sampled in all he da es. In he es o he
moni o ing poin s he numbe o a ailable da a is: 4 (W0), 6 (W1), 8 (W2), 7 (W3 and
W4), 3 (W5) and 2 (W6).
2.3. Me hods o analysis
The analysis o o ganic compounds and hea y me als was conduc ed by he Labo a o y
o Analy ical Chemis y a he Uni e si y o Jaén by using wo di e en analy ical me hods
(Table 2). The sample p e- ea men applied o he isola ion and p e-concen a ion o
non-pola and semi-pola ola ile compounds was a liquid-liquid ex ac ion (LLE) wi h n-
hexane (Robles-Molina e al., 2010), ollowed by gas ch oma og aphy coupled wi h mass
spec ome y analysis (GC-MS). The ins umen used was a CP-3800 gas ch oma og aph
coupled wi h a 300-MS iple quad upole mass spec ome e (Va ian Inc. Walnu C eek,
Cali o nia, USA). This me hodology was sa is ac o ily alida ed and ob ained good
eco e y a es, as well as he RDS (%) o mos compounds. The me hods’ limi s o
de ec ion, oge he wi h he es o alida ion pa ame e s o hose compounds ound in
he samples we e p esen ed in Es é ez e al. (2012). Hea y me als we e de e mined by
mass spec ome e wi h induc i ely coupled plasma (ICP-MS, Agilen Technologies 7500
Se ies) a e acuum il a ion o he samples.
The es o he chemical pa ame e s we e de e mined in he Labo a o y o he Council o
G an Cana ia (Labo a o io Ag oalimen a io y Fi opa ológico Labo a o io del Cabildo de
G an Cana ia): pH and EC; ca ions, SiO2, P and B by ICP coupled by Op ical emission
spec opho ome e (OES) and anions by ionic ch oma og aphy excep ca bona es and
bica bona es (Po en iome ic De e mina ion).
Table 2. Analy ical me hods employed in his wo k oge he wi h he de ec ed and non-
de ec ed compounds which we e classi ied in o he ollowing g oups: pes icides,
Polycyclic A oma ic Hyd oca bons (PAH), pha maceu icals and hea y me als.
GC-MS me hod
P e- ea men Ex ac ion me hod Analy ical Me hod
 No il a ion
 pH adjus men (3-4)
 Liquid-Liquid Ex ac ion
(LLE)
 Sol en : n-Hexane

Gas Ch oma og aphy coupled o T iple
Quad upole Mass Spec ome y (GC-TQMS).
Ope a ion mode: MRM.
 Column: Va ian Fac o Fou VF-5-ms (30m x
0.25mm i.d. x 0.25 µm)
GC-MS: non de ec ed compounds GC-MS: de ec ed compounds
Pes icides: alachlo , ame yn, ald in, a azine dese hyl,
del ame h in, dield in, endosul an sulpha e, e hion,
end in, hep achlo , isod in, ip odione, pa a hion,
pa a hion me hyl, i lu alin, α-HCH, β-endosul an, β-
HCH, δ-HCH.
Pes icides: 4,4’-DDE, 4,4’-DDT, a azine, chlo en inphos,
chlo o olu on, chlo py i os e hyl, diazinon, diu on,
hexachlo obu adiene, hexachlo obenzene, isop o u on,
me oxychlo , oxy luo en, pa a hion e hyl, pen achlo obenzene,
p ocymidone, p opazine, simazine, e bu hylazine, e bu yn*,
α -cype me h in, α-endosul an, γ-HCH.
Pha maceu icals: ace aminophen, an ipy ine.
PAH: acenaph ylene, an h acene, benzo(a)an h acene,
benzo(a)py ene,benzo(b) luo an hene, benzo(g,h,i)pe ylene,
benzo(k) luo an hene, ch ysene, dibenzo(a,h)an h acene,
luo ene, indene(1,2,3-cd)py ene, phenan h ene, py ene.
ICP-MS me hod
P e- ea men Analy ical Me hod
 Vacuum Fil a ion

Mass spec ome e wi h induc i ely coupled
plasma. Babing on nebulize , sp ay chambe
double e ige a ed (2 º C) o Pel ie qua z and
Agilen I-AS au osample .
 RF powe : 1500 W, plasma gas low o 15 Lmin-1;
nebulize gas low: 1 Lm-1; auxilia y gas low: 0.9
min-1; suc ion eloci y o he sample: 0.25mLmin -1.
ICP-MS: non de ec ed compounds ICP-MS: de ec ed compounds
Hea y me als: Hg, Sn, P and Pd Hea y me als: Cd, Cu , Ni, Pb, Zn and Tl.
P io i y subs ances (2008/105/EC) a e in cu si e.

3. RESULTS
3.1. Hyd ogeochemical cha ac e iza ion.
Figu e 2 p esen s Schoelle -Be kalo and S i diag ams ob ained wi h he las analy ical
esul s (Sep embe 2011). As i was desc ibed by Cab e a e al. (2010) GW quali y
emains cons an o e ime, since simila diag ams had been depic ed.
Figu e 2. Schoelle -Be kalo and S i diag ams o he g oundwa e moni o ing
poin s ob ained o Sep embe 2011.
As i was expec ed, W0 ep esen s sodium bica bona e low mine alized g oundwa e ,
simila han he wa e echa ge in his a ea. This g oundwa e coincides signi ican ly in
e ms o mos o he chemical pa ame e s wi h R (Table 1), excep wi h highe con en s
o K+, HCO3-, SiO2 and Fe, esul ing om he olcanic ocks hyd olysis. W3 wa e is
sodium bica bona ed wi h signi ican ly la ge con en o Na+. I s low pH and high con en
o HCO3- indica es ha g oundwa e is been en iching by endogenous CO2 gas
con ibu ions. I coincides jus wi h he well ha exploi s he aqui e mo e deeply.
The wa e pumped om W4 is signi ican ly di e en om he es o he wells in many o
he chemical pa ame e s (EC, NO3-, SO4-2, Cl-2, Na+, K+, Ca+2, Mg+2) excep o SiO2 (Table
1). W4 ep esen s g oundwa e nea he discha ge a ea ( he coas ), whe e g oundwa e
quali y is he esul o he p og essi e mine aliza ion h ough he g oundwa e low
di ec ion, he in luence o saline echa ge wa e due o a idi y in coas al a eas and
an h opogenic ac i i ies.
The chlo ided sodic wa e om he wa e galle y p esen s a de ici o Ca+2, Mg+2 and
HCO3-, an excess o NO3- and he highes P con en de ec ed. This ac would be ela ed
wi h p e e en ial low phenomena. Compa ing wi h R, G is mo e concen a ed and seems
o ecei e also al e na i e wa e sou ces.
3.1. P io i y subs ances and Con aminan s o Eme ging Conce n
Table 3 shows he equency, mean and maximum concen a ion o he moni o ing
ne wo k esul s. In he p e ious s udy (Es é ez e al., 2012) he pes icides and PAH
p esen ing a 100% o equency we e: chlo py i os e hyl, luo ene, phenan h ene and
py ene. Howe e , once he pe iod o ime was ex ended and he moni o ing poin s we e
inc eased, he equency o chlo py i os e hyl de ec ion dec eased o 80% (Table 3). The
concen a ion o his p io i y subs ance (2008/105/CE) is in a ange o 10 ngL-1 (bellow
he 30 ngL-1 AA-EQS), al hough 20% o samples we e o e his alue, exceeding in he
5% o he esul s he Eu opean h eshold limi in g oundwa e (100 ngL-1) (2006/118/CE).
These exceeding alues we e always de ec ed in summe , al hough in summe 2010 i
was only de ec ed in h ee samples and bellow 10 ngL-1 (Figu e 3). The widesp ead
p esence o his chlo ina ed o ganophospha e insec icide, aca icide and nema icide is
ela ed o i s b oad spec um and use in ag icul u al p ac ices, gol cou ses, ca le and
u ban media. The con inued use o his pes icide poses a isk o a mwo ke s and hei
amilies he e o e he EPA is seeking o end ag icul u al use o chlo py i os. Al hough i s
soil pe sis ence may depend on he o mula ion, a e o applica ion, soil ype, clima e and
o he condi ions (Robe s e al., 1999) chlo py i os is s able in soils wi h epo ed hal -
li es anging be ween 7 and 120 days (Ch is ensen e al., 2009). As chlo py i os does no
pa i ion easily om soil o wa e i s p esence in uno wa e is likely a esul o soil-bound
om e oding soil, a he han om dissol ed chlo py i os (EPA, 1999). The high
equency and concen a ion o his adso bable compound de ec ed in he Las Go e as
aqui e a e consis en wi h he p e e en ial low anspo desc ibed in olcanic aqui e s. In
his sense, he highes alues ob ained in g oundwa e coincided wi h highe EC o ni a e
con en s. Hence, i s p esence in high concen a ions seems o co espond o occasional
con amina ion e en s (no ela ed o RW i iga ion) and no o an exis ence o a
dange ous di use con amina ion le el. On Ap il 15, 2009, EPA included chlo py i os e hyl
in he ini ial lis o chemicals o be sc eened o hei po en ial e ec s on he endoc ine
sys em (EPA, 2009), which aims o co e all pes icide chemicals, as well as subs ances
ha may occu in sou ces o d inking wa e o which a subs an ial popula ion may be
exposed. Nowadays, EPA is e iewing es o de esponses and making a ailable he
s a us o es o de esponses (EPA, 2013).
As occu ed in ou p e ious s udy, luo ene, phenan h ene and py ene (PAH compounds)
we e de ec ed wi h equencies o 100%. These compounds a e included in he lis o he
30 mos equen ly de ec ed compounds epo ed in he UK En i onmen al Agency
G oundwa e Mic opollu an Da abase (S ua e al., 2012). The ange concen a ion o
luo ene is less han 7 ngL-1. Phenan h ene and py ene (Figu e 4) concen a ion we e
always below 25 ngL-1 in GW, excep o he anomalous maximum alues desc ibed in
Es e ez e al., (2012) (close o 60 ngL-1). Non seasonal a ia ion was obse ed (Figu e 4)
o hose PAHs.
Table 3. Concen a ion (µgL-1: hea y me als, ngL-1: es o subs ances) and equency
o de ec ion pe sample (i iga ion wa e : R, wa e galle y: G and wells: W0- W6), o
hose compounds de ec ed a leas once in he whole pe iod (July 2009 – Sep embe
2011). Nº: Compound Numbe o de ed by g oup (pes icides: 1-23, PAH: 24-36, hea y
me als: 37-42 and pha maceu icals: 43-44) and by equency o de ec ion, X: mean
concen a ion, Max: maximum concen a ion, n : o al numbe o analysis, nd: numbe o
de ec ions, %T: o al equency (GW and R), %R: eclaimed wa e equency and %GW:
g oundwa e equency.
R G W0 W1 W2 W3 W4 W5 W6
Nº X Max X Max X Max X Max X Max X Max X Max X Max X Max F equency
n = 9 n = 9 n = 4 n = 6 n = 8 n = 7 n = 7 n = 3 n = 2 % T % R %GW
1 5.9 27.2 4.2 9.3 1.3 2.9 2.3 4.1 2.4 9.9 5.3 13.4 3.1 6.8 2.4 4.4 3.6 5.6
nd/n
6/9 6/9 4/4 5/6 8/8 6/7 6/7 3/3 2/2 83.3 66.7 86.7
2* 6.8 18.1 10 39 3.3 5.3 62 223 52 294 7.7 28.2 51 262 3 6.3 5.2
nd/n
6/9 7/9 3/4 5/6 6/8 7/7 6/7 3/3 1/2 79.6 66.7 82.2
3* 9.8 42.3 2.8 4.6 2.6 9.3 13.8 8 25 4.8 7.6 131 624 3 3.7
nd/n
8/9 5/9 1/4 4/6 5/8 4/7 5/7 2/3 61.1 88.9 55.6
4* 6.2 18 1.7 2.8 1 3.8 8.1 2.8 6.3 2 2.6 68 195 0.5
nd/n
8/9 3/9 1/4 5/6 6/8 4/7 3/7 1/3 55.6 88.9 48.9
5 1.8 3.2 2.7 7.6 1.6 2.4 4.5 11.7 2.3 3.4 2.4 7.3 1.3 1.5 0.9 1.6 3.2
nd/n
5/9 4/9 3/4 3/6 5/8 4/7 3/7 2/3 1/2 53.7 55.6 53.3
6 12 36.1 1.8 0.7 1.3 0.9 0.9 0.8
nd/n
9/9 1/9 2/6 4/8 3/7 2/7 38.9 100 26.7
7* 4.1 11.3 1.6 1 2.9 4 5.5 1.7 3.9 126 250
nd/n
8/9 1/9 1/4 2/6 1/8 3/7 2/7 33.3 88.9 22.2
8* 0.4 0.7 0.8 1.9 14 34.5 14 36 164 325
nd/n
1/9 2/9 1/4 3/6 3/8 2/7 22.2 11.1 24.4
9* x 35 191 101
nd/n
9/9 1/7 18.5 100 2.2
10* 1.3 2.5 9.1 13.8 4 6.7 2.8 4.3 242 484
nd/n
1/9 1/9 2/6 2/8 1/7 2/7 18.5 11.1 20
11* 2.2 0.2 2.5 4.4 2.8 1.6 2.3 109 217
nd/n
1/9 1/9 2/6 1/8 2/7 2/7 16.7 11.1 17.8
12 0.4 1.2 1.7 1.6 0.4 0.5 0.3 0.4 0.3 1.0
nd/n
1/9 2/9 1/6 2/8 2/7 1/7 1/3 14.8 11.1 15.6
13 0.8 1.3 2.1 2.8 2.8 6.4 11
nd/n
1/9 2/6 1/8 1/7 2/7 13 0 15.6
14 0.4 1.2 0.5 5.1
nd/n
1/9 1/9 1/4 1/6 9.3 11.1 8.9
15 8 14.7 1.5 1.8
nd/n
2/9 2/4 7.4 22.2 4.4
16 0.1 0.2 0.5
nd/n
1/9 1/7 1/2 5.6 0 6.7
17 6.5 9 8 42
nd/n
1/9 1/4 1/6 1/7 5.6 0 6.7
18 0.2 0.2 1.5
nd/n
1/9 1/6 1/8 5.6 0 6.7
19 3 3
nd/n
2/9 3.7 22.2 0
20 0.3 0.8
nd/n
1/6 1/8 3.7 0 4.4
21 20
nd/n
1/9 1.9 11.1 0
22 0.9
nd/n
1/8 1.9 0 2.2
23 12
nd/n
1/6 1.9 0 2.2
24 8.1 60 1.2 3.1 1 2.2 1.3 3.2 1.9 6.5 1.7 5.6 1.4 2.1 0.7 1.4 1.6 1.8
nd/n
9/9 9/9 4/4 6/6 8 7/7 7/7 3/3 2/2 100 100 100
25 6 18.7 5.7 18 6.4 14 13 57 6.9 18.9 5.8 9.8 2.7 5.8 9.4 13
nd/n
9/9 9/9 4/4 8/8 7/7 7/7 3/3 2/2 100 100 100
26 4.9 17.6 3.9 8.9 4.4 6.7 4.5 6.9 9.4 23 2.5 5 7.1 11
nd/n
9/9 9/9 4/4 6/6 7/7 3/3 2/2 100 100 100
27 1 1.6 0.5 0.6 0.4 0.5 0.4 0.7 0.5 0.8 0.4 0.5 0.4
nd/n
2/9 3/9 1/4 1/6 3/8 3/7 2/7 1/2 27.8 22.2 28.9
28 2.3 6.2 2.7 9.3 0.5 0.9 1.2 4.8 12 11 21.4 8.5 17
nd/n
3/9 4/9 1/4 2/6 3/8 2/7 2/7 25.9 11.1 28.9
29 0.2 0.2 0.3 0.4 0.3 0.4 0.4 0.2 0.4 0.2 0.3
nd/n
5/9 2/9 1/6 2/8 3/7 2/7 24.1 33.3 22.2
30 0.3 0.3 0.3 0.4 0.3 0.4 0.4 0.8 0.5 0.7 0.2 0.2
nd/n
2/9 2/9 2/6 3/8 2/7 2/7 24.1 22.2 24.4
31 0.7 1.2 0.7 0.9 0.5 0.6 0.6 0.6 1.2 1.8 1.3
nd/n
3/9 2/9 2/6 2/8 2/7 1/7 22.2 33.3 20
32 0.3 0.4 0.5 0.8 1.2 1.4 0.4 0.6 0.4
nd/n
1/9 2/9 1/6 2/8 2/7 1/7 16.7 11.1 17.8
33 0.2 0.3 0.4 0.6 1.1 1.2 0.3 0.4 0.4
nd/n
1/9 2/9 1/6 2/8 2/7 1/7 16.7 11.1 17.8
34 0.8 0.9 0.3 0.4 0.3 0.4 0.3 0.4
nd/n
2/9 2/9 2/6 2/7 14.8 22.2 13.3
35* 7.7 14 0.5 105 0.5
nd/n
1/9 1/9 1/8 1/7 1/3 9.3 11.1 8.9
36 0.3 18 0.5
nd/n
1/9 1/4 1/8 5.6 11.1 4.4
37* 425 811 351 1022 280 396 381 1006 292 532 362 563 377 610 216 353 282 317
nd/n
9/9 9/9 3/4 6/6 7/8 7/7 7/7 3/3 2/2 98.1 100 97.8
38* x 347 1732 5.6 24 2.2 3.7 29 140 8.6 34 3.8 6.9 5.4 18 1.2 2 4,3 4,7
nd/n
9/9 8/9 3/4 6/6 6/8 7/7 6/7 2/3 2/2 81.5 100 77.8
39 10 24.7 4.4 15 4.5 5.6 4.9 12.6 15 35.3 10 19 2.5 3,3 6,9 11
nd/n
7/9 9/9 2/4 6/6 7/7 7/7 3/3 2/2 81.5 77.8 82.2
40 0.2 0.4 0.2 0.4 0.2 0.5 0.2 0.3 0.2 0.4 0.1
nd/n
4/9 4/9 4/6 4/8 3/7 1/3 37 44.4 35.6
41 0.3 0.6 0 0.1 0.1 0.1 0.7 0.4 2.7
nd/n
3/9 5/9 1/4 1/6 5/7 1/7 1/3 16.7 33.3 13.3
42 0.05 0.007 0.007 1.1 0.9 0.007
nd/n
1/9 1/9 1/8 1/7 1/3 2/2 13 11.1 13.3
43 51 92
nd/n
5/9 9.3 55.6 0
44 x 1832 35
nd/n
1/9 1/4 3.7 11.1 2.2
*: Compounds e ec ed a leas once in he g oundwa e (G o W0 - W6) a a concen ac ion highe han 0.1 µgL-1.
x: de ec ed a leas once in he eclaimed wa e (R) a a concen a ion highe han 0.1 µgL-1.
Nº = Compound Numbe o de ed by g oup (Pes icides: 1- 23, PAH: , Pha maceu icals: and hea y me als: ) and equency
o de ec ion.
PESTICIDES:
1: hexachlo obenzene, 2*: chlo py i os e hyl, 3*: e bu hylazine, 4*: diu on, 5: oxy luo en, 6: chlo en inphos, 7*: e bu yn,
8*: p ocymidone, 9* x: diazinon, 10*: a azine, 11*: p opazine, 12: pen achlo obenzene, 13: simazine,14:chlo o olu on,
15: γ-HCH, 16: 4,4’-DDT, 17: α-endosul an, 18: 4,4’-DDE, 19: isop o u on, 20: hexachlo obu adiene, 21: α-cype me h in,
22: me oxychlo , 23: pa a hion e hyl.
PAH:
24: luo ene, 25: phenan h ene, 26: py ene, 27:acenaph ylene, 28: ch ysene, 29: benzo(b) luo an hene,
30:benzo(a)an h acene, 31: benzo(ghi)pe ylene, 32: indene(1,2,3-cd)py ene, 33: dibenzo(a,h)an h acene,
34: benzo(k) luo an hene, 35*: an h acene, 36: benzo(a)py ene.
HEAVY METALS:
37*: Zn, 38 x: Cu, 39: Ni, 40: Cd, 41: Pb and 42: Tl.
PHARMACEUTICALS:
43: an ipy ine, 44 x: ace aminophen.