Assessing sediment toxicity risks with bioavailable metal fractions: new factors and index applied to the Colombian tropical Andes hotspot

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En i on Geochem Heal h (2025) 47:222
h ps://doi.o g/10.1007/s10653-025-02536-3
ORIGINAL PAPER
Assessing sedimen oxici y isks wi hbioa ailable me al
ac ions: new ac o s andindex applied o heColombian
opical Andes ho spo
Ing idVanessaRincon‑Vasquez· NicolaFoh e ·
DanielRosado
Recei ed: 5 Decembe 2024 / Accep ed: 1 May 2025 / Published online: 22 May 2025
© The Au ho (s) 2025
Abs ac Hea y me al oxici y isk assessmen s in
sedimen s o en ely on pseudo o al concen a ions,
despi e he highe heo e ical p edic i e po en ial o
bioa ailable ac ions. This s udy in oduces he Bio-
a ailable F ac ion Toxici y Fac o (BT ) and he Bio-
a ailable F ac ion Toxici y Index (BTI) o e alua e
me al oxici y isks using a bioa ailable ac ion cal-
cula ed as he sum o he i s wo s eps o he Tessie
sequen ial ex ac ion p ocedu e. In es iga ing hea y
me al pollu ion (Cd, C , Cu, Mn, Ni, Pb, Zn) in he
Ve as Ri e ca chmen , a c i ical eshwa e sou ce
in he San u bán Pá amo wi hin he T opical Andes
biodi e si y ho spo , he s udy iden i ied a isanal and
small-scale mining as he p ima y d i e o con ami-
na ion. Wa e and sedimen o mining a eas, pa icu-
la ly La Baja C eek and El Volcán Village, exhib-
i ed he highes concen a ions o me als, wi h some
sedimen le els being ca ego ized as s ongly con am-
ina ed by he Geoaccumula ion Index and Pollu ion
Load Index and exceeding he P obable E ec Con-
cen a ion h eshold. Bioa ailable ac ion o me als
in sedimen s we e measu ed. Bioa ailable ac ions
we e highe in mining-a ec ed a eas, sugges ing
g ea e po en ial o me al elease unde acidic con-
di ions. The BT and BTI p o ided a mo e nuanced
unde s anding o me al oxici y isks compa ed o
pseudo o al concen a ions, wi h highe BTI alues
in mining-in luenced si es. These indings unde sco e
he need o mi iga ion measu es o add ess hea y
me al pollu ion and highligh he ecological impo -
ance o he San u bán Pá amo. Fu he esea ch in o
bio emedia ion po en ial using local lo a is ecom-
mended o suppo sus ainable managemen p ac ices.
Keywo ds T ace elemen s con amina ion in
ho spo s· Hea y me al bioa ailabili y· Sedimen
oxici y· A isanal mining in Pa amos· Sequen ial
ex ac ion· En i onmen al moni o ing in Andes
In oduc ion
Hea y me al pollu ion in aqua ic ecosys ems poses a
signi ican en i onmen al challenge wo ldwide (Sojka
& Jaskuła, 2022). These con aminan s en e aqua ic
ecosys ems h ough a ious na u al and an h opo-
genic sou ces, including mining (Ali e  al., 2019;
Huang e al., 2020), end o accumula e in sedimen s
Supplemen a y In o ma ion The online e sion
con ains supplemen a y ma e ial a ailable a h ps:// doi.
o g/ 10. 1007/ s10653- 025- 02536-3.
I.V.Rincon-Vasquez· N.Foh e · D.Rosado(*)
Depa men o Hyd ology andWa e Resou ces
Managemen , Ins i u e o Na u al Resou ce Conse a ion,
Kiel Uni e si y, 24118Kiel, Ge many
e-mail: d osado@hyd ology.uni-kiel.de
D.Rosado
Depa men o Chemical andEn i onmen al Enginee ing,
Highe Technical School o Enginee ing, Uni e sidad
de Se illa, Camino de los Descub imien os s/n,
41092Se ille, Spain
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(Shou e  al., 2022) and, depending on hei bio-
a ailabili y, hey can bioaccumula e and biomagni y
h ough he ood chain. This p ocess poses signi ican
oxici y isks o bo h aqua ic li e and human heal h
(Kachoueiyan e  al., 2023, 2024a; Li e  al., 2022).
The assessmen o hea y me al pollu ion in sedi-
men s o en elies on indices ha consolida e me al
concen a ions in o a single nume ical alue, which
acili a es communica ion (Kuma e al., 2019). These
indices p ima ily ocus on he accumula ion o me als
in sedimen s, highligh ing en ichmen ela i e o na -
u al backg ound le els, and hei calcula ion ypically
in ol es wo s eps. Fi s , he me al concen a ions a e
no malized o a backg ound o e e ence alue, esul -
ing in one alue pe me al pe sample. Examples o
his s ep include he geoaccumula ion index (Mülle ,
1979) and he en ichmen ac o (Salomons & Fö s -
ne , 1984). Second, all he no malized alues o a
gi en sample a e in eg a ed in o a single alue, such
as he pollu ion load index (Tomlinson e al., 1980).
In addi ion o epo ing me al concen a ions and
en ichmen le els, i is necessa y o assess he po en-
ial oxici y isk o bio a (Bi ch, 2017). To add ess
his, esea che s ha e es ablished sedimen quali y
guidelines ha link speci ic me al concen a ions wi h
oxici y isks. These guidelines ypically de ine low
h esholds, below which ad e se e ec s on o gan-
isms a e a e, and high h esholds, abo e which oxic
e ec s a e likely (Bi ch, 2017; Ka aouzas e  al.,
2021). No able examples include he e ec ange low
(ERL) and e ec ange median (ERM) de eloped by
Long e al. (1995) and he h eshold e ec concen a-
ion (TEC) and p obable e ec concen a ion (PEC)
de eloped by MacDonald e al. (2000). Some s udies
ha e u ilized hese guidelines as no maliza ion alues
o p opose new indices based on oxici y isk, using
me hodologies simila o hose employed o assess-
ing an h opogenic impac s on me al concen a ions.
Examples include he mean ERM quo ien (mERMQ)
and he mean PEL quo ien (mPELQ) (Ka aouzas
e al., 2021; Long & MacDonald, 1998; Ya a Ashay-
e i & Kesha a zi, 2019).
Sedimen quali y guidelines adi ionally ely on
o al me al con en o assess oxici y isks. Howe e ,
me als in sedimen s exis in di e en ac ions, each
wi h a ying deg ees o bioa ailabili y. Mo e bio-
a ailable ac ions a e o en mo e indica i e o he
po en ial oxici y e ec s o me als han less a ailable
ones (Fang e al., 2022; Gao e al., 2018; Sau é e al.,
2000; Vale o e al., 2020). Cu en ly, only a ew indi-
ces conside he bioa ailable ac ions o me als in
sedimen s o assess oxici y isks. Among hese a e
he Risk Assessmen Code (RAC) (Pe in e al., 1985;
Saeedi & Jamshidi-Zanjani, 2015) and he Modi ied
Risk Assessmen Code (mRAC) (Benson e al., 2018;
Saeedi & Jamshidi-Zanjani, 2015).
This issue is pa icula ly c i ical in a eas impac ed
by a isanal mining, a signi ican sou ce o hea y
me als in aqua ic ecosys ems wo ldwide (Casso-Ha -
mann e  al., 2022; Ri e a-Pa a e  al., 2021). Such
ac i i ies a e pa icula ly de imen al in biodi e si y
ho spo s like hose in Colombia (Dossou E ui e al.,
2024), whe e in o mal, small-scale, and un egula ed
gold and sil e mining gene a es la ge amoun s o
mining was e con aining me cu y (Hg) and sul ide
mine als such as py i e, chalcopy i e, and py ho i e.
The oxida ion o hese sul ides can p oduce acid mine
d ainage (AMD) ha is en iched wi h hea y me -
als (Hudson-Edwa ds & Dold, 2015; Wol Ca eño
e al., 2005).
F equen ly, a isanal mining akes place in he
Colombian pa amos, high-al i ude moo lands loca ed
abo e he uppe o es line and below he snow-
line (ap ox 2800 and 4700m) isola ed in an a chi-
pelago-like dis ibu ion in he Andean moun ains
be ween la i udes o 11°N and 8°S co e ing app oxi-
ma ely 35,000 km2 (Be ancu -Co edo e al., 2018;
Diazg anados e al., 2021; Llambí e al., 2019). Pa a-
mos ha e po ous soils wi h a high-wa e e en ion
capaci y ha s o es and pu i ies su ace and g ound-
wa e and se e as a eshwa e sou ce o majo ci -
ies ac oss he coun y (Buy ae e al., 2006; C esso
e al., 2020).
The Colombian pa amos a e pa o he opical
Andes ho spo and can be conside ed a ho spo wi hin
his ho spo because o hei high species endemism
deg ee (Cues a e al., 2017; Mye s e al., 2000; Pa iño
e al., 2021). These ecosys ems a e home o app oxi-
ma ely 4700 plan species (To e e  al., 2008) and
3431 ascula plan s species (Mad iñán e al., 2013).
Pa amos also se e as excep ional ca bon sinks (Seg-
u a Mad igal e al., 2019). Along wi h o he ecosys-
ems, hey con ibu e o making Colombia he mos
biodi e se coun y in he wo ld ela i e o land a ea
(Cle ici e al., 2019; Gonzalez-Salaza e al., 2017).
The Ve as Ri e ca chmen , loca ed in he Eas e n
Co dille a o no heas Colombia, has expe ienced
signi ican p essu e due o a 400-yea adi ion o
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mining. The uppe pa o his a ea includes sec ions
o he San u bán pá amo, a c ucial hyd ological and
biological ho spo (Loaiza e al., 2020). In o mal and
small-scale gold and sil e mining in he a ea (Co -
po ación Geoambien al Te ae 2018) ha e p oduced
ele a ed concen a ions o As in wa e and sedimen s
(Alonso Con e as, 2014; Alonso e al., 2020), as well
as Mn and Cu in wa e (Jiménez-Ga cía & Palacio-
Ca eño, 2016; Wol Ca eño e  al., 2005). These
concen a ions signi ican ly exceeded he d inking
wa e h eshold es ablished in Colombian egula ions
by he Resolu ion 2115 o 2007 (Minis y o Housing
o Colombia, 2007), as well as hose om he Uni ed
S a es En i onmen al P o ec ion Agency (USEPA,
2024). The San u bán pá amo is a c i ical ecological
a ea whe e he Ve as, Cha a, Tona, and F io i e s
o igina e. This egion supplies app oxima ely 30%
o he eshwa e o Buca amanga, a majo ci y in
Colombia (Dua e-Abadía e al., 2023).
Despi e he longs anding impac o mining, he e
is s ill a lack o comp ehensi e s udies on he Ve as
Ri e ha examine a wide a ie y o ace elemen s,
hinde ing a ho ough assessmen o he mining
impac s on he ecosys em and he implemen a ion o
e ec i e p o ec ion measu es (Loaiza e al., 2020).
This s udy in oduces he bioa ailable ac ion
oxici y ac o s and he bioa ailable ac ion oxic-
i y index o hea y me als in sedimen s. These me -
ics a e designed o in eg a e he isks associa ed
wi h hea y me als in sedimen s in o a single igu e,
using he h eshold e ec concen a ion (TEC) and
he p obable e ec concen a ion (PEC) es ablished
by MacDonald e al. (2000). Fu he mo e, his s udy
aims o de e mine he hea y me al pollu ion (Cd, C ,
Cu, Fe, Mn, Ni, Pb, and Zn) in sedimen and wa e o
he Ve as Ri e ca chmen o e alua e hei po en ial
oxici y isks o bio a. Gi en he a isanal and small-
scale mining ac i i ies p e alen in he a ea, his
s udy hypo hesizes ha he p esence o mining ac i i-
ies is di ec ly associa ed wi h ele a ed concen a ions
o hea y me als in bo h wa e and sedimen s. This
a ea comp ises a signi ican po ion o he San u bán
Pá amo, a egion o high biodi e si y and pa o he
T opical Andes biodi e si y ho spo .
In addi ion, his s udy epo s on me al concen-
a ions o bioa ailable ac ions (exchangeable and
bound o ca bona es) in sedimen s o he Ve as Ri e
ca chmen using he me hod p oposed by Tessie e al.
(1979) as desc ibed in TableS2. To he bes o he
au ho s’ knowledge, his is he i s ime his me hod
has been applied in his egion in he scien i ic li e a-
u e, p o iding c ucial insigh in o he po en ial bio-
a ailabili y and bioconcen a ion o ace elemen s in
sedimen s. Ul ima ely, his s udy enhances communi-
ca ion abou he isks associa ed wi h hea y me als in
sedimen s o aqua ic bio a.
Ma e ials andme hods
S udy a ea: Ve as Ri e Basin
The Ve as Ri e basin is loca ed app oxima ely
50 km no heas o Buca amanga in he San ande
depa men (no heas e n Colombia). The ca chmen
is si ua ed in wo municipali ies: Ve as and Cali o -
nia (Fig. 1). The i e is he main ibu a y o he
Su a á i e and lows om he San u bán pa amo a
4255m abo e sea le el (m) down o Su a á munici-
pali y a 1656m. The wa e om i s main ibu a ies,
he Paez, La Baja and Mongo a c eeks, is u ilized by
local communi ies o mining, ag icul u e, and d ink-
ing (Alonso e al., 2020).
Acco ding o he Vi e o Su a á wea he s a ion,
main ained by he Ins i u e o Hyd ology, Me eo ol-
ogy and En i onmen al S udies o Colombia (IDEAM
in spanish), he annual p ecipi a ion in he s udy a ea
anged om 660 o 1,200 mm be ween 1968 and
2021. The egion expe iences a bimodal ain all pa -
e n, wi h wo ainy seasons occu ing om Ma ch o
mid-May and om mid-Sep embe o No embe , and
wo d y seasons occu ing om Decembe o Ma ch
and om June o mid-Sep embe (IDEAM, 2024).
The a e age daily maximum empe a u e is 35 °C
in he lowe a eas, while he a e age daily minimum
empe a u e in he pá amo egions is 0°C. The a e -
age ela i e humidi y in he basin is 81%. The e ap-
o a ion a e anges om 700 o 1500mm pe yea ,
while e apo anspi a ion a ies be ween 910 and
1400mm pe yea . Due o i s opical loca ion, hese
alues emain ela i ely s able h oughou he yea
(IDEAM, 2024).
The Ve as Ri e basin, including La Baja C eek,
is well known o i s ex ensi e mining his o y, wi h
nume ous mines and p ocessing plan s equen ly
loca ed along i s banks, ex ending in o he lowe
egions o he San u bán Pá amo (Co ula & Pe -
one, 2024; Fló ez e  al., 2022; Güiza-Suá ez &
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Kau mann, 2024; Mo ales Méndez & Rod íguez,
2016; Zá a e Rueda e  al., 2023; Zá a e-Rueda
e al., 2022). Acco ding o he 2011 census o min-
ing uni s, Cali o nia and Ve as had 147 and 78 min-
ing uni s, espec i ely, being 34% in Cali o nia and
82% in Ve as ope a ing wi hou a license (Minis y o
Mines & Ene gy o Colombia, 2012). Al hough he
Colombia 1930 Ac o 2018 (known as he Pá amos
Law) p ohibi s mining, explo a ion, and exploi a ion
in pá amos (Cong ess o Colombia, 2018), he exac
bounda ies o he San u bán pá amo emain unclea
(Dua e-Abadía & Boelens, 2016). The lack o egu-
la ion in exploi a ion and was e disposal p ac ices o
unlicensed mining poses a signi ican h ea o he
wa e quali y o he Ve as Ri e (Pa da e Li ia &
Bel an Aguila , 2007; Sojka & Jaskuła, 2022).
Mo eo e , be ween 64 and 96% o ocks in he
Ve as ca chmen a e classi ied as high po en ially
acid-gene a ing (PAG) ock (MINESA, 2019), which
is a high sul ida ion epi he mal deposi wi h py i e as
he p ima y o e mine al, ollowed by coppe sul ides
such as chalcopy i e, chalcoci e, bo ni e, and co elli e
(MINESA, 2019). PAG ocks can gene a e sul u ic
acid when exposed o wea he ing condi ions, po en-
ially dissol ing me als and o he ha m ul subs ances
om he ocks (Hudson-Edwa ds & Dold, 2015).
Addi ionally, MINESA (2019) es ima ed ha mine
ailings may con ain app oxima elly 50,8g As, 2,7g
Bi 0,77g Cd, 139g Pb, 23,1g Sb, 2,88g Te, 2,1g
Th, 19g U and 38g Zn pe on. These concen a ions
can cause i e e sible changes in he ecosys em and
wa e quali y.
In si u pa ame e s, sampling and sample
p e- ea men
The sampling campaign was conduc ed in Ma ch
2022 and included 18 sampling poin s in wa e bodies
(VT01-VT18). Ten in he Ve as Ri e ups eam o he
con luence wi h La Baja C eek (VT01-VT10), se en
in la Baja C eek (VT11-VT17) and one in he Ve as
Ri e downs eam o he con luence wi h La Baja
C eek (VT18), e e ed o as he ou le in his a icle.
To assess po en ial mining con amina ion in hese
a eas, sampling poin s we e di ided in o wo g oups.
The i s g oup included poin s loca ed in a eas
una ec ed by mining ac i i y, ei he ups eam o
in mic o basins wi hou mining ac i i y in bo h, he
Ve as Ri e (VT01-VT04, VT07-VT09) and La Baja
C eek (VT12 and VT13). The second g oup included
poin s loca ed ei he in mining dis ic s along he
Ve as Ri e (VT05, VT06, VT10) and La Baja C eek
(VT11, VT14-VT17) o downs eam (VT18). VT05
is loca ed in El Volcán Village. VT02 and VT13
Fig. 1 Loca ion o s udy a ea and sampling poin s in Colom-
bia (Ve as Ri e : VT01-VT10, La Baja C eek: VT11-VT17,
Ou le : VT18). Poin s a e ca ego ized in o wo g oups: hose
ups eam o in mic o basins wi hou mining ac i i ies in he
Ve as Ri e (VT01-VT04, VT07-VT09) and La Baja C eek
(VT12, VT13) ma ked wi h blue do s, and hose in mining
dis ic s in he Ve as Ri e (VT05, VT06, VT10) and La Baja
C eek (VT11, VT14-VT17) o downs eam (ou le , VT18)
ma ked wi h o ange do s. VT05 is loca ed in El Volcán Vil-
lage. Coo dina es in TableS1
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co espond o wo lakes una ec ed by mining, si u-
a ed in he uppe pa o he basin in he Pa amo de
San u bán, while emaining poin s co espond o
c eeks and i e s (Fig.1).
No sedimen samples we e collec ed a poin s
VT09 and VT13 due o s ong cu en s and a lack
o ine sedimen s. In addi ion, wo ap wa e sam-
ples we e collec ed om he municipal adminis a-
i e cen e s o Ve as and Cali o nia. In o al, 20 wa e
samples and 16 sedimen samples we e collec ed.
In si u wa e quali y pa ame e s (pH, conduc i i y,
dissol ed oxygen, and empe a u e) we e measu ed a
each sampling poin a a dep h o 10–20cm. Meas-
u emen s we e aken using a WTW® Mul i 3630
IDS po able mul ipa ame e de ice, calib a ed wi h
s anda d solu ions p io o use.
Samples we e collec ed acco ding o he guidelines
ou lined in he in e na ional s anda d ISO 5667 se ies
(ISO 2020). Wa e samples we e collec ed in 100ml
polye hylene bo les ha had been p e iously washed
and d ied in he labo a o y. A each sampling poin ,
bo les we e insed h ee imes wi h he sample wa e
be o e collec ion, illed comple ely (wi hou ai bub-
bles), and he me ically sealed. A e collec ion, he
wa e samples we e s o ed a 4°C in he da k (ISO
2020). Sedimen samples om he op 5 cm we e
collec ed using a sho el ac oss a c oss-sec ion o he
i e , a oiding a eas wi h signs o leakage o su ace
dis u bance. These samples we e placed in he me i-
cally sealed plas ic bags and s o ed in a da k coole a
4°C. Sedimen samples we e d ied a oom empe a-
u e in an emp y, clean, and closed oom wi hou ai
ci cula ion due o he lack o an on-si e o en. Once
d ied, he samples we e sie ed wi h a plas ic sie e o
a 2mm size. Finally, he samples we e anspo ed
o Ge many o analysis a he labo a o ies o Kiel
Uni e si y.
Hea y me al measu emen in wa e samples
Wa e samples we e il e ed h ough 0.45 μm po e
Te lon il e s, acidi ied wi h a d op o Sup apu ®
ni ic acid and s o ed a 4 °C un il analysis. Me al
concen a ions in wa e we e measu ed using a
The mo Scien i ic ® ICP-OES iCAP 6000 Se ies,
which suppo s bo h axial and adial iews. Cali-
b a ion o he ins umen was pe o med using Ce -
ipu ® ICP mul i-elemen s anda d solu ion IV and
XIII om Me ck, which we e dilu ed a a ios o
1:50, 1:100, and 1:200.
Fo quali y con ol and assu ance (QC/QA), each
measu emen ba ch inco po a ed a p ocedu e blank
( eagen s wi hou sample), a duplica e sample ( an-
domly selec ed o each ba ch) and a e e ence wa e
(ERM-CA615) om he ce i ied e e ence ma e ials
ca alog o he Eu opean Commission’s Join Resea ch
Cen e (JRC).
Pseudo o al con en o hea y me al in sedimen
samples
Sedimen samples we e ini ially d ied a 60 °C o
24h, weighed, d ied o an addi ional wo hou s un il
cons an weigh , disagg ega ed wi h an aga e mo a ,
and inally sie ed o ob ain a ac ion wi h a pa icle
size < 100μm.
Nex , 0.2g o each sedimen sample was diges ed
in 5ml o Sup apu ® ni ic acid using a closed diges-
ion block (Pico ace) a 140°C o 16h. The diges-
a e was hen il e ed in o 50ml olume ic lasks and
s o ed in 50ml plas ic bo les a 4°C un il analysis.
Fo QC/QA pu poses, each diges ion ba ch
included a p ocedu e blank ( eagen s wi hou sam-
ple), a duplica e sample ( andomly selec ed o each
ba ch) and a e e ence soil (SO-4) om he Canadian
Ce i ied Re e ence Ma e ials P ojec . Reco e y a es
o all elemen s consis en ly anged be ween 95 and
105% and, he e o e, we e conside ed sa is ac o y
(Kachoueiyan e al., 2024b).
Hea y me al concen a ions in he diges a es we e
measu ed wi h a The mo Scien i ic ® ICP-OES iCAP
6000 Se ies, ollowing he same p ocedu e desc ibed
o he wa e samples.
Geoaccumula ion Index (Igeo)
The Geoaccumula ion Index (Igeo) is a measu e used
o assess me al pollu ion in aqua ic sedimen s and
solid was e ma e ials. In oduced by Mülle (1979)
and u he de ailed by Fö s ne and Mülle (1981),
e alua es he deg ee o con amina ion based on na u-
al backg ound concen a ions (Fö s ne & Mülle ,
1981; Kowalska e al., 2018). The Igeo is exp essed
as he loga i hmic ans o ma ion o he a io be ween
he me al concen a ion in a sample and a e e ence
concen a ion, accoun ing o possible a ia ions due
o li hologic changes (Fö s ne & Mülle , 1981). I is

En i on Geochem Heal h (2025) 47:222
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ega ded as one o he mos accu a e con amina ion
indices (Kowalska e al., 2018).
The o mula o calcula ing Igeo is:
whe e XSample is he concen a ion o an elemen in
he sample. XBackg ound is he a e age concen a ion in
he uppe con inen al c us o he backg ound alue
o he examined elemen in he a ea. 1.5 is a con-
s an included o minimize e o s due o li hologic
a ia ions.
The sampling poin VT02 was adop ed as he
backg ound alue o his s udy o calcula ing bo h
he geoaccumula ion index and he pollu ion load
index. This choice was made because no an h o-
pogenic in luence was de ec ed a his si e, p o id-
ing a mo e accu a e baseline o he s udy a ea han
a e age e e ence alues o elemen concen a ions
in he uppe con inen al c us , such as hose es ab-
lished by Tu ekian and Wedepohl (1961).
Igeo ca ego izes sedimen quali y in o se en ca -
ego ies based on he deg ee o con amina ion o
indi idual elemen s as ollows (Fö s ne & Mülle ,
1981): ca ego y I (uncon amina ed, ≤ 0), ca ego y
II (uncon amina ed o mode a ely con amina ed,
0 < Igeo < 1), ca ego y III (mode a ely con ami-
na ed, 1 < Igeo < 2), ca ego y IV (mode a ely o
s ongly con amina ed, 2 < Igeo < 3), ca ego y V
(s ongly con amina ed, 3 < Igeo < 4), ca ego y VI
(s ongly o ex emely con amina ed, 4 < Igeo < 5)
and ca ego y VII (ex emely con amina ed,
Igeo ≥ 5).
Pollu ion load index (PLI)
The Pollu ion Load Index (PLI) was o iginally de el-
oped by Tomlinson e al. (1980) o add ess challenges
in assessing hea y me al pollu ion in es ua ies. I p o-
ides a measu e o he con amina ion deg ee om
a se o me als based on he Con amina ion Fac o
(CF), which is he a io o he me al concen a ion in
he sample o he backg ound o e e ence concen-
a ion (Alha bi e al., 2023; Haynes & Zhou, 2022;
Huang e al., 2020; Tomlinson e al., 1980).
The PLI is calcula ed as he n h- oo o he p od-
uc o he n-CF, whe e n ep esen s he numbe o
Igeo
=log2
X
Sample
1.5 ×X
Backg ound
me als conside ed as shown below (Haynes & Zhou,
2022; Huang e al., 2020). In his s udy, n = 6.
Simila o he Igeo calcula ion, he sampling poin
VT02 was used as he backg ound alue o calcula -
ing bo h he Igeo and PLI.
The e is no consensus ega ding he ca ego iza-
ion o he PLI. Acco ding o Tomlinson e al. (1980),
PLI > 1 indica es con amina ion. Fo a deepe in e -
p e a ion o he esul s, his s udy adop s he ollow-
ing ca ego iza ion (A ab & Hakeem, 2022; Jo i
e al., 2017): No pollu ion (PLI ≤ 1), mode a e pol-
lu ion (1 < PLI ≤ 2), hea y pollu ion (2 < PLI ≤ 3),
ex emely high pollu ion (PLI > 3).
Compa ison oguidelines
Re e ence concen a ions o hea y me als we e
based on he Consensus-Based alues de eloped by
MacDonald e al. (2000): h eshold e ec concen a-
ion (TEC) and p obable e ec concen a ion (PEC)
h esholds. The TEC ep esen s he concen a ion
below which ad e se e ec s a e no expec ed o occu ,
in mg/kg: Cd (0.99), C (43.4), Cu (31.6), Pb (35.8),
Ni (22.7), Zn (121). The PEC indica es he concen-
a ion abo e which ad e se e ec s a e expec ed o
occu mo e o en han no , in mg/kg: Cd (4.98), C
(111), Cu (149), Pb (128), Ni (48.6), Zn (459) (Mac-
Donald e al., 2000).
S a is ical analysis: p incipal componen analysis
(PCA) andco ela ion analysis
P incipal Componen Analysis (PCA) was pe -
o med o iden i y and unde s and he ela ionships
among he measu ed a iables. PCA is widely used
o assess hea y me al pollu ion in soils because i
educes he dimensionali y o he da a and e eals
he main sou ces o a ia ion (Aidoo e  al., 2021;
Fagben o e al., 2021; Huang e al., 2020; Io dache
e al., 2022; Liu e al., 2013; Wei e al., 2011). The
Pea son co ela ion coe icien was also calcula ed o
de ine associa ions and dependencies be ween ele-
men s. This me hod is commonly used o e alua e
hea y me al pollu ion in he en i onmen (Fagben o
e al., 2021; Huang e al., 2020; Io dache e al., 2022).
The Kaise –Meye –Olkin (KMO) es and Ba le ’s
PLI =(
CF
Cd ∗
CF
Cu ∗
CF
C ∗
CF
Ni ∗
CF
Pb ∗
CF
Zn)
1
6
En i on Geochem Heal h (2025) 47:222 Page 7 o 20 222
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es we e conduc ed o e alua e he sui abili y o he
da a o p incipal componen analysis (PCA) and co -
ela ion analysis p io o pe o ming hese analyses.
A KMO alue g ea e han 0.5 and a p- alue om
Ba le ’s es less han 0.05 a e conside ed sa is ac-
o y, con i ming he app op ia eness o he da a o
he men ioned s a is ical analyses (Kachoueiyan e al.,
2024b; Mish a e al., 2018). R s udio so wa e e sion
2023.06.1 + 524 (R De elopmen Co e Team, 2023)
was used o p oduce he g aphs and o pe o m s a is-
ical analysis.
Sequen ial ex ac ion o bioa ailable me als in
sedimen s, bioa ailable ac ion oxici y ac o and
bioa ailable ac ion oxici y index
The i s and second s eps o he sequen ial ex ac-
ion me hod p oposed by Tessie e al. (1979) we e
pe o med o ob ain he exchangeable and ca bona es
ac ions om sedimen s. Hea y me als we e sequen-
ially ex ac ed om 1g o sedimen using solu ions
and condi ions lis ed in TableS2. The me al con en
in he esul ing ex ac s was measu ed wi h a The mo
Scien i ic ® ICP-OES iCAP 6000 Se ies ins umen
as desc ibed o wa e samples.
This wo k de eloped he bioa ailable ac ion ox-
ici y ac o (BT ) and he bioa ailable ac ion oxic-
i y index (BTI). The BT no malizes he sum o me al
con en in he exchangeable and ca bona e-bound
ac ions acco ding o he p o ocol de ined by Tessie
e al. (1979), which is equi alen o he acid-ex ac a-
ble ac ion de ined by he BCR-701 me hod (Rau e
e al., 2001) as s a ed be o e (Casalino e al., 2013).
This no maliza ion uses sedimen oxici y guidelines
de eloped by MacDonald e  al. (2000), speci ically
he h eshold e ec concen a ion (TEC) and he
p obable e ec concen a ion (PEC). The BT is cal-
cula ed acco ding o he ollowing equa ions:
I C
m
,
s<
TEC
m
hen BT
m
,
s
=C
m
,
s
∕TEC
m
and 0
<
BT
m
,
s<
1
I TECm
≤C
m,s
<PEC
m
hen BT
m,s
=1+
(
C
m,s
−TEC
m)
∕
(
PEC
m
−TEC
m)
and 1 ≤BT
m,s
<
2
I Cm,s
≥PEC
m
hen BT
m,s
=2+
(
C
m,s
−PEC
m)
∕PEC
m
)and BT
m,s
≥
2
whe e Cm,s is he concen a ion o he me al m in he
sample s, TECm is he TEC o he me al m, BT m,s is
he bioa ailable ac ion oxici y ac o o he me al m
in he sample s, PECm is he PEC o he me al m.
The oxici y ac o s a e in e p e ed as no sedi-
men oxici y (T < 1), possible sedimen oxici y
(1 ≤ T < 2) and p obable sedimen oxici y (T ≥ 2)
acco ding o he in e p e a ion o he TEC and PEC
de eloped by MacDonald e al. (2000).
The bioa ailable ac ion oxici y ac o s o one
sedimen sample we e in eg a ed in o he bioa ailable
ac ion oxici y index (BTI) o exp ess he oxici y o
mul iple me als in a single igu e. The BTI is he geo-
me ic mean o he BT s o one sample:
whe e BTIs is he oxici y index in he sample s,
BT m1,s is he con amina ion ac o o he me al m1
in he sample s, and BT mi,s is he con amina ion ac-
o o he i h me al mi in he sample s. BTI le els a e
di ided in o h ee ca ego ies, simila ly as i was done
be o e o he BT .
Resul s anddiscussion
In-si u pa ame e s
The pH alues in he s udy a ea a ied subs an ially,
wi h a ange o app oxima ely 5 uni s, while con-
duc i i y also showed signi ican a ia ion, spanning
abou 1762 µS/cm (Table S3). Mos pH measu e-
men s ell be ween 6.84 and 7.89, which a e sui -
able o d inking wa e acco ding o Eu opean Union
(Eu opean Pa liamen , 2020) and Colombian (Minis-
y o Housing o Colombia, 2007) guidelines. These
alues also align wi h s anda ds o he p ese a ion
o aqua ic li e se by he USEPA (2023) and com-
ply wi h Colombian egula ions o he discha ge o
BTIs
=
(
BT
m1,s
x BT
m2,s
x…x BT
mi,s)1∕i
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mining wa e s in o wa e bodies (Minis y o En i-
onmen & Sus ainable De elopmen o Colombia,
2015). Howe e , h ee samples loca ed in a eas is-
ibly a ec ed by mining exhibi ed acidic pH alues
ha could be conside ed ou lie s in El Volcán illage
(VT05, 4.48), and La Baja C eek (VT14, 2.78; VT17,
5.02). Thei pH alues a e simila o hose eco ded
in se e ely a ec ed a eas nea ailings and spillage
poin s in he Escale a, Chipchilla, Hoachocolpa, and
A occoma ca i e s in Pe u, whe e Cacciu olo and
Cano (2022) epo ed pH alues be ween 2.5 and
3.2. They a e also compa able o hose in he Odiel
and Tin o i e s in Spain, whe e Olías e al. (2004)
eco ded pH alues be ween 2.5 and 6.3. Poin VT14
can be ca ego ized as ha ing ex emely acidic mine
wa e (No ds om e al., 2000).
The conduc i i y alues had an a e age o 254.8
µS/cm and a s anda d de ia ion o 409.0 µS/cm, indi-
ca ing a highe deg ee o a iabili y compa ed o pH.
Ten sampling poin s had conduc i i y alues below
100 µS/cm, wo we e be ween 100 and 300 µS/cm,
i e anged om 300 o 450 µS/cm, and one exceeded
1500 µS/cm. The h ee pH ou lie s also had highe -
han-a e age conduc i i y alues and we e among he
op i e highes : VT05 (350 µS/cm), VT14 (1787 µS/
cm), and VT17 (377 µS/cm). All hese wa e s would
be sui able o d inking acco ding o he conduc i i y
c i e ia o he Eu opean Union (Eu opean Pa liamen ,
2020), bu VT14 would no mee he Colombian
guidelines (Minis y o Housing o Colombia, 2007).
Lowe - han-a e age pH alues and highe - han-
a e age conduc i i y alues we e p ima ily associa ed
wi h a eas impac ed by mining o loca ed downs eam
(Figu eS1).
Dissol ed oxygen le els a ied by only ~ 1mg/L
and consis en ly emained abo e 7.68mg/L, indica -
ing a high le el close o sa u a ion ha can suppo
aqua ic li e equi ing oxygen. These alues align wi h
he ypically high le els o oxygen obse ed in he
uppe sec ions o i e s, whe e s eepe elie and he
p esence o mo e wa e jumps p omo e oxygena ion
(Ji e al., 2017). Addi ionally, lowe popula ion den-
si y in hese a eas educes pollu ion om un ea ed
sewage, which can deple e oxygen le els in wa e (Ji
e al., 2017). Fu he mo e, mining ac i i ies ha e a
minimal in luence on oxygen concen a ions (Ka aca
e al., 2018).
Tempe a u e a ied by app oxima ely 9°C, wi h
his a ia ion p ima ily a ibu ed o changes in
al i ude, as indica ed by a co ela ion coe icien o
= − 0.7.
The wo ap wa e samples collec ed om he
municipal adminis a i e cen e s o Ve as and Cali o -
nia showed pH le els o 7.27 and 7.09, conduc i i y
o 149 and 158 µS/cm, and dissol ed oxygen le els
o 7.47 and 7.52mg/L, espec i ely. These measu e-
men s comply wi h all he a o emen ioned egula-
ions, indica ing ha , based on hese wa e quali y
pa ame e s, he ap wa e is sui able o d inking.
Hea y me al in wa e samples
Mos o he me al concen a ions in he samples we e
low, o en below de ec ion limi s (Table1). Howe e ,
he d inking wa e h eshold le els o all me als we e
exceeded in a leas one sampling poin . Mn, Ni and
Fe we e he mos equen ly abo e h eshold le els,
posing he g ea es po en ial heal h isks o indi idu-
als consuming his wa e . Sampling poin s in mining
a eas o El Volcán illage (VT05), La Baja C eek
(VT14), he ou le (VT18) as well as, unexpec edly,
an a ea in he uppe pa o he basin no adi ionally
associa ed wi h mining ac i i ies (VT01) exceeded
he limi s he mos o en. In pa icula , Fe and Ni
exceeded limi s a all ou poin s, while Cu, Mn, and
Pb exceeded limi s a h ee poin s, and C and Zn a
wo poin s. A he ou le , Zn eached a signi ican ly
ele a ed concen a ion o 72.94mg/L. No ably, ele-
a ed concen a ions o Cu, Fe, Ni, Pb, and Zn we e
also ound a poin VT01.
These alues in mining dis ic s and downs eam
we e simila o hose ound in se e ely a ec ed min-
ing a eas in he Odiel (Olías e  al., 2004) i e in
Spain, as well as in Mine a Caudalosa in Pe u (Cac-
ciu olo & Cano, 2022) as shown in TableS4 in he
supplemen a y ma e ial.
Wa e om he Ve as Ri e and La Baja C eek is
o en used o i iga ion and o supply households in
u al a eas h ough a isanal aqueduc s, equen ly
wi hou p io ea men (Dua e-Abadía & Boelens,
2016; Dua e-Abadía e al., 2023). Addi ionally, he
Ve as Ri e supplies wa e o he Bosconia wa e
ea men plan , which p o ides eshwa e o Buca a-
manga, one o Colombia’s mos impo an ci ies, wi h
o e 1,200,000 inhabi an s (Alonso e al., 2020; Coz
e al., 2008).
En i on Geochem Heal h (2025) 47:222 Page 9 o 20 222
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The ap wa e samples gene ally had me al concen-
a ions below he de ec ion limi , excep o Zn a he
Ve as municipal adminis a i e cen e , whe e i meas-
u ed 0.02mg/L. This concen a ion is well below he
h eshold le els associa ed wi h heal h isks, indica -
ing ha he wa e is sa e o consump ion acco d-
ing o guidelines es ablished by he Eu opean Union
(Eu opean Pa liamen , 2020) and Colombia (Minis y
o Housing o Colombia, 2007).
Pseudo o al con en o hea y me al in sedimen
samples
Pseudo- o al hea y me al concen a ions in sedi-
men s a e p esen ed in Fig. 2 and Table S5. The
mean concen a ions o me als ollowed he o de : Zn
(261.4 mg/kg) > Cu (187.3 mg/kg) > C (118.5 mg/
kg) > Pb (109.7 mg/kg) > Ni (29.0 mg/kg) > Cd
(3.1mg/kg). The dis ibu ion o me al concen a ions
in sedimen s ac oss sampling si es clea ly co ela ed
wi h mining ac i i ies. Highe concen a ions we e
eco ded in a eas wi h ac i e mining in El Volcán il-
lage (VT05 and VT06) and La Baja C eek (VT11,
VT15-VT17), as can be seen in Fig.2. A hese poin s
Zn, Cu and Pb displayed hei highes alues. In e es -
ingly, VT14, loca ed in La Baja C eek mining dis ic ,
egis e ed lowe sedimen concen a ions han o he
mining a eas, al hough he concen a ions o many
me als in wa e we e one o he highes and exceeded
d inking wa e guidelines se by he Eu opean Union
Di ec i e (Eu opean Pa liamen , 2020) and Colom-
bian Resolu ion 2115 o 2007 (Minis y o Housing
o Colombia, 2007). This can be explained because
o a pH alue in he si e o only 2.78, he lowes
eco ded in he s udy a ea, and he inc ease in hea y
me als solubili y unde acidic condi ions. The alues
Table 1 Concen a ion o Cd, C , Cu, Fe, Mn, Ni, Pb, and
Zn in wa e samples o he Ve as Ri e basin, Colombia, and
guideline alues o d inking wa e p o ided by Eu opean
Union Di ec i e 2020/2184 and he Colombian Resolu ion
2115 o 2007 (Minis y o Housing o Colombia, 2007)
S a ion Cd
(mg/L)
C
(mg/L)
Cu
(mg/L)Fe
(mg/L)
Mn
(mg/L)
Ni
(mg/L)
Pb
(mg/L)
Zn
(mg/L)
Numbe o
imes a
h eshold is
exceeded
VT01 <DL <DL 1.47 10.46 <DL 2.28 2.04 5.10 5
VT02 <DL <DL <DL 0.00 <DL <DL <DL <DL 0
VT03 <DL<DL <DL 0.00 <DL<DL <DL<DL 0
VT04 <DL<DL <DL 0.00 <DL<DL <DL 0.01 0
VT05 <DL 0.05 0.77 16.08 9.43 0.30 0.08 3.04 5
VT06 <DL<DL <DL<DL 3.57 0.03 <DL 0.55 2
VT07 <DL <DL <DL 0.04 <DL <DL <DL <DL 0
VT08 <DL <DL <DL 0.02 <DL <DL <DL <DL 0
VT09 <DL<DL <DL 0.01 <DL<DL <DL 0.01 0
VT10 <DL<DL <DL 0.03 0.85 <DL<DL 0.05 1
VT11 <DL<DL 0.00 0.00 0.61 <DL<DL 0.14 1
VT12 <DL<DL <DL<DL <DL<DL <DL<DL 0
VT13 <DL<DL <DL<DL <DL<DL <DL<DL 0
VT14 0.0006 0.13 6.75 116.40 1.38 0.32 <DL 0.90 5
VT15 <DL <DL <DL 0.03 <DL <DL <DL <DL 0
VT16 <DL<DL <DL 0.00 0.11 <DL<DL 0.02 1
VT17 <DL<DL 0.44 0.08 1.18 0.03 <DL 0.69 2
VT18 0.13 <DL 9.36 21.14 22.85 7.35 3.12 72.94 7
D inking wa e guidelines
Di ec i e (EU) 2020/2184 0.005 0.025 2 0.2 0.05 0.02 0.005 –
Colombian d inking -wa e
egula ions
Resolución 2115 o 2007
0.003 0.05 1 0.3 0.1 0.02 0.01 3
Numbe o imes a h eshold
is exceeded12348632
Reddish cells indica e concen a ions exceeding a leas one o hese guidelines. G een cells indica e non-exceed concen a-
ions. < DL = below he de ec ion limi
En i on Geochem Heal h (2025) 47:222
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Vol:. (1234567890)
Depa men o Hyd ology and Wa e Resou ces Managemen ,
Kiel Uni e si y o hei suppo .
Au ho con ibu ions I. V. Rincon-Vasquez: Concep ualiza-
ion, Me hodology, Valida ion, Fo mal analysis, In es iga ion,
Da a Cu a ion, W i ing—O iginal D a , W i ing—Re iew &
Edi ing, Funding acquisi ion. N. Foh e : Concep ualiza ion,
Resou ces, W i ing—Re iew & Edi ing, Supe ision, P ojec
adminis a ion, Funding acquisi ion. D. Rosado: Concep ual-
iza ion, Me hodology, Valida ion, Fo mal analysis, In es iga-
ion, Resou ces, Da a Cu a ion, W i ing—O iginal D a , W i -
ing—Re iew & Edi ing, Visualiza ion, Supe ision, P ojec
adminis a ion, Funding acquisi ion.
Funding Open Access unding enabled and o ganized by
P ojek DEAL. This esea ch ecei ed no speci ic g an om
any unding agency in he public, comme cial, o no - o -p o i
sec o s.
Da a a ailabili y The da ase s gene a ed du ing and/o ana-
lysed du ing he cu en s udy a e a ailable om he co e-
sponding au ho on easonable eques .
Decla a ions
Con lic o in e es The au ho s ha e no compe ing in e es s
o decla e ha a e ele an o he con en o his a icle.
Open Access This a icle is licensed unde a C ea i e Com-
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medium o o ma , as long as you gi e app op ia e c edi o he
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included in he a icle’s C ea i e Commons licence and you
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he pe mi ed use, you will need o ob ain pe mission di ec ly
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