Evaluation of antimony availability in a mining context: Impact for the environment, and for mineral exploration and exploitation

Chemosphe e 311 (2023) 137086 A ailable online 2 No embe 2022 0045-6535/© 2022 The Au ho s. Published by Else ie L d. This is an open access a icle unde he CC BY license (h p://c ea i ecommons.o g/licenses/by/4.0/). E alua ion o an imony a ailabili y in a mining con ex : Impac o he en i onmen , and o mine al explo a ion and exploi a ion. Jos´ e Ma ía Esb í a , b , * , Ca melo M. Minang a , So ía Ri e a a , Me cedes Mad id-Illescas a , c , E a Ga cía-Nogue o a , Ana Gonz´ alez-Valoys a , d , Mai e Magu egui e , Hugues Thouin , Fabienne Ba aglia-B une , E ic Gloaguen , Pablo Le´ on Higue as a a Ins i u o de Geología Aplicada, Escuela de Ingenie ía Mine a e Indus ial de Almad´ en, Uni e sidad de Cas illa-La Mancha, Plaza M. Meca 1, Almad´ en, Ciudad Real 13400, Spain b Depa amen o de Mine alogía y Pe ología, Uni e sidad Complu ense de Mad id, Jos´ e An onio No ais 12, 28040 Mad id, Spain c Depa amen o de Ingenie ía Química, Uni e sidad de Cas illa-La Mancha, E.I.M.I. 13400 Almad´ en, Ciudad Real, Spain d Cen o Expe imen al de Ingenie ía, Uni e sidad Tecnol´ ogica de Panam´ a, Vía Tocumen, 0819-07289 Panama Ci y, Panama e Depa amen o de Química Analí ica, Uni e sidad del País Vasco, Facul ad de Fa macia, P.◦de la Uni e sidad, 7, 01006 Vi o ia-Gas eiz, ´ Ala a, Spain ISTO, UMR7327, Uni e si ´ e d’O l´ eans, CNRS, BRGM, F-45071 O l´ eans, F ance HIGHLIGHTS GRAPHICAL ABSTRACT •Mo e han 99% Sb was in he esidual ac ion in BCR ac iona ion applied o soil. •Soil heal h can be a ec ed due o poo dehyd ogenase ac i i ies in he s udied soil. •Pollu an s om soil o Que cus lea es we e ew, wi h bioaccumula ion ac o s <0.1520 •Low Sb (III) o ma ion and oxicological isk. ARTICLE INFO Keywo ds: Sb Que cus A ailabili y S ibni e Enzyma ic ac i i y BCR ABSTRACT This wo k aims o es ablish Sb mobili y, i s ans e o bio a and i s e ec on soil heal h in a semi-a id clima e. The esul s show he p esence o s ibni e (Sb 2 S 3 ) as he main p ima y Sb compound, bindhemi e (Pb 2 Sb 2 O 6 (O, OH)), and mino p opo ions o s ibiconi e (Sb 3+ (Sb 5+ ) 2 O 6 (OH)) as oxidised Sb species. This esea ch also ob- se es e y high o al Sb con en s in mining ma e ials (max: 20,000 mg kg −1 ) and soils (400–3000 mg kg −1 ), wi h physical dispe sion a ound mining ma e ials es ic ed o 450 m. The soil- o-plan ans e is e y low, (bioaccumula ion ac o : 0.0002–0.1520). Mos Sb emains in a esidual ac ion (99.9%), a e y low ac ion is bound o Fe and Mn oxy-hyd oxides o o ganic ma e , and a negligible p opo ion o Sb is leachable. The highe Sb mobili y a es has been ound unde oxidising condi ions wi h a long con ac ime be ween solids and wa e . The main ac o s ha explain he poo Sb mobili y and dispe sion in he mining a ea a e he low annual ain all a es ha slow down he Sb mobilisa ion p ocess and he sca ce o ma ion o oxidised Sb compounds. All hese da a sugges poo Sb (III) o ma ion and a low oxicological isk in he a ea associa ed wi h pas mining ac i i ies. * Depa amen o de Mine alogía y Pe ología, Uni e sidad Complu ense de Mad id, Jos´ e An onio No ais 12, 28040 Mad id, Spain. E-mail add ess: [email p o ec ed] (J.M. Esb í). Con en s lis s a ailable a ScienceDi ec Chemosphe e jou nal homepage: www.else ie .com/loca e/chemosphe e h ps://doi.o g/10.1016/j.chemosphe e.2022.137086 Recei ed 14 July 2022; Recei ed in e ised o m 28 Oc obe 2022; Accep ed 30 Oc obe 2022 Chemosphe e 311 (2023) 137086 2 The low mobili y o Sb sugges s ad an ages o u u e sus ainable mining o such o e deposi s in a semi-a id clima e and is also indica i e o he limi a ions o geochemical explo a ion in he sea ch o new Sb deposi s. 1. In oduc ion and backg ound An imony (Sb) has been conside ed by he Eu opean Union (EU) o be a C i ical Raw Ma e ial, gi en he ele ance o his elemen o Eu- opean economy and i s poo a ailabili y. China (74%), Tajikis an (8%) and Russia (4%) a e he main coun ies ha supply Sb wo ldwide (Eu- opean Union, 2020). In 2020, he EU o ally depended on impo s o ensu e he supply o his elemen , which is essen ial in indus ial sec o s like lame e a dan s, de ence applica ions and lead-acid ba e ies (Eu- opean Commission, 2020). The EU has been p omo ing esea ch o sol e his p oblem by eusing and eco e ing Sb in mining o indus ial acili ies, and by also p omo ing he iden i ica ion o Sb o e deposi s o be sus ainably exploi ed. Wi hin he EU Co unded ERA-MIN Join Call 2021 amewo k (ERAMIN, 2021), he AUREOLE esea ch p ojec aims o gene a e he bes p ospec ing and exploi a ion echniques o Sb de- posi s o inc ease he po en ial Sb esou ces in wes e n Eu ope (F ance, Spain and Po ugal). This las aspec is pa icula ly signi ican in he ci cula economy con ex adop ed by he EU, whe e he alue o p od- uc s, ma e ials and esou ces will be main ained in economy as long as possible by minimising was e gene a ion. Al hough Sb has a high ecy- cling inpu a e, de eloping he ci cula economy concep will be essen ial o ensu e i s p oduc ion. The Ibe ian Peninsula encompasses all he Sb deposi ypes, whe e he main mine al ca ie o Sb is s ibni e (Sb 2 S 3 ), and hese an imony-bea ing deposi s ep esen he la ges Sb deposi s wo ldwide. O he sca ce ypes o deposi s whe e Sb is a co- o by-p oduc a e ep esen ed by in usion- ela ed gold and polyme allic deposi s, whe e Sb is hos ed by sul osal s (Schwa z-Schampe a e al., 2014). This s udy ocuses on s ibni e de- posi s. Acco ding o Gumiel and A ibas (1987), he e a e 61 Sb deposi s and occu ences, including ein- ype deposi s, s a a-bound deposi s and Sb deposi s in olcanic dykes, in he Ibe ian Peninsula. Mos o hese Sb deposi s a e ela ed o he Va iscan o ogeny and p e e en ially loca ed in he sou he n Cen al Ibe ian zone. The mos equen mine al associa ion is qua z-s ibni e (La Balanzona, among o he s), bu he e a e o he s wi h impo an deposi s like qua z-s ibni e-gold (Ma i-Rosa mine, O ega e al., 1996), ca bona e-qua z-s ibni e-sphale i e-gold (Ribei o da Ig eja mine), ca bona e-qua z-s ibni e-galena-sil e (Diogenes mine), qua z-s ibni e-sphale i e (Naza ena mine, Boixe eu Vila and Fe n´ ande- z-Ley a, 2019), qua z-s ibni e-scheeli e (San An onio mine, A ibas and Gumiel, 1984; ´ Al a ez-Ayuso e al., 2022) and qua z-s ibni e-co elli e (Accesos mine, cha ac e is ic o he sou he n b anch o he Va iscan bel ) (Gumiel and A ibas, 1987). Acco dingly, he di e si y o mine al associa ions is wide in he Ibe ian Peninsula, which implies conside able complexi y when e alua ing Sb mobili y in such he e ogeneous con ex s. Py i e, chalcopy i e and a senopy i e a e common in some o hese de- posi s and p esen an acid mine d ainage (AMD) gene a ion po en ial ha would inc ease he mobili y o no only Sb, bu o o he me als and me alloids (Bolan e al., 2022). Howe e , o he ac o s may be in ol ed in Sb mobili y, especially clima e condi ions, which de e mine he wea h- e ing a e o hese mine al deposi s (Casio e al., 2007; Bo ˇ cino ´ a Rad- ko a e al., 2020). In o e deposi s, Sb can be eleased by s ibni e dissolu ion unde oxidising condi ions, which p oduces se e al Sb seconda y mine als like ipuhyi e (FeSbO 4 ), sena mon i e (Sb 2 O 3 ), omei e (Ca 2 Sb 2 O 6 OH), ce an i e (Sb 2 O 4 ), ke mesi e (Sb 2 S 2 O) and alen ini e (Sb 2 O 3 ) (Cou - in-Nomade e al., 2012; Rope e al., 2012). Sb mobili y is ela ed o he ou oxida ion Sb s a es in he en i onmen (−III, 0, III, V), and Sb (III) and Sb (V) a e componen s o he mos equen mine al species. In ini ial s ibni e wea he ing s ages, Sb (III) usually o ms alen ini e (Sb III 2 O 3 ), and a mix u e o Sb (III) and Sb (V) o ms s ibiconi e (Sb III (Sb V ) 2 O 6 (OH)) (Szakall e al., 2000; Ashley e al., 2003). Sb (III) is gene ally expec ed o be he majo phase unde anoxic condi ions, wi h Sb (V) unde ae obic condi ions (Filella e al., 2007). I Sb (III) is de ec ed in g oundwa e , Sb (V) is gene ally he main aqueous Sb species in su ace wa e s (Li e al., 2016). The impo an ac o s in ol ed in Sb mobili y a e pH and mic oo ganisms (Loni e al., 2020). Sb in soil is p e e en ially abso bed in Fe oxyhyd oxides (Johns on e al., 2020). The ole o SOM in Sb e en ion is s ill being discussed because bioa ailable Sb e en ion p ocesses ha e been desc ibed o plan s (S eely e al., 2007), as ha e dissolu ion p ocesses a e applying compos o con amina ed soils (Ve beeck e al., 2020). Mu ciego e al. (2007) desc ibed Sb accumula ion pa e ns o h ee sh ub plan species: Cy isus s ia us, Cis us ladani e and Di ichia iscosa. Low Sb concen a ions we e ound in Cy isus s ia us (0.06 mg kg −1 in he Ma i Rosa mine), wi h highe con en s in Cis us ladani e ( eaching 79.3 mg kg −1 in he San An onio mine) and much highe ones in Di ichia iscosa (1136 mg kg −1 in he San An onio mine). Cy isus s ia us p e- sen ed Sb exclude cha ac e is ics, whe eas Di ichia iscosa specimens showed signi ican Sb bioaccumula ion. The p esen wo k aims o in es iga e Sb mobili y unde ou c op condi ions o in abandoned mining exploi a ions o explo e he in lu- ence o soil and/o sedimen geochemis y on he disco e y o Sb de- posi s, and o p edic Sb leachabili y in ese oi s and mining was e. These wo seconda y objec i es will also con ibu e o imp o e me hods o p ospec ing and exploi ing his ype o deposi s. To mee hese ob- jec i es, an o e deposi ype was selec ed in he Cen al Ibe ian a ea, namely he de elic La Balanzona mine (C´ o doba, Spain). 2. Expe imen al sec ion 2.1. Sampling The sampling s a egy included a i s s age o ecognise he main Sb mines in he Guadalmez syncline. I was ollowed by a second phase ha consis ed in he sys ema ic sampling o he soils and local ege a ion in he La Balanzona mine. In he i s sampling phase, ock samples, mining was e ma e ials, soils and sedimen s we e collec ed a he abandoned La Balanzona mining si e and also in nea by ou c ops (dis ance <5 km), ound ollowing ec onic alignmen s. Rock samples we e collec ed om ou c ops (mainly qua zi es) using a geologis ’s hamme and we e bagged wi h an iden i ying code. Mining was e ma e ials we e collec ed om dumps using a plas ic sho el o ine ma e ials and la ge o e blocks we e collec ed by hand. Finally, he soil and sedimen samples we e collec ed using an Ejkelkamp sample capable o collec ing wo samples a di e en dep hs: supe icial (dep h 0–15 cm) and deep (dep h 15–30 cm). A each sampling loca ion, h ee subsamples we e collec ed wi hin a 5-m adius and a composi e sample weighing abou 4 kg was ob ained a e mixing. In he second su eying phase, a sampling ne wo k was designed o collec soil samples a he La Balanzona mine. Samples we e sepa a ed by 120 m, and densi ica ion in he mining ope a ions a ea included a 60- m sepa a ion. Fi y-se en soil samples we e aken a wo dep hs ollowing he me hodology se ou in he p e ious pa ag aph (Fig. 1). Samples o Que cus o undi olia lea es ( he mos ubiqui ous and ep esen a i e ascula plan ) we e collec ed om se e al adul speci- mens ( ully de eloped ees) in an a emp o sample all he space di- ec ions om each ee a an app oxima e heigh o 2 m. Each lea sample was cu om he ee using p uning shea s and was s o ed in a pape en elope labelled wi h he sample code o be anspo ed o he labo a o y. J.M. Esb í e al. Chemosphe e 311 (2023) 137086 3 2.2. Sample p epa a ion Soil sample p epa a ion included d ying a oom empe a u e o 15 days, disagg ega ion, and homogenisa ion p io o sie ing a 2 mm o ob ain wo ep esen a i e aliquo s o 50 g: one o he analysis, which was g ound in an aga e mo a o 2 min un il an app oxima e g ain size o 100 μ m was ob ained; ano he o he physico-chemical de- e mina ions, including eac i i y (pH), sal con en s (elec ic conduc- i i y), soil o ganic ca bon (SOC) and dehyd ogenase ac i i y (DHA), which emained wi h hei o iginal g anulome y. T ee lea es we e ho oughly washed wi h deionised wa e and d ied in an o en a 42 ◦C o 168 h. Subsequen ly, lea es we e sepa a ed om s ems by hand using ni ile glo es and g ound in a scien i ic mill. 2.3. Mine alogical cha ac e isa ion and geochemical analysis Mine alogical cha ac e isa ion was conduc ed using X-Ray Di ac- ion (XRD) conduc ed on he milled samples. Di ac og ams we e ob- ained a IRICA-UCLM wi h B uke D8 Ad ance A25 equipmen du ing a 15-min wo k p og amme. Measu ed pa e ns we e quali a i ely and quan i a i ely analysed wi h he Ma ch .3 and he Fullp o so wa e o Rie eld analyses, espec i ely (Moo e and Reynolds, 1997). Di ac o- g am in e p e a ion ocused on iden i ying he p esence o qua z, Fe oxides and mine al phases con aining Sb. Majo and ace elemen s om he soil and bio a samples we e quan i a i ely de e mined by Ene gy dispe si e X- ay luo escence (EDXRF) using a Panaly ical de ice (Epsilon 2 model). Each sample was analysed in duplica e du ing a 24-min un o pe o m ou ene gy passes o he selec ed g oups o elemen s. The quali y con ol consis ed in analysing bo h duplica es and ce i ied e e ence ma e ials: NIST 2710a o soils and BCR62 o lea es. To al Hg was de e mined by a omic abso p ion spec ome y (AAS) wi h a Lumex RA-915 M de ice equipped wi h a Py o-915+py olysis uni . Samples we e py olysed a 900 ◦C acco ding o a gaseous Hg a omisa ion me hod, which is d awn by a s eam o ca ie ai a 3 L min −1 o he analy ical cell (Esb í e al., 2021). The quali y con ol included he analysis o he p e iously men ioned ce i ied e e ence ma e ial o he soil and lea samples, wi h a eco e y a e o 99–105% and 92–114%, espec i ely. 2.4. Sb mobili y and enzyma ic ac i i y Dehyd ogenase ac i i y was measu ed ollowing colo ime ic ech- niques using a Bioch om Lib a S60 spec opho ome e (Bioch om, UK) unning a 485 nm and acco ding o he iphenyl e azolium chlo ide (TTC) me hod desc ibed by Casida (1977), as modi ied by Ba ajas (2008) and Mon ejo e al. (2012). A homogenised soil sample (1.5 g) was placed inside a es ube and mixed wi h 1.5 mL o deionised wa e , 0.015 g o CaCO 3 and 0.250 mL o TTC (3% /w) o be o exed (2 min) and incuba ed (Memme In 30) a 37 ◦C o 24 h. A e wa ds, samples we e o exed using me hanol as an ex ac an agen and ubes we e cen i uged (O oal esa, Unicen 21) a 4000 pm o 10 min. The Fig. 1. Sampling g id in he La Balanzona mine. A) Mine si e loca ion; B) O hopho og aphy o he mine si e wi h ele a ion lines (10 m spacing); C) Geological ske ch map. J.M. Esb í e al. Chemosphe e 311 (2023) 137086 4 supe na an was analysed in a UV– isible spec opho ome e a 485 nm (Gonzalez-Valoys e al., 2021). Da a we e exp essed as μ g TPF g soil −1 day −1 . To s udy Sb leachabili y and bioa ailabili y, modi ied BCR sequen- ial ex ac ion was ca ied ou . This sequen ial ex ac ion p ocedu e (SEP) consis ed in h ee successi e ex ac ions om which h ee ex ac s and he esidual ac ion we e ob ained. The me hodology was based on he BCR me hod (Que au ille e al., 1997), adap ed o a 4-s ep scheme as epo ed by, o ins ance, Sahuquillo e al. (1999) and Delgado e al. (2011). B ie ly, he di e en SEP s eps allowed ou ac ions o be di e en ia ed: he i s ac ion (F1), ex ac ed by a solu ion o 0.11 M ace ic acid, eleases he species ha a e soluble in wa e , easily leached by weak acids and associa ed wi h soluble ca bona es; he second ac- ion (F2), ex ac ed by 0.5 M hyd oxylamine hyd ochlo ide (pH 1.5 wi h 2 M ni ic acid), consis s o easily educible species associa ed wi h Fe and Mn oxy-hyd oxides; he hi d ac ion (F3) includes diges ion by 8.8 M hyd ogen pe oxide (se e al hou s a 85 ◦C) and a la e ex ac ion wi h 1.0 M ammonium ace a e (pH 2.0 wi h concen a ed acid ni ic), and comp ises easily oxidisable species, mainly associa ed wi h o ganic ma e and sulphide mine als. The esidual ac ion was de e mined by making a calcula ion be ween he di e ence o pseudo- o als and mobile ac ions. BCR 701 ce i ied e e ence ma e ial was used o e alua e Pb eco e y (be ween 95 and 98%). As Sb is no ce i ica ed in his e e - ence ma e ial, i s eco e y could no be e alua ed. Samples we e also subjec ed o mic owa e-assis ed acid diges ion wi h aqua egia acco ding o EPA me hod 3051A (USEPA, 2007) o analyse acid-ex ac able ac ion concen a ions (Melaku e al., 2005; Higue as e al., 2017). A e il e ing wi h Wha man il e s (8 μ m), he analysis o he o al Sb and Pb ac ions was pe o med by High-Resolu ion A omic Abso p ion Spec ome y wi h Analy ic Jenna Con AA-800D equipmen . To quan i y Sb, A omic Fluo escence Spec- oscopy by Hyd ide Gene a ion (AFS-HG) was applied using a PSAna- ly ical, Millennium Excalibu model wi h 0.1 μ L −1 sensi i i y o he explo ed concen a ion ange. Ce i ied e e ence ma e ial NIST 2710A was also diges ed and analysed in iplica e, wi h 92% and 95% eco e y o Pb and Sb, espec i ely. Long- e m (2 mon hs) leaching expe imen s we e pe o med wi h h ee soil samples. They p esen ed: high (BA 001; 20,260 mg kg −1 ), medium (BA 002; 17,352 mg kg −1 ) and low (BA 003; 3377 mg kg −1 ) Sb concen a ions. Slu ies we e p epa ed wi h 20 g o d y soil and 200 mL o mine al wa e (composi ion close o ainwa e , Mon Roucous wa e , pH =6.38, elec ical conduc i i y =160 μ S cm −1 , Cl- =56 μ M, NO 3 − = 24 μ M, SO 4 2− =16 μ M, Na + =109 μ M, K + =7.7 μ M, Ca 2+ =25 μ M, Mg 2+ =21 μ M). Ae obic incuba ions we e pe o med in 500 mL e len- meye lasks sealed wi h co on s oppe s. Anae obic incuba ions we e ca ied ou in 500 mL Sho bo les sealed wi h ubbe s oppe s and illed wi h N 2 85% H 2 15% as a gas phase (1 a m abo e ambien p essu e). Sampling e en s we e un once weekly o he i s mon h, and hen a he end o incuba ion (day 64). A e pH measu emen s, 5 mL samples we e il a ed (0.45 μ m), acidi ied wi h concen a ed HNO 3 and hen analysed by o en SAA (Va ian) o he o al Sb de e mina ions. 3. Resul s and discussion 3.1. Rock and soil samples cha ac e isa ion Main mine al phases o he a ea has been iden i ied on ock samples (qua zi e) by XRD as s ibni e (Sb 2 S 3 ), wi h bindehimi e (Pb 2 Sb 2 O 6 (O, OH)) and s ibiconi e (Sb 3+ (Sb 5+ ) 2 O 6 (OH)) as he main oxidised phases. The esul s o he mul ielemen al analysis pe o med wi h he soil samples showed ha Si, Al, Fe, Ti, K, P and Ca we e he majo elemen s in dec easing o de o concen a ion, oge he wi h Mn, Z , Sb, Co, Pb, Ba, V, C , Zn, Ni, Rb, Sn and S as he ace elemen s in dec easing o de o concen a ion (abo e 50 mg kg −1 ). Cu, Y, Yb, As, Nb, Ga, Cs, Mo, Th, B , Pd and Re we e quan i ied below 50 mg kg −1 (Table S1). Que cus lea es showed a mo e educed dis ibu ion o majo elemen s (Mn >Cl >Eu >Zn >Sn) han soils, wi h he ollowing mos impo an ace elemen s in dec easing o de o concen a ion: Ni >B >S >Ce >Rb > Sb >Z >Pb (Table S1). Wi h an a e age SiO 2 con en close o 50%, he La Balanzona a ea soils can be de ined as siliceous, wi h high Fe 2 O 3 con en s and Sb and Pb as he mos impo an ace elemen s. These wo elemen s appea ed in he a ea a highe concen a ions, while he dis ibu ion o he da a in a p obabili y plo (Fig. S1) showed ha Sb had a backg ound popula ion a e y low concen a ions, ano he ansi ion popula ion be ween 23.4 mg kg −1 and 524.8 mg kg −1 , and a las anomalous popula ion abo e 524.8 mg kg −1 . This dis ibu ion is consis en wi h he sampling design being so close o he mine alisa ion and mining a ea, and wi h only a ew backg ound alues among he analysed da a. The o he ace elemen ob ained a app eciable concen a ions was Pb, which showed a di e en dis ibu ion in wo popula ions: one wi h a b oade back- g ound (below 380.2 mg kg −1 ) and ano he anomalous one abo e 380.2 mg kg −1 . These di e ences be ween da a popula ions imply ha , al hough hese wo elemen s appea ed in he a ea, he e had o be an addi ional sou ce o anomalous Pb alues he e o explain hese di e - ences, o he Sb and Pb p ima y mine alisa ions we e no syngene ic. The spa ial dis ibu ion o hese wo elemen s also p esen ed di e en dis ibu ion pa e ns (Fig. 2). The a e age pH alue o soils was 6.0 wi h alues close o neu ali y. EC alues we e a ound 38 μ S cm −1 , which implies qui e low sal con en alues. SOC con en s we e 4% on a e age, which a e low, bu no pa icula ly a e alues o poo de eloping soils o sca ce ag icul u al use. None o hese alues showed signi ican di e ences be ween he supe icial and deep samples (Table S2) which, acco ding o hese a - iables, implies low deg ees o he modi ica ion o soil cha ac e is ics by mining ac i i y. 3.2. To al and a ailable Sb and Pb concen a ions and hei spa ial dis ibu ion The o al Sb concen a ion in he mining a ea was a ound 62- old highe han he lowes concen a ion ob ained in he ag icul u al soils loca ed a om he mine (1175.2 mg kg −1 s. 19.4 mg kg −1 ). The e e ence Sb alue o he Cas illa-La Mancha (Spain) soils was 2.76 mg kg −1 (Jim´ enez Balles a e al., 2010), which was below he minimum o al Sb alue in he s udied samples. The e o e, he en i e a ea could be conside ed o be Sb-en iched, since he low Sb con en each 7 imes his backg ound alue. Locally, he e e ence alue mus be highe in he Palaeozoic ma e ials o he Guadalmez syncline han in he e e ence alues o he en i e Cas illa-La Mancha egion. The mos ecen da a indica es a o al Sb alue o 9.1 mg kg −1 in syncline soils (Ri e a-Ju ado e al., 2021), which was a ound 2- old lowe compa ed o he minimum concen a ion eco ded a La Balanzona (19.4 mg kg −1 ). In his wo k, we conside ed a local geochemical backg ound Sb le el a concen a ions below 23.4 mg kg −1 , which implies clea Sb composi ional anomaly in he wo king a ea, p obably p oduced by he p esence o he Sb mine al masses he e. Mining ma e ials indica ed ex eme Sb concen a ions o a ound 20,000 mg kg −1 (Ba aglia-B une e al., 2021). These alues a e simila o he highes alues published in mining a eas (Wang e al., 2010). The dis ibu ion o he main ace elemen s (Sb, Pb, C , Ni) e ealed h ee di e en ia ed zones in he s udy a ea: (i) a cen al zone wi h high Sb alues in luenced by he p esence o o e deposi s and mining wo k; (ii) a second a ea loca ed SW and domina ed by ma ic elemen s linked wi h he ou c op o a mass o diabases o dole i es; (iii) a hi d zone occupied by ag icul u al soils wi h Sb alues below he local geochem- ical backg ound o belonging o he ansi ion popula ion da a in he mining dispe sion a ea o in luence (Fig. 2). The cen al a ea ex ension is con olled by opog aphy due o he loca ion o he o e mass in he highes pa o he qua zi e elie . Al hough Sb dis ibu ion is a ou ed by slopes o 11–32%, he a ea o in luence showing concen a ions >120 mg kg −1 is e y na ow, wi h abou 450 m in he di ec ion o he J.M. Esb í e al. Chemosphe e 311 (2023) 137086 5 Fig. 2. Dispe sion a ea a ound he La Balanzona mine o he main moni o ed ace hea y me als: Sb, Pb, C and Ni. In e pola ion me hod: In e se Dis ance Weigh ing. See Fig. 1 o geological ea u es. Fig. 3. BCR ac iona ion o Sb (a) and Pb (b) and long- e m soils in leaching es s and e olu ion o he dissol ed Sb concen a ion in ae obic (c) and anae obic condi ion (d). J.M. Esb í e al. Chemosphe e 311 (2023) 137086 6 qua zi e s a a and 500 m wide in he pe pendicula di ec ion owa ds bo h sides o he elie . The ex ension o he a eas espec i ely con amina ed by Sb and Pb signi ican ly di e s. The Pb con amina ion a ea appea s o ex end mo e owa ds he W and SSW di ec ions han he Sb a ea, pe haps due o di e ences in Sb–Pb o e deposi s emplacemen o due o di e ences in mobili y pa e ns o hese wo po en ially oxic elemen s. This inding sugges s ha Pb could be mo e mobile han Sb. The second a ea has a diabase ou c op ex ension because o he la opog aphy and wi hou an app eciable slope o a ou physical dispe sion. The highes C and Ni concen a ions we e 67–108 mg kg −1 and 87–149 mg kg −1 , espec i ely, which a e much highe han he e e ence alues o Cas illa-La Mancha o 56.5 and 20.8 mg kg −1 , espec i ely (Jim´ enez Balles a e al., 2010). The Sb concen a ion in he hi d a ea was below 120 mg kg −1 wi h a coinciden al ex ension o ag icul u al soils. These soils p esen anoma- lous Cl con en s, pe haps o an h opic o igin, and a e mainly om he po ash e ilise s ex ac ed om na u al deposi s (Susa la e al., 1999) and/o he manu e o igina ing om in ensi e li es ock ac i i ies (Wan e al., 2018). BCR sequen ial ex ac ion di e en ia ed ou ac ions wi h g aded mobili y. The i s ac ion (F1) was ich in species soluble in wa e , and easily leached by weak acids and associa ed wi h soluble ca bona es. The second (F2) consis ed o easily educible species associa ed wi h Fe and Mn oxyhyd oxides. The hi d ac ion (F3) included he easily oxi- disable species, mainly associa ed wi h o ganic ma e and sulphide mine als. The ou h (F4) con ained hose species ex ac ed om sili- ca es o sulphides wi h e y low solubili y. The BCR ex ac ion da a e ealed ha he esidual ac ion was he mos dominan o Sb, wi h 99.9% alues o all he samples excep o wo, o which he o he ac ions eached p opo ions o 0.15 and 0.05 (Fig. 3a). This means ha he amoun o Sb in mobile o a ailable ac ions was negligible. This is consis en wi h p e ious da a indica ing 97.6–99.6% Sb in esidual ac ions (´ Al a ez-Ayuso e al., 2012 and 2022) in ag icul u al soils pollu ed by mining ac i i ies in he Zamo a p o ince (Spain) and in San An onio mine, espec i ely. Pe land use ype, only he e y mino Sb ac ions F1, F2 and F3 we e quan i ied in mining soils, mainly due o he de ec ion limi o A omic Abso p ion analysis ( o al Sb concen a- ions in mining soils we e much highe han in o he s). Howe e , Pb beha iou seemed di e en wi h a esidual ac ion ha o en emained dominan (40–90%), bu wi h la ge Pb ac ions bound o Fe and Mn oxides (F2) and a e y low p opo ion bound o o ganic ma e /sul- phides (F3) (Fig. 3b). Some samples showed e y small Pb p opo ions (<5%) easily leached by weak acids and associa ed wi h soluble ca - bona es (F1). Pe land use ype, he dis ibu ion pa e n o he Pb ac- ions seemed mo e signi ican , wi h e y cons an and la ge Pb ac ions bound o Fe–Mn oxyhyd oxides (F3) in diabase soils, and majo i y e- sidual ac ions in mine soils. Ag icul u al soils p esen ed e y wide a iabili y, wi h simila esidual ac ions (RF) o hose ound in diabase soils and a a iable Pb p opo ion bound o Fe–Mn oxyhyd oxides. The long- e m leaching es s esul ed in g ea e Sb mobili y unde ae obic s. anae obic condi ions (Fig. 3c and d). A e 60 leaching days, dissol ed Sb ep esen ed be ween 0.1% and 0.3% o he o al soil Sb o he anae obic condi ions, and be ween 0.6% and 1% o he o al soil Sb o he ae obic condi ions. 3.3. Enzyma ic ac i i y (DHA) Dehyd ogenase ac i i y (DHA) was s udied in a selec ion o samples ep esen ing di e en soil ypes: diabase, ag icul u al and mining. The esul s indica ed ha he DHA alues ell wi hin a na ow ange (59.4–181.2 μ g TPF g −1 d −1 ) and gene ally ook low alues. They we e much lowe han he DHA alues desc ibed by Campos e al. (2018) o Hg-con amina ed soils in Almadenejos (484 ±269), bu simila o hose in Hinojosa e al. (2004) o soils con amina ed by hea y me als due o he Aznalcolla spill (70 μ g TPF g −1 d −1 ) (Fig. S2a), and highe han he DHA alues a he San Quin ín si e, whe e a Pb–Zn mine ob ained 70.98 ±50.92 o he e e ence soils nea he mine, and 2.85–2.52 in dumps and ailings, espec i ely (Gallego e al., 2021). A clea g ada ion o dec easing DHA alues was obse ed o he soils on diabase o ag i- cul u al soils and mine soils ( he loca ion o hese soils is seen in Fig. 2). We hink ha hese DHA di e ences in he soils on diabase can be explained by composi ional di e ences o being soils unde simila physiog aphical and use condi ions as he ag icul u al soils o he No h and Sou h o he qua zi e idge whe e he s ibni e deposi is loca ed. A s a is ically signi ican ela ion was ound be ween SOM and DHA ( 2 = 0.74) (Fig. S2b). I is unclea whe he he low DHA alues in mine soils we e due o low SOM con en s because hese soils de elop in an ele a ed a ea wi h poo edaphic de elopmen and spa se o es y, o due o he nega i e e ec o Sb and/o associa ed elemen s like Pb on soil mic oo ganisms. 3.4. Que cus lea es In he analysed Q. o undi olia lea es, he iden i ied majo elemen s (>1000 mg kg -1 ) included Ca, K and Si a a e age concen a ions o 6,722, 4469 and 1363 mg kg -1 , espec i ely. A second g oup o elemen s eached signi ican concen a ions: Al (942 mg kg -1 ), P (741 mg kg -1 ), Mn (662 mg kg -1 ), Fe (190 mg kg -1 ) and Cl (113 mg kg -1 ). Ti, Zn, Sn, B , Cu, S , Ni, Sb, Rb, Z and Pb we e also iden i ied a ace le els. The Sb concen a ion ange was e y na ow (1.45–3.85 mg kg -1 ) wi h sligh a iabili y. The only elemen s o he plan bioconcen a es wi h highe alues we e Ca, S and Mn and, o a lesse ex en , B . The Sb da a pop- ula ion showed an anomaly h eshold a 2.51 mg kg -1 wi h a e y ex ensi e anomalous da a popula ion in he s udy a ea (Fig. 4). I can be s a ed ha all he quan i ied elemen s had bioaccumula ed in lea es by oo up ake and ansloca ion o he ae ial pa o by di ec up ake om he a mosphe e in he o m o gas (especially o Hg, as shown by o he s udies; see Naha o e al., 2020 and e e ences wi hin). The Bioaccumula ion ac o s (BAFs) showed e y ew bio- concen a ed elemen s (BAF >1). On a e age, only B , Mn, Ca and S, plus some da a abou Eu and Cu, p esen ed BAF >1 (Fig. 4). The BAFs o he elemen s p esen in mine alisa ion (Sb and Pb) had e y low alues in he o de o 0.0002–0.1520 o Sb and 0.0000–0.0168 o Pb. These alues indica ed e y poo up ake o bo h hese elemen s and a e simila o hose epo ed o he Bombi a mine, a Pb–Zn–Cu mine in Spain (0.006 ±0.006), bu lowe han hose o o he nea by Pb–Zn mines like San Quin ín (0.048 ±0.060) and La Romanilla (0.062 ± 0.071) (Higue as e al., 2017). An oniadis e al. (2022) desc ibed a low abso p ion capaci y o Sb in oli e ees. Mu ciego e al. (2007) shows highe BAF le els o Di ichia iscosa (a sh ub plan species) in he San An onio mine. The dis ibu ion o hese BAFs in he s udy a ea e ealed ha only Cu bioaccumula ed in he cen al qua zi e zone whe e min- e alisa ion was loca ed, and o a lesse ex en Mn, while he o he ele- men s had highe BAF alues in ag icul u al soils o on diabase, wi h B clea ly illus a ing his end (Fig. 4). 3.5. Discussion O e all, he ob ained esul s desc ibe a ba ely ex ended s udy a ea (0.6 km 2 ), in which s ibni e (Sb 2 S 3 ) mine alisa ion is loca ed on he cen al qua zi e massi in a opog aphically ele a ed posi ion. Gi en he ele a ed physiog aphic posi ion o he mine alised body, physical and chemical dispe sions a e a ou ed, bu he dispe sion halo o high Sb concen a ions does no exceed a adio o 120 m a ound mining wo ks. The o al Sb dis ibu ion in he a ea sugges s his elemen ’s low mobili y. This was con i med by he BCR ex ac ion ca ied ou o Sb and Pb, which o e whelmingly (>99.9%) indica ed Sb p opo ions in he e- sidual phase, p obably linked wi h sulphides. Pb mobili y was g ea e , wi h a sum o mobile ac ions (F1 +F2 +F3) wi hin he 20–50% ange, bu no acidi y was gene a ed in he a ea du ing and a e mining exploi a ion. The e ec o Sb and Pb on he enzyma ic ac i i y o soil J.M. Esb í e al. Chemosphe e 311 (2023) 137086 7 mic oo ganisms was no signi ican . O ganic ma e was a mo e in lu- en ial ac o on he DHA alues han he highe o lowe Sb and Pb concen a ions in soil. Diqua o e al. (2020) also ound e y low DHA alues in soils doped wi h Sb (V), and hei es ima ed p obable cause was he impo ance o Sb concen a ions in educing soil enzyma ic ac i i y by in e ac ing wi h he enzyme-subs a e complex, enzyme dena u a ion o in e ac ing wi h p o ein-ac i e g oups (Nannipie i e al., 2003). In ou case, he low SOM alues seemed o ac as a limi ing ac o , which could be impo an gi en hese low DHA alues. Finally, he soil-plan ans e was no high o Sb o Pb, al hough he bio- concen a ion o o he elemen s (i.e. Mn) was obse ed in Q. o undi olia lea es. In his oxida ion scena io o a p ac ically monome allic deposi , he BCR sequence ex ac ion esul s e ealed an ex emely low p opo ion o Sb-soluble phases (F1 +F2 +F3) compa ed o ha o Pb. These esul s sugges an impo an ole o Fe–Mn oxyhyd oxides as immobilise s o Pb unde oxidising condi ions, bu no in con as o Sb as p e iously desc ibed by Belzile e al. (2001). Cappuyns e al. (2021) epo ed e y simila esul s in mining was e and soils in an Sb mine in Vie nam, whe e less han 1% o he o al Sb con en in samples was eleased o wa e du ing sho - e m leaching es s. He e long- e m leaching es s we e pe o med wi h he La Balanzona soils, whose du a ion allowed mic obial p ocesses o occu , and e ealed g ea e Sb mobili y unde oxidising condi ions s. educing condi ions. These esul s ag ee wi h p e ious epo s (Casio e al., 2007; Li e al., 2022), which sugges ha mic obial sulphu and Sb (III) oxidising ac i i ies migh mobilise Sb. Howe e , his mobilisa ion implies a long con ac ime be ween solids and wa e , which is ha dly a compa ible scena io o he clima e and opog aphic condi ions a he La Balanzona si e. In ano he con ex , Okkenhaug e al. (2011) desc ibed high Sb leaching le els a an ac i e mining si e in China con olled by he p esence o Ca [Sb(OH) 6 ] 2 . Howe e , his case is no compa able o he La Balanzona mine condi ions. The he ein desc ibed low Sb mobili y in an oxidising en i onmen , oge he wi h no ela ion linking Sb, Pb and soil enzyma ic ac i i y, cons i u e a amewo k o a ou able condi ions o exploi ing simila deposi s unde compa able en i onmen al condi ions wi hou ha ing o implemen expensi e mining e luen con ol sys ems ha limi he dispe sion o he ex ac ed elemen . Howe e , he use o soil geochem- ical da a o p ospec Sb deposi s is se iously limi ed by his low mobili y. Ne e heless, by using pa h inde elemen s (As, Mn) pa e ns, in which single-elemen Sb pa e ns ailed, could be a way o imp o e he de ec ion o Sb mine alisa ion (Lemi` e e e al., 2020). The dispe sion o he elemen s o an o e deposi depends on ac o s like edox, acid-base o Fig. 4. P obabili y g aph o he Sb concen a ions in he Q. o undi olia lea es om he La Balanzona mine (le ); he bioaccumula ion ac o o some selec ed elemen s ( igh ) and he spa ial dis ibu ion o he BAFs o some selec ed elemen s a he La Balanzona mine (see Fig. 1 o geological ea u es). All alues a e exp essed as mg kg −1 . J.M. Esb í e al. Chemosphe e 311 (2023) 137086 8 hyd olysis p ocesses ha ecycle mine als and hei associa ed elemen s by inco po a ing hem in o soil. The e a e h ee componen s in he seconda y geochemical dispe sion o elemen s: physical, chemical o biogenic. In he Balanzona mine, only physical dispe sion seems o ac because mine alisa ion is loca ed in a opog aphically ele a ed posi ion on ocks ha wi hs and wea he ing and gene a e a moun ainous elie . Chemical dispe sion seems e y limi ed by he low solubili y o Sb compounds, a p edic able ac o p ima y mine als, bu no o oxidised phases. I is necessa y o highligh ha oxidised phases in qua zi e a e sca ce and es ic ed o he ock ac u es in he mos ex e nal zones o qua zi es. Wha do we know abou biogenic dispe sion? The Sb con en s in Q. o undi olia lea es do no o e p omising esul s, wi h e y na ow a iabili y and hei spa ial dis ibu ion is incohe en wi h he p esence o mine alisa ion. In gene al e ms, woody ege a ion o en accumula es mo e Sb han non-woody ege a ion. Species like Picea glauca a e capable o bioaccumula ing Sb in hei oo s (Busby e al., 2021), al hough i seems ha ansloca ion o he ae ial pa is inhibi ed, p obably due o he elemen ’s oxic cha ac e . Gua ino e al. (2021) desc ibed high Sb le els in Olea eu opaea lea es whose o igin is ai bo ne pa icles. So woody ee lea es a e no expec ed o be used o p o- spec ing Sb o e deposi s by emo e sensing echnologies (Wang e al., 2018), bu can p o ide aluable da a as biomoni o s du ing mining ope a ions. 4. Conclusions Sb mobili y and ans e we e in es iga ed in an abandoned mine wi h a semi-a id clima e whe e oxida ion p ocesses p edomina e. The main indings a e: - Ve y high o al Sb con en s appea in mining ma e ials (max: 8450 mg kg -1 ), dispe sed in a e y small a ea a ound he o e deposi (<300 m). Pb con en s a e also signi ican and o m pa o he oxidised Sb phases - BCR ex ac ion indica es ex emely low Sb mobili y, suppo ed by a sligh Sb ans e o he lea es o he mos conspicuous plan species in he a ea: Que cus o undi olia ees - The e ec o Sb on soil enzyma ic ac i i y could no be es ablished because soils showed sligh enzyma ic ac i i ies ela ed o poo ly de eloped soils wi h low o ganic ma e con en The La Balanzona mine esul s limi Sb chemical dispe sion unde a semi-a id clima e and wi h absence o acid mine d ainage gene a ion. This con ex es ic s he geochemical explo a ion possibili ies o Sb o e deposi s bu a ou s hei mining exploi a ion by limi ing e luen con- ol measu es. Consen o publish Jos´ e Ma ía Esb í, Resea che , PhD, as esponsible o he manusc ip en i led “E alua ion o an imony a ailabili y in a mining con ex : impac o he en i onmen , and o mine al explo a ion and exploi a- ion”, au ho ed by mysel and Ca melo M. Minang, g adua e; So ía Ri e a, MsC; Me cedes Mad id-Illescas, MsC; E a Ga cía-Nogue o, PhD; Ana Gonzalez-Valois, MsC; Mai e Magu egui, PhD; Hugues Thouin, PhD; Fabienne Ba aglia-B une ; PhD; E ic Gloaguen, PhD and Pablo Le´ on Higue as, PhD. On behal o he es o coau ho s, wi h his documen I wa an ee and sign ha his manusc ip does no con ains any indi idual pe son’s da a in any o m (including any indi idual de ails, images o ideos). -Au ho s con ibu ions Jos´ e Ma ía Esb í (JME), Resea che , PhD, as esponsible o he manusc ip en i led “E alua ion o an imony a ailabili y in a mining con ex : impac o he en i onmen , and o mine al explo a ion and exploi a ion”, au ho ed by mysel and Ca melo M. Minang (CM), g ad- ua e; So ía Ri e a, MsC; Me cedes Mad id-Illescas (MMI), MsC; E a Ga cía-Nogue o (EG), PhD; Ana Gonzalez-Valois (AG), MsC; Mai e Magu egui (MM), PhD; Hugues Thouin (HT), PhD; Fabienne Ba aglia- B une (FB); PhD; E ic Gloaguen (EG), PhD and Pablo Le´ on Higue as (PH), PhD. On behal o he es o coau ho s, wi h his documen I wa an ee and sign ha he con ibu ions done by he lis ed au ho s ha e been he ollowing: - Concep ualiza ion JME, FBB, MM, EG, PH, - Da a cu a ion JME, FB, HT, PH - Fo mal analysis JME, HT - Funding acquisi ion EG and PH - In es iga ion JME, CM, SR, HT, FB, PH - Me hodology JME, CM, SR, MMI, EG, AG, HT, FB - P ojec adminis a ion EG and PH - Resou ces JME - So wa e JME, SR, HT, - Supe ision JME, EG, FB, MM, PH, - Valida ion JME, HT, PH - Visualiza ion JME, PH - Roles/W i ing – o iginal d a JME, MM, FB, PH - W i ing – e iew & edi ing JME, MM, FB, EG, PH Funding in o ma ion This s udy is a con ibu ion o he AUREOLE P ojec , unded by he ERA-MIN2 Eu opean P ojec h ough he Spanish PCI2019-103779 and F ench ANR-19-MIN2-0002-01 g an ag eemen s. Decla a ion o compe ing in e es The au ho s decla e ha hey ha e no known compe ing inancial in e es s o pe sonal ela ionships ha could ha e appea ed o in luence he wo k epo ed in his pape . Da a a ailabili y Da a will be made a ailable on eques . Acknowledgemen s We wish o hank Helen Wa bu on o p oo eading he manusc ip , and also he IRICA-UCLM labo a o ies o hei analy ical suppo in he mine alogical de e mina ions. 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.2022.137086. Re e ences ´ Al a ez-Ayuso, E., O ones, V., Mu ciego, A., Ga cía-S´ anchez, A., Regina, I.S., 2012. An imony, a senic and lead dis ibu ion in soils and plan s o an ag icul u al a ea impac ed by o me mining ac i i ies. Sci. To al En i on. 439, 35–43. h ps://doi. o g/10.1016/j.sci o en .2012.09.023. ´ Al a ez-Ayuso, E., Mu ciego, A., Rod íguez, M.A., Fe n´ andez-Pozo, L., Cabezas, J., Na anjo-G´ omez, J.M., Mosse -Ruck, R., 2022. An imony dis ibu ion and mobili y in di e en ypes o was e de i ed om he exploi a ion o s ibni e o e deposi s. Sci. To al En i on. 816. h ps://doi.o g/10.1016/j.sci o en .2021.151566. 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