scieee Open visual document viewer

Traditional agricultural practices enable sustainable remediation of highly polluted soils in Southern Spain for cultivation of food crops

Madejón, P.; Barba Brioso, Cinta; Lepp, N. W.; Fernández-Caliani, J. C.

Abstract

This study relates elemental content of a range of edible crops grown in soils severely polluted by metals and metalloids as affected by traditional smallholder management practices. Five agricultural plots close to a sulfidic waste dump were monitored. Soil analysis demonstrated elevated concentrations of As, Cu, Pb and Zn that were greatly in excess of maximum statutory limits for agricultural soils in the studied region. The main vegetables (lettuce, chard, onion, potatoes) and lemon, together with their associated soils, were measured for elemental content. Extractable soil element concentrations were very low. There were differences in elemental accumulation between crops, but none exceeded statutory concentrations in edible parts. Soil-plant transfer factors were uniformly low for all elements and crops. It is concluded that traditional soil management practices (annual liming and application of animal manures) have created conditions for sustainable long-term safety use, with potential for multiple end-use, of these highly polluted soils.

Full text

1 T adi ional ag icul u al p ac ices enable sus ainable emedia ion o highly 1 pollu ed soils in Sou he n Spain o cul i a ion o ood c ops. 2 3 Madejón, P.1*, Ba ba-B ioso, C. 2 Lepp, N.W.3, and Fe nández-Caliani J.C.4 4 5 1 Ins i u o de Recu sos Na u ales y Ag obiología de Se illa (IRNAS-CSIC), A . Reina 6 Me cedes 10, 41012 Se illa, Spain. [email p o ec ed] 7 8 2 Depa amen o de C is alog a ía, Mine alogía y Química Ag ícola. Facul ad de 9 Química. Uni e sidad de Se illa. C/ P o eso Ga cía González s/n, 41012 Se illa, 10 Spain. cin a.ba [email protected] 11 12 3 35, Vic o ia Road, Fo mby, Li e pool L37 7DH, UK. [email p o ec ed] 13 14 4 Depa amen o de Geología, Facul ad de Ciencias Expe imen ales. Uni e sidad de 15 Huel a, 21071, Huel a, Spain. [email p o ec ed] 16 17 *Co esponding au ho : [email p o ec ed]. Telephone numbe 0034 954624711 18 FAX: 0034 9544624002 19 20 *Manusc ip Click he e o iew linked Re e ences 2 Abs ac 21 This s udy ela es elemen al con en o a ange o edible c ops g own in soils se e ely 22 pollu ed by me als and me alloids as a ec ed by adi ional smallholde managemen 23 p ac ices. Fi e ag icul u al plo s close o a sul idic was e dump we e moni o ed. Soil 24 analysis demons a ed ele a ed concen a ions o As, Cu, Pb and Zn ha we e g ea ly in 25 excess o maximum s a u o y limi s o ag icul u al soils in his egion. The main 26 ege ables (le uce, cha d, onion, po a oes) and lemon, oge he wi h hei associa ed 27 soils, we e measu ed o elemen al con en . Ex ac able soil elemen concen a ions 28 we e e y low. The e we e di e ences in elemen al accumula ion be ween c ops, bu 29 none exceeded s a u o y concen a ions in edible pa s. Soil-plan ans e ac o s we e 30 uni o mly low o all elemen s and c ops. I is concluded ha adi ional soil 31 managemen p ac ices (annual liming and applica ion o animal manu es) ha e c ea ed 32 condi ions o sus ainable long- e m sa e y use, wi h po en ial o mul iple end-use, o 33 hese highly pollu ed soils 34 35 Keywo ds: T ace elemen s, edible plan s, soil pollu ion, Tha sis mines, Spain 36 37 1. In oduc ion 38 Plan s a e he i s compa men o he e es ial ood chain. Due o hei 39 capaci y o accumula e po en ially oxic ace elemen s, hey can ep esen a h ea o 40 animals and humans ha consume hem (In awongse and Dean, 2006; Liu e al., 2006). 41 The isk ha ace elemen s pose o he en i onmen and human heal h is a 42 unc ion o hei specia ion in soils and subsequen accumula ion and pa i ioning wi hin 43 plan s (Kaba a-Pendias, 2004). The solubili y o ace elemen s a ies widely because 44 many ac o s in luence hei concen a ion in he soil solu ion: edaphic cha ac e is ics 45 (pH, ex u e and o ganic ma e con en ), clima ic condi ions, and ag onomic 46 3 managemen (Alloway, 1995, Chojnacka e al., 2005; Tokalioğlu and Ka al 2006). The 47 a e o me al ansloca ion om he soil o edible and ha es ed pa s o cul i a ed plan s 48 depends, in addi ion, on ege a ion ype and me al in ol ed, besides he soil and 49 clima ic ac o s (Alloway, 1995; McLaughlin e al., 1999). 50 Chaney (1980) in oduced he concep o he „soil-plan ba ie ‟ and classi ied 51 ace elemen s in ou g oups wi h espec o hei po en ial o ood chain ans e : 52 G oup 1 (Ag, C , Sn, Ti, Y and Z ) wi h low isk o human heal h because hey a e no 53 usually aken up by plan s due o hei low solubili y in soil. G oup 2 (As, Hg and Pb) 54 which a e s ongly so bed by soil colloids, o may be immobilized in plan oo s wi h 55 e y limi ed ans e o edible shoo issues, and he e o e pose ma ginal isks. G oup 3 56 (B, Cu, Mn, Mo, Ni and Zn) a e phy o oxic a concen a ions ha pose li le isk, 57 al hough „ he soil-plan ba ie ‟ p o ec s he ood chain om hese elemen s. G oup 4 58 consis s o Cd, Co, Mo and Se, which pose human o animal heal h isks a plan issue 59 concen a ions ha a e no phy o oxic. 60 Soil pollu ion wi h ace elemen s, mainly hose om G oups 2 and 3 desc ibed 61 abo e, ep esen s one o he mos p ominen en i onmen al haza ds om abandoned 62 mine si es in he Ibe ian Py i e Bel (Fe nández-Caliani e al. 2009a, b; Fe nández-63 Caliani and Ba ba-B ioso, 2010). Pas mining and o e p ocessing ac i i ies esul ed in 64 de o es a ion and des uc ion o he na u al ege a ion, ans o ming soils in o ma ginal 65 lands unable o sus ain comme cial ag icul u e. Howe e , adi ional small-scale 66 ag icul u e has pe sis ed on limi ed a eas o a able land adjacen o he mining illages 67 in his egion. 68 The goals o he s udy epo ed he e we e o: 1) de e mine o al concen a ions o ace 69 elemen s in di e en pa s o ui and ege ables, and in he soil in which hey g ew, 70 ocusing on hei edible pa s; 2) assess he mobile and po en ially-mobile ac ions o 71 4 he soil ace elemen pools and he soil-plan ans e ac o s o he c ops g own he e; 72 and 3) e alua e he long- e m sus ainabili y o he adi ional soil managemen p ac ices 73 used in his egion o ma ginal o soils o low e ili y in ela ion o soil-plan ans e 74 o ino ganic pollu an s. 75 76 2. Si e desc ip ion 77 The Tha sis Mines (UTM coo dina es: X= 666,746 and Y= 4,162,779) a e 78 loca ed in one o he oldes and bes -known mining dis ic s in he Ibe ian Py i e Bel 79 (Sou h-Wes Spain), wi h a leng hy his o y o exploi a ion ha da es back o p e-Roman 80 imes (Checkland, 1967). The mos in ensi e pe iod o mining ope a ions occu ed 81 be ween he end o he 19 h cen u y and he middle o he 20 h cen u y, when py i e was 82 he main aw ma e ial used o sulphu ic acid manu ac u e by he Eu opean chemical 83 indus y. Pas mining and smel ing ac i i ies we e ca ied ou wi hou conce n o e en 84 awa eness o hei nega i e en i onmen al impac , esul ing a p esen -day landscape o 85 la ge opencas mines, was e ock piles and ailings dams ha encompass an a ea o 86 abou 350 ha (Figu e 1a). 87 Du ing mining and a e closu e, pollu an s ha e been ans e ed om he mine 88 was es o nea by soils by acid mine d ainage and/o a mosphe ic deposi ion o wind-89 blown dus . Soils and ege a ion show ele a ed ace elemen concen a ions up o 2-3 90 km away om he mining a ea (Chopin and Alloway, 2007a,b). The e a e also a numbe 91 o small holdings, none o which exceeds one hec a e in ex en , loca ed in he 92 immedia e icini y o he mine was e dumps, all a isk o con amina ion wi h me als. 93 Fi e ag icul u al plo s, close o he sul idic was e dumps o he “Filón No e” 94 open pi (Figu e 1 b, c) we e selec ed o his s udy. The allu ial soils o hese plo s a e 95 de o ed o adi ional ho icul u e, despi e he ac ha hey a e occasionally looded by 96 5 acid wa e s emana ing om nea by was e dumps and su ace mine wo kings. To co ec 97 soil acidi y, a me s ou inely amend soils wi h lime, oge he wi h egula addi ions o 98 animal manu e. These p ac ices ha e aken place o a leas 25 yea s in he in es iga ed 99 plo s, a ac es ablished by in e iews wi h each plo owne . The main c ops cul i a ed 100 by he smallholde s a e ege ables, ypically le uce (Lac uca sa i a L.), cha d (Be a 101 ulga is (L.) a . cicla K. Koch), onion (Allium is ulosum L.) and po a o (Solanum 102 ube osum L.). Some plo s also con ain ma u e Lemon ees (Ci us limon L. B um). 103 104 3. Me hodology 105 3.1 Ma e ials and me hods 106 A sui e o ege able samples, comp ising lea , bulb, ube and ui c ops, along 107 wi h hei associa ed soils we e andomly collec ed om each plo in Ap il 2008 a he 108 indica ed s age o ma u i y (Table 1). 109 Composi e soil samples we e aken o a dep h o 20 cm (Ap ho izon) om each 110 plo whe e sampled ege ables we e g owing. These we e anspo ed o he labo a o y 111 in polye hylene bags, ai d ied, disagg ega ed wi h a wooden olle , passed h ough a 2 112 mm s ainless s eel sie e, and homogenized p io o analysis. The pa icle-size 113 dis ibu ion was de e mined by a combina ion o sie ing and lase di ac ion (Mal e n 114 Mas e Size ins umen ) me hods. The pH, Eh and elec ical conduc i i y alues we e 115 measu ed wi h calib a ed glass elec odes in a 1:2.5 (w/ ) soil o wa e suspension. The 116 con en o o al o ganic ma e was de e mined by oxida ion wi h po assium dich oma e 117 in a s ong acid medium (Walkley-Black me hod), as desc ibed by Pansu and 118 Gau hey ou (2006), and he ca bona e con en was measu ed by he Be na d calcime y 119 me hod. 120 Soil mine alogy was in es iga ed in bo h bulk samples (<2 mm) and clay-size 121 6 ac ions (<2 µm) by powde X- ay di ac ion (XRD) on a B uke -AXS D8-Ad ance 122 di ac ome e , using monoch oma ic CuK adia ion a 40 kV and 30 mA. The ine 123 ac ion was sepa a ed by sedimen a ion and analyzed in o ien ed agg ega es o ai -124 d ied, e hylene glycol- ea ed and he mal- ea ed samples o clay mine al 125 iden i ica ion. Selec ed soil samples we e examined by scanning elec on mic oscopy 126 using a JEOL JSM-5410 ins umen coupled wi h an ene gy dispe si e X- ay 127 spec ome e (SEM-EDS). 128 To al concen a ions o po en ially oxic ace elemen s (As, Cu, Pb and Zn) in 129 soil samples we e de e mined by induc i ely coupled plasma-op ical emission 130 spec ome y (ICP-OES), (Jobin Y on ULTIMA 2), a e 4-acid (HF-HClO4-HNO3-131 HCl) diges ion o 0.1 g soil sample o en d ied o 24 hou s a 110 °C. Quali y con ol 132 included he use o a me hod eagen blank and se e al ce i ied e e ence ma e ials 133 (SARM-1 and SARM-4 o soil analysis) o check accu acy and p ecision o he 134 analy ical da a ( ela i e s anda d de ia ion below 10%). 135 In o de o de e mine he mos labile me al pools, an aliquo o each soil sample 136 (2 g) was subjec ed o single ex ac ions by shaking o one hou wi h deionised wa e , a 137 mild neu al sal solu ion (0.01 M CaCl2) o a complexing agen (0.05 M EDTA a pH 138 7) a a soil:solu ion a io o 1:10 (w/ ) (e.g. Houba e al. 1996; U e e al., 1996). The 139 i s wo soil ex ac solu ions we e analyzed a e cen i uga ion ( o 10 min a 4500 140 pm) by induc i ely coupled plasma mass spec ome y (ICP-MS), using a Hewle 141 Packa d 4500 ins umen wi h de ec ion limi s o 0.01 µgL-1, whils EDTA-ex ac able 142 me als we e de e mined by ICP-OES. All ace elemen concen a ions we e epo ed on 143 an o en-d y basis. 144 All plan samples (lea es, oo s, bulbs, peel and seeds) we e washed ( o 10 s 145 app oxima ely) wi h a solu ion o phospha e- ee de e gen , hen wi h a 0.1 N HCl 146 7 solu ion and inally wi h dis illed wa e . Plan ma e ial was o en-d ied a 70ºC, g ound 147 and passed h ough a 500 µm s ainless s eel sie e. A 0.5 g aliquo was diges ed by we 148 oxida ion wi h concen a ed HNO3 unde p essu e in a mic owa e diges e (Jones and 149 Case, 1990). Th ee consecu i e s eps (5 min. each) o powe (250 W, 450 W and 600 150 W) we e applied, and hen hese ex ac s we e dilu ed o 50 ml olume wi h deoinised 151 wa e o 18 mΩ quali y. The analysis o ace me als in he diges s was pe o med by 152 ICP-MS. The accu acy and p ecision o he analy ical me hod we e assessed by ou ine 153 analyses o he e e ence sample CRM-279 (Sea le uce) and CS DC73350 (popla 154 lea es). Reco e y a es o e e ence plan samples we e be ween 90 and 110%. 155 156 3.2 T ea men o analy ical da a 157 Quan i a i e assessmen o o e all soil pollu ion was based on he pollu ion load 158 index (PLI), as de ined by Tomlinson e al., (1980), aking in o conside a ion he 159 concen a ion ac o (CF), which is he a io be ween each ace elemen in he soil and 160 i s backg ound alue. The PLI o each soil sample was calcula ed by de i ing he n- h 161 oo o he n ac o s (CF1xCF2xCF3x...CFn). Thus, alues o PLI close o one indica e 162 hea y me al loads nea he backg ound le el, while alues >1 indica e soil pollu ion 163 (Cab e a e al., 1999). 164 In o de o ind ou wha p opo ion o he o al soil me al concen a ion was 165 a ailable and ans e ed o di e en o gans o he ege ables g own by he 166 smallholde s, he ans e coe icien (TC) was calcula ed. This is de ined as he a io o 167 me al concen a ion in he plan , [M]plan , o he o al me al concen a ion in he soil, 168 [M]soil (Ad iano, 2001). 169 TC = [M]plan / [M] soil 170 8 The da a was s a is ically analysed using S a So S a is ica 7.0 o ecognize 171 a iables ends and g oupings. Kolmogo o -Smi no and Shapi o-Wilk‟s no mali y 172 es s we e ca ied ou o all a iables, e using he no mal dis ibu ion o almos all o 173 hem. Because he a iables equi ed a non-pa ame ic analyses, a Spea man co ela ion 174 ma ix (signi icance le el p<0.01) was ob ained, co ela ing o al ace elemen con en s 175 in soils wi h hose measu ed in soil ex ac s and plan s. 176 177 4. Resul s and discussion 178 4.1 Soil cons i uen s and p ope ies 179 The uppe pa o he soil p o ile shows a well-de eloped o ganic ho izon wi h 180 g anula s uc u e and had simila edaphic p ope ies in all he sampled soils (Table 2). 181 The soil is b own (10YR 5/3, 10YR 6/3 d y) in colou and has a sil y loam ex u e wi h 182 <10% o clay-sized pa icles. Some soil samples con ain signi ican amoun s o coa se-183 g ained componen s (g ea e han 2 mm), consis ing o sub-angula li hic agmen s o 184 he e ogeneous was e ocks and slag esidues. 185 The soil had an a e age pH alue o 7.4, and elec ical conduc i i y anged 186 be ween 0.15 and 0.95 mS cm-1, indica ing a low salini y le el in he soil solu ion. The 187 soil appea s o be well d ained and ae a ed spanning a na ow ange o posi i e Eh 188 alues (457-505 mV) ha e lec mode a ely oxidizing condi ions. 189 The soil has a high con en o o al o ganic ma e (8.1-14.9%) and ca bona es 190 (up o 14%) esul ing om he applica ion o o ganic amendmen s and lime o imp o e 191 soil e ili y and o p e en soil acidi y. 192 Soil mine als, iden i ied by XRD, we e composed o phyllosilica es (50-60%), 193 qua z (30-40%), eldspa s (5-10%), calci e (<5%) and dolomi e (<5%). The clay 194 mine al assemblage was domina ed by illi e and kaolini e, wi h mino e miculi e 195 9 and/o poo ly de ined mixed-laye phases. In addi ion, SEM-EDS analysis e ealed he 196 occu ence o amo phous o poo ly c ys alline Fe oxyhyd oxides and a numbe o 197 accesso y mine als, such as ba y e, apa i e and monazi e. 198 199 4.2 To al concen a ions o ace elemen s in soil 200 The sampled soils con ained high le els o As, Cu, Pb and Zn (Table 3), 201 al hough o al concen a ions a ied, depending on he loca ion o he sampling plo 202 (Figu e 1). The highes concen a ions o ace elemen s (up o 621 mg kg-1 As, 752 mg 203 kg-1 Cu, 2395 mg kg-1 Pb, and 593 mg kg-1 Zn) we e ound in plo s 4 and 5, loca ed in 204 he immedia e icini y o he mine was es. Simila o al soil elemen concen a ions 205 ha e been epo ed o cul i a ed soils adjacen o o he abandoned mine si es in he 206 Ibe ian Py i e Bel (López e al., 2008; Fe nández-Caliani e al. 2009a). 207 The o al concen a ions o As, Cu, Pb and Zn in hese soils a e be ween one and 208 wo o de s o magni ude abo e bo h he egional geochemical baseline (Galán e al. 209 2008) and no mal le els ound in Spanish ag icul u al soils (López-A ias and G au-210 Co bí, 2005). Fu he mo e, hese alues g ea ly exceed he maximum allowable 211 concen a ions o ag icul u al soils es ablished by he Regional Go e nmen o 212 Andalusia (Aguila e al., 1999). This indica es po en ial heal h isks associa ed wi h 213 consuming edible c ops g own in hese soils. 214 The Concen a ion Fac o , CF, de ined as he a io be ween each ace elemen in 215 he soil sample and i s backg ound alue (50 h pe cen ile), was pa icula ly ele a ed o 216 As (up o 24.8), Cu (up o 23.5), and Pb (up o 63.0), indica ing soil pollu ion. The 217 lowes CF alues we e ound o Zn, al hough he a io was highe han 1 o all 218 samples. Pollu ion load indices (PLI) a each plo a e shown in Table 3. The PLI alues 219 16 onions, he high As TC in oo s, (TC= 3.03) coupled wi h he g ea ly educed ans e o 369 ae ial pa s (TC= 0.03) and bulb (TC= 0.001) would indica e ha he As accumula ed in 370 oo issues. In case o Cu and Zn, TC we e always low, wi h maximum alues ound in 371 onion oo s (TC= 0.15 o Cu and 0.18 o Zn). Simila esul s we e ound o o he 372 plan s g owing in mul i-elemen pollu ed soils by Madejón e al. (2007). The p esen 373 esul s imply ha he e is a low ans e o pollu an s om hese soils o p ima y 374 p oduce s. 375 376 5. Conclusions 377 The e a e se e al conclusions ha can be d awn om his s udy: 378 Fi s : The e is limi ed soil-plan ans e o po en ially haza dous ace elemen s (As, 379 Cu, Pb, Zn) o selec ed ege ables and ui cul i a ed on a mine-pollu ed soil. One 380 eason may be he cu en managemen p ac ices employed on he ag icul u al small 381 holdings unde in es iga ion such as egula inpu s o o ganic ma e and lime o 382 main ain soil pH close o neu ali y. 383 Second: The ege ables in es iga ed a e ypical o hose g own in his egion, and no 384 edible pa showed elemen accumula ion ha could be conside ed as a signi ican isk 385 o human heal h, based on s a u o y limi s o ood c ops. The ege ables showed 386 di e en pa e ns o ace elemen accumula ion: highes concen a ions in non-edible 387 pa s o onions and lowes concen a ions in po a oes ube s. 388 Thi d: The da a om his su ey is a clea illus a ion o he use o simple, ou ine 389 ag onomic p ocedu es as a means o a) cul i a ing c ops on po en ially phy o oxic soils 390 and b) educing he concen a ions o po en ially oxic elemen s (As, Pb) in hei edible 391 issues. Rou ine applica ion o a combina ion o li es ock manu e and ag icul u al lime 392 has c ea ed a soil en i onmen whe e he labile pools o As and Pb a e e y low, in 393 17 con as o he e y ele a ed o al con en o hese elemen s in he soil. In addi ion, his 394 ea men has egula ed plan up ake o bo h Cu and Zn, educing po en ial phy o oxici y 395 whils s ill p o iding a sou ce o ace concen a ions o bo h mic onu ien s o main ain 396 no mal g ow h. The ad hoc ea men s applied by he smallholde s appea o ha e 397 success ully con ibu ed o he sa e use o he pollu ed soils whe e i can sus ain c op 398 p oduc ion o e an ex ended pe iod o ime. The e a e clea lessons o u u e 399 de elopmen o ield scale emedia ion o soils wi h mixed me al/me alloid pollu ion 400 om he success ul and sus ainable ou come o he „in si u‟ ea men s applied o hese 401 highly pollu ed soils by he smallholde s who use adi ional p ac ices o a m hese 402 si es. Howe e i is impo an o conside ha he success ob ained in his case canno 403 be gene ally ex ended o o he si ua ions whe e soil and clima e condi ions, as well as 404 ype o c op species, a e di e en . 405 406 Re e ences 407 Ad iano, D.C., 2001. T ace elemen s in Te es ial En i onmen s. Biogeochemis y, 408 Bioa ailabili y, and Risks o Me als, second ed. Sp inge , New Yo k. 409 Aguila , J., Do onso o, C., Gómez-A iza, J.L., Galán, E., 1999. Los c i e ios y 410 es ánda es pa a decla a un suelo con aminado en Andalucía y la me odología y écnica 411 de oma de mues as y análisis pa a su in es igación. In es igación y desa llo en 412 Andalucía. Se illa: se icio de publicaciones de la Uni e sidad de Se illa. 413 Alan, M.G.M., Tokunaga, S., Maekawa, T., 2003. A senic and hea y me al 414 con amina ion o ege ables g own in Sam a illage, Bangladesh. Sci. To al En i on. 415 308, 83-96. 416 Alloway, B.J., 1995. Hea y me als in Soils, second ed. Blackie Academic & 417 P o essional, London. 418 18 Ba ba-B ioso, C., Sánchez, E., Fe nández-Caliani, J.C., 2007. E ec os del d enaje 419 ácido de minas sob e la composición química y mine alógica de suelos ag ícolas: una 420 ap oximación expe imen al, in: Bellin an e, N., Jo dán, A. (Eds), Tendencias Ac uales 421 de la Ciencia del Suelo. Se illa, pp. 194-200. 422 Cab e a, F., Clemen e, L., Díaz Ba ien os, E., López, R., Mu illo, J.M., 1999. 423 Hea y me al pollu ion o soils a ec ed by he Guadiama oxic lood. Sci. To al 424 En i on. 242, 117-129. 425 Chaney, R.L., 1980. Heal h isks associa ed wi h oxic me als in municipal sludge, 426 in: Bi on, G., Dam o, B.L., Da idson, G.T., Da idson, J.M. (Eds.), Sludge-Heal h 427 Risks o Land Applica ion.:Ann A bo Sci Publ, USA, pp. 59-83. 428 Checkland, S.G., 1967. The Mines o Tha sis. Roman, F ench and B i ish 429 en e p ise in Spain. Allen & Unwin, London. 430 Chojnacka, K., Chojnacki, A., Gó ecka, H., Gó ecki, H. 2005. Bioa ailabili y o 431 hea y me als om pollu ed soils o plan s. Sci. To al En i on. 337, 175-182. 432 Chopin, E.I.B., Alloway, B.J., 2007a. T ace elemen pa i ioning and soil pa icle 433 cha ac e isa ion a ound mining and smel ing a eas a Tha sis, Río in o and Huela a, SW 434 Spain. Sci. To al En i on. 373, 488-500. 435 Chopin, E.I.B., Alloway, B.J., 2007b. Dis ibu ion and mobili y o ace elemen s in 436 soils and ege a ion a ound he mining and smel ing a eas o Tha sis, Río in o and 437 Huel a, Ibe ian Py i e Bel , SW Spain. Wa e Ai Soil Pollu . 182, 245-261. 438 Dahal, B.H., Fue hache , M., Men le , A., Ka ki, K.B., Sh es ha, R.R., Blum, 439 W.E.H., 2008. A senic con amina ion o soils and ag icul u al plan s h ough i iga ion 440 wa e in Nepal. En i on. Pollu . 155, 157-163. 441 E ns , W.H.O., Ve kleij, J.A.C., Scha , H. 1992. Me al ole ance in plan s. Ac a 442 Bo anica Nee landica 41, 229-248. 443 19 FAO. 1985. Wa e quali y guidelines o maximum c op p oduc ion. Food and 444 Ag icul u e O ganiza ion/UN. 445 Fe nández-Caliani, J.C., Ba ba-B ioso, C., González, I., Galán, E., 2009a Hea y 446 me al pollu ion in soils a ound he abandoned mine si es o he Ibe ian Py i e Bel 447 (Sou hwes Spain). Wa e Ai Soil Pollu . 200, 211-226. 448 Fe nández-Caliani, J.C., Ba ba-B ioso, C., De la Rosa, J., 2009b. Mobili y and 449 specia ion o a e ea h elemen s in acid mine soils and geochemical implica ions o 450 i e wa e s in he sou hwes e n Ibe ian ma gin. Geode ma 149, 393-401. 451 Fe nández-Caliani, J.C., Ba ba-B ioso, C., 2010. Me al immobiliza ion in 452 haza dous con amina ed mine soils a e ma ble slu y was e applica ion. A ield 453 assessmen a he Tha sis mining dis ic (Spain). J. Haza d. Ma e . 181, 817-826. 454 Galán, E., Fe nández-Caliani, J.C., González, I., Apa icio, P., Rome o, A., 2008. 455 In luence o geological se ing on geochemical baselines o ace elemen s in soils. 456 Applica ion o soils o Sou hwes Spain. J. Geochem. Explo . 98, 89-106. 457 Gup a, S.K., Vollme , M.K., K ebs, R., 1996. The impo ance o mobile, 458 mobilisable and pseudo o al hea y me al ac ions in soil o h ee-le el isk 459 assessmen and isk managemen . Sci. To al En i on. 178, 11-20. 460 Ha ley, W., Edua ds, R., Lepp, W.N., 2004. A senic and hea y me al mobili y in 461 i on oxide-amended con amina ed soils as e alua ed by sho and long e m leaching 462 es s. En i on. Pollu . 131, 495-504. 463 Houba, V.J.G., Lexmond, Th.M., No ozamsky, I, Van de Lee, J.J., 1996. S a e o 464 he a and u u e de elopmen s in soil analysis o bioa ailabili y assessmen . Sci. To al 465 En i on. 178, 21-28. 466 20 Huang, R-Q., Gao, S-F., Wang, W-L., S aun on, S., Wang, G., 2006. Soil a senic 467 a ailabili y and he ans e o soil a senic o c ops in subu ban a eas in Fujian P o ince, 468 sou heas China. Sci. To al En i on. 368, 531-541. 469 In awongse, M., Dean, J.R., 2006. Up ake o hea y me als by ege able plan s 470 g own on con amina ed soil and hei bioa ailabili y in he human gas oin es inal ac . 471 Food Addi . Con am. 23, 36-48. 472 Ja el, W.M., Be e ly, R.B., 1981. The dilu ion e ec s in plan nu i ion s udies. 473 Ad . Ag on. 34, 197–224. 474 Jones, J.B., Case, V.W., 1990. Sampling, handling, and analyzing plan issue 475 samples, in: Wes e man, R.L. (Ed.), Soil es ing and plan analysis, hi d ed. SSA book 476 se ies, no. 3. Soil Science Socie y o Ame ica, Madison, pp. 389–427. 477 Juhasz, A.L., Smi h, E., Webe , J., Rees, M., Ro e, A., Kuchel, T., Sansom, L., 478 Naidu, R., 2008. Applica ion o an in i o swine model o he de e mina ion o a senic 479 bioa ailabili y in con amina ed ege ables. Chemosphe e 71, 1963–1969. 480 Kaba a Pendias, A., Pendias, H., 1999. Biogeochemis y o ace elemen s, second 481 ed. Wyd Nauk PWN, Wa sow. 482 Kaba a-Pendias, A., Pendias, H., 2001. T ace elemen s in soils and plan s, hi d ed. 483 CRC P ess, Boca Ra on. 484 Kaba a-Pendias, A., 2004. Soil-plan ans e o hea y me als-an en i onmen al 485 issue. Geode ma 122, 143-149. 486 Kaba a-Pendias, A., Mukhe jee, A.B., 2007. T ace elemen s om soil o human. 487 Sp inge , Be lin. 488 Lim, H-S., Lee, J-H., Chon, H-T., Sage , M., 2008. Hea y me al con amina ion and 489 heal h isk assessmen in he icini y o he abandoned Songcheon Au-Ag mine in 490 Ko ea. J. Geochem. Explo . 96, 223-230. 491 21 Liu, W.X., Li, H.H., Li, S.R., Wang, Y.W., 2006. Hea y me al accumula ion o 492 edible ege ables cul i a ed in ag icul u al soil in he Subu b o Zhengzhou ci y, 493 People‟s Republic o China. Bull. En i on. Con am. Toxicol. 76, 163-170. 494 López, M., González, I., Rome o, A. 2008. T ace elemen s con amina ion o 495 ag icul u al soils a ec ed by sulphide exploi a ion (Ibe ian Py i e Bel , SW Spain). 496 En i on. Geol. 54, 805-818. 497 López-A ias, M., G au-Co bí, J.M. 2004. Me ales pesados, ma e ia o gánica y o os 498 pa áme os de la capa supe icial de los suelos ag ícolas y de pas os de la España 499 peninsula I: Resul ados Globales. Ins i u o–Nacional de In es igación y Tecnología 500 Ag a ia y Alimen a ia. Minis e io de Educación y Ciencia, Mad id. 501 Madejón, E., Madejón, P., Bu gos, P., Pé ez de Mo a, A., Cab e a, F., 2009. T ace 502 elemen s, pH and o ganic ma e e olu ion in con amina ed soils unde assis ed na u al 503 emedia ion: A 4-yea ield s udy. J. Haza d. Ma e . 162, 931–938. 504 Madejón, P., Ma añón, T., Mu illo, J.M., 2006. Biomoni o ing o ace elemen s in 505 he lea es and ui s o wild oli e and holm oak es. Sci. To al En i on. 355, 187–203. 506 Madejón, P., Mu illo, J.M., Ma añón, T., Lepp, N.W. 2007. Fac o s a ec ing 507 accumula ion o hallium and o he ace elemen s in wo wild B assicaceae 508 spon aneously g owing on soils con amina ed by ailings dam was e. Chemosphe e 67, 509 20–28. 510 McLaughlin, M.J., Pa ke , D.R., Cla ke, J.M., 1999. Me als and mic onu ien s-511 ood sa e y issues. Field C op Res. 60, 143-163 512 McLaughlin, M.J., Hamon, R.E., McLa en, R.G., Spei , T.W., Roge s, S.L., 2000. 513 Re iew: A bioa ailabili y-based a ionale o con olling me al and me alloid 514 con amina ion o ag icul u al land in Aus alia and New Zealand. Aus . J. Soil Res. 38, 515 1037-1086. 516 22 Menzies, N.W., Donn, M.J., Kopi ke, P.M., 2007. E alua ion o ex ac an s o 517 es ima ion o he phy oa ailable ace me als in soils. En i on. Pollu . 145, 121-130. 518 Mohamed, A.E., Rashed, M.N., Mo y, A., 2003. Assessmen o essen ial and oxic 519 elemen s in some kinds o ege ables. Eco ox. En i on. Sa e. 55, 251–260. 520 Pansu, M., Gau hey ou J., 2006. Handbook o Soil Analysis: Mine alogical, 521 O ganic and Ino ganic Me hods. Sp inge , Be lin.Pillay, V., Jonnalagadda, S.B., 2007. 522 Elemen al up ake by edible he bs and le uce (La uca sa i a). J En i on. Sci. Heal h 523 Pa B 42, 423-428. 524 Relly, C., 1991. Me al con amina ion o Food, second ed. Else ie , Essex, UK. 525 Sahuquillo, A., Rigol, A., Rau e , G., 2003. O e iew o he use o 526 leaching/ex ac ion es s o isk assessmen o ace elemen s in con amina ed soils and 527 sedimen s. T ends Anal. Chem. 22, 152-159. 528 Tokalioğlu, Ş., Ka al, Ş., 2006. S a is ical e alua ion o he a ailabili y o hea y 529 me als om con amina ed soils o ege ables. Bull. En i on. Con am. Toxicol. 76, 311-530 319. 531 Tomlinson, D.L., Wilson, J.G., Ha is, C.R., Je ey, D.W. 1980. P oblems in he 532 assessmen s o hea y me al le els in es ua ies and o ma ion o a pollu ion index. 533 Helgol Mee esun e s 33, 566-575. 534 U e, AM. 1996. Single ex ac ion schemes o soil analysis and ela ed applica ions. 535 Sci. To al En i on. 178, 3-10. 536 537 23 FIGURE AND TABLE CAPTIONS 538 Figu e 1. Pano amic iew (a) o he Tha sis mining a ea (pho o cou esy: E. Rome o) 539 showing he loca ion o he ag icul u al plo s selec ed o his s udy (b,c). 540 Figu e 2. Pe cen ages o elemen s ex ac ed wi h (a) deionised wa e , (b) CaCl2, and (c) 541 EDTA in soil g owing young onion (C1, C3, C4, C5), ipe onion (C2), le uce (L1, L2, 542 L3), cha d (A1, A2, A3), lemon (S5), and po a o (S12). 543 Figu e 3. Dis ibu ion o ace elemen s (mean alues in mg kg-1) in di e en pa s o 544 he onion. 545 Figu e 4. Dis ibu ion o ace elemen s (mean alues in mg kg-1) in di e en pa s o 546 he le uce. 547 Figu e 5. Dis ibu ion o ace elemen s (mean alues in mg kg-1) in di e en pa s o 548 he lemon ee. 549 550 Table 1. Plan species, analyzed o gans (numbe o samples in b acke s) and hei 551 associa ed soil samples. 552 Table 2. Physico-chemical pa ame e s o he soils whe e ege ables a e cul i a ed. 553 Table 3. Mean and s anda d de ia ion o he o al ace elemen concen a ions and 554 pollu ion load index (PLI) and ace elemen s ex ac ed wi h deionized wa e , CaCl2 and 555 EDTA. All alues a e exp essed in mg kg-1. Numbe o samples (n) appea s in b acke s 556 Table 4. T ace elemen con en (mean and ange alues in mg kg-1) in di e en o gans 557 o ege ables g owing in he ag icul u al plo s. 558 Table 5. T ans e coe icien s (TC) o As, Cu, Pb and Zn in he di e en o gans o he 559 s udied ege ables. 560 1 Figu e 2 Figu e 2 4 Table 4. T ace elemen s con en s (mean and ange alues) in di e en o gans o ege ables g owing in he ag icul u al plo s unde s udy. * * Possible backg ound alues compiled by Kaba a-Pendias and Mukhe jee (2007); **Sze e and N iagu, (2007); *** Da is and Whi e (1981) Plan species O gan As Cu Pb Zn Ripe Onion (n=6) Lea es 7.14 (0.75-15.2) 12.1 (3.5-31.4) 0.65 (0.10-1.92) 14.1 (12.8-16.2) Bulbs 0.31 (0.1-1.2) 4.15 (2.9-5.0) 0.33 (0.1-0.83) 23.9 (14.9-29.1) Roo s 627 (267-905) 53.3 (39.5-80.5) 44.5 (35.9-51.8) 82.0 (43.2-135) Onion bulbs* - 4.0-6.0 1.1-2.0 22-32 Young Onion (n=6) Lea es 9.56 (0.10-15.2) 20.4 (14.1-20.5) 3.44 (0.1-8.8) 24 (19.2-28.0) Bulbs 8.81 (1.95-23.5) 13.3 (9.0-18.0) 2.65 (3.01-8.3) 62.4 (34.9-101) Le uce (plo 1, n=3) Lea es 1.00 (0.86-1.1) 13.5 (13.3-13.6) 0.76 (0.75-0.77) 64 (61.6-66.0) Le uce (plo 2, n=3) Lea es 0.93 (0.2-1.6) 9.48 (7.6-11.7) 0.45 (0.35-0.65) 49 (37.6-60.3) Le uce lea es* - 6.0-8.0 0.7-3.6 44-73 Cha d (plo 1, n=3) Lea es 0.45 (0.20-0.70) 14.8 (13.6-15.9) 0.90 (0.75-1.1) 43.9 (41.4-46.4) Cha d (plo 2, n=3) Lea es 1.07 (0.77-1.30) 18.4 (16.0-19.9) 1.50 (1.2-1.76) 79.8 (54.2-110) Po a o (n=5) Peel 0.1 11.5 (8.9-12.6) 0.1 21.1 (19.2-24.0) Tube 0.1 10.3 (8.2-12.0) 0.1 25.0 (20.8-28.8) Po a o ube s* - 3.0-6.6 0.5 10-26 No mal le els in ege ables** 0.0001-0.46 0.04-2.4 0.0004-0.8 0.5-118 S a u o y limi s*** 1.00 - 1.00 5 Table 5. T ans e coe icien s (TC) o As, Cu, Pb and Zn a he di e en o gans o he s udied ege ables. Vege able o gan As Cu Pb Zn Ripe onion Lea es (n=6) 0.034 0.034 0.001 0.03 Bulbs (n=6) 0.001 0.011 0.0004 0.05 Roo s (n=3) 3.03 0.150 0.052 0.18 Young onion Lea es (n=7) 0.020 0.03 0.002 0.04 Bulbs (n=7) 0.017 0.02 0.001 0.11 Le uce Lea es (n=6) 0.003 0.03 0.0005 0.13 Cha d Lea es (n=6) 0.003 0.04 0.001 0.14 Lemon Lea es (n=3) 0.003 0.015 0.0007 0.03 Pulp (n=3) 0.0002 0.010 0.0001 0.02 Peel (n=3) 0.0002 0.005 0.0002 0.01 Seed (n=3) 0.0002 0.014 0.00005 0.04 Po a o Peel (n=5) 0.0002 0.015 0.00004 0.035 Tube (n=5) 0.0002 0.014 0.00004 0.04