An Evaluation of the Effectiveness of Sorbents in the Remediation of Soil Contaminated with Zinc

Transcription

1 Wter ir oil Pollut (8) 9: 35 n Evlution of the Effetiveness of orents in the Remedition of oil Contminted with Zin Rfł trhel & Jdwig Wyszkowsk & łgorzt ćmg Reeived: 9 Ferury 8 /epted: June 8 /Pulished online: July 8 # The uthor(s) 8 strt Zin exerts negtive effets on soil nd ontriuting to the degrdtion of soil eosystems. New solutions for restoring helthy soil tivity re therefore needed. The im of this study ws to evlute the effetiveness of sorents in the iologil remedition of soil ontminted with zin. pot experiment ws onduted on lomy snd. The tested plnt ws mize (Ze mys). oil ws ontminted with zin hloride doses of,, 3, nd 9 mg Zn + kg D soil (dry mtter of soil). lginte, iohr, sepiolite, lined hlloysite, nd moleulr sieve were dded to soil in mounts orresponding to.5% of soil weight to minimize zin s potentilly toxi effets on the iologil properties of soil. The pplition of zin stimulted the prolifertion of ll nlyzed miroil groups. Zin exerted negtive effets on the eophysiologil diversity (EP) of fungi nd the tivity of dehydrogenses, tlse, nd id phosphtse. The pplied sorents modified the miroiologil nd iohemil properties of soil. In zin-ontminted soil, lginte, iohr, nd moleulr sieve inresed the ounts of orgnotrophi, oligotrophi, nd tinoteri. orents were not highly effetive in promoting fungl growth nd exerted vried effets on the tivity of soil enzymes. The moleulr sieve stimulted the tivity of ll soil enzymes, exluding β-gluosidse. lginte minimized the negtive influene of zin on dehydrogenses nd id phosphtse, nd iohr on tlse, sepiolite, nd lined hlloysite R. trhel : J. Wyszkowsk (*) :. ćmg Deprtment of iroiology, University of Wrmi nd zury in Olsztyn, Pl Łódzki 3, -77 Olsztyn, Polnd e-mil: jdwig.wyszkowsk@uwm.edu.pl on id phosphtse. y modifying the iologil properties of soil, the tested sorents ontriuted to n inrese in mize yields nd derese in zin uptke y mize plnts. Keywords Pollution. orents. Remedition of soil. iroorgnisms. Enzymes. iodiversity Introdution Over the dedes, humn tivities hve ontriuted to disruption in soil iologil tivity. Environmentl pollution used y hemil ompounds, inluding hevy metls, exerts negtive effets on eosystems nd rop prodution (hr et l. 6). evy metls re persistent pollutnts, nd they pose prolem in oth urn nd rurl res when their umultion in soil exeeds sfe levels. The quntity of tre elements in the environment does not hnge over time, nd these elements n only e trnsformed into iologilly ville or unville forms (Khlid et l. 7). The vilility of hevy metls in soil is losely ssoited with the physiohemil properties of soil. iologilly ville hevy metls re present in the soil solution or they our s exhngele frtions ound to orgni or inorgni soil omponents. etls tht re not ville to plnts re strongly ound to soil prtiles; they re present in the rystl lttie of soil minerls or form insolule deposits. Chnges in the physiohemil properties of soil, i.e., p, tion-exhnge pity, ontent of orgni mtter, ly minerls, Fe, l, nd n oxides, nd redox potentil, n led to the

2 35 Pge of 8 Wter ir oil Pollut (8) 9: 35 trnsformtion of iologilly unville ompounds into plnt-ville forms (ydinlp nd rinov 3). Zin is n essentil element for living orgnisms (Krężel nd ret 6). owever, elevted zin onentrtions n disrupt the iologil lne (trhel et l. 7). Exessive umultion of zin in soil n deteriorte the physiohemil nd iologil properties of soil, whih leds to soil degrdtion nd renders soil unfit for griulturl prodution (Wyszkowsk et l. 6). In zinontminted hitts, effetive mesures re required to restore the iologil funtions of soil. oil remedition is one of the most populr solutions tht ddress this prolem. Pollutnts n e extrted from soil, ut the relevnt mesures re ostly nd time-onsuming. oil pollutnts n lso e stilized with the use of vrious sustnes tht derese the moility of hevy metls. olutions pplied in situ re less expensive nd n e pplied over lrger res of ontminted lnd (Pérez de or et l. 5). The use of orgni nd inorgni dsorents to stilize the hemil omposition of soil ontminted with hevy metls is n eonomil nd environmentlly friendly remedition method. dsorents immoilize hevy metls nd minimize their dverse effets on living orgnisms, in prtiulr soil-dwelling miroorgnisms nd plnts (lndrino et l. ). Vrious orgni sustnes re inresingly often used to redue the vilility of metls in soil nd minimize the dverse environmentl impt of zin. These sustnes redue the moility of ontminnts y inding hemil elements or modifying lol environmentl onditions to derese their soluility (rdl 4). The influene of sorents with remedition potentil on zin-ontminted soil ws investigted in this study. The effetiveness of lginte, iohr, sepiolite, lined hlloysite, nd moleulr sieve ws evluted in soil otminted with zin. Due to the omplexity of the soil environment, the remedition potentil of the tested sorents ws nlyzed sed on hnges in the ounts nd diversity of soil-dwelling miroorgnisms, hnges in the iohemil tivity nd physiohemil properties of soil, nd the development of mize plnts. terilsndethods. oil The experiment ws performed on rown li soil developed from lomy snd. oil ws smpled t the re north-estern Polnd (53.76 N,.467 E). The properties of the experimentl soil hve een desried in detil in previous study trhel et l. (7).. orents Five sorents were evluted in pot experiment: lginte, iohr, sepiolite, lined hlloysite, nd moleulr sieve. lginte ws mnuftured y Vázsony- zövetkezeti Kft. (ungry). This minerl ompound is rih soure of nutrients. ording to lel dt, the produt ontins (g kg ): humi sustnes 3, C 3, N 3 5, P 5 6, K 6 9, nd g 8. lginte lso ontins tre mounts of n, Cu, Zn, Fe,, nd o. The p vlues of lginte re p KCl 6.7 nd p O 7.. iohr ws mnuftured y Fluid ompny (Polnd). The produt is mde from orgni mteril vi pyrolysis. iohr hs the following hemil omposition: stle C more thn 77%, voltile mtter 7%, sh less thn 6%, hlorides, sulfur, nd merury less thn.%. The p vlues of iohr re p KCl 8. nd p O 9.. epiolite 6/ ontins sepiolite (g 4 [i 6 O 5 (O) ]6 O), nd it ws mnuftured y the epiols iners Group (pin). epiolite is hydrted mgnesium silite with dsorptive properties. ording to lel dt, the produt ontins 7% sepiolite, inluding 85% of prtiles with the size of 75 to 7 μm. The p vlues of sepiolite re p KCl 7. nd p O 7.. lloysite (l i O 5 (O) 4 ) is ly minerl whih is used in the prodution of losor minerl sorents (Intermrk, Polnd). The minerl used in this experiment ws mined in Dunino (Polnd), nd it hs the following hemil omposition: io 4 ± %, Fe O 3 /FeO 8 ± %, TiO ± %, l O 3 33 ± %, go.5 ±.%, CO.3 ±.%, N O.%, nd K O.%. lloysite is hrterized y lrge speifi surfe re, high porosity, nd high tionexhnge pity. lloysite ws lined efore the experiment. The p vlues of hlloysite re p KCl 5.9 nd p O 6.5. The ylosiv 3 moleulr sieve ws mnuftured y Gre Dvison Compny (U). This syntheti nnoporous mteril onsists of rystlline luminosilite with.3-nm miropores. oleulr sieve powder is zeolite with three-dimensionl pore system nd extensive dsorption pity. It is ville in the form

3 Wter ir oil Pollut (8) 9: 35 Pge 3 of 8 35 of white odorless powder. The p vlues of moleulr sieve re p KCl 8.5 nd p O...3 Experimentl Design pot experiment ws onduted in the greenhouse in five replitions. oil mteril in the mount of 3 kg of ir-dried soil ws pled in 3.5-dm 3 polyethylene pots with vrious doses of zin, remedition sustnes, nd minerl fertilizers. Zin ws pplied s ZnCl in doses of,, 3, nd 9 mg Zn + kg D soil. The tested sorents lginte, iohr, sepiolite, lined hlloysite, nd moleulr sieve were pplied to soil in mounts orresponding to.5% of soil weight. Four zin doses nd six types of sorents were nlyzed in five replitions totl of pots. The tested plnt ws mize whih ws grown for 6 dys. Wter ontent t the level of 5% of the mximum pity of the soil ws mintined throughout the entire experimentl period. The following minerl fertiliztion ws pplied (pure element per mg kg soil): N, P 5, K, g 5, Cu 5, n 5, o.5, nd В.33. inerl fertilizers were pplied in the following forms: nitrogen s CO(N ),phosphorus s K PO 4,potssium s K PO 4 +KCl, mgnesium s go 4 7 O, opper s CuO 4 5 O, mngnese s ncl 4 O, molydenum s N oo 4 O, nd oron s Н 3 ВO 3. ize ws sown t seeds per pot. eedlings were thinned to leve nine plnts per pot. ize plnts were hrvested in stge C 53 (infloresene emergene tip of infloresene visile) nd dried t temperture of 6 C until the hievement of onstnt weight. iroiologil nd iohemil nlyses of soil were performed in triplite for eh soil smple on dys 3 nd 6 of the experiment. The physiohemil properties of soil were determined on dy 6, in triplite for eh smple..4 nlyses iroil ounts nd enzyme tivity in soil smples were determined in three replites on experimentl dys 3 nd 6. The physiohemil properties of soil nd zin onentrtions in soil nd plnt mteril were determined on dy 6. iroiologil nlyses were rried out y the plting method to determine the ounts of miroorgnisms. The ounts of orgnotrophi teri, tinoteri, nd fungi were estimted over period of dys in dily intervls to determine the eophysiologil diversity (EP) index of miroorgnisms ording to Eq. () (De Leij et l. 993). The tivity of dehydrogenses, tlse, urese, id phosphtse, lkline phosphtse, nd β-gluosidse ws determined in soil. iroiologil nd enzymti nlyses hve een desried in detil in study orowik et l. (7). The tivity of soil enzymes (dehydrogenses, tlse, id phosphtse, lkline phosphtse, urese, nd β-gluosidse) ws used to lulte the soil iohemil qulity index () sed on Eq. () (Wyszkowsk et l. 3) nd to determine soil resistne (R) to zin pollution ording to Eq. (3) (Orwin nd Wrdle 4). iroil ounts nd enzyme tivitywerelsousedtolultethezinimptftor IF Zn (Eq. 4) nd the sorent impt ftor IF s (Eq. 5) (Kzyńsk et l. 5). EP ¼ ðpi log piþ ðþ where EP pi eophysiologil diversity index of miroorgnisms, shre of individuls of the i th speies in the ommunity reltive to the totl numer of individuls in the ommunity ¼ Deh þ Ct þ P þ Pl þ Ure þ Glu where ðþ iohemil qulity index, Deh tivity of dehydrogenses (μmol TFF kg D of soil h ), Ct tivityoftlse(molo kg D of soil h ), P tivityofidphosphtse (mmol PNP kg D of soil h ), Pl tivity of lkline phosphtse (mmol PNP kg D of soil h ), Ure tivity of urese (mmol N-N4 kg D of soil h ), Glu tivity β-gluosidse (mmol PNP kg D of soil h ). jd j Rðt Þ ¼ C þ jd j where ð3þ

4 35 Pge 4 of 8 Wter ir oil Pollut (8) 9: 35 R soil resistne index; C soil resistne under nturl onditions over time t ; P resistne of soil sujeted to pressure over time t ; D = C P. The soil resistne index (R) vries from to.if the vlue of R is nd, zin exerts very strong effet on soil. If the vlue of R pproximtes, soil is more resistnt to zin. IFZn ¼ Zn where IF Zn Zn IFZn ¼ where zin impt ftor, enzyme tivity or miroil ounts in soil ontminted with zin, enzyme tivity or miroil ounts in unontminted soil. ð4þ ð5þ IF s sorent impt ftor, enzyme tivity or miroil ounts in soil with the ddition of sorents, enzyme tivity or miroil ounts in soil without the ddition of sorents. The physiohemil prmeters of soil nd the ontent of plnt-ville zin nd totl zin in soil (flme tomi sorption spetrometry method - F) were determined ording to rris (6). The detetion limit ws 96 μg dm 3 for totl zin nd 3 μg dm 3 for ioville zin. Unertinty ws estimted t onfidene level of p =.95 nd overge ftor k =. To determine totl zin ontent, soil smples were digested in mixture of onentrted Cl nd NO 3. ioville zin ontent ws determined fter extrtion with Cl. The distriution of zin in plnts ws determined sed on zin onentrtions in the eril prts nd roots of mize plnts (Zhini et l. 9)..5 ttistil nlysis The results were proessed sttistilly in ttisti. softwre (ttoft In. 4) t signifine level of p =.5. The perentge ontriution of the experimentl ftors to the oserved vrition (η ) ws determined. iroil ounts nd enzyme tivity were sujeted to prinipl omponent nlysis (PC). omogeneous groups were identified y Tukey s D test. 3Results 3. iroil Properties of oil The results of the study (Tle ) indite tht the type of sorent exerted the gretest influene on miroil ounts, rnging from 37.7% for opiotrophi teri to 5.8% for orgnotrophi teri. Zin dose indued somewht smller hnges in miroil ounts, nd its influene rnged from 5.9% for orgnotrophi teri to 33.7% for opiotrophi teri. iroil ounts were lest ffeted y the dte of nlysis (.33 to 5.93%). In the prinipl omponent nlysis (Fig. ), soil miroorgnisms were divided into two groups sed on their responses to the experimentl ftors. The first group ws omposed of orgnotrophi teri, opiotrophi teri, oligotrophi teri, nd tinoteri. The seond group onsisted of fungi whih responded differently to the nlyzed ftors. The ounts of teri nd tinoteri were most influened y iohr, moleulr sieve, nd lginte, nd they were lest influened y sepiolite (Fig. ). The ove results were inferred from the projetion of ses desriing tretments with the tested sorents Tle Perentge ontriution of the experimentl ftors to the oserved vrition (η ) in miroil ounts in zin-ontminted soil Ftors Org Cop Olig t Fun Dose of Zn () orents () Time () Error Zn zin, Org orgnotrophi teri, Cop opiotrophi teri, Olig oligotrophi teri, t tinoteri, Fun fungi

5 Wter ir oil Pollut (8) 9: 35 Pge 5 of 8 35 PC :.38% Org t Cop Olig -. Fun PC : 7.44% Fig. iroil ounts in zin-ontminted soil in prinipl omponent nlysis (PC). Projetion of vetors onto plne desriing miroil ounts. Projetion of ses onto the plne. Org orgnotrophi teri, Cop opiotrophi teri, Olig PC :.38% I -I C-I -II -I -I -III -I -II -II -II -II -IV C-II -III -III C-III -IV C-IV -IV -IV -III PC : 7.44% -III -IV oligotrophi teri, t tinoteri, Fun fungi, dose of zin (mg Zn + kg D soil): I, II, III 3, IV 9; orents: C ontrol, lginite, iohr, sepiolite, hlloysite, moleulr sieve reltive to the vetors desriing miroil ounts. Fungl ounts were highest in tretments with zin doses of 3 nd 9 mg Zn + kg D soil. The lulted vlues of IF Zn indite tht zin exerted vried effets on miroil ounts (Fig. ). In tretments without sorents, inresing doses of zin ( to 9 mg Zn + kg D soil) inresed the prolifertion of opiotrophi teri, oligotrophi teri, tinoteri, nd fungi. The growth of orgnotrophi teri ws inhiited only y the highest zin dose (9 mg Zn + kg D soil). sed on the lulted vlues of IF Zn, the evluted soil-dwelling miroorgnisms were rrnged in the following order (from most resistnt to most sensitive): opiotrophi teri < fungi < tinoteri < oligotrophi teri < orgnotrophi teri. The lulted vlues of IF s indite tht the prolifertion of soil-dwelling miroorgnisms ws lso influened y the type of sorent (Fig. 3). In tretments not ontminted with zin, the ddition of lginte, iohr, nd moleulr sieve stimulted the prolifertion of orgnotrophi teri, opiotrophi teri, oligotrophi teri, nd tinoteri. The tested sorents did not stimulte the growth nd development of fungi whose IF s vlues rnged from.9 (moleulr sieve) to. (hlloysite). lginte, iohr nd moleulr sieve stimulted the prolifertion of orgnotrophi teri, oligotrophi IF Zn mg Zn + 3 mg Zn + 9 mg Zn Org Cop Olig t Fun Fig. Influene of zin (IF Zn ) on soil miroil ounts in tretments without sorents (men vlues independent of time). Org orgnotrophi teri, Cop opiotrophi teri, Olig oligotrophi teri, t tinoteri, Fun fungi. omogeneous groups (, ) were reted seprtely for eh miroil group (n =9;p =.5)

6 35 Pge 6 of 8 Wter ir oil Pollut (8) 9: 35 Orgnotrophi teri Copiotrophi teri IF IF 3 d Oligotrophi teri tinomyetes 4 3 IF 3 IF Fungi mg Zn+ mg Zn+ 3 mg Zn+ 9 mg Zn+ IF + Fig. 3 Influene of sorents (IFs) on soil miroil ounts (men vlues independent of time). lginite, iohr, sepiolite, hlloysite, moleulr sieve. Dose of zin,, 3, nd 9 mg Zn kg D soil. omogeneous groups ( d) were reted seprtely for eh miroil group nd eh sorent (n = ; p =.5) teri, nd tinoteri. The growth of opiotrophi teri ws intensified in tretments with the ddition of iohr nd moleulr sieve. The tested sorents inhiited the prolifertion of fungi whose IFs vlues rnged from.5 (moleulr sieve, zin dose of 3 mg Zn+ kg D soil) to.5 (hlloysite, zin dose of 9 mg Zn+ kg D soil). Despite the ove, the moleulr sieve ws most effetive in stimulting the growth of soildwelling miroorgnisms. oil ontmintion with zin not only led to hnges in miroil ounts, ut lso ffeted the diversity of soil-dwelling miroorgnisms (Fig. 4). Fungl diversity ws most ompromised the vlue of the EP index determined for fungi deresed from.39 to.7 under exposure to the highest zin dose of 9 mg Zn+ kg D soil. The influene of zin on the EP index of orgnotrophi teri nd tinoteri ws more miguous. In zinontminted tretments, EP vlues were determined

7 Wter ir oil Pollut (8) 9: 35 Pge 7 of Orgnotrophi teri Control lginite iohr epiolite lloysite oleulr sieve EP Index Dose of Zn (mg Zn + kg - D of soil)..9 tinomyetes Control lginite iohr epiolite lloysite oleulr sieve EP Index Dose of Zn (mg Zn + kg - D of soil) EP Index Fungi Control lginite iohr epiolit e lloysite oleulr sieve 3 9 Dose of Zn (mg Zn + kg - D of soil) Fig. 4 Eophysiologil diversity (EP) of miroorgnisms in zin-ontminted soil. n = 3; points, men vlue; lines, stndrd devition in the rnge of.8 to.839 for orgnotrophi teri, nd.73 to.768 for tinoteri. orents signifintly modified the EP index of soil-dwelling miroorgnisms. In tretments with the highest zin dose (9 mg Zn + kg D soil), the pplition of ll of the tested sorents, exluding lined hlloysite, deresed the EP vlues of orgnotrophi teri. The EP index of tinoteri exposed to the sme zin dose inresed only in soil treted with the moleulr sieve. The remining sorents did not indue signifint hnges in the EP index of tinoteri fter the pplition of zin dose of 9 mg Zn + kg.unlike in orgnotrophi teri nd tinoteri, the pplied sorents signifintly influened the EP vlues of fungi. The moleulr sieve inresed the EP index of fungi reltive to tretments without this sorent. reverse

8 35 Pge 8 of 8 Wter ir oil Pollut (8) 9: 35 reltionship ws noted in tretments with the ddition of hlloysite. derese in the EP index of fungi ws noted reltive to tretments where sorents were not pplied. The highest EP vlues were oserved in orgnotrophi teri, nd the lowest EP vlues were noted in fungi. 3. iohemil Properties of oil The iohemil properties of soil re determined y the soil miroiome, nd therefore they re relile inditors of soil ontmintion, inluding with zin. The tivity of soil enzymes ws influened mostly y zin dose nd the pplied sorents (Tle ). Zin dose hd the gretest impt on dehydrogense tivity (5.35%), nd the pplied sorent on urese tivity (79.84%). The gretest vritions in tlse tivity (7.8%) were oserved etween nlytil dtes. The evluted enzymes were divided into three groups sed on their responses to the experimentl ftors. The first group onsisted of urese nd lkline phosphtse, the seond group inluded dehydrogenses nd tlse, nd the third group omprised β- gluosidse nd id phosphtse (Fig. 5). The projetion of ses reveled tht the tivity of dehydrogenses nd tlse deresed with rise in zin ontmintion levels. lginte nd iohr stimulted the tivity of oxidoredutses. The tivity of lkline phosphtse nd urese ws stimulted y the moleulr sieve nd lginte. The tivity of id phosphtse nd β-gluosidse ws highest in tretments without Tle Perentge ontriution of the experimentl ftors to the oserved vrition (η ) in enzyme tivity in zin-ontminted soil Ftors Deh Ct P Pl Ure Glu Dose of Zn () orents () Time () Error Zn zin, Deh dehydrogenses, Ct tlse, P id phosphtse, Pl lkline phosphtse, Ure urese, Glu β-gluosidse sorents nd in tretments mended with sepiolite (Fig. 5). The vlues of IF Zn onfirmed tht zin exerted vried effets on the iohemil properties of soil (Fig. 6). The tivity of dehydrogenses, tlse, nd id phosphtse deresed with inresing zin doses, prtiulrly in tretments with the highest zin dose (9 mg Zn + kg D soil). The tivity of lkline phosphtse, urese, nd β-gluosidse ws stimulted y zin doses of nd 3 Zn + kg D soil. Dehydrogenses were most sensitive to high onentrtions of zin. In tretments not ontminted with zin (Fig. 7), lginte nd moleulr sieve enhned the tivity of urese (IF s of.5 nd 9.6, respetively) nd lkline phosphtse (IF s =.649 nd.484, respetively). iohr nd sepiolite stimulted the tivity of lkline phosphtse (IF s =.55 nd.354, respetively), nd hlloysite inresed the tivity of id phosphtse (IF s =.54) nd urese (IF s =.38). The tested sorents were less effetive stimulnts of dehydrogenses, tlse, nd β-gluosidse. The tivity of dehydrogenses ws stimulted only y lginte (IF s =.596). The vlues of IF s indite tht the tested sorents exerted vried effets on soil iohemil tivity. The moleulr sieve stimulted the tivity of dehydrogenses, tlse, lkline phosphtse, nd urese. lginte enhned the tivity of dehydrogenses, lkline phosphtse, nd urese. In tretments ontminted with zin doses of 3 nd 9 mg Zn + kg D soil, iohr nd sepiolite inhiited dehydrogense tivity. lloysite ws n effetive stimulnt of id phosphtse, nd it lso inresed the tivity of dehydrogenses nd urese in tretments ontminted with the highest zin dose (9 mg Zn + kg D soil). None of the sorents were effetive stimulnts of β-gluosidse tivity whose IF s vlues rnged from.66 (hlloysite, zin dose of 3 mg Zn + kg D soil) to.3 (sepiolite, zin dose of 3 mg Zn + kg D soil). The vlues of the R index, lulted sed on the index, indite tht enzyme tivity deresed with rise in zin ontmintion (Fig. 8). In tretments exposed to zin dose of mg Zn + kg D soil, the pplied sorents deresed enzyme resistne to zin. owever, the tested remedition gents exerted protetive effets in tretments ontminted with zin doses of 3 nd 9 mg Zn + kg D soil. The moleulr sieve ws most effetive in minimizing the dverse effets of zin on soil iohemil tivity.

9 Wter ir oil Pollut (8) 9: 35 Pge 9 of 8 35 PC : 9.84% Ure -IV -II -IV -III -IV Pl -III C-IV -IV -II -IV -I -III Deh -III -II -I C-III Ct - -I -II C-II Glu -II C-I - -I -III P PC : 9.84% -I PC : 4.69% Fig. 5 Enzyme tivity in zin-ontminted soil in prinipl omponent nlysis (PC). Projetion of vetors onto plne desriing enzymes tivity. Projetion of ses onto the plne. Deh dehydrogenses, Ct tlse, P id phosphtse, Pl 3.3 Physiohemil nd Chemil Properties of oil The results of this study indite tht the pplition of zin nd sorents indued hnges in the si physiohemil properties of soil (Tle 3). In tretments ontminted with zin, soil p nd totl exhngele ses deresed with rise in zin dose, whih ontriuted to n inrese in hydrolyti idity. oil sorption pity nd se sturtion deresed in response to high zin onentrtions. In tretments exposed to the highest zin dose (9 mg Zn + kg D soil), soil sorption pity deresed y 3.5% nd se sturtion deresed y 5.8% reltive to the ontrol smple. PC : 4.69% lkline phosphtse, Ure urese, Glu β-gluosidse, dose of zin (mg Zn + kg D soil): I, II, III 3, IV 9; sorents: C ontrol, lginite, iohr, sepiolite, hlloysite, moleulr sieve The nlyzed remedition gents exerted vried effets on the physiohemil properties of soil. lginte, sepiolite, nd moleulr sieve signifintly inresed soil p nd totl exhngele ses. The remining sorents hd minor effet on the evluted physiohemil prmeters of soil. owever, hydrolyti idity deresed in response to ll sorents, exluding hlloysite. lginte, sepiolite, nd moleulr sieve indued the gretest hnges. The tested sorents inresed soil sorption pity nd se sturtion reltive to tretments without sorents. The pplied sorents did not derese the onentrtions of ioville zin in soil (Fig. 9). In the most hevily ontminted IF Zn mg Zn + 3 mg Zn + 9 mg Zn +. Deh Ct P Pl Ure Glu Fig. 6 Influene of zin (IF Zn ) on the tivity of soil enzymes in tretments without sorents (men vlues independent of time). Deh dehydrogenses, Ct tlse, P id phosphtse, Pl lkline phosphtse, Ure urese, Glu β-gluosidse. omogeneous groups ( ) were reted seprtely for eh enzyme (n = 9; p =.5)

10 35 Pge of 8 Wter ir oil Pollut (8) 9: 35 Dehydrogenses Ctlse 5 4 d IF IF 3 id phosphtse lkline phosphtse 3 d d d d IF IF d d Urese β-gluosidse 8 6 IF IF d d 4 mg Zn+ mg Zn+ 3 mg Zn+ 9 mg Zn+ Fig. 7 Influene of sorents (IFs) on the tivity of soil enzymes (men vlues independent of time). lginite, iohr, sepiolite, hlloysite, moleulr sieve. Dose of zin,, 3, nd 9 mg Zn+ kg D soil. omogeneous groups ( d) were reted seprtely for eh enzyme nd eh sorent (n = ; p =.5) tretments, sorents inresed the ontent of plntville zin reltive to the pplied zin dose. In tretments with zin dose of 9 mg Zn+ kg, ioville zin ontent inresed reltive to ontrol soil s follows:.5-fold fter the pplition of lginite,.4fold fter the pplition of iohr nd hlloysite,.fold fter the pplition of sepiolite, nd.6-fold fter the pplition of moleulr sieve. The moleulr sieve ontriuted to the highest inrese in ioville zin ontent reltive to soil without sorents. 3.4 ize Yield Zin ontmintion indued signifint hnges in the yield of the eril prts nd roots of mize plnts (Fig. ). In tretments without sorents, the highest zin dose (9 mg Zn+ kg D soil) deresed the yield of eril plnt prts y 69.4% nd root yield y 35.66%. orents minimized the dverse effets of zin on mize yield. In tretments ontminted zin dose of 9 mg Zn+ kg D soil, the yield of eril plnt

11 Wter ir oil Pollut (8) 9: 35 Pge of Control: y = *x lginite: y = *x iohr: y = *x Indeks R epiolite: y = *x lloysite: y = *x oleulr sieve: y = *x Dose of Zn (mg Zn + kg - D of soil) Control lginite iohr epiolite lloysite oleulr sieve Fig. 8 oil resistne (R) to zin ontmintion expressed y hnges in the vlues of the soil iohemil qulity index () prts inresed y 87.3% in response to lginte, 47.% in response to iohr, 55.8% in response to sepiolite, 3.8% in response to hlloysite, nd 4.58% in response to the moleulr sieve. The nlyzed sorents lso ontriuted to signifint inrese in root yield. In tretments with the highest zin dose, root yield inresed.-fold in response to lginte,.8-fold in response to iohr,.5-fold in response to sepiolite,.67-fold in response to hlloysite, nd 34-fold in response to the moleulr sieve. The moleulr sieve deresed zin uptke y the roots nd inresed zin uptke y the eril prts of mize plnts (Tle 4). Despite the ove, the moleulr sieve did not indue hnges in zin umultion ptterns in plnts (Fig. ). The zin ontent of plnts ws similr in tretments without sorents nd in tretments ontining the moleulr sieve. Zin onentrtions were higher in the roots thn in the eril prts of mize plnts (Fig. ). % ville Zn Control lginite iohr epiolite lloysite oleulr sieve Dose of Zn (mg Zn + kg - D of soil) Fig. 9 Perentge ontent of ioville zin reltive to the totl zin ontent of soil

12 35 Pge of 8 Wter ir oil Pollut (8) 9: 35 hoots mg Zn+ 6 g D pot- mg Zn+ 3 mg Zn+ 4 9 mg Zn+ C 3 mg Zn+ 9 mg Zn+ Roots mg Zn+ 5 g D pot- mg Zn+ 5 C Fig. Dry mtter yield of mize (g pot ). C ontrol, lginite, iohr, sepiolite, hlloysite, moleulr sieve. omogeneous groups ( ) were reted seprtely for eh sorent (n = ; p =.5) Plnts exposed to vrious zin doses did not differ in their zin umultion ptterns. 4 Disussion The soil miroiome n e modified under exposure to externl ftors, inluding sustnes with toxi effets. In the present study, zin intensified the prolifertion of soil-dwelling miroorgnisms. iroil growth ws determined y oth the zin dose nd the dte of nlysis. The stimultory effets of zin on the undne of soil miroorgnism hve lso een oserved y other uthors Wyszkowsk et l. (3). owever, exessive zin onentrtions ( mg Zn+ kg D soil) n disrupt the soil miroiome nd redue miroil undne (Wyszkowsk et l. 6). ording to iju et l. (3), the zin ontent of soil of to

13 Wter ir oil Pollut (8) 9: 35 Pge 3 of 8 35 Tle 3 Physiohemil properties of soil ontminted with zin nd mended with sorents Dose of Zn (mg Zn + kg ) Control lginite iohr epiolite lloysite oleulr sieve p KCl d d ydrolyti idity (C) m(+) kg D soil Totl exhngele ses (TE) m(+) kg D soil d 3.33 Ction exhnge pity (CEC) m(+) kg D soil d 4.33 se sturtion () % d 9.6 Zn zin. omogeneous groups ( d) were reted seprtely for the physiohemil properties of soil nd the pplied sorents (n =; p =.5) 7. mg kg my led to dverse hnges in the miroiologil prmeters of soil eosystems. Kouhou et l. (7) noted derese in the ounts of fungi nd tinoteri nd n inrese in teril Tle 4 Zin ontent of mize plnts in tretments without sorents nd in tretments where moleulr sieve ws pplied Dose of Zn (mg Zn + kg ) Control oleulr sieve mg Zn + kg Derese (%) hoots Roots

14 35 Pge 4 of 8 Wter ir oil Pollut (8) 9: 35 Control oleulr sieve % 9% 8% 7% 6% 5% 4% 3% % % % hoots Roots Fig. Zin distriution in mize dry mtter (%) Dose of Zn (mg Zn + kg - D of soil) ounts in soil ontining 9. mg Zn + kg,ompred with ontrol soil. In the present study, the highest zin dose (9 mg Zn + kg D soil) exerted toxi effet on orgnotrophi teri nd deresed the ounts of the remining miroil groups in tretments ontminted with zin doses of nd 3 mg Zn + kg D soil. The ove zin doses lso indued hnges in the EP index of soil-dwelling miroorgnisms. Zin pplied t the highest dose (9 mg Zn + kg ) ould exert toxi effet on soildwelling miroorgnisms, whih ws refleted in hnges in miroil diversity. Exessive zin onentrtions in soil mde it impossile for the miroorgnisms to dpt to the existing onditions. When present in high onentrtions, the hevy metl ould penetrte the ell memrnes of miroorgnisms, leding to hnges in the struture nd funtion of ell orgnelles, followed y ell deth. The oserved hnges in iodiversity ould lso result from miroil suession. The soil environment ws dominted y miroil speies resistnt to high zin onentrtions, whih eliminted the remining miroorgnisms. The negtive effet of zin on soil iologil tivity ws lso oserved y Epelde et l. () who found tht zin dose of mg kg inhiited the prolifertion of totl teri nd nitrifying teri. Other uthors lso reported derese in the ounts of orgnotrophi teri, teri of the genus zototer, tinoteri, nd fungi in soil ontminted with zin doses of 5 to mgzn + kg D soil (Wyszkowsk et l. 5). ording to donld et l. (8), longterm pplition of hevy metls, inluding zin, my led to hnges in the prolifertion nd struture of miroorgnisms. Zin doses of 5 45 mg Zn + kg signifintly ffeted the struture of miroil ommunities, in prtiulr fungi. Chnges in the miroiologil properties of soil lso disrupt soil iohemistry nd derese enzyme tivity (orowik et l. 4; Wiezorek et l. 4; Wyszkowsk et l. 6; Yng et l. 6). oil enzymes rpidly respond to ontmintion, nd they re good inditors of the hnges indued y xenoiotis. In the urrent study, zin inhiited the tivity of ll nlyzed soil enzymes (dehydrogenses, tlse, urese, id phosphtse, lkline phosphtse, β-gluosidse). The highest zin dose (9 mg Zn + kg D soil) hd prtiulrly inhiitory influene on enzyme tivity. imilr results were reported in study evluting the influene of zin doses of 5, 3, 6, nd mg Zn + kg D soil on the tivity of dehydrogenses, urese, id, nd lkline phosphtse (oros et l. ). The ited uthors oserved tht enzyme tivity deresed with inresing zin levels. ordingtoorowiketl.(4), zin doses of 3 to 4 mg Zn + kg D soil n suppress enzyme tivity in soil. In the work of Kuhrski et l. (), soil enzymes were rrnged in the following order sed on their sensitivity to zin ontmintion: rylsulftse > dehydrogenses > id phosphtse > urese > β- gluosidse. Exess zin n lso ompromise plnt growth nd development. In our study, zin doses of to 9 mg Zn + kg D soil deresed the yield of mize roots nd eril prts. ustnes with soil remedition potentil re inresingly used to limit the negtive onsequenes of

15 Wter ir oil Pollut (8) 9: 35 Pge 5 of 8 35 soil ontmintion with tre elements. These sustnes derese the moility of hevy elements y modifying soil properties suh s p, ontent of ly minerls nd orgni mtter, tion-exhnge pity, nd soil type (rdl 4). Other remedition sustnes promote miroil growth, intensify the iologil tivity of soil nd, onsequently, improve soil fertility. In our study, the tested sorents, in prtiulr lginte nd iohr, ontriuted to the prolifertion of orgnotrophi teri, oligotrophi teri, opiotrophi teri, nd tinoteri. Fungl ounts deresed in response to the pplied soil remedition gents. The pplition of sorents ould led to the immoiliztion of soil miroorgnisms, thus inhiiting their prolifertion nd soil enzymti tivity. The presene of mutul intertions etween soil-dwelling miroorgnisms nd iohr ws reported y Lehmnn nd Rondon (6). iohr n modify hitt onditions, wheres miroorgnisms n lter the quntity nd properties of iohr. iohr is hrterized y high dsorption pity (Ling et l. 6) ndlrge speifi surfe re whih retes supportive onditions for the immoiliztion of soil miroorgnisms (Lehmnn et l. ). In tretments not ontminted with zin, the pplition of iohr inresed the EP vlues of miroorgnisms. In study y teiner et l. (8), iohr lso stimulted the soil miroiome y inresing miroil iomss nd miroil tivity ssessed sed on miroil respirtion. iohr inreses the iovilility of soil nutrients nd soil p, whih not only ontriutes to rop yields, ut lso enles rop prodution in previously degrded res (Lehmnn nd Rondon 6). In study evluting the influene of sepiolite on the soil environment, the nlyzed minerl stimulted the prolifertion of teri nd tinoteri(un et l. 3). In our study, sepiolite did not indue signifint hnges in the ounts of the nlyzed miroil groups. Clined hlloysite ws not highly effetive in improving the miroiologil properties of soil. In the work of Wyszkowsk et l. (5), ellulose nd fermented rk llevited the negtive effets of zin on the undne of zototer teri, orgnotrophi teri, nd tinoteri, wheres kertin stimulted fungl growth. The nlysis of enzyme tivity in soil lso reveled tht the pplied sorents minimized the toxi effets of zin. The evluted sorents stimulted the tivity of dehydrogenses nd tlse whih re good inditors of soil miroil tivity. In tretments remedied with lginte, the ove effets n e ttriuted to inresed orgni mtter ontent (heng et l. 4). ording to oreno et l. (9), enzyme tivity is less ompromised y zin in soils with higher orgni mtter ontent. Extrellulr enzymes re immoilized or form omplexes with orgni mtter nd exert protetive effets (Kızılky et l. 4). The ddition of orgni mtter to soil stimultes miroil prolifertion nd inreses the iodiversity nd tivity of enzymes, thus minimizing the dverse effets of zin (trhel et l. 7). Orgni mtter ontins humi sustnes whih ply n importnt role in the environment due to their ffinity for soil ontminnts (zó 4). heng et l. (4) demonstrted tht lge nd lgl derivtives were effetive in deresing the iovilility of hevy metls. These effets n e ttriuted to the funtionl groups of ell wll polyshrides. In the work of Ti et l. (), n lginte-sed sustne with high dsorption pity inresed soil p. umi sustnes lso inrese hevy metl uptke y plnts, whih is n importnt onsidertion in the proess of soil phytoremedition. umi sustnes nd hevy metls form stle omplexes, whih dereses the moility of toxi ompounds in the soil solution (lim et l. 3). In study y oros et l. (), ellulose nd fermented rk stimulted enzyme tivity in soil, wheres kertin inhiited the tivity of ll evluted enzymes (dehydrogense, urese, id, nd lkline phosphtse) nd did not llevite the toxi effets of zin. In the urrent study, lined hlloysite stimulted tlse tivity. ording to Zhi et l. (), hlloysite ontriuted to enzyme stility under dverse environmentl onditions. imilrly to sepiolite, hlloysite is ly minerl with lrge speifi surfe re whih effetive sors pollutnts, inluding hevy metls (Wu et l. 6). lloysite inds tre elements through tion exhnge or the formtion of surfe omplexes (Yun et l. 5). In ddition, mterils with high dsorption pity regulte the miroiologil nd iohemil properties of soil. ording to Lehmnn et l. (), these sustnes ontriute to the retention of wter nd nutrients in soil nd immoilize miroorgnisms on their surfe. In the work of un et l. (6), entonite, whih is lso ly minerl, exerted protetive effets on the soil miroiome nd soil enzymes. entonite inresed the ounts of tinoteri nd stimulted tlse tivity. In our study, sepiolite indued hnges in the tivity of lkline phosphtse nd β-gluosidse. The enefiil

16 35 Pge 6 of 8 Wter ir oil Pollut (8) 9: 35 effets of sepiolite were lso reported in study y un et l. (3) where this minerl enhned the tivity of urese nd invertse. epiolite n lso ontriute to inresing soil respirtion nd the tivity of dehydrogense nd lkline phosphtse (d-vlle et l. 6). epiolite immoilizes hevy metls, inluding zin, y repling mgnesium ions on the oundries of othedrl mgnesium lyers in the sustrte (De Lim et l. 7). In our study, the moleulr sieve indued the gretest inrese in soil resistne (R) to zin, determined sed on the index. These hnges were most pronouned in tretments ontminted with the highest zin dose (9 Zn + kg soil D). ording to rh et l. (7), the presene of nnopores in the moleulr sieve supports intertions with the ions nd moleules of hemil ompounds. The ove mehnism ould e responsile for the oserved inrese in the ounts of teri nd tinoteri nd enzyme tivity. These oservtions lso suggest tht sustnes with lrge speifi surfe re exert protetive effets y immoilizing miroorgnisms nd enzymes on their surfe. Chnges in the miroiologil properties of soil nd enzyme tivity influene the rte of metoli proesses nd, onsequently, the physiohemil properties of soil. In our study, the pplied sorents did not derese the ontent of ioville zin reltive to totl zin onentrtion in soil. It ws found tht the moleulr sieve deresed zin uptke y the roots nd inresed zin uptke y the eril prts of mize plnts. The tested sorents inresed mize yield, in prtiulr in the most highly ontminted tretments. Our results suggest tht the ontent of ioville zin in soil ws signifintly modified y nutrient yling nd root seretions. The nlyzed soil remedition sustnes minimized the toxi effets of zin minly y promoting the growth of soil-dwelling miroorgnisms, inluding orgnotrophi teri, oligotrophi teri, nd tinoteri, nd y stimulting most soil enzymes, whih ontriuted to n inrese in mize yield. 5 Conlusions Inresing levels of environmentl pollution prompt the serh for new solutions to gurntee glol food seurity. In the desried experiment, high zin doses deteriorted the soil environment y deresing the ounts nd iodiversity of miroorgnisms nd disrupting iohemil proesses in soil. Zin hd n dverse effet on the growth nd development of mize, nd it deresed the yield of eril plnt prts. Remedition sustnes ple of soring pollutnts were pplied to limit the dverse influene of zin on the soil environment. The tested sorents generlly minimized the toxi effets of zin on soil miroorgnisms nd enzymes. The nlyzed sustnes lso indued hnges in the miroiologil diversity of soil. The evluted sorents did not limit the iovilility of zin in soil, ut deresed the umultion of zin in mize plnts. Our findings indite tht not ll of the tested sorents n e effetively used to remedite zin-ontminted soil. The gretest inrese in soil fertility ws oserved under the influene of lginte, iohr, nd moleulr sieve. The moleulr sieve emerged s the most effetive sustne for the remedition of soil ontminted with zin. Funding Informtionientifi reserh ws finned y the inistry of iene nd igher Edution funds for sttutory tivity. Open ess This rtile is distriuted under the terms of the Cretive Commons ttriution 4. Interntionl Liense ( retiveommons.org/lienses/y/4./), whih permits unrestrited use, distriution, nd reprodution in ny medium, provided you give pproprite redit to the originl uthor(s) nd the soure, provide link to the Cretive Commons liense, nd indite if hnges were mde. Referenes d-vlle, P., Álvrez-yuso, E., uriego,., & Pellitero, E. (6). ssessment of the use of sepiolite mendment to restore hevy metl polluted mine soil. Geoderm, 8, iju, L., onghi, W., Peiling, G., & ong-zhi, X. (3). Chemil frtion on Cu nd Zn their impts on miroil properties in slightly ontminted soils. Interntionl Journl of griulturl Reserh Innovtion & Tehnology, 3(), 5. ydinlp, C., & rinov,. (3). Distriution nd forms of hevy metls in some griulturl soils. Polish Journl of Environmentl tudies,, oros, E., ćmg,., Kuhrski, J., & Wyszkowsk, J. (). The usefulness of orgni sustnes nd plnt growth in neutrlizing the effets of zin on the iohemil properties of soil. Fresenius Environmentl ulletin, (), orowik,., Wyszkowsk, J., Kuhrski, J., ćmg,., oros-ljszner, E., & Tomkiel,. (4). ensitivity of soil enzymes to exessive zin onentrtions. Journl of Elementology, 9(3),

17 Wter ir oil Pollut (8) 9: 35 Pge 7 of 8 35 orowik,., Wyszkowsk, J., & Wyszkowski,. (7). Resistne of eroi miroorgnisms nd soil enzyme response to soil ontmintion with Ekodiesel Ultr fuel. Environmentl iene nd Pollution Reserh, 4, rh,., Dormieux, L., Kondo, D., & Viro, G. (7). trength properties of nnoporous mterils: 3-lyered sed nonliner homogeniztion pproh with interfe effets. Interntionl Journl of Engineering iene, 5, 8 4. rdl,.. (4). dsorption of hevy metl ions on soils nd soils onstituents. Journl of Colloid nd Interfe iene, 77(), 8. De Leij, F...., Whipps, J.., & Lynh, J.. (993). The use of olony development for the hrteriztion of teril ommunities in soil nd on roots. iroil Eology, 7, DeLim,J..,Cmilo,F.F.,Fez,R.,&Cruz,..(7). new pproh to sepiolite dispersion y tretment with ioni liquids. pplied Cly iene, 43, Epelde, L., eerril, J.., Kowlhuk, G.., Deng, Y., Zhou, J., & Grisu, C. (). Impt of metl pollution nd Thlspi erulesens growth on soil miroil ommunities. pplied nd Environmentl iroiology, 76(3), lim,., Conte, P., & Piolo,. (3). Potentil vilility of hevy metls to phytoextrtion from ontminted soils indued y exogenous humi sustnes. Chemosphere, 5(), rris D.C. (6). Quntittive hemil nlysis. ihelson Lortory Chine Lke U. W Freemn nd Compny 7th edition, 8. Kzyńsk, G., orowik,., & Wyszkowsk, J. (5). oil dehydrogenses s n inditor of ontmintion of the environment with petroleum produts. Wter, ir, & oil Pollution, 6(), 37. Khlid,., hhid,., Neel, N. K., urtz,., ii, I., & Dumt, C. (7). omprison of tehnologies for remedition of hevy metl ontminted soils. Journl of Geohemil Explortion, 8(Prt ), Kızılky, R., şkın, T., yrklı,., & ğlm,. (4). iroiologil hrteristis of soils ontminted with hevy metls. Europen Journl of oil iology, 4(), 95. Kouhou,., Ris, N., Elsss, F., Duply, J., Fhli, N., & Ghhtouli, N. E. L. (7). Effets of long-term hevy metls ontmintion on soil miroil hrteristis in lreous griulturl lnds (iss plin, North oroo). Journl of terils nd Environmentl ienes, 8(), Krężel,., & ret, W. (6). The iologil inorgni hemistry of zin ions. rhives of iohemistry nd iophysis, 6, 3 9. Kuhrski, J., Wiezorek, K., & Wyszkowsk, J. (). Chnges in the enzymti tivity in sndy lom soil exposed to zin pressure. Journl of Elementology, 6(4), Lehmnn, J., & Rondon,. (6). io-hr soil mngement on highly wethered soils in the humid tropis. In N. Uphoff (Ed.), iologil pprohes to sustinle soil systems (pp ). o Rton: CRC Press. Lehmnn, J., Rillig,. C., Thies, J., siello, C.., okdy, W. C., & Crowley, D. (). iohr effets on soil iot review. oil iology nd iohemistry, 43(9), Ling,., Lehmnn, J., olomon, D., Kinyngi, J., Grossmn, J., O Neill,., kjemstd, J. O., Thies, J., Luizão, F. J., Petersen, J., & Neves, E. G. (6). lk ron inreses tion exhnge pity in soils. oil iene oiety of meri Journl, 7, donld, C.., Cmpell, C. D., on, J. R., & ingh,. K. (8). ultiple profling of soil miroil ommunities identifies potentil geneti mrkers of metl-enrihed sewge sludge. FE iroiology Eology, 65, hr,., Wng, P., li,., wsthi,. K., Lhori,.., Wng, Q., Li, R., & Zhng, Z. (6). Chllenges nd opportunities in the phytoremedition of hevy metls ontminted soils: review. Eotoxiology nd Environmentl fety, 6,. lndrino,., ollino, O., uoso,., Giomino,., L Gioi, C., & entsti, E. (). umultion of hevy metls from ontminted soil to plnts nd evlution of soil remedition y vermiulite. Chemosphere, 8(), oreno, L., stid, F., Ros,., ernández, T., & Grí, C. (9). oil orgni ron uffers hevy metl ontmintion on semirid soils: effet of different metl thresholds levels on soil miroil tivity. Europen Journl of oil iology, 45(3), 8. Orwin, K.., & Wrdle, D.. (4). New indies for quntifying the resistne nd resiliene of soil iot to exogenous disturnes. oil iology nd iohemistry, 36,97 9. Pérez de or,., Orteg-Clvo, J. J., Crer, F., & dejón, E. (5). Chnges in enzyme tivities nd miroil iomss fter in situ^ remedition of hevy metl-ontminted soil. pplied oil Eology, 8(), heng, P. X., Ting, Y.-P., Chen, J. P., & ong, L. (4). orption of led, opper, dmium, zin, nd nikel y mrine lgl iomss: hrteriztion of iosorptive pity nd investigtion of mehnisms. Journl of Colloid nd Interfe iene, 75(), 3 4. ttoft In. 4. ttisti (dt nlysis softwre system), version.. ville t teiner, C., Ds, K. C., Gri,., Förster,., & Zeh, W. (8). Chrol nd smoke extrt stimulte the soil miroil ommunity in highly wethered xnthi Ferrlsol. Pedoiologi, 5(5), trhel, R., Wyszkowsk, J., & mg,. (7). The role of ompost in stilizing the miroiologil nd iohemil properties of zin-stressed soil. Wter, ir, & oil Pollution, 8, 349. un, Y., un, G., Xu, Y., Wng, L., Ling, X., & Lin, D. (3). ssessment of sepiolite for immoiliztion of dmiumontminted soils. Geoderm, 93-94, un, Y., Zho, D., Xu, Y., Wng, L., Ling, X., & hen, Y. (6). Effets of sepiolite on stiliztion remedition of hevy metl-ontminted soil nd its eologil evlution. Frontiers of Environmentl iene & Engineering, (), zó, L. P. (4). Chrteriztion of lginite humi id ontent. Deslintion, 63, Ti, D., Udovi,., & Lestn, D. (). Immoiliztion of potentilly toxi metls using different soil mendments. Chemosphere, 85(4), Wiezorek, K., Wyszkowsk, J., & Kuhrski, J. (4). Influene of zin, opper, nikel, dmium nd led in soils on id

18 35 Pge 8 of 8 Wter ir oil Pollut (8) 9: 35 phosphtse tivity. Fresenius Environmentl ulletin, 3(), Wu, X., Liu, C., Qi,., Zhng, X., Di, J., Zhng, Q., Zhng, L., Wu, Y., & Peng, X. (6). ynthesis nd dsorption properties of hlloysite/ron nnoomposites nd hlloysitederived ron nnotues. pplied Cly iene, 9, Wyszkowsk, J., orowik,., Kuhrski,., & Kuhrski, J. (3). Effet of dmium, opper nd zin on plnts, soil miroorgnisms nd soil enzymes. Journl of Elementology, 8(4), Wyszkowsk, J., oros-ljszner, E., & Kuhrski, J. (5). iroiologil nd iohemil properties of soil ontminted with zin nd fertilized with fermented rk, kertin nd ellulose. Fresenius Environmentl ulletin, 4(), Wyszkowsk, J., oros-ljszner, E., orowik,., ćmg,., Kuhrski, J., & Tomkiel,. (6). Implition of zin exess on soil helth. Journl of Environmentl iene nd elth - Prt, 5(5), 6 7. Yng, Z. X., Liu,. Q., Zheng, D. W., & Feng,. D. (6). Effets of dium, zin nd led on soil enzyme tivities. Journl of Environmentl ienes, 8(6), Yun, P., Tn, D., & nni-ergy, F. (5). Properties nd pplitions of hlloysite nnotues: reent reserh dvnes nd future prospets. pplied Cly iene,, Zhini,., Pietrini, F., ugnozz, G.., Iori, V., Pietrosnti, L., & ssi,. (9). etl tolerne, umultion nd trnslotion in poplr nd willow lones treted with dmium in hydroponis. Wter, ir, & oil Pollution, 97,3 34. Zhi, R., Zhng,., Liu, L., Xie, Y., Zhng,., & Liu, J. (). Immoiliztion of enzyme iotlyst on nturl hlloysite nnotues. Ctlysis Communitions, (4),