PerspectivesPerspectivesfor for useuse ofof induced induced phytoremediatonphytoremediatonfor for reclamationreclamation oof soils polluted f soils polluted by by thethe emissionsemissions from copper smeltersfrom copper smelters–– inin thethe lightlight ofof preliminarypreliminary pot pot

experimentexperiment

Anna Karczewska, Cezary Kabała, Dawid Anna Karczewska, Cezary Kabała, Dawid PańczukPańczuk

InstituteInstitute ofof SoilSoil Science Science andand AgriculturalAgricultural Environment Environment ProtectionProtection, , AgriculturalAgricultural UniversityUniversity ofof Wroclaw, Wroclaw, PolandPoland

International Workshop „Current Developments in Remediation of Contaminated Lands” 27-29 October 2005, IUNG, Puławy

TheThe problem problem ofof soilsoil pollutionpollution withwithheavyheavy metalsmetals inin PolandPoland

-- ofof locallocal importanceimportance, eg.:, eg.:

TheThe neighbourhoodneighbourhood ofof smelterssmelters andand metallurgicalmetallurgicalplantsplants, , FormerFormer centrescentres ofof metal metal miningmining andand processingprocessingOtherOther sitessites, , likelike big big citiescities ((parksparks, , allotmentallotment gardensgardensetc.)etc.)

PolandPoland –– thethe biggestbiggest EuropeanEuropeanproducerproducer ofof coppercopper

CopperCopper IndustryIndustry Region Region Legnica & GłogówLegnica & Głogów

P O L A N D

Warszawa(Warsaw)

Kraków(Cracow)

Wrocław

CopperCopper SmelterSmelter Głogów:Głogów:Cu Cu inin surfacesurface soilsoil horizonshorizons

SourceSource: : GeochemicalGeochemical Atlas Atlas ofof PolandPoland, PIG, PIG

Close vicinity ofcopper smelterLegnica

1983-1990

TheThe strategystrategy ofof reclamationreclamation appliedapplied previouslypreviously ::-- to to immobilizeimmobilize Cu Cu andand Pb Pb inin soilsoil

Methods

1. Liming !2. Enrichment in

organic matterand clay minerals

Solidphase

SoilSolution

Me MeMeMe

Me

MeMe

Me

Surroundings ofcopper smelterLegnica

after reclamation(2001)

Surroundings of copper smelter Głogówafter reclamation(2003)

CurrentCurrent PolishPolish law:law:„„TheThe law law ofof environmentalenvironmental protectionprotection”, 2001”, 2001

ReclamationReclamation ofof pollutedpolluted soilsoil shouldshould leadlead to to removalremoval ofof excessiveexcessive amountsamounts ofof pollutantspollutants, , soso thatthatsoilsoil fulfillsfulfills thethe requirementsrequirements ofof soilsoil standardsstandardsStandardsStandards for for agriculturalagricultural, , forestedforested andand inhabitedinhabitedareasareas (data for a (data for a surfacesurface soilsoil layerlayer):):–– Cu: 150 mg/kg, Pb: 100 mg/kgCu: 150 mg/kg, Pb: 100 mg/kg

A A newnew strategystrategy ofof soilsoil reclamationreclamation ::to to mobilizemobilize metalsmetals ……

… andremovethemfrom soil

Soilsolution

Solid phase

PhytoextractonPhytoextracton= = removalremoval ofofpollutantspollutants togethertogetherwithwith thethe biomassbiomass ofofcultivatedcultivated plantsplants

1. 1. mobilizationmobilization2. 2. uptakeuptake by by rootsroots3. transport to 3. transport to thethe

greengreen partsparts ofof plantplant

1 23

RequirementsRequirements

Plant Plant tolerancetolerance to high metal to high metal concentrationconcentration inin soilsoil

High High efficiencyefficiency ofof metal metal removalremoval::

1.1. High High biomassbiomass concentraionconcentraion(„(„hyperaccumulatorshyperaccumulators”)”)

2.2. LargeLarge biomassbiomass (eg. (eg. willowwillow, , poplarpoplar, , miscanthusmiscanthus, …), …)

3.3. BothBoth: : 1+21+2

InducedInduced hyperaccumulationhyperaccumulation: :

CommonCommon plantsplants, , withwith relativelyrelatively high high biomassbiomassmaizemaizeIndian Indian mustardmustardsunflowersunflower

IntensiveIntensive metal metal uptakeuptake–– inducedinduced by by applicationapplication ofof substancessubstances

dramaticallydramatically increasingincreasing metal metal solubilitysolubility inin soilsoil::ComplexingComplexing agentsagents ((chelatorschelators) ) –– EDTA, DTPAEDTA, DTPAMineralMineral andand organicorganic acidsacidsOtherOther compoundscompounds ((likelike aminoacidsaminoacids), ….. (?)), ….. (?)

SeveralSeveral promisingpromising experimentsexperiments, eg: , eg: HuangHuang & & CunninghamCunningham 19961996

PromisingPromising experimentexperiment((HuangHuang i i CunninghamCunningham 1996, 1996, New JerseyNew Jersey))

InitialInitial soilsoil Pb: Pb: 25002500 mg/kgmg/kgEDTA: 1EDTA: 1--2 g/kg2 g/kgplant: plant: maizemaize ((ZeaZea maysmays))biomassbiomass Pb Pb concentrconcentr. . -- maxmax. . 1100011000 mg/kg mg/kg d.md.m..BiomassBiomass yieldyield: 25 : 25 tonnestonnes/ha/haRequiredRequired Pb Pb concentrationconcentration inin soilsoil 600 mg/kg 600 mg/kg TimeTime neededneeded -- 7 7 yearsyears

ProblemsProblems andand disadvantagesdisadvantagesofof inducedinduced hyperaccumulationhyperaccumulation

• Temporal increase of soluble metal forms insoil affects biota

• Metal leaching into underground water

• Specifity - various metals show differentaffinity to mobilization and various uptake by plants

• plant species, mobilizing agents, theirratio and other parameters should be thoroughly optimized !

OurOur questionquestion::

?? ApplicabilityApplicability ofof inducedinduced hyperraccumulationhyperraccumulation for for removalremoval ofof excessiveexcessive metalsmetals fromfrom soilssoils pollutedpolluted by by thethe emisssionsemisssions fromfrom coppercopper smelterssmelters

??ExperimentalExperimental approachapproach::–– Step 1 Step 1 –– determiningdetermining ofof chemicalchemical formsforms ofof heavyheavy metalsmetals

inin soilssoils–– Step 2 Step 2 –– efficiencyefficiency ofof metal metal mobilizationmobilization by by chelationchelation–– Step 3 Step 3 –– a pot a pot experimentexperiment

Step 1 Step 1 DeterminingDetermining ofof chemicalchemical formsforms ofof heavyheavymetalsmetals inin soilssoils

OperationallyOperationally defineddefined formsforms–– sequentialsequential estractionestraction

by by ZeienZeien & & BrummerBrummer, 1989, 1989–– f1) mobile, f1) mobile, –– f2) exchangeable and chemically f2) exchangeable and chemically sorbedsorbed, , –– f3) occluded in f3) occluded in MnOxMnOx, , –– f4) organically bound, f4) organically bound, –– f5) occluded in amorphous f5) occluded in amorphous FeOxFeOx, , –– f6) occluded in crystalline f6) occluded in crystalline FeOxFeOx–– f7) residual f7) residual

ExaminedExamined: : surface surface (I) (I) andand subsurface subsurface (II) (II) horizons of soilshorizons of soils

Basic Basic propertiesproperties::–– TotalTotal Cu: (I): 248Cu: (I): 248--1080 mg/kg, (II): 251080 mg/kg, (II): 25--138 mg/kg138 mg/kg–– VariousVarious texturetexture (4(4--54 % 54 % clayclay))–– VariousVarious OM (< 4%)OM (< 4%)–– pHpH: 4.9: 4.9--7.07.0

0

200

400

600

800

1000

1200m

g/kg

1 2 3 4 5

Soil No.

Cu

1 - soluble

2 - exch.

3 - MnOx

4 - organic

5 - am. FeOx

6 - cr. FeOx

7 - residual

Surface horizons

0

50

100

150

200

250

300

350m

g/kg

1 2 3 4 5

Soil No.

Pb

1 - soluble2 - exch.

3 - MnOx4 - organic5 - am. FeOx6 - cr. FeOx

7 - residual

Surface horizons

ResultsResults –– Cu & Pb Cu & Pb speciationspeciation

PPredominantredominant fractionsfractions inin surfacesurface horizonshorizons: :

–– f2 f2 ((exchangeableexchangeable andand sorbedsorbed specificallyspecifically)), ,

–– f4f4 ((organicorganic))

different relations between them, different relations between them, asasdependependentdent on soil properties. on soil properties.

ResultsResults –– Cu Cu speciationspeciation

PPredominantredominantfractionsfractions ininsurfacesurface horizonshorizons: : f2 and f4f2 and f4((exchangeableexchangeableandand sorbedsorbed + + organicorganic)), ,

different different relations relations between them, between them, asas dependependentdent on on soil properties. soil properties.

0%

20%

40%

60%

80%

100%

1 2 3 4 5 6

f1f2f3f4f5f6f7

Step 2Step 2CheckingChecking ifif metalsmetals cancan be be mobilizedmobilizedby by chelatingchelating agentsagents

0

200

400

600

800

1000

1200

1A 2A 3A 4A 5A 6A 1B 4B 6B

pl pglp płi płi gs gc ps płi gc

TotalEDTA-Na

Cu

mg/

kg

0

100

200

300

400

1A 2A 3A 4A 5A 6A 1B 4B 6B

TotalEDTA-Na

Pb

In surface (polluted)horizons:

78-95% of total Cu

65-91% of total Pb

extractable by EDTA-Na

DependenceDependence ofof mobilizingmobilizing efectefect on on thetheamountamount ofof complexingcomplexing agentagent appliedapplied to to soilsoil::

1. Sandy soil: 1080 mg/kg Cu, 2. Silty loam: 271 mg/kg Cu

0

50

100

150

200

0102040100

Conc e ntration o f c itric ac id, mg/dm3

mg/kg Cu

Soil 1

Soil 2

DependenceDependence ofof mobilizingmobilizing efectefecton on soilsoil pHpH

Sandy soil, 1080 mg/kg Cu

0

50

100

150

2 3 4 5 6 7 8 9 10 11

0

KWin

KCyt

Ox

KFu

KHu

Cumg/kg

ConclusionsConclusions concerningconcerning metal metal mobilizationmobilization::

ChelatingChelating compoundscompounds: EDTA & : EDTA & citriccitric acidacidmaymay be be usedused as as goodgood Cu Cu andand PbPb--mobilizingmobilizingagentsagentsinin thethe experimentexperiment on on inducedinduced phytoextractionphytoextraction

Step 3:Step 3:A pot A pot experimentexperiment

2 2 variousvarious soilssoils: : –– siltysilty loamloam (Cu: 513, Pb: 180, Zn: 182 mg/kg)(Cu: 513, Pb: 180, Zn: 182 mg/kg)–– sandsand (Cu: 975, Pb: 206, Zn: 270 mg/kg)(Cu: 975, Pb: 206, Zn: 270 mg/kg)

3 Plant 3 Plant speciesspecies ((basedbased on on literatureliterature): ): –– Indian Indian mustardmustard, , –– CommonCommon vetchvetch–– MaizeMaize

2 2 complexingcomplexing agentsagents appliedapplied to to soilsoil::–– EDTA, EDTA, citriccitric acidacid–– DoseDose: 100 mg/kg: 100 mg/kg

PlantsPlants cutcut andand analysedanalysedSoilSoil leachedleached twicetwice (3rd (3rd andand 30th 30th dayday afterafter harvestingharvesting) ) leachatesleachates analysedanalysed

ExperimentalExperimental plotsplots::Pot Pot experimentexperiment

ControlControlIndian Indian mustardmustard

11

MaizeMaize

CommonCommon vetchvetch

PlantPlant

EDTAEDTA77

CitricCitric acidacid66

ControlControl2. 2. SandSand55

EDTAEDTA44

ControlControl33

EDTAEDTA

1. 1. SiltySilty loamloam

22

AdditionAdditionSoilSoilNoNo

PhotoPhoto::Pot Pot experimentexperiment

PhotoPhoto::Pot Pot experimentexperiment

PhotoPhoto::Pot Pot experimentexperiment

ResultsResults

Metal Metal uptakeuptake by by plantsplants::Pot Pot experimentexperiment

Metal Metal concentrationconcentration inin plant plant biomassbiomass, mg/kg , mg/kg d.md.m..

SoilSoil & & plantplantNoNo

338338

2727

2424152152

13131301305858

CuCu

3,73,71. 1. SiltySilty loamloamI. I. mustardmustard

11

2. 2. SandSandMaizeMaize

1. 1. SiltySilty loamloamC. C. vetchvetch

9,59,577

0,40,466

0,80,8554,64,644

0,40,4335,85,822

PbPb

MetalsMetals inin leachatesleachates::Pot Pot experimentexperiment

434434

1111

6,96,9540540

7,37,33853856,76,7

Cu IICu II

385385

4141

3,03,04040

0,570,573753750,490,49

Cu ICu I

MeanMean metal metal concentrationsconcentrations ininleachatesleachates I I andand II, mg/LII, mg/L

SoilSoil & & plantplantNoNo

2525

1,341,34

0,340,343,23,2

0,340,343030

0,250,25

Pb IPb I

0,910,911. 1. SiltySilty loamloamI. I. mustardmustard

11

2. 2. SandSandMaizeMaize

1. 1. SiltySilty loamloamC. C. vetchvetch

8,18,177

0,410,4166

0,380,3855212144

3,423,4233161622

Pb IIPb II

DecreaseDecrease inin soilsoil concentrationconcentration::Plant Plant uptakeuptake vsvs. . leachingleaching

7373

4,64,6

0,880,882626

0,350,353434

0,320,32

Cu (L)Cu (L)

0,280,28

0,020,02

0,020,020,300,30

0,020,020,170,170,040,04

Cu (P)Cu (P)

DecreaseDecrease inin soilsoil concentrconcentr., mg/kg, ., mg/kg, duedue to: plant to: plant uptakeuptake (P) (P) andandleachingleaching (L) (L)

SoilSoil & & plantplantNoNo

0,010,01

0,000,00

0,000,000,010,01

0,000,000,010,010,000,00

Pb (P)Pb (P)

0,050,051. 1. SiltySilty loamloamI. I. mustardmustard

11

2. 2. SandSandMaizeMaize

1. 1. SiltySilty loamloamC. C. vetchvetch

2,92,977

0,160,1666

0,060,06551,11,144

0,170,17332,12,122

Pb (L)Pb (L)

DecreaseDecrease inin soilsoil concentrationconcentration dueduetoto plant plant uptakeuptake andand leachingleaching

wykres

Plan uptake

Leaching

ConclusionsConclusions (1)(1)

Addition of EDTA significantly increased Cu Addition of EDTA significantly increased Cu phytoavailabilityphytoavailability and solubility in both soils and solubility in both soils

However, the highest Cu concentration in biomass However, the highest Cu concentration in biomass (338 mg/kg (338 mg/kg -- in maize), remained far below those in maize), remained far below those considered as typical for considered as typical for hyperaccumulationhyperaccumulation. .

EDTA caused intensive Cu leaching from soilsEDTA caused intensive Cu leaching from soils. .

Technical parameters of induced Technical parameters of induced phytoremediationphytoremediationchosen for this experiment should be therefore chosen for this experiment should be therefore considered as far from being optimized.considered as far from being optimized.

ConclusionsConclusions (2):(2):DirectionsDirections ofof furtherfurther researchresearch::

AttentionAttention shouldshould be be paidpaid to to optimize the kind and optimize the kind and doze of chelating agentdoze of chelating agent

AlternativeAlternative compoundscompounds shouldshould be be examinedexamined to to choosechoose thosethose::–– EasilyEasily transportedtransported inin thethe plantplant–– EasilyEasily biodegradablebiodegradable

FinalFinal questionquestion::

IsIs therethere a a realreal needneed for for removalremoval ofof excessiveexcessive metalsmetalsform form soilssoils??

WhichWhich strategystrategy wouldwould be be moremore environmentalenvironmental--friendlyfriendly: : –– mobilizationmobilization oror immobilizationimmobilization ??

For For nownow ––we do not we do not havehave anyany promisingpromising resultsresults

ThankThank youyou for for youryourattentionattention!! 1 2

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