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Remediation of metal polluted Remediation of metal polluted
urban soils and evaluation of dangerurban soils and evaluation of danger
to human health assessed by to human health assessed by
in vitroin vitro oral bioaccessiblity testsoral bioaccessiblity tests
Roussel H.Roussel H., Waterlot C., Pruvot C., Bacquet M., , Waterlot C., Pruvot C., Bacquet M.,
Martel B., Leprêtre A., Ciesielski H., Philippe S., Martel B., Leprêtre A., Ciesielski H., Philippe S.,
Mazzuca M., Douay F.Mazzuca M., Douay F.
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ContextContext
•• Historic Historic
contaminationcontamination
� Metaleurop Nord (Noyelles-Godault) = Lead smelter
� Umicore (Auby) = Zinc smelter
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Pb isoconcentration curves (mg/kg)
ContextContext
Agricultural topsoils
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ContextContext
•• Ratio of Ratio of UrbanUrban vs vs RegionalRegional agricultural agricultural topsoilstopsoils
•• Ratio of Ratio of UrbanUrban vs vs Local agricultural Local agricultural topsoilstopsoils
METALEUROP (Pb smelter)
UMICORE (Zn smelter)
0
20
40
60
80
100
120
140
Ag As Bi Cd Co Cr Cu Hg In Ni Pb Sb Se Sn Th Tl U Zn
0
1
2
3
4
5
6
7
8
Ag As Bi Cd Co Cr Cu Hg In Ni Pb Sb Se Sn Th Tl U Zn
ME
UM
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ContextContext
•• SoilSoil ingestion ingestion withwith hand to hand to mouthmouth transfertransfer
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6
Lead blood level (> 100 µg L-1)
� 10 to 15 % of children (2 to 4 years old, from 1994 to 2002)
� up to 30 % under the prevailing winds
� 2.4 % in 2004 after smelter closedown
But the actual mean lead blood level is still over the national mean value (42 µg L-1 instead of 27 µg L-1 respectively)
ContextContext
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SoilSoil remediationsremediations
•• SoilSoil removalremoval
•• PhytomanagmentPhytomanagment
•• AmendmentsAmendments
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AimsAims
•• Immobilize metals in soilsImmobilize metals in soils
•• Reduce metal bioavailability to biotaReduce metal bioavailability to biota
•• Lower children exposureLower children exposure
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MaterialsMaterials and and methodsmethods
•• SoilSoil physicophysico--chemicalchemical parametersparameters
Garden pH CEC C/N Organic Matter CaCO3 total P2O5
cmol+/kg g/kg g/kg g/kg
1 7.1 22.5 14.8 72.5 7.69 1.29
2 7.8 13.8 21.2 97.8 32.70 2.07
Garden distance Sand Clay Cd Pb Zn
m % % mg/kg mg/kg mg/kg
1 ME 459 19.2 28.8 29.9 1830.2 1050
2 U 899 30.6 18.9 21.5 623.0 2970
2 urban topsoils were sampled (0-25 cm):
�Close to the Pb smelter (garden 1)�Close to the Zn smelter (garden 2)
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MaterialsMaterials and and methodsmethods
•• 4 Amendment types4 Amendment types
–– InorganicsInorganics : :
•• PhosphatePhosphate
•• Fly ashFly ash
–– Organics : Organics :
•• D60D60
•• polypolyββCDCD--CTRCTR
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MaterialsMaterials and and methodsmethods
–– 2 2 InorganicsInorganics : :
•• Phosphate (Phosphate (diammoniumdiammonium phosphate + phosphate +
hydroxyapatitehydroxyapatite ))
•• Fly ashFly ash
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PhosphateDiammonium phosphate + hydroxyapatite
3,4Zn
40 700N
111 000P2O5
< 2Pb
< 0,5Cd
Concentration
(mg kg-1)Elements
3,4Zn
40 700N
111 000P2O5
< 2Pb
< 0,5Cd
Concentration
(mg kg-1)Elements
Applied dose: molecular ratio P/(Cd+Pb+Zn) = 3/5
Chemical Parameters
MaterialsMaterials and and methodsmethods
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Fly ash
Silico-aluminate fly ashfrom Carling (SEDELINE®)
5 460S soluble (mg kg-1)
3,7Se
21,4As
0,87Hg
1,0Cd
142Pb
31,5Co
93,8Ni
168,5Cr
257Zn
717Mn
81Cu
122200Al
37900Fe
Total contents(mg kg-1)
1,92K+ échangeable (cmol+ kg-1)
14,55Mg2+ échangeable (cmol+ kg-1)
0,59Na+ échangeable (cmol+ kg-1)
101,4Ca2+ échangeable (cmol+ kg-1)
5,1CEC (cmol+ kg-1)
0,094P2O5 (g kg-1)
21CaCO3 total (g kg-1)
0,22N (g kg-1)
5 460S soluble (mg kg-1)
3,7Se
21,4As
0,87Hg
1,0Cd
142Pb
31,5Co
93,8Ni
168,5Cr
257Zn
717Mn
81Cu
122200Al
37900Fe
Total contents(mg kg-1)
1,92K+ échangeable (cmol+ kg-1)
14,55Mg2+ échangeable (cmol+ kg-1)
0,59Na+ échangeable (cmol+ kg-1)
101,4Ca2+ échangeable (cmol+ kg-1)
5,1CEC (cmol+ kg-1)
0,094P2O5 (g kg-1)
21CaCO3 total (g kg-1)
0,22N (g kg-1)
Applied dose: 6%
Chemical parameters
MaterialsMaterials and and methodsmethods
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MaterialsMaterials and and methodsmethods
–– Organics : Organics :
•• D60 (industrial polymer made of D60 (industrial polymer made of
polyacrylatepolyacrylate from ATOCHEM)from ATOCHEM)
•• polypolyββCDCD--CTR CTR (synthesised polymer (synthesised polymer
made of made of cyclodextrinecyclodextrine and citric acid) and citric acid)
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Orgnic polymer made of polyacrylate, under industrial licence (ARKEMA)
Pb2+ Cd2+ Zn2+
430 288 205
Saturation capacity of D60 expressed in mg/g
- Cationic exchange capacity: 8.4 mmol g-1
- N°CAS : 9033-79-8- water absorption rate: (« tea bag » technic: 65g/g)- Apparent density: 0.75 g/cm3.
D60
MaterialsMaterials and and methodsmethods
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(1) Martel, B.; Ruffin, D.; Weltrowski, M.; Lekchiri, Y.; Morcellet, M. J. Appl. Polym. Sci. 2005, 97, 433-442
Polymer made of cyclodextrine and citric acid
polyββββCD-CTR
10 min 120 min 10 min 120 min 10 min 120 min
76 % 85 % 77 % 100 % 50 % 100 %
Cationic exchange capacity : 4.3 mmol g-1
Cd2+ Pb2+ Zn2+
(2) Ducoroy, L.; Bacquet, M.; Martel, B.; Morcellet, M. Reactive & Functional polymers 2008, 68, 594-600
Percentages of metal absorbed at different time (pH = 5) [Me2+]t=0 = 100 mg L-1
Materials and methodsMaterials and methods
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Materials and methodsMaterials and methods•• 2 Topsoils 2 Topsoils
•• Drying <40Drying <40°°CC
•• Grinding <Grinding <1010 mm mm
•• Soil homogeneisation (Soil homogeneisation (10 min)10 min)
•• Maturation for 6 months at 20 % humidity with tap water Maturation for 6 months at 20 % humidity with tap water (pH=7)(pH=7)
•• Pots of 3 LPots of 3 L
Incubation
IncubationBefore mixing
Homogeneisation After mixing
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Materials and methodsMaterials and methods•• In vitroIn vitro Bioaccessibility test (following Bioaccessibility test (following
BARGE protocol)BARGE protocol)
Gastro-intestinal
extraction
+ 27 mL jus Duodenal+ 9 mL Bile
Centrifugation3000 g - 5 min
End-over-endrotation
4h00 - 37°C
Residual soil
..............Chyme
............
(pH = 6.3+_ 0.5)
Filtration 27µm(Whatman n°41)
Analysis AAS
............
0.6 g soil
............................................................ ........................
+ 9 mL Saliva
+ 13.5 mL Gastric juice pH = 1.2 - 1.7
....................................
(pH = 6.5+_ 0.5)
Manualshaking
5 - 15 min
Chyme
..........................Residual soil
1h00 - 37°C
End-over-endrotation
Centrifugation3000 g - 5 min
Gastric extraction
Filtration 27µm(Whatman n°41)
Analysis AAS
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ResultsResults
•• Reference NIST 2710Reference NIST 2710
Total (mg kg-1)
(Ellickson et al., 2001) (Denys et al., 2007)(Oomen
et al.,2004)This study
Gastric Intestinal Gastric Intestinal Intestinal Gastric Intestinal
Cd 21,8 55-65 57,1 ±±±±2,8 27,2 ±±±± 8,3
Pb 5532 76,1 ± 11 10,7 ± 2,3 79 ± 4 25 ± 1 30-35 55 ±±±± 6,7 30,6 ±±±± 2,5
Zn 6952 20,5 ±±±± 3,8 11,1 ±±±± 1,2
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ResultsResults
•• Difference between Difference between
bioaccessibility bioaccessibility
percentages of percentages of
amended over nonamended over non--
amended soils. amended soils.
Mean and SD Mean and SD
(n=6).(n=6).
-30
-20
-10
0
10
20
30
Cd
PbZn
-14
-12
-10
-8
-6
-4
-2
0
2
4
6
Phosphate Fly ash D60 BCD-TCR
A
B
-30
-20
-10
0
10
20
30
-30
-20
-10
0
10
20
30
-30
-20
-10
0
10
20
30
Cd
PbZn
Cd
PbZn
-14
-12
-10
-8
-6
-4
-2
0
2
4
6
-14
-12
-10
-8
-6
-4
-2
0
2
4
6
-14
-12
-10
-8
-6
-4
-2
0
2
4
6
Phosphate Fly ash D60 BCD-TCRPhosphate Fly ash D60 BCD-TCR
A
B Gastro-intestinal
Gastric
*
**
*
*
***
*
* Significant Wilcoxon paired t test
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DiscussionDiscussion
•• Interesting effects of organic amendments Interesting effects of organic amendments
for the for the reductionreduction of gastroof gastro--intestinal intestinal
bioaccessibility of Cd, Pb and Zn in soils.bioaccessibility of Cd, Pb and Zn in soils.
•• Decrease of Decrease of 4 to 9 4 to 9 % of bioaccessibility.% of bioaccessibility.
•• High variation to be refine with more tests High variation to be refine with more tests
(including other compartments as plants, (including other compartments as plants,
animals, etc.).animals, etc.).
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ConclusionConclusion
•• More work should be done on amendment More work should be done on amendment
effects and fine particles (<50 effects and fine particles (<50 µµm)m)
•• LongLong--term effects of all amendments and term effects of all amendments and
especially on polymers ?especially on polymers ?
•• Amendments and dust ?Amendments and dust ?
•• Tests on Eisenia and plants (Ray Grass Tests on Eisenia and plants (Ray Grass
and Clover)and Clover)
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•• Thank you for your attention !Thank you for your attention !
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Post Doctoral position Post Doctoral position
availableavailable
Oral bioavailability assessment Oral bioavailability assessment
of trace elements in soils and of trace elements in soils and
dust from an area heavily dust from an area heavily
contaminated by a former lead contaminated by a former lead
smeltersmelter