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Research Project:Assessing the Impact of Chromium in
the Environment• Assessing the Impact of Chromium in the
Environment
• Funding provided by the Florida Department of Environmental Protection RCRA Program
Master of Engineering Thesis Topic:
Chromium Speciation in Environmental Media
Impacted by the Wood Preservative Chromated
Copper Arsenate
Mr. Jin-Kun Song
Chromium Exists as Several Chemical Species
Most common oxidation states: 0, +3, +6
0: Elemental Chromium (Cr)
+3: Trivalent ChromiumSpecies: Cr+3, Cr2O3
+6: Hexavalent ChromiumSpecies: CrO4
2-, Cr2O7-
Chromium Speciation Important!
• The characteristics and properties of trivalent chromium and hexavalent chromium are greatly different.
• Cr(VI) is much more toxic and mobile than Cr(III)
Difference between Cr(VI) and Cr(III) Factored into Regulations
RCRA Regulations
40 CFR 261.4(b)(6)(i)
A solid waste that is a characteristic or listed hazardous waste solely because of chromium is not hazardous if…..
• (A) The chromium in the waste is exclusively (or nearly exclusively) trivalent chromium; and
• (B) The waste is generated from an industrial process which uses trivalent chromium exclusively (or nearly exclusively) and the process does not generate hexavalent chromium; and
• (C) The waste is typically and frequently man-aged in non-oxidizing environments.
Cr(III) versus Cr(VI)
• Hexavalent chromium exists in alkaline, strongly oxidizing environments
• Trivalent chromium exists in moderately oxidizing and reduced environments
pH
1.2
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
Cr2O3
CrO4 2-
Cr2O7 -
Cr 3+
Eh
(vo
lts)
0 2 4 6 8 10 12 14
Chromium Eh-pH Diagram
Fate of Chromium in CCA-Treatment Process
– CrAsO4
– Cu(OH)CrAsO4
– CuCrO4
– Cr(OH)3
– Cr6+/wood complexes– Cr3+/wood complexes– Cu2+/wood complexes
•CrO3
•CuO•As2O5
Treating Solution Treated Wood
Cr+6 Cr+3
Research Objective
• Examine the fate and behavior of hexavalent chromium in various environmental media impacted by CCA
Methods of Cr(VI) Analysis
• Typical chromium measurements are total chromium (Cr(III) + Cr(VI) + other)
• Methods have been developed for Cr(VI) analysis
• Sample holding time is minimal
Methods of Cr(VI) Analysis
• Solvent extraction followed by total chromium analysis
• Colorimetric and Ion Chromatography Methods being Used
The Method of Analysis
• SW-846 Method 7199
(Determination of Hexavalent Chromium in Drinking Water, Groundwater and Industrial Wastewater Effluents by Ion Chromatography)
Experiment 1
• Examination of the fate of hexavalent chromium in soils spiked with CCA solution
• Cr(VI)/Cr(total) concentrations were measured over time
• Leachable Cr(VI) and Cr(III) concentrations measured over time (SPLP)
0
100
200
300
400
500
600
0 5 10 15 20 25
Time (days)
Co
nc
. o
f C
rVI
(mg
/kg
)
Sand CrVI (mg/kg)
Clay CrVI (mg/kg)
Organic CrVI (mg/kg)
Reduction in Total Cr+6 with Time
0
100
200
300
400
500
600
0 20 40 60 80 100 120 140 160 180 200Time (days)
Co
nc
. o
f C
rVI
(mg
/kg
)
Sand CrVI (mg/kg)
Clay CrVI (mg/kg)
Organic CrVI (mg/kg)
Reduction in Total Cr+6 with Time
0
5
10
15
20
25
0 5 10 15 20 25Time (days)
Co
nc
. o
f C
rVI
(mg
/l)
Sand CrVI (mg/l)
Clay CrVI (mg/l)
Organic CrVI (mg/l)
Reduction in Leachable Cr+6 with Time
0
5
10
15
20
25
0 20 40 60 80 100 120 140 160Time (days)
Co
nc
. o
f C
rVI
(mg
/l)
Sand CrVI (mg/l)
Clay CrVI (mg/l)
Organic CrVI (mg/l)
Reduction in Leachable Cr+6 with Time
Results
• Alkaline digestions on CCA-treated wood samples show Cr+6 concentrations in the range 7 to 250 mg/kg (less 3% of all Chromium)
• SPLP leachates have no detectable Cr+6 concentrations
0
5
10
15
20
25
30
35
0 2 4 6 8 10 12 14pH
Con
c. o
f C
r (m
g/l)
Cr(mg/l)
CrVI(mg/l)
Chromium Leachability as a Function of Time(weathered wood sample)
0
5
10
15
20
25
30
35
0 2 4 6 8 10 12 14pH
Con
c. o
f C
r (m
g/l)
Cr(mg/l)
CrVI(mg/l)
Chromium Leachability as a Function of Time(weathered wood sample)
TCLP &SPLP
MSW LandfillLeachate
AlkalineLeachate
0
0.1
0.2
0.3
0.4
0.5
0.6
0.25 pcf CCA Wood 0.6 pcf CCA Wood 2.5 pcf CCA WoodSample
Co
nc
. o
f C
r (m
g/l
)
Cr(mg/l)
CrVI(mg/l)
Chromium Leaching in Concrete Leachate
0
5
10
15
20
25
30
35
40
45
Untreatedwood
0.25 pcf CCAWood
0.6 pcf CCAwood
2.5 pcf CCAwood
WeatheredCCA wood
(0.6 pcf)
C&DRecyclingFacility B
C&DRecyclingFacility C
Sample
Co
nc
. o
f C
r (m
g/l
)
Total Cr (mg/kg)
CrVI (mg/kg)