Review of Chromium

Speciation Research
 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
 Chromium Exists as Several
Chemical Species
Most common oxidation states: 0, +3, +6

0: Elemental Chromium (Cr)

+3: Trivalent Chromium
Species: Cr+3, Cr2O3
+6: Hexavalent Chromium
Species: CrO42-, 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)
Chromium Eh-pH Diagram
1.2
1.0 Cr2O7 -
0.8
0.6
Eh (volts)

0.4 3+ CrO4 2-
Cr
0.2
0.0
-0.2 Cr2O3
-0.4
-0.6

0 2 4 6 8 10 12 14
pH
 Fate of Chromium in CCA-
Treatment Process
Treating Solution Treated Wood

CrO3 CrAsO4
CuO Cu(OH)CrAsO4
As2O5 CuCrO4
Cr(OH)3
Cr6+/wood complexes
Cr3+/wood complexes
Cu2+/wood complexes

Cr+6 Cr+3
 Research Objective
Examine the fate and behavior of
hexavalent chromium in various
environmental media impacted by CCA
0.0 mg Cr+6/l 0.3 mg Cr+6/l 0.6 mg Cr+6/l
Alkaline Digestion
SW-846 Method 3060A
 IC System
Detector

Analytical
Integrator
Column

Guard
Column

LC Pump
 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)
Soil Types
 Reduction in Total Cr+6 with Time

600 Sand CrVI (mg/kg)

Clay CrVI (mg/kg)
Organic CrVI (mg/kg)
500
Conc. of CrVI (mg/kg)

400

300

200

100

0
0 20 40 60 80 100 120 140 160 180 200
Time (days)
Experiment 2

How Much CrVI is in

CCA-Treated Wood
 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
 Experiment 3

Under what leaching conditions

would Cr+6 form?
 Chromium Leachability as a Function of Time
(weathered wood sample)
35
Cr(mg/l)
CrVI(mg/l)
30

25
Conc. of Cr (mg/l)

20

15

10

0
0 2 4 6 8 10 12 14
pH
 Chromium Leachability as a Function of Time
(weathered wood sample)
35
MSW Landfill Cr(mg/l)
Leachate CrVI(mg/l)
30
Alkaline
Leachate
25 TCLP &
Conc. of Cr (mg/l)

SPLP
20

15

10

0
0 2 4 6 8 10 12 14
pH
 Experiment 4

Will Cr+6 be formed in simulated

alkaline leachate?
Scenario: saturated concrete
 Chromium Leaching in Concrete Leachate

Cr(mg/l)
0.6 CrVI(mg/l)

0.5
Conc. of Cr (mg/l)

0.4

0.3

0.2

0.1

0
0.25 pcf CCA Wood 0.6 pcf CCA Wood 2.5 pcf CCA Wood
Sample
 Experiment 5

Is Cr+6 formed during combustion

of CCA-treated wood?
 45 Total Cr (mg/kg)
CrVI (mg/kg)
40

35
Conc. of Cr (mg/l)

30

25

20

15

10

0
Untreated 0.25 pcf CCA 0.6 pcf CCA 2.5 pcf CCA Weathered C&D C&D
wood Wood wood wood CCA wood Recycling Recycling
(0.6 pcf) Facility B Facility C
Sample