Supplemental Study for Year 3
Reason for Supplemental Study

Accelerate new lines of research.
Tasks Assoc. with Supplemental
Funds
In-Service Issues


Depletion of Cr, Cu, and As during the service life of CCAtreated wood (task 1)
Quantity of CCA-treated wood used by major industries
(task 2)
Disposal

TCLP and SPLP tests for unburned CCA-treated wood
(task 5)
Literature Review


Laboratory Methods for Cr and As speciation (task 3)
Identify laboratory methods for organics analysis assoc. with
alternative chemicals (task 4)
Task 5:
TCLP and SPLP Tests on
Unburned CCA-Treated Wood
CCA-Treated Wood and
Mulch Leaching Tests
Background


Year 1 Study -- Collected samples of processed
wood from C&D debris recycling facilities in
Florida. Found that approximately 6% of wood
stream was CCA-treated.
Year 2 Study -- Characterized ash from the
combustion of CCA-treated wood and wood
mixtures. Found that the presence of 5% CCAtreated wood caused ash to fail TCLP and be
characterized as a hazardous waste.
Background

No leaching studies were conducted on
unburned CCA-treated wood as part of year
1 and 2 studies.
When is Leaching a Concern?
Leaching during In-Service Use
 Leaching during Storage
 Leaching upon Reuse of Mulch
 Leaching during Disposal

Leaching Tests on Unburned CCA-Treated
Wood in Year 3 Supplemental Project

Leaching of new CCA-treated wood using
standardized regulatory leaching tests

Leaching of wood mulch produced by C&D
debris recycling operations
Leaching of new CCA-treated wood
using standardized regulatory
leaching tests
Types of Leaching Tests

Batch Tests
 Toxicity
Characteristic Leaching Procedure
(TCLP)
 Synthetic Precipitation Leaching Procedure
(SPLP)
Column Tests
 Field Tests

Testing Results to be Discussed

Ten samples of CCA-treated wood
purchased from home supply stores
 TCLP
 SPLP
 Particle

Size
One sample
 TCLP,
SPLP, EP, WET, MEP
Reminder for Arsenic
 Toxicity
Characteristic
 Arsenic:
5 mg/l
 Chromium: 5 mg/l
 Groundwater
 Arsenic:
Cleanup Target Level
0.05 mg/l
 Chromium: 0.10 mg/l
 Copper: 1 mg/l
How are TCLP and SPLP Tests Applied?



TCLP: To determine if solid waste is hazardous by
toxicity characteristic. Note: Discarded arsenicaltreated wood is exempt under RCRA.
TCLP: To determine is hazardous waste can be
land disposed.
SPLP: To determine if land-applied waste or
contaminated soil presents a risk to groundwater
from chemical leaching.
TCLP and SPLP
•Batch tests.
•TCLP: Municipal Landfill
•SPLP: Acidic Rain
•100 g of waste per 2 L of
leaching solution.
•Extracted for 18 hours.
•Leachate if filtered and
analyzed.
TCLP: Arsenic
(Sawdust)
14
Concentration (mg/L)
12
10
8
6
4
2
0
A
B
C
D
E
F
G
H
I
J
TCLP: Chromium
(Sawdust)
4.5
Concentration (mg/L)
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
A
B
C
D
E
F
G
H
I
J
TCLP: Copper
(Sawdust)
18
Concentration (mg/L)
16
14
12
10
8
6
4
2
0
A
B
C
D
E
F
G
H
I
J
SPLP: Arsenic
(Sawdust)
9.0
Concentration (mg/l)
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
A
B
C
D
E
F
G
H
I
J
SPLP: Chromium
(Sawdust)
Concentration (mg/l)
2.5
2.0
1.5
1.0
0.5
0.0
A
B
C
D
E
F
G
H
I
J
SPLP: Copper
(Sawdust)
4.0
Concentration (mg/l)
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
A
B
C
D
E
F
G
H
I
J
14
TCLP Arsenic
Impact of Particle Size
Concentration (mg/L)
12
10
8
6
4
2
0
Sawdust
Chips
5 Blocks
1 Block
9.0
8.0
SPLP (mg/L)
7.0
6.0
5.0
4.0
Comparison of
SPLP & TCLP (As)
3.0
2.0
1.0
0.0
0.0
2.0
4.0
6.0
8.0
TCLP (mg/L)
10.0
12.0
14.0
8.0
Comparison of
SPLP & TCLP (Cu)
Concentration SPLP (mg/L)
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
0.0
5.0
10.0
Concentration TCLP (mg/L)
15.0
20.0
40.0
35.0
Arsenic (mg/L)
30.0
25.0
Comparison of
Batch Leaching Tests
(Arsenic)
20.0
15.0
10.0
5.0
0.0
TCLP
SPLP
EP
WET
6.0
Multiple Extraction Procedure
(Arsenic)
As Concentration (mg/L)
5.0
4.0
3.0
2.0
1.0
0.0
0
2
4
6
Time (Days)
8
10
Implications of Leaching Tests
Without the exclusion, CCA-treated wood
would often be a characteristic hazardous
waste.
 If SPLP results are compared to GWCTLs,
should not be disposed in an unlined landfill
(based on current policy for other wastes).

What About Reuse Outside the
Landfill (wood mulch)?
Mulch
Bagging
Operation
Leaching from Land Applied Mulch

The SPLP is the test most commonly used to
assess leaching from a land applied waste.
6
C&D Wood Mulch
As in SPLP Leachates
Total Samples: 58
Mean: 153 ug/l
Range: 21 to 658 ug/l
51 Samples > 50 ug/l
5
Observations
4
3
2
1
0
0 50 100
200
300
400
500
Arsenic Concentration (ug/l)
600
Implications for Mulch
When considering SPLP leaching, CCAtreated wood must be present at levels of
less than 1% in wood mulch to meet current
groundwater standards.
 Most C&D wood samples are already greater
than 1%.

Task 2:
Major Use Sectors
Cumulative Arsenic Quantities
60000
Imported
50000
40000
28,800 tons
Net
26,300 tons
30000
20000
10000
Disposed
2,500 tons
Year
2030
2020
2010
2000
1990
1980
0
1970
Cumulative As (tons)
70000
CCA-Treated Wood Production, Florida
AWPI, 94
Total
L&T
Poles
Fence
Cross Ties
2000
1997
1994
1991
1988
1985
1982
1979
1976
1973
1970
Other
1967
50
45
40
35
30
25
20
15
10
5
0
1964
Million cubic feet
Florida Production
U.S. Southern Pine Markets
(From SFPA)
Export
Framing
Other
Foundations
Outdoor
Decks
Highw ay
10%
36%
Marine
18%
Fences
8%
Landscape
15%
Double-Check Values for Florida
 Focus
 Transportation
 Utility
Poles
 Docks
Sector
Transportation Sector

Initial contact with FDOT Districts
Utility Poles
 Compiled
volume of treated wood for
1998 from questionnaires sent out last
year
 Scaled data by population served
 Scaled 1998 data against US historical
pole production statistics
Utility Poles

Preliminary Results
 1600 tons of As (Cumulative)
 6% of all As associated with CCA-treated
wood that is currently in service
Residential Docks
Evaluated data for 3 counties (Alachua,
Dade and Leon)
 For each county, we
 Obtained copies of dock building permits
 Contacted the Property Appraisers Office
 Reviewed aerial photographs
 Contacted dock manufacturers

Results from permits

Alachua



Dade



41 permits reviewed
Approx 486 (freshwater) docks permitted since recording
in 1994
100 permits reviewed
Approx 6000 (marine) docks permitted since recording in
1980
Leon


71 permits reviewed
Approx 450 (freshwater) docks permitted since recording
began in 1993
Material distribution in Alachua County Docks
other + CCA 5%
no CCA
5%
concrete + CCA
5%
only unknown
wood
29%
only CCA
57%
Predominantly Freshwater Docks
Material distribution in Dade County Docks
concrete + all other
9%
no CCA
7%
CCA + all other
15%
only CCA
49%
only concrete
9%
only unknown wood
11%
Predominantly Salt water Docks
Material distribution in Leon County Docks
all other
14%
only CCA
31%
only unknown
wood
55%
Predominantly Freshwater Docks
Preliminary Results
Obtained Typical Retention Levels
 Average Dock Size (Surface Area)
 Typical Design
 Scale Data to County Population


Numbers Computed Appear Low
Possible Reasons for Small No.
Not all docks have been permitted
 Other marine applications (Piers, Bulkheads,
etc….
 SFPA estimates that docks represent 32% of
marine applications

Task 1:
Depletion During Service Life
Task 1: Depletion During Service Life
Methods
Literature Review
 Sample Soils Below CCA-Treated Decks
 Analyze Soil Samples

Task 1: Depletion During Service Life
Sample soils below CCA-Treated Decks

A total of nine decks sampled






3 in Gainesville
3 in Miami
2 in Tallahassee (1 other deck sampled, not CCA-treated)
Samples collected in a grid-like fashion below each deck
Initially, at least 2 background samples were collected near
each deck. Later, a total of 8 were collected
A core sample/sawdust collected
Paynes Prairie
Gainesville Decks
Foot Bridge at NW 34th St
Bivens Arm Park
Miami Decks
A.D. Barnes Park
Oleta River Park
Tropical Park
Tallahassee Decks
Maclay Gardens
Lake Talquin
Tom Brown Park
Sampling Grid
Soil Core
Stains, wood bore, &
Sawdust
XRF Analysis by
Robbins Manufacturing
Deck Retention Levels
Sample Deck Age,yrs XRF Result,pcf
Gainesville
BR
5
0.755
BP
14
0.477
PP
15
Miami
AD
9
0.261
TP
6
0.206
OP
14
Tallahassee
MG
4
0.412
LT
19
0.008
TB
2
0.247
Stains
positive
positive
positive
positive
positive
positive
positive
negative
positive
Grain Size Analysis
Sample ID
Avg. Grain size (mm)
Gainesville
BR
BP
PP
0.343
0.387
0.370
AD
TP
OP
0.339
0.284
0.293
MG
LT
TB
0.387
0.393
0.390
Miami
Tallahassee
Volatiles vs. As concentration
120
OP
Average As conc.
100
80
60
AD
BP
MG
40
TB
20
BR
PP
TP
LT
0
0
5
10
15
Average % Volatile
20
25
30
Percent volatile vs. As conc (Tal)
45.0
12.0
40.0
As
35.0
10.0
% Volatile
8.0
25.0
6.0
20.0
15.0
4.0
10.0
2.0
5.0
0.0
0.0
TB
S01
(T)
TB
S02
(T)
TB
S03
(T)
TB
S04
(T)
TB
S05
(T)
TB
S06
(T)
TB
S07
(T)
TB
TB
TB
S08 Ctrl 1 Ctrl 2
(T)
% Volatile
mg/kg of As
30.0
Metal Concentrations in Soil
Under Sampled Decks
Background Information
The Florida Department of Environmental
Protection has developed a set of risk-based
concentration levels of chemicals in soil:
The Soil Cleanup Target Levels (SCTL)
 Direct Exposure

 Residential
SCTL for As is 0.8 mg/kg.
 Industrial SCTL for As is 3.7 mg/kg.
Background Information
The naturally occurring As concentration in
Florida soils has been measured (Ma et al.
1999).
 Geometric Mean = 0.42 mg/kg

 73%
of soil samples were less than 0.8 mg/kg
 >90% of soil samples were less than 3.7 mg/kg
Location
N
Minimum Maximum
(mg/kg)
(mg/kg)
Mean
(mg/kg)
Mean of
Controls
(mg/kg)
Gainesville: BP
8
15.6
87.9
41.6
7.0
Gainesville: BR
9
4.1
33.2
10.7
0.2
Gainesville: PP
8
3.5
18.1
9.6
0.9
All Gainesville
Samples
25
3.5
87.9
20.2
2.1
Location
N
Minimum Maximum
(mg/kg)
(mg/kg)
Mean
(mg/kg)
Mean of
Controls
(mg/kg)
Tallahassee: LT
8
0.3
0.5
0.5
0.3
Tallahassee: TB
8
8.6
17.2
17.2
1.4
Tallahassee: MG
8
5.1
34
34.0
0.5
All Tallahassee
Samples
24
0.3
17.2
16.4
0.8
Location
N
Minimum Maximum
(mg/kg)
(mg/kg)
Mean
(mg/kg)
Mean of
Controls
(mg/kg)
Tallahassee: LT
8
0.3
0.5
0.5
0.3
Tallahassee: TB
8
8.6
17.2
17.2
1.4
Tallahassee: MG
8
5.1
34
34.0
0.5
All Tallahassee
Samples
16
5.1
17.2
16.4
1.0
Location
N
Minimum Maximum
(mg/kg)
(mg/kg)
Mean
(mg/kg)
Mean of
Controls
(mg/kg)
Miami: AD
8
15.5
81.2
33.9
1.6
Miami: TP
8
1.2
7.5
4.3
1.1
Miami: OP
8
31.7
216.7
79.1
0.5
All Miami Samples
24
1.2
216.7
39.1
1.1
Location
All Samples
N
65
Minimum Maximum
(mg/kg)
(mg/kg)
1.2
216.7
Mean
(mg/kg)
Mean of
Controls
(mg/kg)
28.5
1.5
Summary
The mean As concentration under 8 of the 9
decks exceeded the industrial Florida SCTL
of 3.7 mg/kg.
 Sixty one of 73 of the individual soil samples
exceeded the industrial Florida SCTL.

Additional Sample Collection

Additional control samples were collected
and analyzed to assist with statistical
comparison
100
Arsenic Concentration (mg/kg)
90
Gainesville Site BP
Deck Samples: As = 41.6 mg/kg (n = 8)
Control: As = 7.0 mg/kg (n = 2)
80
70
60
50
40
30
20
10
0
BPC01 BPC02 BP01
BP02
BP03
BP04
BP05
BP06
BP07
BP08
100
80
70
60
50
40
30
20
10
0
BP
C0
1
BP
C0
2
BP
C0
3
BP
C0
4
BP
C0
5
BP
C0
6
BP
C0
7
BP
C0
8
BP
01
BP
02
BP
03
BP
04
BP
05
BP
06
BP
07
BP
08
Arsenic Concentration (mg/kg)
90
Gainesville Site BP
Deck Samples: As = 41.6 mg/kg (n = 8)
Control: As = 2.6 mg/kg (n = 8)
Copper and Chromium Analysis

Analysis of Copper and Chromium has been
completed
250
Comparison of Chromium
and Arsenic
Cr (mg/kg)
200
150
100
50
0
0
50
100
150
As (mg/kg)
200
250
250
Comparison of Copper
and Arsenic
Cu (mg/kg)
200
150
100
50
0
0
50
100
150
As (mg/kg)
200
250
Soil Cores

One soil core was collected from underneath
each deck
Metal Concentration (mg/kg)
0
50
100
150
200
250
0
Depth (in)
1
2
3
4
5
6
Miami Site OP
Soil Core Data
• Arsenic
Metal Concentration (mg/kg)
0
20
40
60
80
0
Depth (in)
1
2
3
4
5
6
Miami Site OP
Soil Core Data
• Arsenic
Metal Concentration (mg/kg)
0
20
40
60
80
0
Depth (in)
1
2
3
4
5
6
Miami Site OP
Soil Core Data
• Arsenic
• Chromium
Metal Concentration (mg/kg)
0
20
40
60
80
0
Depth (in)
1
2
3
4
5
6
Miami Site OP
Soil Core Data
• Arsenic
• Chromium
• Copper
Questions?