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TCE and 1,2-DCE Biotransformation Inside a Biologically Active Zone

Environmental Science and Engineering Rice University, Houston, Texas

Chlorinated Solvents
Chlorinated solvents (including PCE and TCE) are a major concern for a number of U.S. industries. Generally resistant to biodegradation under aerobic subsurface conditions. TCE can biodegrade under anaerobic conditions in groundwater to form 1,2-DCE, vinyl chloride, or ethene. Anaerobic biodegradation requires a substrate.

Types of Biodegradation (from Wiedemeier et al., 1996)

Type I - microbial substrates added along with chlorinated solvents


biodegradation is generally rapid and dehalogenation is promoted

Type II - microbial substrates exist naturally, in lower levels than in Type I


biodegradation/dehalogenation rates slower than Type I

Type III - low substrate availability


nearly non-existent biodegradation/dehalogenation

Objectives of Study
Develop a mechanism to account for the rapid decline in concentrations near a source, followed by a slow decline throughout the off-site plume. Incorporate biologically active zone (BAZ) into Bioplume II. Model the biodegradation process for chlorinated hydrocarbons at an actual field site. Test the model against measured field data near the source and in the plume.

BAZ Concept
A

Biologically Active Zone is a zone where

significant co-disposal of substrates has occurred, and significant dechlorination is taking place. Inside the BAZ, TCE 1,2-DCE is approximated by a first-order decay reaction (k1). DCE VC is also a first-order decay reaction with independent decay constant (k2). The BAZ is surrounded by areas of negligible dechlorination activity.

Anatomy of a BAZ
Direction of Flow Contamination (TCE) ADVECTION DISPERSION BIODEGRADATION ADVECTION DISPERSION

Degradation Product (DCE)

ADVECTION DISPERSION BIODEGRADATION

ADVECTION DISPERSION

Substrate (Acetone, IPA)

ADVECTION DISPERSION BIODEGRADATION

Biologically Active Zone (BAZ)

Phoenix Site Background


Detection of TCE in wells (1981) led to the discovery of three distinct plumes of chlorinated solvents. A 5+ mile long shallow plume extends downgradient from former industrial use of TCE, acetone, and isopropyl alcohol. 1,2-DCE plume follows TCE plume; DCE is higher than TCE near source, much lower downgradient.

Plan view of Phoenix site


Phoenix Mtns.
0 1 (miles) 2 Arizona Grand Canal Canal Old Crosscu t Canal

Camelback Mtns .

F'

N
Rid Canal

Papag o Butte s Salt

River

Regional Geologic Cross-section


130 0
Elevat ion in feet above MSL

Canal

Site

Elevation in feet above MSL

+1400 ft
70 0
1 0 0 0 ft

Area of detai

MSL

Vertical exaggeration 5:1


-2000 ft

3 mile s

Phoenix TCE Plume

N
50 g/L

/L 5 g

g/ L 0 100

50
500 g/L 100 g/L

L g/ 0

Study Facility 5000 ft Approximate Model Boundary

5 g/L Bedrock Ridge

Phoenix Contamination Sources


Over 400,000 kg of TCE disposed of or spilled on site between 1957 and 1974. DCE was never used at the site. Most chemicals were deposited in a dry well along with large quantities of acetone and isopropyl alcohol (IPA). Off-site monitoring showed no acetone or IPA. Maximum TCE levels were 307,000 g/L.

1992 TCE and DCE Centerline Concentrations


5 4 3 2 1 0 0 2000 4000 6000 8000 10000 12000 14000 TCE 1,2-DCE

Log(Conc, g/L)

Distance from Source (ft)

Co-Disposed Substrates
Along with the TCE, over 200,000 gallons of IPA and almost 100,000 gallons of acetone were disposed at the site. The equivalent substrate mass necessary to convert all the TCE to VC was compared with the substrate mass disposed. Enough substrate was co-disposed to consume over 10 times the total TCE disposed at the site.

Domenico Analytical Solution


Analytical solution to vertical plane source with constant concentration (Domenico et al., 1982). Approximates the concentrations downgradient from a source assuming no biodegradation. Without a BAZ, the source concentration would be 300,000 g/L, which produces concentrations of 100,000 g/L about 1 2.5 miles downgradient. Actual downgradient concentrations are 500 1000 g/L.

Domenico Analytical Solution


(cont.)

Concentrations 3000 g/L measured just downgradient of BAZ. Domenico solution was also applied starting at the downgradient edge of the BAZ. The Domenico solution using C0 = 3000 g/L more accurately represents the measured plume 1 2.5 miles downgradient of the BAZ.

1991 Measured Concentrations Domenico Analytical Solution


5 4

Domenico results for TCE

Log(Conc, g/L)

3 2 1 0 0 2000 4000 6000 8000 10000 12000 14000 TCE C0 = 3000 1,2-DCE C0 = 100,000

Distance from Source (ft)

First-Order Rate Constants


Several first-order studies were presented at the USEPAs Symposium on Natural Attenuation of Chlorinated Organics in Ground Water, 1996. TCE k1 values ranged from 0.0008 to 0.0115 /day. DCE k2 values ranged from 0.0002 to 0.0090 /day. Substrates in these studies were BTEX and petroleum hydrocarbons.

BIOPLUME II Modifications
Renamed O2 and HC TCE and DCE. Changed biodegradation code to remove TCE from the system and add an equivalent amount of DCE. Model with two spatially variable first-order decay constants for TCE (k1) and DCE (k2). Kept track of difference in molecular weights of TCE and DCE. Tracked the production of VC for mass balance calculations.

Bioplume II Model of Phoenix Site


5000 ft 5000 ft sub-area modeled using modified Bioplume II. Uplifted bedrock downgradient of source affects groundwater flow and transport. Site is characterized by very high hydraulic conductivity (5 10-2 cm/sec). BAZ modeled as 500 ft 500 ft square around sources.

BIOPLUME II Model Results


First-order constants (k1, k2) of 0.01/day for TCE and DCE provided best results. Concentrations near source 100,000 g/L. Concentrations downgradient 1,000 g/L. 75 85% of the TCE converted to VC or ethene. Without the BAZ, concentrations > 100,000 g/L modeled downstream. With a uniform decay constant, the plume disappears less than a mile downstream.

Modeled TCE and 1,2 DCE concentrations for 1991 (from Phoenix site)

1 g/L

10 g/L

100 g/L

1000 g/L

10,000 g/L

Modeled vs. Measured TCE (from Bioplume II)

Modeled TCE Concentrations for 1991 Assuming No Biodegradation

1 g/L 10 g/L 100 g/L 1000 g/L 10,000 g/L 100,000 g/L

Conclusions
Dechlorination in the subsurface near the source occurs where co-disposed substrates are available, fostering microbial growth. Rapid reduction of contaminant concentration near the source indicates the presence of a BAZ. In the BAZ, the TCE diminishes rapidly (from over 100,000 to 3000 g/L).

Conclusions (cont.)
Off-site, the slow reduction of concentrations indicates the absence of dechlorination. The off-site concentration profile can be approximated with the Domenico solution. Downgradient, the plume resembles the constant source results from the Domenico solution with C0 3000 g/L.

Conclusions (cont.)
Bioplume II model shows both the rapid decline in concentrations across the BAZ and the slow dispersive decline in concentrations downgradient of the BAZ. In a BAZ, a significant portion (> 80%) of the disposed solvent can be degraded. It is important to recognize and properly model different biodegradation mechanisms, including areas of rapid dechlorination.