1) An 11-month field pilot test was conducted using permeable reactive barriers of EHC™ and KB-1® to treat groundwater contaminated with TCE, cis-1,2-DCE, and VC at a site near a river. 2) The treatment successfully reduced contaminant concentrations to below regulatory levels at the riverbank and reduced TCE by 99.5% in the source area. 3) Monitoring of secondary effects showed that the treatment did not increase concentrations of arsenic or manganese as initially feared, but instead significantly reduced concentrations of iron, cyanide, sulfate and manganese through precipitation reactions under low redox conditions.

1. Anticipating Secondary Concerns with In-situ Chemical Reduction:
Data from an Integrated Pilot Study of EHC™ and KB-1™
James Peale (jpeale@mfainc.org), Erik Bakkom – Maul Foster & Alongi, Inc.
Fayaz Lakhwala, Jim Mueller, Josephine Molin, Andrzej Przepiora – Adventus Americas
ABSTRACT: Groundwater at a silicon wafer manufacturing facility in Portland, Oregon
was impacted by TCE and its degradation products, cis-1,2-DCE and VC, up to
maximum concentrations of 592, 90, and 5 mg/L, respectively. Groundwater discharges
to a river approximately 450 ft downgradient of a suspected source area. An 11-month
field pilot test was conducted in the source area and at the riverbank area. Permeable
reactive barriers (PRBs) consisting of EHC™ and KB-1® were installed at depths
ranging from approximately 50 to 130 feet below ground surface. At the riverbank, TCE
and its degradation products were reduced to below regulatory screening levels or
detection limits, and chlorinated VOC mass reduction of 99.99% was achieved. In the
source area, TCE concentrations were reduced by approximately 99.5%, and overall
concentrations of chlorinated VOCs (CVOCs) were reduced by between 46-99%.
Significant concentrations of fully dechlorinated ethene were produced. Degradation rates
were increased above background by 90-94%. The data confirmed that enhanced in-situ
bioremediation (EIB) was successful, but concerns regarding the technology remain.
First, mobilization of redox-sensitive metals (arsenic [As] and manganese [Mn]) due
to increased reducing conditions was identified as a concern for receptors in the receiving
surface water body. Increased downgradient concentrations of iron (Fe, due to the zero-
valent iron component of EHC™) were also a concern. The pilot study data confirmed
that in-situ chemical reduction (ISCR) using EHC™ does not increase concentrations of
As and Mn downgradient of the PRB – instead, significant reductions were observed. As
an unanticipated benefit, weak-acid dissociable cyanide concentrations were also
significantly reduced.
INTRODUCTION
EHC™ is composed of controlled-release, complex organic carbon plus zero-valent
iron (ZVI). When applied to the subsurface environment, EHC induces extremely low
redox (Eh) conditions that facilitate the rapid and complete destruction of chlorinated
organics via in situ chemical reduction reactions. KB-1 is a specialized inoculum
containing Dehalococcoides ethenogenes (Dhc) and other microbes that enhance
complete mineralization of certain compounds. Both EHC and KB-1 are established
commercial products with documented success at remediating sites with CVOCs.
Prior to this project, injection of EHC had not been attempted at depths corresponding
to those presented at this site. Similarly, EHC and KB-1 had not been field tested at sites
with TCE concentrations characteristic of the presence of non-aqueous phase liquid
(NAPL). Details regarding the installation and monitoring of the field-scale pilot study
were summarized previously (Peale, 2007). Figure 1 generally describes the layout of the
riverbank pilot study area, which is the focus of this paper.

2. FIGURE 1: Riverbank pilot study area layout.
The results confirmed that the combined approach was successful – regulatory
screening levels were achieved at the riverbank, and TCE DNAPL (if present) was
degraded in the source area. The CVOC results are summarized in Table 1.
TABLE 1: Concentrations of CVOCs in groundwater – baseline and 18 months post-injection.
Riverbank Area Concentration (ug/L) Percent Reduction
Well Date TCE DCE VC CVOCs Total CVOC
--
Regulatory Screening Level 3 70 2.4
WS-22-112 Jun-06 584 3,074 474 4,132 -
(within PRB) Feb-08 ND ND ND ND 99.99%
WS-11-125 May-06 22.9 10,557 2,490 13,069 -
(Downgradient, with Feb-08 ND 80 16.4 96.4 99.3%
MGP DNAPL)
WS-20-112 Jun-06 1,100 10,067 1,610 12,777 -
(Downgradient) Feb-08 ND 0.73 ND 0.73 99.99%
Source Area Concentration (ug/L) Percent Reduction
Well Date TCE DCE VC CVOCs Total CVOC
WS-19-71 Jun-06 6,500 89,010 30 95,540 -
(within PRB) Feb-08 ND 120 10,500 10,620 88.9%
WS-19-101 Jun-06 92,900 39,497 22 132,419 -
(within PRB) Feb-08 ND 94.3 156 250 99.8%
WS-18-71 Jun-06 7,990 91,624 26 99,640 -
(Downgradient) Feb-08 102 6,541 16,600 23,243 76.7%
WS-18-101 Jun-06 198,000 34,133 41 232,174 -
(Downgradient) Feb-08 2,920 97,315 24,900 125,135 46%

3. The analytical results confirmed the success of the combined approach for EIB, and
may be discussed in more detail under separate cover. In short, the primary concern (will
EIB achieve regulatory screening levels for CVOCs) has been addressed. This paper
investigates the secondary effects of the amendment on groundwater geochemistry that
could affect remediation decisions by the property owner and the regulatory agency.
SITE DESCRIPTION
Operations at the facility began in 1980, after the site had been developed by filling
during the 1970s. Prior to development, portions of the property were used for waste
disposal from a manufactured gas plant (MGP). The MGP waste included spent oxide
material, which was incorporated into the fill, along with dredge and quarry spoils.
Waste disposal resulted in elevated iron (average concentration ~ 40 mg/L) and CN
(avg. ~ 0.6 mg/L). Elevated concentrations of Mn (avg. ~ 10 mg/L) and S (as SO4-2) (avg.
20 mg/L) in groundwater may also be related to the MGP legacy impacts. The current
owner of the property is engaged in remediating the CVOC plume, which occurs within
the larger plume of MGP-related impacts. Investigation of these legacy impacts by the
successor to the MGP operator is underway, but not yet complete.
EIB was evaluated for the source area and riverbank in a focused feasibility study
(FFS). The FFS included evaluation of balancing factors, including effectiveness, long-
term reliability, implementability, and implementation risk. Mobilization of redox-
sensitive metals and potential discharge from groundwater to surface water were
identified as implementation risks.
Analytical data collected during the pilot study were used to evaluate potential
implementation risks associated with mobilization of redox-sensitive metals. Mechanisms
for precipitation of As, Mn, sulfur (S), and WAD CN were also identified. The results
indicate that EIB does not result in undesirable secondary impacts to groundwater due to
increased reducing conditions.
DATA SUMMARY
At the riverbank pilot study area, monitoring wells were installed 25 ft upgradient
(WS-21-112), within (WS-22-112), and 20 ft downgradient of the PRB (WS-20-112).
Monitoring wells were screened from 96-111 ft bgs. An existing monitoring well (WS-
11-125) was located 10 ft downgradient of the PRB, screened from 109-124 ft bgs. Pilot
study sampling commenced immediately after installation of the PRB (baseline sampling
event May/June 2006) and then on a monthly schedule. The wells were sampled for
metals and cyanide (total and weak acid dissociable+free) throughout the pilot study (in
addition to CVOCs).
Figure 2 shows log molar (M) concentrations for Fe (dissolved), S (as sulfate), Mn
(dissolved), As (dissolved), and CN (weak acid dissociable+free) from the riverbank
wells. Concentrations of Fe, CN, and Mn decreased roughly two-fold, while sulfate was
reduced to non-detect. Arsenic concentrations were much lower (approaching the method
reporting limit of 1 ug/L) and did not change significantly.

4. -2.00
-2.50
Iron
-3.00
-3.50
Sulfur (as SO4)
Average Concentration (Log[M])
-4.00
Manganese
-4.50
-5.00
-5.50
Cyanide
-6.00
-6.50
Arsenic
-7.00
-7.50
-8.00
Jun-06 Jul-06 Sep-06 Nov-06 Jan-07 Mar-07 May-07 Jul-07 Sep-07 Nov-07 Jan-08
Date
FIGURE 2: Fe, S, Mn, As, and CN in groundwater. Averages from 3 wells.
-75 12
11
ORP
-125 10
9
-175 8
ORP (mV)
pH
7
-225 6
pH
5
-275 4
3
-325 2
Apr-06 May-06 Jul-06 Sep-06 Nov-06 Jan-07 Mar-07 May-07 Jul-07 Sep-07 Nov-07
Date
FIGURE 3: ORP and pH of groundwater from riverbank samples.

5. Field measurements of pH and redox potential (ORP) are shown on Figure 3. pH
remained stable, between 6 and 8, with a slight increasing trend. ORP decreased
significantly, from +152 mV (prior to injection; not shown) to -300 mV. Dissolved
oxygen data (not shown) was generally below 0.5, confirming anaerobic conditions.
The data show that the reducing conditions do not result in elevated concentrations of
the redox-sensitive metals As and Mn. Also, elevated concentrations of iron (relative to
site background, about 40 mg/L, or 10-3 M) do not persist after injection. In addition,
concentrations of CN are significantly reduced. The monitoring data suggest that Fe, Mn,
CN, and S are undergoing redox reactions that lead to their precipitation or adsorption.
Further research was conducted to identify likely reactions for these species, as
summarized below.
Fe-CN Reactions The spent oxide waste is the most likely source of elevated iron and
cyanide at MGP sites (Ghosh et al., 2004). Under the site conditions, the uncomplexed
iron in solution is likely to occur as Fe2+. Iron forms strong acid-dissociable (SAD) CN
complexes such as ferricyanide [Fe(CN)6]3-] and ferrocyanide [Fe(CN)6]4-], which can
be precipitated under reducing conditions by reacting with additional iron (Young et al.
1995). The decrease in CN (present as HCN or weak complexes) can be attributed to the
additional iron from the EHC PRB, which would have formed strong CN complexes and
subsequent precipitates, via the following reactions (Meeusen et. Al, 1996):
HCN(aq) + Fe2+ Fe(CN)xy- + H+ (where x and y depend on ORP) followed by
Fe(CN) xy- + Fe2+ Fex[Fe(CN)y]z(s) (where (s) denotes solid)
The decrease in CN can also be due to the slight increase in pH following injection.
Fe-Mn-CN Reactions The average background concentration of dissolved Mn detected
in the riverbank area is about 10 mg/L. The source of the Mn likely originated from
leaching of spent oxide materials. Under the site conditions, Mn would likely be present
in solution as Mn+2. Precipitation of Mn along with the ferricyanide complexes has been
documented (Rennert, 2005) under reducing conditions, via the following reaction:
Fe(CN) 64- + 2Mn2+ Mn2Fe(CN)6(s)
Since the inital concentration of Mn2+ was much higher than that of CN (Figure 1),
complexation by ferricyanide was one of the processes that controlled the observed losses
in dissolved Mn2+ concentration. Other potential mechanisms were likely driven by the
observed increases in pH [precipitation as Mn(OH)2(s)] and decreases in ORP
[precipitation as MnS(s)]. Figure 4 shows the predominance areas for Mn2Fe(CN)6(s).
Fe-S Reactions The source of the sulfate is likely related to the spent oxide materials
which were used for H2S(g) scrubbing. The background total S concentration of 10 mg/L,
assumed to be all sulfate under the background ORP, were reduced completely after the
EHC amendment. Under reducing conditions, sulfate (SO42-) is reduced to sulfide (S2-).
Precipitation of iron sulfides such as pyrite (and potentially mackinawite, pyrrhotite, or
troilite) is the likely mechnism for the removal of S, via the following reactions:
SO42- + 9H+ + 8e- ↔ HS- + 4H2O
Fe2+ + HS- → FeS(s) + H+

6. Figure 4: Eh-pH Diagram for Mn-Fe-CN Species.
Figure 5 – Eh-pH Diagram for Arsenopyrite (from Craw et al., 2003)
Samples were not analyzed for sulfide during early monitoring. Later monitoring
confirmed that sulfide was not present, suggesting that removal of S from the system

7. (potententially via formation of iron sulfide) may have occurred relatively quickly
following injection since sulfate reduction is mediated by biological activity (Drever,
1997). As indicated above, MnS(s) is also a possible mineral phase of reduced sulfate.
Fe-As-S Reactions Arsenic concentrations, detected at the site at about 1-3 ug/L, are
representative of naturally-occuring background, and were orders of magnitude lower
than the other ions. The data confirm that the reducing conditions created by the EHC
injection did not mobilize arsenic. Any arsenic dissolved from the aquifer matrix (as
arsenic-oxyhydroxides) would likely be precipitated as arsenopyrite, consistent with
Figure 5.
Concentrations of As remained very low, suggesting that either no As mobilization
occurred, or that the reductive precipitation process above prevented mobilization of As
present in the site aquifer material.
Concentrations of other major cations (e.g., magnesium, aluminum) were relatively
unchanged, suggesting that these ions are not reacting with the CN or S in solution.
Concentrations of carbon species (i.e., carbonate, bicarbonate) are also relatively
unchanged, but similar to iron (i.e., approximately 10-2.5 M) suggesting that removal of
iron or manganese by formation of siderite (FeCO3) or rhodochrosite (MnCO3) is
occurring. Review of an Eh-pH diagram for iron-carbonate species confirms the potential
for these reactions (see Figure 6).
FIGURE 6: Eh-pH Diagram for Siderite (FeCO3)(s).

8. CONCLUSIONS
Data from a field pilot of EIB using EHC™ and KB-1® was very encouraging with
respect to meeting potential remedial action objectives for TCE and its degradation
products. EIB outscored other technologies (pump and treat, thermal, in-situ chemical
oxidation) in technology screens and feasibility studies for the site. However,
mobilization of Fe, As and Mn, with potential discharge to the adjacent river, was
suggested by the regulatory agency as an implementation risk.
The potential risk was anticipated in the pilot test design, and secondary data were
collected, including metals and cyanide. The data from the pilot test confirm that the risk
of mobilization and undesirable downgradient impacts is minimal. Concentrations of
dissolved Fe and Mn decreased significantly in the EHC-amended zone. Surprisingly,
concentrations of the relatively toxic form of cyanide were also reduced. Further
evaluation of the data, along with literature research, helped identify likely reaction
mechanisms for Fe, As, Mn, CN, and S in the groundwater.
In addition to demonstrating the success of a combined approach for enhanced in-situ
bioremediation, the results of this pilot study demonstrate that anticipated secondary
impacts – mobilization of redox sensitive metals – are not a foregone conclusion
following implementation of ISCR. The results also demonstrate the value of anticipating
secondary concerns and collecting appropriate data throughout a pilot study, such that
disputes regarding conclusions are avoided, and progress toward remediation is
unimpeded.
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