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Validation of a Feasibility Study Foot Print at a
Sediment Site Using a Weight-of-Evidence (WOE) Approach
D.G.
Gunster, Battelle, Duxbury, MA
Dan
Michael, Neptune and Company, Los Alamos, NM
Jeff Ward, Battelle Marine Science Laboratory, Sequim, WA
James Leather, SPAWAR Systems Center, San Diego, CA
Michael
Pound, SOUTHWESTNAVFACENGCOM, San Diego, CA
Monitored
Biotransformation of RDX in a Saturated Soil: Alternative
e- Acceptors Alter Microbial Community
Structure and Function
David
Ringelberg, USACE-CRRELL, Hanover, NH
Mike
Reynolds, USACE-CRRELL, Hanover, NH
Karen Foley, USACE-CRRELL, Hanover, NH
Lauren Raymond, USACE-CRRELL, Hanover, NH
Larry Perry, USACE-CRRELL, Hanover, NH
Metabolic
Biomarkers for Detecting Anaerobic PAH Biodegradation in
Groundwater and Sediments
Craig
D. Phelps, Rutgers University, New Brunswick, NJ
L.Y. Young, Rutgers
University, New Brunswick, NJ
Bacterial
Degradation of Polycyclic Aromatic Hydrocarbons in Surface
Sediments of Coastal Ecosystems
Michael
T. Montgomery, Naval Research Laboratory, Washington, DC
Chris
L. Osburn, Naval Research Laboratory, Washington, DC
Thomas J. Boyd, Naval Research Laboratory, Washington, DC
Sheila Reatherford, Geo-Centers, Inc., Newton Center, MA
David C. Smith, University of Rhode Island, Narragansett,
RI
Remediation
of PCB-Contaminated Sediments Using Colloidal Zero-Valent
Iron
Kevin
H. Gardner, University of New Hampshire, Durham, NH
Deana Aulisio, University of New Hampshire, Durham, NH
Jean C. Spear, University of New Hampshire, Durham, NH
Pilot-Scale
Demonstration of In-Pile Thermal Destruction of
Chlorobenzene Contaminated Soil and Sediments
Ralph
S. Baker, Ph.D., TerraTherm, LLC, Ftichburg, MA
Robert J. Bukowski, P.E., TerraTherm, LLC, Ftichburg, MA
Hugh McLaughlin, Ph.D., P.E., Groton, MA
A
Toxicity Assessment Approach for Evaluation of In-Situ
Bioremediation of PAH Contaminated Sediments
Henry H. Tabak,US EPA, Cincinnati,
OH
James M. Lazorchak, US
EPA, Cincinnati, OH,
Mark E. Smith, SoBran,
Inc, Cincinnati, OH,
Jim Ferretti, US EPA,
Region 2, Edison, NJ
Validation
of a Feasibility Study Footprint at a Sediment Site using
a Weight-of-Evidence (WOE) Approach
Donald
Gunster, Senior
Research Scientist/Program Manager, Battelle, Coastal
Resources and Environmental Management, 397 Washington
Street, Duxbury, MA 02332
Dan Michael, Neptune and Company, 1505 15th Street ,
Suite B, Los Alamos, NM 87544 Tel: 505-662-0707 ext. 20
Jeff Ward, Battelle Marine Science Laboratory, 1529
West Sequim Bay Road, Sequim, WA 98382 Tel: 360-681-3669
James Leather, SPAWAR Systems Center, Marine
Environmental Quality Branch, Code D362, 53475 Strothe
Road, San Diego, CA 92152-6310, Tel: 619-553-6240
Michael Pound, Installation Restoration Program
Technical Manager, SOUTHWESTNAVFACENGCOM, 1220
Pacific Highway, San Diego, CA 92132, Tel: 619-532-2546
The
primary objective of this study was to more clearly define
the extent of sediments that pose an unacceptable risk to
the environment and require evaluation in a Feasibility
Study (FS). Three
lines of evidence (sediment chemistry, toxicity bioassays,
and bioaccumulation studies) were used to validate a
preliminary remedial footprint developed for the offshore
sediments at this site.
Data for the three lines of evidence were evaluated
using a WOE framework modified from an approach developed
for the State of Massachusetts (Menzie et al. 1996). The
WOE approach comprises the following five steps: (1) Determine
the weight of the endpoint.
This study considered four equally weighted
endpoints: sediment chemistry, toxicity to amphipods,
toxicity to echinoderm larvae, and bioaccumulation.
(2) Determine
the nature (i.e., whether the finding is positive or
negative) and magnitude of the result.
Numeric scores were assigned for various WOE
categories based on consensus criteria developed with
regulatory agencies. (3) Integrate
the weight, finding and magnitude for a given endpoint
result. The
weight, finding and magnitude for each endpoint result
were integrated to determine (a) whether or not the result
for that endpoint validates inclusion in the FS footprint,
and (b) the level of certainty associated with that
conclusion. (4) Integrate
all endpoint results for a given sample location.
All endpoint results for a given station were
integrated to determine if the location (a) should remain
in the FS footprint, (b) should be excluded from the FS
footprint, or c) required the consideration of additional
inputs to make a determination (i.e., the WOE results were
equivocal, resulting in a “gray” area). (5) Map
WOE results from Step 4. The WOE results for all
stations were mapped to provide an illustration of the
preliminary FS footprint.
Monitored Biotransformation of RDX in a Saturated Soil:
Alternative e- Acceptors Alter Microbial
Community Structure and Function
David
Ringelberg,
USACE-CRREL, 72 Lyme Rd., Hanover, NH 03755, Tel:
603-646-4744
Fax:
603-646-4516
Mike Reynolds,
USACE-CRREL, 72 Lyme Rd., Hanover, NH 03755, Tel:
603-646-4394
, Fax:
603-646-4516
Karen Foley,
USACE-CRREL, 72 Lyme Rd., Hanover, NH 03755, Tel:
603-646-4626
, Fax:
603-646-4516
Lauren
Raymond,
USACE-CRREL, 72 Lyme Rd., Hanover, NH 03755, Tel:
603-646-4626
, Fax:
603-646-4516
Larry Perry,
USACE-CRREL, 72 Lyme Rd., Hanover, NH 03755, Tel:
603-646-4624
Fax: 603-646-4516
Past
actions taken by the Environmental Protection Agency (EPA)
with regards to the Massachusetts Military Range (MMR)
highlights the importance of examining the fate of
explosives contamination on military training ranges. The bio-treatability of a cold region military training
facility surface soil contaminated with
hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) was recently
determined. Two critical parameters were examined in the
establishment of laboratory microcosms, soil moisture
tension and the use of alternative e- acceptors
in treating the saturated soils.
Throughout the biotreatability study, RDX loss,
intermediate formation and the associated microbiology
were monitored. RDX
became non-detectable within three weeks of study
initiation under the saturated condition whereas RDX
remained near the original concentration following 5-weeks
of incubation at field moisture.
The microbial community occurring under the
saturated condition showed an increased percentage of PLFA
indicative of facultative anaerobic Gram-negative
heterotrophs. The
addition of Fe0 and SO4 accelerated
the rate at which RDX was lost whereas a NO3
addition significantly impaired RDX biotransformation/biodegradation.
Each e- acceptor supplement induced the
formation of a unique microbial community and associated
catabolic function. Results
from this study suggest that RDX remediation can be
accelerated (in this cold region soil) via the addition of
specific alternative e- acceptors and that the
effectiveness of the treatment can be monitored through
the associated microbiology.
Metabolic
Biomarkers for Detecting Anaerobic PAH Biodegradation in
Groundwater and Sediments
Craig
D. Phelps,
Rutgers University, Biotech Center, 59 Dudley Road / Foran
Hall, New Brunswick, NJ 08901-8520, Tel: 732-932-8165
x314, Fax: 732-932-0312
L.Y.
Young,
Rutgers University, Biotech Center, 59 Dudley Road / Foran
Hall, New Brunswick, NJ 08901-8520, Tel: 732-932-8165
x312, Fax: 732-932-0312
In
order to implement biodegradation protocols for
remediating contaminated groundwater and sediments, it is
critical that to be able to monitor the biological
activity taking place in
situ. By
understanding the mechanisms of specific biodegradation
pathways it has been possible to identify unique metabolic
products that can be used as biomarkers for the
biodegradation process of interest.
Studies of anaerobic naphthalene, methylnaphthalene
and phenanthrene metabolism have determined that a direct
carboxylation of the aromatic rings is the initial step in
degrading these small PAHs.
Carboxylation is followed by sequential reduction
reactions before ring cleavage occurs.
These pathways result in the formation of several
unique metabolites that may be used as biomarkers for
monitoring in situ
PAH biodegradation. For instance, 2-naphthoic acid (2-NA),
tetrahydro-2-naphthoic acid (TH-2-NA) and
hexahydro-2-naphthoic acid (HH-2-NA) are all intermediate
metabolites generated by sulfate-reducing bacteria
degrading naphthalene. Similar metabolites are produced during methylnaphthalene and
phenanthrene. We
have developed methods for detecting these biomarkers in
groundwater, and have validated their usefulness at a
well-characterized field site.
Groundwater samples were taken from wells
distributed throughout an anaerobic, creosote-contaminated
aquifer in Stockton, CA. Each sample was extracted,
derivatized and analyzed by gas chromatography coupled to
a mass spectrometer. All four of the anaerobic metabolites
were detectable in various samples from the site. The
concentration of 2-NA at each monitoring well was
quantified and correlated to the zones of naphthalene
contamination. Presence of the other biomarkers in the
same wells as 2-NA was used as confirmation that the
anaerobic pathways were indeed active at this site. Taken
together with measurements of the aquifer's physical
characteristics, this biomarker data was used to describe
the spatial extent of naphthalene biodegradation at this
site. These
same techniques are being modified to detect PAH
biodegradation in polluted harbor sediments from Norfolk,
VA.
Bacterial
Degradation of Polycyclic Aromatic Hydrocarbons in Surface
Sediments of Coastal Ecosystems
Michael
T. Montgomery, Chris L. Osburn, Thomas J. Boyd,
Naval Research Laboratory, 4555 Overlook Avenue,
Washington, DC 20375, Tel: 202-404-6419, Fax:
202-404-8515
Sheila
Reatherford,
Geo-Centers, Inc., 7 Wells Ave, Newton Center, MA 02459,
Tel: 202-404-1735,
Fax:
202-404-8515
David C. Smith,
Graduate School of Oceanography, University of Rhode
Island, Narragansett, RI 02882, Tel: 401-874-6172, Fax:
401-874-6240
Anthropogenic
inputs of aromatic hydrocarbons are a common stress to
coastal ecosystems. Petroleum-derived
compounds can accumulate in surface sediments and change
the associated biota. Elevated hydrocarbon concentrations can provide a selective
pressure for strains that can metabolize these compounds,
but the response of the assemblage can also be affected by
environmental factors.
We examined the effect of various chemical and
physical conditions on bacterial production and aromatic
hydrocarbon mineralization in surface sediments of five
coastal ecosystems that have significant anthropogenic
impacts. The
data were gathered during thirty-eight research cruises
over the past four years in Pearl Harbor, San Diego Bay,
Charleston Harbor Estuary, Chesapeake Bay, San Francisco
Bay and Delaware Bay.
Sediment from temperate coastal systems had large
seasonal variation in mineralization rates and turnover
times of sentinel aromatic hydrocarbons (i.e. naphthalene,
phenanthrene, and fluoranthene), though there was little
correlation with temperature.
Aromatic hydrocarbon mineralization, as measured
using 14C-radiotracer additions, was
dramatically reduced when bottom water dissolved oxygen
saturation was below 70%.
Ambient hydrocarbon concentration below 10 mg
g-1 sediment did not appear to support
bacterial assemblages capable of rapid mineralization of
the hydrocarbons. Hydrocarbon
mineralization rates generally ranged from 10-6
to 100 mg
C g-1 sediment d-1 in both temperate
and tropical systems but were highest in chronically
impacted sediments in Charleston Harbor (7.0 x 10-1
mg
C fluoranthene g-1 sediment d-1) and
Pearl Harbor (1.21 x 10-1 mg
C fluoranthene g-1 sediment d-1).
In many ecosystems, high PAH concentration
correlated with low bacterial production though this was
not seen in Pearl Harbor.
In this tropical ecosystem, production generally
increased with PAH concentration, as did PAH
mineralization. Understanding
environmental factors that control hydrocarbon metabolism
by the natural bacterial assemblages may help us determine
the capacity for estuarine sediments to assimilate
contaminants as well as identify areas that are at risk of
ecological damage.
Remediation
of PCB-Contaminated Sediments Using Colloidal Zero-Valent
Iron
Kevin
H. Gardner,
Environmental Research Group, University of New Hampshire,
Durham, NH 03824 Tel: 603-862-4334, Fax: 603-862-3957
Deana
Aulisio,
Environmental Research Group, University of New Hampshire,
Durham, NH 03824
Tel:
603-862-1197, Fax: 603-862-3957
Jean
C. Spear,
Environmental Research Group, University of New Hampshire,
Durham, NH 03824
Tel:
603-862-1445, Fax: 603-862-3957
Chemical
transformation of halogenated organic compounds (HOCs) by
colloidal zero-valent iron (ZVI) is one of the latest
innovative technologies in environmental remediation.
This research project is developing and evaluating
a treatment technology that uses colloidal elemental iron
to effect the reductive dechlorination of PCBs to
biphenyl. The
objective of this work is to develop a robust technology
to remediate PCBs in marine and fresh water sediments
under ambient conditions in a cost-effective manner.
Experiments
are being conducted using PCB-contaminated sediment from
the Housatonic River and New Bedford Harbor, both in
Massachusetts, under conditions approximating those in the
sediment pore water.
Extensive laboratory batch studies are underway, in
which iron type, concentration, and number of applications
are being investigated.
A mass balance is being developed to determine the
breakdown mechanisms and if, in fact, the PCBs are being
reduced to biphenyl.
Results
have shown that PCBs can be reduced by 63% in a
fine-grained, organic-rich marine sediment and by 95% in a
sandy river sediment in approximately one day with one
application of 3% ZVI to sediment.
Rate constants for dechlorination were estimated to
be 0.1422 d-1 and 3.2871 d-1,
respectively. Adding
a greater concentration of ZVI did not increase removal
proportionally, and no substantial reduction took place
after one day. It was concluded, therefore, that more than one application
of ZVI is necessary to reduce the PCBs to lower levels due
to the fast corrosion kinetics of the iron.
Preliminary results also indicate that higher
chlorinated PCBs do indeed dechlorinate to lower
chlorinated PCB congeners upon reaction with colloidal ZVI.
Pilot-Scale
Demonstration of In-Pile Thermal Destruction of
Chlorobenzene-Contaminated Soil and Sediments
Ralph
S. Baker, Ph.D.
and Robert J. Bukowski, P.E., TerraTherm, Inc.,
356-B Broad St., Fitchburg,
MA 01420
Hugh McLaughlin, Ph.D., P.E.,,
151 Hill Road, Groton, MA
01450-1609, Tel: 978-448-6066,
Fax:
978-448-6414
At
the Eastland Woolen Mill Superfund site in Corinna, Maine,
decades of textile manufacturing led to contamination of
approximately 75,000 cubic yards (57,300 cubic meters) of
soil by mono-, di-, and trichlorobenzenes, which were components of the
dyes used to add color to wool.
Roy F. Weston, Inc., under the direction of the
U.S. Army Corps of Engineers (USACE) pursuant to an
Interagency Agreement with USEPA, is charged with
implementing a Non-Time Critical Removal Action (NTCRA).
Under the NTCRA, TerraTherm, Inc. performed a pilot
test and evaluated the applicability of its In-Pile
Thermal Destruction (IPTD) technology for treatment of
contaminated soils in an aboveground soil pile.
TerraTherm’s IPTD technology is an ex-situ
version of In-Situ Thermal Destruction (ISTD), by which
TerraTherm utilizes simultaneous application of thermal
conduction heating and vacuum to treat contaminated soil
and sediment without excavation. In IPTD, as with ISTD, the applied heat volatilizes both
water and organic contaminants within the soil, enabling
them to be carried in the air stream toward vacuum
extraction wells for destruction within the soil and
transfer of the remaining vapor to an air quality control
(AQC) unit. It
is anticipated that >95% of the contaminant mass will
be destroyed in the heated soil.
The pilot test was conducted in two 55-gallon (208 L) drums.
Drum 1 was filled with contaminated soils from the
site and Drum 2 contained clean fill.
During the treatment phase of the pilot test the
drums were connected in series with clean air entering
Drum 1 and the vapors flowing from Drum 1, through Drum 2,
and then on to the AQC unit.
The second drum was pre-heated to the target
treatment temperature prior to initiating heating of the
first drum. The
primary objectives of the pilot test were to demonstrate
whether the soil in the pre-heated drum, representing a
treated soil pile, could serve as an effective vapor
pre-treatment medium; and if the exhaust from the
pre-heated soil drum has low levels of emissions. The
pilot test indicated that TerraTherm’s IPTD technology
is potentially capable of removing chlorinated benzenes
from the soils at the Eastland Woolen Mill site and
ultimately meeting the remedial target soil
concentrations. A
mass balance performed on the data from the pilot test
indicated that 60 to 75 percent of the original
chlorobenzenes were destroyed by IPTD. The majority of the
destruction likely occurred in Drum 1 after the steam
drive. The chlorinated benzenes that were steam-stripped
from Drum 1 during the steam drive were largely
transported through Drum 2 and removed effectively by the
GAC canister. Vapor
emissions from the GAC drum indicated that TerraTherm’s
IPTD would be capable of attaining the applicable
emissions standards.
Although the overall performance of the pilot test
was promising, design and operational limitations
prevented a true evaluation of the feasibility and
effectiveness of using a heated/treated soil pile for
pre-treatment of the vapors.
The pilot test did demonstrate that in situ
distillation and steam-stripping processes can effectively
remove chlorinated benzenes at temperatures below their
boiling points. It
is believed that if the vapors produced during the
distillation and steam-stripping phase had passed through
a typical superheated region around a heater/vacuum well
(soil temperatures of 400-500°C), very high in-situ destruction efficiencies (e.g., 95-99%) would have
occurred.
A
Toxicity Assessment Approach for Evaluation of In-Situ
Bioremediation of PAH Contaminated Sediments
Henry H. Tabak,US EPA,
Environmental Research Center, ORD, National Risk
Management Research Laboratory,
26 West Martin Luther King Drive, Cincinnati, OH
45268,Tel:513-569-7681,
Fax:
513/569-7105, Email: tabak.henry@epa.gov
James M.
Lazorchak, US EPA, Environmental Research Center, ORD, National Exposure Research
Laboratory, 26 West Martin Luther King Drive, Cincinnati,
OH 45268, Tel: 513-569-7076,
Fax:
513/569-7609, Email: lazorchak.jim@epa.gov
Mark E.
Smith, SoBran, Inc,
26 West Martin Luther King Drive, Cincinnati, OH 45268,
Tel: 513-569-7161, Fax: 513/569-7554, Email: smith.mark@epa.gov
Jim Ferretti,
US EPA, Region 2, 2890 Woodbridge Avenue, Edison, NJ
08837, Tel: 732-321-6728, Fax:
732/906-6165 Email: ferretti.jim@epa.gov
Freshwater and marine
sediment toxicity tests were used to measure baseline
toxicity of sediment samples collected from New York/New
Jersey Harbor (NY/NJH) (with traces of PAHs) and East
River (ER) (PAH contaminated) sediments. The tests were
undertaken to determine how effective were the developed
biotreatment strategies in reducing ecotoxicity of the
contaminated sediments and to provide a measure of
biotreatment efficiency based on ecotoxiciy values. The
objective of running the tests was to relate the reduction
of contaminant concentration to the reduction of
ecotoxicity (lethal, sublethal or bioaccumulative
endpoints) based on biological assay points.The four
freshwater toxicity tests were: (1) Amphipod, Hyaella
azteca mortality and growth tests : a standard 10-day
USEPA method using 100 ml sediment and 175 ml overlaying
water and two 7-day exposure methods (the EMAP
method.using 40 ml sediment and 160 ml overlaying water
and a reduced volume method, developed by us, that uses 17
ml sediment and 30 ml overlaying water); (2) a 7-day
aquatic worm, Lumbriculus
variegatus, mortality and budding test; (3) a 7/8
embryo larval survival and teratogenic test with Pimephales
promelas (fathead minnow) (FHM-EL) USEPA method that
uses 40 ml sediment and 60 ml overlaying water and (4) a
4-day vascular or aquatic plant, Lemna
minor(Duckweed), a frond number/growth/chlorophyl test
that uses 15 ml sediment and 2 ml overlaying water. Two
marine tests were also used: (1) a marine amphipod , Ampelisca
abdida, 10-day mortality test that uses 200 ml sediment and 600 ml
overlaying water and (2) a sheppshead minnow, Cyprinodon veriagata, embryo-larval sediment(SHM-EL) mortality test.
The reduced freshwater amphipod test was developed and
used in this study since existing volume requirement of
USEPA standard methods exceeded the amounts available from
the enhanced biotreatment studies.To determine the cause
the of toxicity in these sediments, five sediment
manipulations were performed: (1) a sediment purge
procedure, where 2 to 4 volumes of lab water were replaced
over the sediment in a 24-hr period: (2) a sediment
aeration procedure, where sediment samples( 80 ml of
sediment (140 g) to a 250 ml glass graduated cylinder and
120 ml of overalaying water) were aerated for 24-48-hr
period.; (3) an Ambersorb treatment procedure, where
sediment samples were tretaed with 2 types of resins (Ambersorb
563 (AS 563) and Ambersorb 572(AS 572) for removal of
organics and (5) an Amberlite treatment procedure, where
an inorganic (metal) removal resin , Amberlite IRC -178
was mixed with the sediment.
ER sediment was found
to be highly toxic to all freshwate and marine organisms
tested while the NY/NJH sediment showed no significant
toxicity to the marine amphipod but was slightly toxic to
the freshware worm and
to freshwater and marine fish larvae. For all tests
ran on ER sediment with the freshwater organisms and the
one marine amphipod, no survival was found except for one
freshwater amphipod test (55%). The ER sediment
significantly reduced frond production (58.3%) and
chlorophyl a levels (35.4%) in the freshwater duckweed
test.
Results from the five
sediment manipulation studies showed that freshwater
amphipod survival was improved with sediment aeration
procedure, with 8% AS 563 and AS 572 as well as with AL
IRC-718 treatments.
Toxicity can also be reduced with the sediment dilution
techique (100 fold) .These manipulations and analyses for
the specific inorganic and organic contaminants revealed
that hydrogen sulfide, PAHs and metals were factors
in ER sediment toxicity. Results from Hyalella azteca
toxicity tests using ER and NY/NJH sediments treated by
aerobic biodegradation slurry approaches showed reductions
in toxicity to H.
Azteca equal to or greater than that achieved through
chemical or mechanical manipulations of the sediment
samples. H. azteca survival
after various aerobic bioslurry treatments of ER sediment
ranged from 35% to 65%, compared to survival of 20% in ER
sediment tested by aeration and addition of 8% AS
572.resin.
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