United States
Environmental Protection
Agency
October-December
1988
Research and Development
&EPA Research Report
Environmental
Research
Laboratory
Athens, GA 30613
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OAR
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: A101 AIR
ISSUE: F Stratospheric Ozone
PPA (L): 75 STRATOSPHERIC OZONE
PPA (S): STRATOSPHERIC OZONE
RC: K ERL ATHNS
PROJECT: 42 Stratospheric Ozone Modification
PROJECT OFFICER: R. G. Zepp PHONE: FTS-250-3428
******************************************
PLANNED START: 10/01/88 PLANNED END: 09/30/94
******************************************
PROJECT DESCRIPTION:
GOAL: Develop reliable methods of estimating the harmful exposure of ecosystems
to UV-B radiation received under current & projected climatological conditions.
RATIONALE: Evaluation of risk to ecosystems posed by decreased strat. ozone
requires ability to estimate current & future expected doses of UV-B under
different scenarios. Estimation procedures must account for physical
dependencies & variations in concentrations of UV-B absorbing species in the
environment as well as action spectra for harmful UV-B effects.
APPROACH: Existing models will be modified to evaluate effects of decreased
strat. ozone on UV-B exposure rec'd by organisms at land surface and in aquatic
ecosystems. Models will be developed to estimate transport effects on UV-B
exposure in aquatic ecosystems & effects of UV-B on geochemical cycles.
These models will be field tested to evaluate their accuracy & to correct any
deficiencies that may be revealed. This will be accomplished by measurements
of solar irradiance reaching the ground under a variety of atmospheric
conditions, & by experimental & field work to test & improve the estimation
methods for hydrospheric transmissivity as a function of the concentration of
light-absorbing constituents.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
0.5 FTE was allocated to ERL-Athens in FY89 for project 42. Inhouse work
has begun on exposure assessment methodologies.
Activities during the quarter included the initiation of research on the
development of an appropriate UV-3 chemical actinometer for evaluating exposure
model predictions of solar UV-B irradiance reaching the earth's surface and
downwelling into aquatic ecosystems. Systems examined included actinometers
based on the photoreactions of two ketones, valerophenone and 2-pentanone, in
water. Quantum yield and temperature studies were initiated during the
quarter. Results indicate that both actinometers may be very useful. Each has
-------
a reaction quantum yield near unity with virtually no temperature dependence
between 10 and 40 degrees C. For comparison, the temperature dependence for
direct photolysis of the actinometer p-nitroanisole also was examined during
the quarter; this photoreaction also was found to be little affected by
temperature changes.
Dr. Richard Zepp presented a paper on "Consequences of Stratospheric Ozone
Depletion: Actinometers for Evaluating Integrated UV-B Exposure" at the Annual
Meeting of the Society of Environmental Toxicology and Chemistry, Washington,
DC in November.
No RSD funds have yet been authorized for expenditure by ERL-Athens
on project 42. Plans are being made, however, to fund an inhouse contract to
provide laboratory personnel support, and to conduct a workshop on DV-B effects
on geochemical processes in aquatic and terrestial ecosystems, probably to be
held next spring at Woods Hole Oceanographic Institute.
Planning for a field program to test our current models of light
transmission in the hydrosphere, to be initiated during the spring in area
lakes, was begun this quarter. Personnel were identified and recruited, and
general project objectives outlined.
A currently used model of UVB transmission in the atmosphere (developed at
the University of Chicago) was acquired and implemented on the Wyse
workstation. Analysis of this model will help define the upgrade path for the
EXAMS atmospheric transmission model and may indicate some alternative models
for additional study. In preparation for expansion of the EXAMS program to
accommodate DVB exposure analysis during this quarter, the suite of EXAMS
implementations that had been developed to accommodate machine-specific feature
of the various supported platforms (DSI board, MS-DOS, VAX, Siemens computers)
were integrated into a single code set. This was accomplished primarily by
converting machine-dependent input/output routines into Fortran run-time
formats controlled by datasets that incorporate the results of an analysis of
the relevant machine dependencies.
STATUS AND SCHEDULE OF DELIVERABLES:
8219 DUE: 06/30/89 REVISED: COMPLETED:
Report: Assessments of UV-B effects on photochemical transients in aquatic
and terrestrial ecosystems.
8220 DUE: 09/30/89 REVISED: COMPLETED:
Report: The Scientific Assessment of Existing Mathematical Models for
Exposure of Terrestrial and Aquatic Biota to UV-B Radiation.
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OAR
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: A101 AIR
ISSUE: G 2
PPA (L): 94 Ecological Effects of Global Climate Change
PPA (S): Ecol. Glo. Climate
RC: K ERL ATHNS
PROJECT: 34 Effects of Climate Change on Physicochexical Processes
PROJECT OFFICER: Richard G. Zepp PHONE: FTS-250-3145
******************************************
PLANNED START: 04/01/89 PLANNED END: 09/30/98
******************************************
PROJECT DESCRIPTION:
GOAL: Develop physicochemical process models to describe effects of climate
changes on emissions and dry deposition of greenhouse gases.
RATIONALE: Long-term climate changes will have important effects on the various
physicochemical processes affecting natural emissions and dry deposition of
radiatively important gases in land and water. Even small increases in flux of
natural emissions may induce significant effects on global climate. Process
models and kinetic and equilibrium data are needed to assess such effects under
various climate scenarios.
APPROACH: Develop models for volatilization, sorption, chemical reactions and
photochemical reactions involved in the natural emission and reposition of
radiatively important gases. Physical process studies include partitioning
between air and water, and water and soil, plus volatilization from water and
soil. Temperature effects and, for soils, moisture and composition will be
included. Chemical studies will focus on mechanisms and decay rates of ozone.
Effects of temperature and factors such as pH and chemical composition will be
examined. The influence of photochemical processes (rates and mechanisms) will
be determined. Trace metal, pH, and humic effects, and soil composition and
origin will be included in developing relationships and models.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
No FTE's were allocated to ERL-Athens for this project for FY89, and no
R&D funds have yet been authorized for expenditure. Plans are being made,
however, for both inhouse and extramural research once resources are available.
STATUS AND SCHEDULE OF DELIVERABLES:
NO DELIVERABLES AVAILABLE
-------
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OAR
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: A101 AIR
ISSUE: G 2
PPA (L): 94 Ecological Effects of Global Climate Change
PPA (S): Ecol. Glo. Climate
RC: K ERL ATHNS
PROJECT: 36 Biogenic Production of Nitrous Oxide and Methane in the Env.
PROJECT OFFICER: David Lewis PHONE: FTS-250-3358
******************************************
PLANNED START: 04/01/89 PLANNED END: 09/30/98
******************************************
PROJECT DESCRIPTION:
GOAL: Elucidate the relative contributions of bacterial production of nitrous
oxide and methane among different environments (wetlands, soils, etc.), and the
environmental factors affecting the production rates.
RATIONALE: Nitrous oxide and methane, major products of microbial metabolism,
have great potential for adversely affecting the global climate. Global
monitoring data indicate significant shifts in ambient concentrations of these
gases in the atmosphere; therefore, an improved understanding of microbial
production and of transformation of these gases is needed to provide
capabilities for predicting future global climatic changes and guiding resource
management.
APPROACH: A group of experts will be convened in a workshop to arrive at a
consensus concerning which ecosystems and environmental parameters merit the
highest research priority. Laboratory and field studies will be conducted to
elucidate which microorganisms and environments most significantly contribute
to nitrous oxide and methane production, and what rate-limiting processes and
environmental parameters most critically affect gas production rates.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
We have reviewed the literature, and formulated tentative research plans
regarding biogenic contributions of nitrous oxide. The organization of a
workshop, and subsequent pursuance of high priority research topics awaits
funding of this task.
Recent research indicates that radiatively important trace gases other
than carbon dioxide are also likely to influence global climate changes
significantly. These gases include methane, nitrous oxide, and tropospheric
ozone. In addition, carbon monoxide (CO), although not itself radiatively
important, has significant effects on the atmospheric concentration of methane
and tropospheric ozone.
-------
The atmospheric concentrations of these gases are regulated, in part, by
chemical and biological processes that occur in the biosphere. Microorganisms
in terrestrial and aquatic ecosystems produce large quantities of methane and
nitrous oxide. Carbon monoxide is produced through chemical and photochemical
oxidation of natural organic matter in natural water bodies. In addition,
methane, nitrous oxide, and carbon monoxide are metabolized by microbiota and
ozone is removed from the troposphere through reactions with vegetation, soil,
and natural water.
Our research focuses on developing generalizable mathematical
relationships that can be used to model the effects of climate changes on
biological and geochemical processes that are important sources and sinks of
methane, nitrous oxide, carbon monoxide and tropospheric ozone in terrestrial
and aquatic ecosystems. The results are used in terrestrial and aquatic
systems level mathematical models to predict the net fluxes of these gases as a
function of various hypothesized land use or climate scenarios. These studies
will provide improved capabilities to determine both current and potential
global contributions of biogeochemical versus anthropogenic sources of these
trace gases as well as to evaluate the effects of various remediation options.
We will discuss our current research efforts to provide a better
assessment of contributions of microbial activities to global nitrous oxide,
methane, and carbon monoxide concentrations through an improved understanding
of (1) the relative significance of different environments as sources and sinks
and (2) the environmental factors affecting production rates of these trace
gases, and well as our research efforts to improve the understanding of the
geochemical processes in land and water on the production, decay, and biosphere
-troposphere exchange of carbon monoxide, ozone, methane, and nitrous oxide.
An abstract, "Sources and Sinks of Radiatively Important Trace Gases in
the Biosphere" (Rogers, Burns, Zepp and Lewis), was submitted upon invitation
for presentation at the 1989 annual meeting of the Air and Waste Management
Association, June 25-30. Dr. Rogers will present the paper.
STATUS AND SCHEDULE OF DELIVERABLES:
8232 DUE: 07/31/89 REVISED: COMPLETED:
Report: Microbial processes that influence emissions of radiatively
important gases
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OWRS
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: B101 WATER QUALITY
ISSUE: A WQBA/PERMITTING
PPA (L): 10 WASTELOAD ALLOCATION MODELING AND SUPPORT
PPA (S): WASTELOAD ALLOCATION
RC: K ERL ATHNS
PROJECT: 06 Environmental Process Characterization
PROJECT OFFICER: Richard G. Zepp PHONE: FTS-250-3428
******************************************
PLANNED START: 10/01/80 PLANNED END: 09/30/90
******************************************
PROJECT DESCRIPTION:
GOAL: Characterize key environmental processes (direct-indirect photolysis,
redox, sorption/desorption, metal speciation and transport) in water and
sediment systems to improve exposure and risk assessment models.
RATIONALE: The role of inorganics in pollutant transformation by photolysis
and the kinetics of redox reactions are inadequately understood for reliable
use in exposure assessment models. Sorption of ionizable organics also
significantly affects pollutant transport. Toxic metal speciation and
transport needs further investigation since metal toxicity depends upon the
species.
APPROACH: Using natural waters, sediments and reference materials, equations
for the kinetics of materials will be tested. The studies will provide
rate/equilibrium constants required in the models. Compounds and reaction
conditions will be selected to permit generalizations about changes in
molecular structure and environmental conditions. Studies will examine effects
of inorganics on photochemistry, biotic influences on redox reactions in abiotic
systems, binding characteristics of metals and humics, and sorption processes
of ionizable organics on sediments. Distribution coefficients of metals will be
determined for various solid substrates.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Research was continued on the influence of light on the oxidation of
organic substrates by manganese oxides. Kinetic studies of the oxidation of
p-chlorophenol were conducted using monochromatic radiation corresponding to
the maximum absorption of manganese dioxide (336 nm). The pH dependence of the
oxidation rate of p-phenylphenol in manganese oxide suspensions exposed to
sunlight also was investigated. Studies of the influence of light on the
oxidation of anilines by manganese oxides were initiated; the oxidation of
p-chloroaniline was examined. Work on the photoredox reactions of copper was
also continued. Quantum yields were determined as a function of pH for the
-------
photoreduction of copper (II) complexed by nitrogen ligands. Kinetic studies
were conducted in sunlight for comparison. Two journal articles were submitted
for publication during the quarter: "Hydrogen Peroxide Decay in Waters with
Suspended Sediments: Evidence for Biologically Mediated Processes" and "Aquatic
Humic Substances as Sources and Sinks of Photochemically Produced Transient
Reactants."
Studies of the effects of pH on the adsorption of anionic organic
compounds to sediments have been initiated. Titration of a well characterized
sediment using a pH-stat constructed here has shown that, between the ambient pH
value of 7.8 to approximately pH 5.5, hydrogen ion activity can be controlled by
the addition of acid (HC1) to within about 0.5 units. Titration of
pentachlorophenol (POP, pKa equal to 4.8) between pH values of 7.8 and 4.0 in
EPA 11 sediment (10 g sediment in 200 ml water) shows the concentration of
pentachlorophenol in the aqueous phase to range from 80% of total added (at pH
7.8) to approximately 4Z (at pB 4.0). Between pH values of 3 and 4 no difference
was observed in the partition coefficient. This is highly consistent with
octanol-water partitioning data for POP in the same pH ranges. Further studies
controlling the pH at higher values with the addition of base (NaOH) are
anticipated, along with titration of other compounds having different
properties.
A paper on the homogeneous hydrolysis rate constants for selected
chlorinated methanes, ethanes, ethenes and propanes has been drafted. This
paper contains alkaline hydrolysis rate constants and activation parameters for
15 chlorinated hydrocarbons. The data will provide a basis for developing a
structure reactivity relationship for estimation of rate constants for other
halogenated hydrocarbons. A draft journal article entitled "Hydrolysis of
Chlorostilbene Oxide II. Hydrolysis in Aquifer Samples and in Sediment-Water
Systems" contains results that provide support for a model that quantitatively
describes abiotic hydrolysis in heterolytic systems.
Kinetic studies of the degradation of Solvent Red 1 in anaerobic
sediment-water systems show that the disappearance of the dye followed
pseudo-first-order kinetics over two half-lives. The half-lives in two
sediments were 94.6 and 67.9 hours.
Studies progressed on the degradation of diphenyl- and dialkyl-N-nitroso-
amines in anaerobic sediments. While diphenyl-N-nitrosoamine was degraded to
diphenylamine with a half-life of 11.8 h, diethyl-, dipropyl-, and dibutyl-
N-nitrosoamines were stable over a period of 14 days. Sorption studies indicate
the dialkyl-N-nitrosoamines do not sorb to the sediment and that the
diphenyl-N-nitrosoamine is only weakly sorbed. These results indicate that the
dialkyl-N-nitrosoamines will be persistent and highly mobile in groundwater
environments.
STATUS AND SCHEDULE OF DELIVERABLESt
8149 DUE: 06/30/89 REVISED: COMPLETED:
Report: Sorption Processes for lonizable Organics on Sediments.
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OWRS
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: B101 WATER QUALITY
ISSUE: A WQBA/PERMITTING
PPA (L): 10 WASTELOAD ALLOCATION MODELING AND SUPPORT
PPA (S): WASTELOAD ALLOCATION
RC: K ERL ATHNS
PROJECT: 11 Biodegradation & Bioaccumulation Processes and Systems Res.
PROJECT OFFICER: David L. Lewis PHONE: FTS-250-3358
******************************************
PLANNED START: 10/01/85 PLANNED END: 09/30/95
******************************************
PROJECT DESCRIPTION:
GOAL: Test the predictive accuracy and determine the applicability of
microbial transformation rate coefficients for water quality models and
evaluate bioaccumulation of toxicants in aquatic organisms in relation to
thermodynaroic equilibrium processes.
RATIONALE: This research is required to produce a reliable approach for
predicting biologically mediated accumulation and degradation of pollutants to
improve water quality and risk assessment models.
APPROACH: Rate coefficents for microbial transformation of xenobiotic chemicals
will be determined using microbial populations collected from lakes and streams.
Bioaccumulation in organisms of varying size and lipid content and of different
species will be determined using toxic chemicals that have varying partition
coefficients. Coefficients determined in the laboratory will be compared with
field data. Predictions based on thermodynamic calculations will be compared
with experimental results.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
One paper, "Special applications of insect gut microflora in kinetic
studies of microbial stubstrate removal rates" (Lewis & Said) was accepted for
publication in the Journal of Environmental Toxicology and Chemistry.
Laboratory microcosm studies regarding nitrification rates have been described
in a manuscript "Nitrification by attached bacteria in an aquatic ecosystem"
(Said, Lewis, Holm & Kollig), which is being internally reviewed.
STATUS AND SCHEDULE OF DELIVERABLES;
8150 DUE: 08/31/89 REVISED: COMPLETED:
Internal report on microbial process highlights.
-------
10
-------
PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OWRS
FIRST QUARTER STATUS REPORT ON FY*89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: B101 WATER QUALITY
ISSUE: A WQBA/PERMITTING
PPA (L): 10 WASTELOAD ALLOCATION MODELING AND SUPPORT
PPA (S): WASTELOAD ALLOCATION
RC: R ERL ATHNS
PROJECT: 19 Wasteload Allocation Modeling and Support
PROJECT OFFICER: Tom Barnwell PHONE: FTS-250-3210
******************************************
PLANNED START: 10/01/80 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Assemble, modify or develop, and test arrays of wasteload allocation
(WLA) and exposure assessment models for conventional and toxic pollutants for
streams, rivers, lakes, and estuaries and provide OW with guidance and user
assistance through the Center for Exposure Assessment Modeling (CEAM).
RATIONALE: Water quality-based NPDES revisions, WLAs, AWT assessments,
use-attainability activities, and BMP selection by OW, Regions, States, and
local governments require scientifically defensible modeling packages including
documentation, data bases, training, and user assistance.
APPROACH: Gaps in existing WQ modeling packages will be identified through
applied studies conducted in cooperation with OW and with ORD Laboratories.
Developments or modifications will fill scientific gaps (e.g., metals
speciation and sediment-water pollutant exchange routines) and improve
ease-of-use (e.g., interactive model setups and microcomputer packages). User
assistance will include developing guidance documents, operating the CEAM to
provide modeling packages/manuals/tapes and data bases on request, conducting
training seminars and workshops as required, and providing hands-on user
assistance as resources permit.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Cooperative researchers at Tufts University revised a paper, "DO Model
Uncertainty with Correlated Inputs," based upon reviewer comments and
resubmitted it to the Journal of the Environmental Engineering Division.
Continuing work on graphical presentation of uncertainty information is
complete and a master's thesis describing the work is in preparation.
Cooperative researchers at Cornell University continue to make good
progress with the CORMIX model. Funding was received this quarter from the
Office of Water to complete work on this project. Links between program models
were completed this month and model validation, including calibration of
11
-------
coefficients, has begun. Abstracts have been submitted for the 1989 ASCE
Hydraulics and Environmental Engineering Division summer conferences and for
the International Association for Hydraulic Research Congress. Additional
funding was received to incorporate the work in a short course this summer.
A LOTUS spreadsheet model was developed to reproduce the calculations by
the Environmental Defense Fund in their paper "Polluted Coastal Waters: The
Role of Acid Rain." A seminar reviewing procedures used in. the report was
presented.
Testing, preparation of code, composition of support documentation, and
master file/diskette creation for the distribution version of WASP for VAX and
PC systems for release 4.14 is in progress.
Allen Medine conducted the course "Metal Contamination in Surface Waterst
Methods for Assessment and Control" for Region 8 and states December 13-14 in
support of the 304(1) program. Max Dodson, Region 8 Water Management Division
Director, sent a memo of thanks, declaring the workshop a
success.
We continued migration of CEAM model distribution and registered user data
base from VAX to PC environment. We also began implementation of a CEAM
database for all CEAM training and model distribution activities. Initial
preparation of CEAM's FY89 training courses began including selection of
tentative dates, course descriptions, and venus. Five courses are planned this
summer including:
- QUAL2E with Uncertainty Analysis July 10-14
- Exposure and Bioaccumulation Models July 24-28
- MINTEQ August 22-24
- Estuarine Wasteload Allocation September 11-15
- RUSTIC September 18-22
CEAM BBS and Model Distribution Statistics
BBS Statistics: Total Calls 477
New Users Added 70
Total Uploads 14
Total Downloads 270
Model Distribution:
Model Diskette BBS Tape
WASP4 27 16 0
SWMM3 15 4 0
HSPF9 23 0 3
MINTEQ 57 3 1
QUAL2E 44 6 1
DYNTOX 10 7 0
EXAMSII 20 3 2
PRZM 16 11 3
LC50 560
SARAH 910
12
-------
FGETS 13 1 0
GCSOLAR 730
TOTAL 246 + 61 + 10 - 317
STATUS AND SCHEDULE OF DELIVERABLES:
7851 DUE: 07/31/88 REVISED: 07/31/89 COMPLETED:
Report on Expert Advisor for CORMIX Model
2/88 - delay to 7/89 a result of FY-88 Congressional Budget
actions; 5/88 - transferred from B-101 A-15 during FY-89
PPA devel. process and title change
13
-------
14
-------
PRINT DATE: 01/30/89
PMS-060 ,
CLIENT OFFICE
OWRS
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
BUDGET SUB- ACTIVITY ;
ISSUE:
PPA (L):
PPA (S) :
RC:
PROJECT:
PROJECT OFFICER:
CODE TITLE
B101 WATER QUALITY
A WQBA/ PERMITTING
13 ECOLOGICAL RESEARCH WITH THE PEOPLE'S REPUBLIC OF CHINA
CHINA AGREEMENT - WQ
K ERL ATHNS
20 Ecological Research with the Peoples Republic of China (PRC)
Roseraarie C. Russo PHONE: FTS-250-3134
********
**********************************
PLANNED START: 10/01/84 PLANNED END: 09/30/90
******************************************
PROJECT DESCRIPTION;
GOAL: Participate jointly with PRC scientists and engineers in the refinement,
application and field testing of environmental fate and exposure models for
pollution control strategy development and assessment and in the study of
environmental transformation processes.
RATIONALE: To support U.S. policy to provide scientific and technological
cooperation with the PRC, specifically Annex 3 of the 1980 US-PRC Environmental
Protection Protocol.
APPROACH: Via a combination of tailored model refinement and application
projects and technology transfer workshops and symposia, the PRC will be
helped to acquire and apply an array of appropriate environmental assessment
methodologies for their use. Athens ERL will design and monitor PRC field
evaluations of selected models. The technology developed and transferred will
also be high priority for region/ state use in the U.S. Chemical and
microbiological process characterization studies will also be conducted to
elucidate the transformation and transport of metals and organics in surface
and subsurface environments.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Dr. George Bailey attended the International Symposium on Environmental
Life Elements and Health, November 1-5, 1988, in Beijing China. He and Mr. Lin
Yuhuan each presented a scientific paper. Two manuscripts were submitted for
publication in the symposium proceedings. Dr. Bailey presented seminars at the
Research Center for Eco-Environmental Sciences, Chinese Research Academy of
Sciences, Beijing; the Chinese Research Academy of Environmental Sciences,
Beijing and Shaanzi, and the Environmental Protection Bureau (National
Environmental Protection Agency) , Xian. Dr. Bailey presented a third paper
based on Mr. Lin's work at the American Society of Agronomy (ASA) National
Meeting, Anaheim, California, November 2 7 -Dec ember 2, 1988.
15
-------
Titles of manuscripts/presentations are:
"Metal Interactions at Sulfide Mineral Surfaces: Part II. Adsorption and
Desorption of Lanthanum," Lin Yuhuan, George W. Bailey and Alan T. Lynch
(presented and submitted for publication in Symposium proceedings).
"Metal Interactions at Sulfide Mineral Surfaces: Part III. Metal
Affinities in Single and Multiple Ion Adsorption Reactions," Lin Yuhuan, George
U. Bailey and Alan T. Lynch (presented and submitted for publication in
Symposium proceedings).
"Metal Interactions at Sulfide Mineral Surfaces: Part IV. Adsorption and
Precipitation Reactions," Lin Yuhuan, George W. Bailey and Alan T. Lynch
(presented at ASA National Meeting).
STATUS AND SCHEDULE OF DELIVERABLES;
8152 DUE: 09/30/89 REVISED: COMPLETED:
Internal Report: Joint US-PRC Studies on Pollutant Transformation
Processes, Metals Speciation and Assessment Models.
16
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OWRS
PMS-060
FIRST QUARTER STATUS REPORT ON FY*89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: B101 WATER QUALITY
ISSUE: C WASTE WATER TREATMENT TECHNOLOGY
PPA (L): 46 IDENT. OF TOXIC CHEMICALS IN INDUSTRIAL EFFLUENTS
PPA (S): TOXICS IDENT.
RC: R ERL ATHNS
PROJECT: 02 Identify and Compile Data on Occurrence of Organics
PROJECT OFFICER: John M. McGuire PHONE: FTS-250-3185
******************************************
PLANNED START: 10/01/82 PLANNED END: 09/30/92
******************************************
PROJECT DESCRIPTION:
GOAL: Identify and determine distribution of unlisted
chemicals in industrial wastewaters. Compounds identifiable by empirical mass
spectra matching and those eluding identification by this technique will be
included.
RATIONALE: As new industrial technology is implemented, different chemicals are
introduced to wastewaters. Lists of regulated chemicals must be continually
updated, otherwise the listing may contain compounds that occur infrequently
and not contain other hazardous or toxic chemicals that, in fact, may occur
more frequently. Determining the distribution of unlisted hazardous and toxic
chemicals will permit maintenance of relevant lists for regulation.
APPROACH: Computer programs will be developed and applied to search stored
GC/MS data from industrial wastewater samples for nonpriority pollutants; mass
spectra will be compared with library spectra for identification. Compounds
that elude identification by spectra matching will be identified by reanalysis
of samples using multispectral techniques (low res. electron impact MS, low
res. chemical ionization MS, high res. MS, FTIR spec.). Computerized multi-
spectral interpretation approaches will be developed to improve efficency.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
As reported last quarter, one list of target compounds for confirmation
and another for multi-spectral identification of hits and misses have been
generated from the study of POTW and organic industry GC/MS tapes from the
Industrial Technology Division. Due to the last minute arrival of retained
extracts from 10 samples, the list is being reconsidered before final
multi-spectral analysis is completed.
STATUS AND SCHEDULE OF DELIVERABLES;
7579 DUE: 12/30/88 REVISED: 11/30/89 COMPLETED:
Report on Multi Spectral Identifications of MIS LIB Compounds. (K)
2/88 - delay to 11/89 a result of FY-88 Congressional Budget
actions
17
-------
18
-------
PRINT DATE* 01/30/89 CLIENT OFFICE ODW
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: C104 DRINKING WATER
ISSUE: F GROUNDWATER
PPA (L): 82 Ground Water Methods, Information Transfer & Applications
PPA (S): GW MTHDS,INFO,& APPL
RC: K ERL ATHNS
PROJECT: 22 Identify Unlisted Contaminants in Potential DW Sources
PROJECT OFFICER: John McGuire PHONE: FTS-250-3185
******************************************
PLANNED START: 10/01/87 PLANNED END: 12/31/99
*********************** * * *****************
PROJECT DESCRIPTION;
GOAL: Identify and determine frequency of occurrence of unlisted compounds
that may pose a hazard to human health in potential drinking water sources with
emphasis on potential groundwater contamination so that the contaminants can be
prioritized for health assessments.
RATIONALE: The 1986 Amendments to the Safe Drinking Water Act require that
lists of Recommended Maximum Contaminant Levels (RMCL) and monitoring
requirements be published January 1, 1988, and every three years following for
previously unregulated contaminants that pose a health risk in drinking water.
Most monitoring programs identify only currently regulated compounds, therefore
reanalysis of monitoring raw data is needed to identify unregulated compounds
as candidates for listing.
APPROACH: Computer programs will be used to search GC/MS raw data from
analyses of groundwater and other potential DW sources to identify unregulated
compounds. Mass spectra will be compared with library spectra for
identification. Compounds that cannot be identified by spectra matching will
be identified by reanalysis of samples using multispectral techniques (low
resolution electron impact MS, high resolution MS, Fourier transform IR
spectrometry, chemical ionization MS).
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
The ether extracts of the pilot plant chlorination referred to last
quarter showed the concentrations of most analytes to be too low for effective
use of GC/FT-IR. One GC peak present as a moderate level and corresponding to
one of the unidentified, unchlorinated compounds in earlier Risk Reduction
Engineering Laboratory studies was examined by GC/FT-IR, but no definite
conclusions could be reached concerning its structure.
STATUS AND SCHEDULE OF DELIVERABLES:
8117 DUE: 08/31/90 REVISED: COMPLETED:
Report: Ozonation Products of Drinking Water.
19
-------
20
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OSW
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY} D109 HAZARDOUS WASTE
ISSUE: C WASTE CHARACTERIZATION
PPA (L): 28 LAND DISPOSAL ASSESSMENT & EVALUATION OF OTHER MGMT SYSTEMS
PPA (S): LAND DISPOSAL ASSESS
RC: K ERL ATHNS
PROJECT: 03 Determine Chemical Transformation Pahways and Rates
PROJECT OFFICER: Jackson Ellington PHONE: FTS-250-3197
******************************************
PLANNED START: 10/01/85 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION;
GOAL: Prepare transformation pathway profiles of RCRA regulated chemicals in
order to provide data for environmental risk assessments.
RATIONALE: Under Subparts B and C of RCRA Part 261, listed chemicals are being
evaluated for their potential hazard to the environment when improperly
treated, stored, transported or disposed of. The chemicals already listed under
Subpart B are being subjected to mathematical modeling to determine acceptable
concentrations in leachates for each listed chemical and its transformation
products. Unlisted chemicals are being similarly evaluated under Subpart C as
candidates for listing. Assessments of concentrations resulting from
anticipated environmental conditions are necessary in order to determine
acceptable leachate concentrations.
APPROACH: Transformation processes, products and rates will be evaluated on a
theoretical basis to identify those that are likely to be significant. When the
evaluation indicates a need for experimental confirmation of reaction rates or
transformation products, appropriate experiments will be conducted. Results of
the theoretical considerations and laboratory experiments will be published as
transformation pathway profiles.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
A Research Brief was drafted entitled "Pathway Analysis of Chemical
Hydrolysis for 14 RCRA Chemicals." The brief identifies the pathway profiles
of hydrolysis, the intermediate and/or final products and rates of hydrolysis
(including references) of parents and intermediate products. A preliminary
report of the pathway analysis was provided to OSW.
Laboratory measurement of second-order acid hydrolysis rate constants for
seven substituted acetanilides are in progress. The rate constants will be
correlated with molecular spectroscopic properties to determine property-
reactivity correlations.
21
-------
Dr. Ellington chaired a session on the RCRA/Superfund: Toxics Monitoring
Symposium at the Southeast Regional American Chemical Society Meeting held in
Atlanta on November 9-11, 1988.
An attempt was made to determine the photolysis product of N,N-diphenyl
nitrosamine in water. Due to possible instrumental effects, the compound was
identified as either 9-nitroso-9H-carbazole or 9H-carbazole. The uncertainty
is due to the fact that the nitroso compound would decompose to the carbazole
at the temperature of the 60 injection port.
Two peaks from hydrolysis of 1,2-dichloroethane were identified. One was
identified as hydrogen chloride and the other ethylene glycol.
The identities of 16 compounds to be used in degradation studies were
confirmed by mass spectrometry.
Hydrolysis products of phorate and phorate sulfoxide were identified. The
phorate sample showed both phorate and diethyl sulfide; the sulfoxide sample
showed no sulfoxide and only very small peaks corresponding to alkyl sulfides
and thiols. None of the observed compounds seems a likely hydrolysis product
of either phorate or of the phorate sulfoxide.
STATUS AND SCHEDULE OF DELIVERABLESt
7950 DUE: 06/30/89 REVISED: COMPLETED:
Report on Hydrolysis Rate Constants for Enhancing Property-Reactivity
Correlations.
22
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OSW
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: D109 HAZARDOUS WASTE
ISSUE: C WASTE CHARACTERIZATION
PPA (L): 28 LAND DISPOSAL ASSESSMENT & EVALUATION OF OTHER MGMT SYSTEMS
PPA (S): LAND DISPOSAL ASSESS
RC: K ERL ATHNS
PROJECT: 07 Environmental Process Characterization - Metals
PROJECT OFFICER: Arthur W. Garrison PHONE: FTS-250-3145
******************************************
PLANNED START: 10/01/84 PLANNED ENDi 12/31/99
******************************************
PROJECT DESCRIPTION;
GOAL: Provide data on fate and transport of toxic metals for development of
exposure assessment models for implementing the Hazardous Waste Management
Amendments, including evaluating waste management and treatment needs based on
potential human health and environmental impacts.
RATIONALE: Current activities, including RCRA Reauthorization requirements
relative to Land Disposal Evaluation, demonstrate the lack of consistent
exposure assessment methods and data for determining the health and
environmental impact of various regulatory options. Data on fate and transport
of toxic metals are needed for inclusion in models for exposure assessment,
especially MINTEQ.
APPROACH: Thermodynamics and kinetics of sorption of metal cations,
metal-ligand complexes and other metal species on soils, sediments, and aquifer
substrates will be studied. Distribution coefficients will be determined using
plasma emission spectroscopy. Metal-ligand interactions will be studied using
laser spectroscopy. Kinetic equations and equilibrium constants will be
determined for use in exposure and risk models. Measurement, distribution, and
significance of redox potential of aquifer systems will be studied.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Major progress has been achieved by our University of Georgia cooperators
in their application of a Gaussian distribution model for competitive metal
binding with dissolved organics to fit their Lanthanide ion probe spectroscopic
titration data. The paper "Characterization of Metal Binding Sites in Humic
Acids by Lanthanide Ion Spectroscopy" was accepted for publication in
Analytical Chemistry, and a draft of another, "A Study of the Competitive
Binding of Protons and Metal Ions in Fulvic Acids by Lanthanide Ion
Spectroscopy," is currently undergoing final revision before submission for
journal publication. Currently, a draft of a paper on the binding of aluminum
by dissolved organics in natural waters is being prepared. At ERL-Athens,
Lanthanide ion probe titration spectroscopy has been used successfully to study
the binding of lead by dissolved organic matter.
Georgia Institute of Technology (GIT) cooperators have completed the major
portion of their matrix titration experiments using total dissolved organic
23
-------
matter from the Suwannee River (SRDOM), carried out at three different ionic •
strengths. These data are needed to completely characterize the proton binding
properties of SRDOM. This information is essential for application of the
Gaussian distribution model to the study of competitive metal binding. These
cooperators also have successfully isolated a substantial quantity of SRDOM by
the reverse osmosis technique they developed last year. About 10 grams of SRDOM
was give to ERL-Athens for use in our metal-organic binding studies.
The possibility of incorporating a metal-organic complexation component
into MINTEQ, the metal speciation model currently used for exposure assessment
of toxic metals by OSW, was discussed at a joint meeting of U6A, GIT, and
ERL-Athens cooperators in December. There was a concensus that development of
an algorithm for this component is quite achievable and should be the immediate
focus of the cooperators.
pH-dependent cationic adsorption profiles for six aquifer material
samples were completed this quarter. At present, modeling the adsorption of
anionic species to aquifer materials is unsatisfactory. Hence, additional
experimental work soon will begin using individual ionizable species. In
December, 30 aquifer material samples were collected at the joint ERL-Athens/
USGS field testing site near Globe, AZ for further studies of metal-metalloid
adsorption on aquifer solids. Four out of five attempted well installations at
this site were successful.
A methodology has been developed using orthogonal functions for
deconvoluting mixed emission spectra on the ICP. In addition, preliminary work
on salt concentration effects on ICP nebulizer efficiency has led to the
implementation of a scandium internal standard procedure in the ICP analytical
protocol. Previous dilution procedures often led to significant sensitivity
losses.
Work also has been completed on a cation exchange resin preconcentration
procedure for measuring contaminant concentrations at background levels in
groundwater.
Technical assistance (in conjunction with the ERL-Athens Assessment
Branch) was provided tot 1) Ed Bates (ERL-Cincinnati), Big 5 Wetlands Project,
and 2) EPA Risk Assessment Forum, on use of MINTEQA2 as a tool for
investigating the potential bioavailability of metals, especially lead.
Work continues at the University of Guelph on desorption of various metals
found on bacterial cell walls and cell wall-clay complexes. A draft manuscript
entitled, "Immobilization of Metallic Ions by Escherichia coli Envelope and
Bacillus subtilis wall - clay Mixtures" is undergoing internal review and
clearance. Preliminary work has started at the University of Arkansas on metal
sorption—Cu(II), Cd(II), Ag(I) and La(III)—by three fungi:Aspergillus niger,
Rhodotorula ulzamae and Saccharomyces cerevisiae.
STATUS AND SCHEDULE OF DELIVERABLES:
8157 DUE: 08/31/89 REVISEDi COMPLETED:
Comprehensive Report on Applying Electrostatic Adsorption Theory to Natural
Systems
8158 DUE: 03/31/89 REVISED: COMPLETED:
Report Defining Metal Complexation/Chelation Sites in Humic Materials
24
-------
PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OSW
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: D109 HAZARDOUS WASTE
ISSUE: C WASTE CHARACTERIZATION
PPA (L): 28 LAND DISPOSAL ASSESSMENT & EVALUATION OF OTHER MGMT SYSTEMS
PPA (S): LAND DISPOSAL ASSESS
RC: K ERL ATHNS
PROJECT: 17 Environmental Process Characterization (Biological)
PROJECT OFFICER: John E. Rogers PHONE: FTS-250-3592
******************************************
PLANNED START: 03/01/85 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Provide integrated (multimedia) methods and data for implementing the
Hazardous Waste Management Amendments, including evaluating waste management
and treatment needs based on potential human health and environmental impacts.
RATIONALE: Current regulatory activities including,RCRA Reauthorization
requirements relative to land disposal evaluation, are demonstrating the lack of
consistent methods and data for determining the health and environmental impact
of various regulatory options. Integrated (multimedia) methods that
accommodate knowledge of uncertainty are needed for more accurate and
consistent decision-making on waste management options.
APPROACH: Mechanisms of anaerobic biotransformations of xenobiotic chemicals
will be characterized using kinetic concepts. Laboratory studies will be
conducted to test these models and to identify environmental parameters that
affect the rates and extent of the biotransformation processes.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
The effects of the composition of headspace gas on the degradation of
2,4-dichlorophenol (DiCP) in anaerobic sediments were observed. Reaction
bottles containing 10 ml of sediment/water slurry (Ig dry sediment to 10 ml
water) were amended with 10 mg/1 of 2,4 DiCP. The initial headspace
compositions were H2/N2 (5Z/95Z), C02/N2 (52/952), N2 (99.92) or compressed
air. Two experimental approaches were used. In the first, the headspace gas was
periodically exchanged with the initial gas composition during the incubation
period and in the second the headspace gas was not exchanged over the entire
incubation period. The degradation rate was greatest in sediments in which the
headspace composition was exchanged. In these studies, degradation of 2,4 DiCP
was complete by day 10 for C02/N2 and air and by day 14 for H2/N2 and N2. In
reaction bottles in which the headspace was not exchanged, 2,4 DICP was absent
in C02/N2 after 14 days and present in sediments with headspace of air or N2
after 17 days and in H2/N2 headspace bottles after 28 days. The results
25
-------
indicate that in all treatments the methane production reached an exponential
level before 2,4 DiCP degradation began.
Reductive dechlorination of dichlorophenols was investigated in pond
sediments from two sites in the Athens area. Fresh Cherokee Pond sediment
dechlorinated 2,4- and 3,4-dichlorophenol to monochlorophenols within 31 days,
whereas fresh Bolton's Pond sediment dechlorinated 2,3-, 2,4-, and
2,6-dichlorophenol to monochloro- products after approximately 17, 12, and 41
weeks, respectively. Adapted Cherokee Pond sediments dechlorinated 2,4- and
3,4-dichlorophenol within 4 days, whereas Bolton's Pond sediment was
significantly slower, dechlorinating the 2,3-, 2,4-, and 2,6-dichlorophenol
isomers within 3, 2, and 4 weeks, respectively. When 2,3-, 2,4-, 2,5-, 2,6-,
3,4-, and 3,5-dichlorophenol were added individually to subsamples of the
adapted sediments from both sites, differences in monochloro- products and
dechlorination rates were observed. The differences in adaptation, product
formation, and dechlorination rate appear to be site specific.
The following two abstracts were submitted for the 1989 ASM Meeting to
be held in New Orleans, LA, in May: (1) Effect of Gas Phase Composition on
Anaerobic Biodegradation of 2,4-Dichlorophenol (Howard, Hale & Struijs),
(2) A Comparison of the Reductive Dechlorination of Dichlorophenols in Fresh
and Acclimated Sediments from Two Ponds (Hale & Rogers).
Laboratory experiments on the microbial degradation rates of methyl -
chlorobenzoate, methyl parathion, and 2,4-D butoxyethyl ester relative to a
benchmark chemical, 2,4-D methyl ester, have been completed. Kinetic data were
obtained using biofilm, water, and sediment samples (separately) collected from
field sites in Georgia and Florida. Degradation rates varied widely, depending
on the test chemical and environmental sample. However, degradation rates
relative to the benchmark chemical degradation rates were constant. These data
will be used in a journal article "Microbial substrate removal rate
coefficients relative to a benchmark chemical" (Newton, Lewis, Gattie).
The UGA cooperative agreement has not been funded; therefore, we have no
progress to report on our planned research on microbial adaptation to chemical
degradation (Hodson) or biofilm species composition effects on microbial
degradation and nutrient cycling (Shotts).
STATUS AND SCHEDULE OF DELIVERABLES;
7690 DUE: 07/31/89 REVISED: 11/30/89 COMPLETED:
INTERNAL REPORT ON EQUATION FOR PREDICTING ANAEROBIC TRANSFORMATIONS WITHIN
THE SATURATED ZONE
3/87-transf. from Ada to Athens to correct mistake on FY-87
final version PPA's; 5/87-due date revised as a result of
reprogramming of HW R&D resources to Wetlands program during
FY-88 PPA planning process
uut: ut/ju/ay KJSVISJSU: uuruui&ir.u:
Report on Evaluating the Utility of Current Methods for Estimating Anaerobic
Degradation Rates for Use in Evaluative Models
6/88 - moved from Y-105 B-02/33 to D-109 C-28/17
26
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OSW
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: D109 HAZARDOUS WASTE
ISSUE: C WASTE CHARACTERIZATION
PPA (L)« 28 LAND DISPOSAL ASSESSMENT & EVALUATION OF OTHER MGMT SYSTEMS
PPA (S): LAND DISPOSAL ASSESS
RC: K ERL ATHNS
PROJECT: 21 Multimedia Modeling with Uncertainty Analysis
PROJECT OFFICER: Lee A. Mulkey PHONE: FTS-250-3160
******************************************
PLANNED START: 09/01/85 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Provide multimedia methods complete with uncertainty analysis
capabilities for implementing the Hazardous Waste Management Amendments,
including evaluating waiver petitions, listing procedures, and delisting
petitions based on human health and environmental impacts.
RATIONALE: Current regulatory activities, including RCRA Reauthorization
requirements relative to Land Disposal Evaluation, are demonstrating the lack of
consistent methods and data for determining the health and environmental impact
of various regulatory options. Integrated (multimedia) methods that
accommodate knowledge of uncertainty are needed for more accurate and
consistent decision-making on waste management options.
APPROACH: The regulatory modeling system under development by OSW will be
enhanced, tested, and further developed to produce a comprehensive multimedia
exposure assessement system. A major part of this approach will include data
analysis, monte carlo programming, and error analysis to derive uncertainty
estimates. Field testing and case study applications will be completed to
further evaluate uncertainties.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Dr. Dave Brown, Dr. Nick Loux, Jerry Allison, Terry Allison and Lee Mulkey
developed metal speciation and transport modeling results for lead from soils
to human gastrointestinal tracts. Dr.Brown presented the results at the Risk
Assessment Forum Colloquium on Assessing Bioavailability of Lead and Other
Metals December 7 and 8 in Washington, DC. The effort was well received by the
Colloquium attendees and will be followed-up with an outline of the effort that
would be required to implement such an approach as part of the overall risk
assessment scenario for lead in soils. If implemented, this project should
substantially reduce the uncertainties inherent in current risk assessment
procedures.
Effort this quarter in direct support of OSW's development of a new rule
for waste characteristics included the development of a new plan for research
and model development activities geared for developing proposed regulations for
metals by December 1989 and promulgating final rules by July 1990. Dr. Brown
and Dr. Loux met with headquarters OSW technical staff December 8 to
discuss model development issues. A joint planning meeting in Athens is planned
for February 2 and 3 to finalize model development plans.
27
-------
A series of four additional monitoring wells were installed at the Globe,
AZ mine waste site involved in our EPA/USGS cooperative efforts for obtaining
data sets to test the MINTEQA2 metal speciat.ion/transport model. Core samples
from the bore holes were collected and returned to ERL-Athens for
characterization.
Other OSW modeling support activities included:
o Development and testing of an overlayed version of the Multimedia Model for
execution on PC.
o The EPA CML code was modified to meet needs of the OSW transient case
modeling project and a series of modeling runs was completed for
conservative chemicals to be covered in the next round of rule making.
Results of these exercises will be incorporated in the upcoming rule.
o Extensive modeling runs were completed for G. Michaels of the Economic
Analysis Branch OPA/OPPE to help evaluate the impact of the upcoming rule
on the pulp and paper industry.
o A new verison of MINTEQ (MINTEQA2) was released for distribution. The new
code was first used in the context of the MINTEQA2 course presented in
Boulder, CO during September. It incorporates updated sorption algorithms and
a substantially revised preprocessor code (PRODEFA2). The new sorption
algorithm, based on the diffuse layer model and augmented by a newly
developed database of intrinsic constants for Fe03 sorbents was tested on
several saturated zone matrix materials. The algorithm successfully predicted
sorption of several OSW metals, but failed for those metals that have
predominantly anionic solution species (Cr, As, Se).
Draft final reports completed this quarter include:
o Evaluation of the Application of Geochemical Equilibrium Programs to
Regulatory Assessment.
o A Pilot Study on the Selection of the Optimum Set of Components for
Multicomponent Chemical Equilibrium Problems: Selection, Transformation,
and Performance.
STATUS AND SCHEDULE OF DELIVERABLESi
8046 DUE: 06/30/89 REVISED: COMPLETED:
Report on Impact of Treayed Waste Forms on Exposure/Risk From Land Disposal
pf Hazardous Waste
8/87- added due to re-orientation of research program; this
replaces J7353-A which was deleted since the contents of
that project were no longer needed by the program office
8159 DUE: 07/31/89 REVISED: COMPLETED:
User's Manual for Site-Specific, Multimedia Model for Ranking Closure
Options at RCRA Land Disposal Operations.
8160 DUE: 08/31/90 REVISED: COMPLETED:
User's Manual for Model Defining Metal Species Transport in the Subsurface
28
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OSW
PMS-060
FIRST QUARTER STATUS REPORT ON FY*89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATMS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: D109 HAZARDOUS WASTE
ISSUE: C WASTE CHARACTERIZATION
PPA (L): 28 LAND DISPOSAL ASSESSMENT & EVALUATION OF OTHER MGMT SYSTEMS
PPA (S): LAND DISPOSAL ASSESS
RC: K ERL ATHNS
PROJECT: 38 Environmental Process Characterization - Organics
PROJECT OFFICER: N. Lee Wolfe PHONE: FTS-250-3429
******************************************
PLANNED START: 10/01/84 PLANNED END: 12/31/90
******** * * ********************************
PROJECT DESCRIPTION:
GOAL: Provide data on fate and transport of anthropogenic organic compounds
for development of exposure assessment models for implementing the Hazardous
Waste Management Amendments, including evaluating waste management and
treatment needs based on potential human health and environmental impacts.
RATIONALE: Current activities including RCRA Reauthorization requirements
relative to Land Disposal Evaluation demonstrate the lack of consistent
exposure assessment methods and data for determining the health and
environmental impacts of various regulatory options. Data on fate and
transport of anthropogenic organic compounds are needed for inclusion in models
for exposure assessment.
APPROACH: Detailed laboratory kinetic studies will be conducted to describe
soil mediated hydrolysis and abiotic redox transformation reactions of
organics as a function of pH and redox potential in the sorbed and bulk
aqueous phase of soil-water systems. Molecular and system variables that
govern redox, sorption, and other processes will be related and quantified.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Studies of the effects of pH on the adsorption of anionic organic
compounds to sediments have been initiated. Titration of a well characterized
sediment using a pH-stat constructed here has shown that between the ambient pH
value of 7.8 to approximately pH 5.5, hydrogen ion activity can be controlled
by the addition of acid (HC1) to within about 0.5 units. Titration of
pentachlorophenol (PCP, pKa equal to 4.8) between pH values of 7.8 and 4.0 in
EPA 11 sediment (10 g sediment in 200 ml water) shows the concentration of
pentachlorophenol in the aqueous phase to range from 80% of total added (at pH
7.8) to approximately 4Z (at pH 4.0). Between pH values of 3 and 4, no
difference was observed in the partition coefficient. This is highly consistent
with octanol-water partitioning data for PCP in the same pH ranges. Further
studies controlling the pH at higher values with the addition of base (NaOH)
29
-------
are anticipated, along with titration of other compounds having different
properties.
A draft paper on the homogeneous hydrolysis rate constants for selected
chlorinated methanes, ethanes, ethenes and propanes has been written. This
paper contains alkaline hydrolysis rate constants and activation parameters for
15 chlorinated hydrocarbons. The data will provide a basis for developing a
structure reactivity relationship for estimation of rate constants for other
halogenated hydrocarbons of importance to OSW. A draft jounal article entitled
"Hydrolysis of Chlorostilbene Oxide II. Hydrolysis in Aquifer Samples and in
Sediment-Water Systems" contains results that provide support for a model that
quantitatively describes abiotic hydrolysis in heterolytic systems.
A manuscript, "Reduction of Phorate Sulfoxide in Anaerobic Sediment
Slurries," was submitted to Environmental Toxicology and Chemistry in November
1988. This paper describes hydrolysis and redox processes in sediment and soil
samples. It shows that, at temperatures between 25 and 45 degrees C, reduction
is the dominant transformation pathway, between 45 and 65 degrees oxidation
dominates, and above 65 degrees hydrolysis dominates. A second paper,
"Characterization of Reducing Properties of Anaerobic Sediment Slurries Using
Redox Indicators," also submitted to Environmental Toxicology and Chemistry in
November, provides a basis for using redox indicators as a tool to describe the
redox state of sediments, soils and aquifer materials.
Kinetic studies of the degradation of Solvent Red 1 in anaerobic
sediment-water systems show that the disappearance of the dye followed
pseudo-first-order kinetics over two half-lives. The half-lives in two
sediments were 94.6 and 67.9 hours.
Studies progressed on the degradation of diphenyl- and dialkyl-N-
nitrosoamines in anaerobic sediments. While diphenyl-N-nitrosoamine was
degraded to diphenylamine with a half-life of 11.8 hours, diethyl-, dipropyl-,
and dibutyl-N-nitrosoamines were stable over a period of 14 days. Sorption
studies indicate the dialkyl-N-nitrosoamines do not sorb to the sediment and
that the diphenyl-N-nitrosoamine is only weakly sorbed. These results indicate
that the dialkyl-N-nitrosoamines will be persistent and highly mobile in
groundwater environments.
STATUS AND SCHEDULE OF DELIVERABLES;
7355 DUE: 06/30/88 REVISED: 07/31/89 COMPLETED:
REPORT ON PHOTODEGRADATION EVALUATION OF DIOXIN (2,3,7,8-TCDD) IN
SOILS
12/86 - delay to 9/88 a result of G-R-H tap 3/86; 2/88 - de-
lay to 7/89 a result of FY-88 Congressional Budget actions;
5/88 - transferred from D-109 D-54 during FY-89 PPA devel.
process
7689 DUE: 12/30/88 REVISED: 04/30/89 COMPLETED:
Report Describing the Kinetics of Redox Reactions in Soil-water
Environments.
5/87 - due date revised during FY-88 PPA planning process
as a result of reprogramming HW R&D resources into Wetlands
program
30
-------
PRINT DATEt 01/30/89
PMS-060
CLIENT OFFICE
OSW
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNSi OCTOBER - DECEMBER 1988
*****************************************
CODE TITLE
BUDGET SUB-ACTIVITY: D109
ISSUE: C
PPA (L): 96
PPA
HAZARDOUS WASTE
WASTE CHARACTERIZATION
Waste Futures and Aquatic Impacts
(S): HW Aquatic Impacts
RC: K ERL ATHNS
PROJECT: 30 Assessment Methods for HW Characteristics and Constituents
PROJECT OFFICER: Thomas Barnwell PHONE: FTS-250-3175
******************************************
PLANNED START: 01/31/88
PLANNED END: 09/30/95
**********************************
PROJECT DESCRIPTION;
GOAL: Develop methods and models to predict (1) impact of future waste forms
and regulatory levels on aquatic life and habitats and (2) regulatory
thresholds for aquatic life and habitat impacts.
RATIONALE: OSW is redefining the waste characteristics that will set the future
form, concentrations, and treatment levels for hazardous wastes. Little
consideration has been given to aquatic impacts except as an exposure pathway
to humans. Among these are organism toxicity, habitat alteration from oily
wastes and sludges/slurries, and damages from flooded facilities. No methods
exist to estimate the likelihood and consequences of future waste problems.
Methods to properly define "safe" waste futures are not available for aquatic
environmental impacts.
APPROACH: Relationships among future waste forms (component chemical
concentration levels, treatment systems, oily wastes, disposal systems).
release modes/rates and aquatic impacts will be identified and modeled within
the OSW framework for defining appropriate waste characteristics. Data gaps
will be identified and filled, and developed methodologies will be tested.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
This task is concerned with the development and validation of biological
procedures that can be effectively used as part of monitoring efforts at
hazardous waste sites. The procedure being evaluated is based on an
ERL-Corvallis test for the bioassessment of waste site locations. The method
has been tested at actual waste sites and found to be one of the better
screening techniques for detecting the presence of potentially hazardous
compounds. The current evaluation (and the subject of this quarterly report)
will establish the data quality that can be achieved within a single
laboratory, it will provide a basis for deciding whether the procedure merits
collaborative testing and will more clearly define the method's potential for
inclusion as part of an operational monitoring network.
The Chlorophyta Assay Using Soil and Sample Material is used to assess the
potential toxicity of soil samples such as might be collected in the vicinity
of hazardous waste sites. Water is added to individual soil samples and the
resulting eluate is tested for toxicity using green algae (Selenastrum
capricornutura). Since an aqueous eluate is intially acquired from the original
31
-------
soil sample, and since this eluate is filtered and diluted prior to toxiclty
testing, the procedure does not really address nonwater soluble chemicals nor
does it test for the presence of volatile compounds. In addition, problems
associated with the collection of soil samples (e.g., representative sampling
of a waste site area) are not addressed. Based on the ecological importance of
unicellular algae, however, this relatively simple technique can provide an
environmental hazard assessment for those chemicals that are, in fact, the
compounds most likely to be transported to surface and ground waters.
The method protocol has been reviewed, revised, and reviewed a second time
as steps toward achieving a "consensus* method. Water eluates were also taken
from different types of soil, and tested using Selenastrum Sp., before a clay
loam soil (characterized as being 221 sand, 51% silt, and 27% clay) was
selected for use during the evaluation. After the soil selection was made, a
suitable quantity of soil (approximately 275 kg) was collected so that enough
soil would be available for the entire single laboratory effort. The soil was
thoroughly homogenized, first by grinding, and then by being placed in a
mechanical soil mixer and mixed for several hours. A ruggedness test, to
identify procedural variables that must be carefully controlled, also was
conducted.
If the Chlorophyta procedure is "rugged" it will not be susceptible to the
inevitable, modest departures in routine and the final test result will not be
altered by these slight variations. However, moderate procedural variations
definitely altered the final Chlorophyta test result when they occurred at
certain critical steps. Steps that must apparently be followed strictly as
written concern the amount of water added to the dry soil sample, the pH of the
resulting soil eluate that is actually used during the assay, and the specific
eluate concentrations (dilutions) prepared for the assay dilution series. The
Chlorophyta protocol has consequently been revised to emphasize strict
adherence to these critical instructions.
The SARAH2 computational algorithms were completed this quarter. Work
began on development of a new user interface using the AIDE user interface
toolkit developed under the Ecorisk research program. This interface should be
completed in early February 1989. Implementation of the Monte Carlo shell is
on hold pending completion of the new interface.
A review of flooding regulations for solid waste management was completed
by Aqua-Terra Consultants and delivered to Mark Schuknicht of OSW.
A report on feasibility of incorporation of the Habitat Suitability Index
(HSI) in SARAH is under review by the authors (Aqua-Terra) and also will be
complete by the end of January.
Significant technical support in support of hazardous waste
characterization and aquatic impacts included:
o Provided Bill Vocke, OSW Economic Analysis Branch, information on the
oily waste model and CEAM work on wood-preserving waste for OSW and Superfund.
o Sent Dr. Shin Chang, New Jersey Department of Environmental Protection,
a set of chemical hydrolysis transformation rates, sorption coefficients, and
water solubilities for use in landfill model in concentration based listing
program.
STATUS AND SCHEDULE OF DELIVERABLES;
NO DELIVERABLES AVAILABLE
32
-------
PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OPP
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
BUDGET SUB- ACTIVITY:
ISSUE:
PPA (L):
PPA (S):
RC:
PROJECT:
PROJECT OFFICER:
CODE TITLE
E104 PESTICIDES
D ECOLOGY: TRANSPORT /FATE /FIELD VALIDATION
07 GROUNDWATER: PEST. CONTAMINATION AND PROCESS STUDIES
PEST. GROUNDWTR RES.
K ERL ATHNS
24 Validation of Predictive Techniques for Environ. Exposure
David S. Brown PHONE: FTS-250-3310
******************************************
PLANNED START: 04/01/81 PLANNED END: 09/30/90
******************************************
PROJECT DESCRIPTION;
GOAL: Refine, parameterize, and evaluate via field and other studies the
capability of single and multimedia pesticide exposure models that predict the
multimedia and intermedia transport and fate of pesticides, especially through
soils (including an evaluation of their leaching potential), sediments, and
other porous media to ground and surface waters.
RATIONALE: Optimum pesticide regulation requires field-evaluated assessment
techniques to assure that scientifically defensible decisions are made using
cost-effective data specifications and assessment methods.
APPROACH: As single and multimedia pesticide exposure assessment packages are
developed or assembled from SOA components on application/drift, runoff,
leaching, surface stream, river and lake simulation, etc., and become
operational, they will be systematically evaluated via application to "real
world" OPP and state problems and via retrospective comparison studies. Limited
special field studies also will be initiated in concert with OPP, states,
Regions, and other agencies to generate required data bases to test either
complete model packages or specific components. Current emphasis is on the
Dougherty Plain leaching study.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
All monitoring equipment was removed from the Dougherty Plain test site
and the site was released to the cooperating farmer. An additional set of 597
soil samples were taken for bromide tracer analysis from sidewalls, the large
excavations developed in removing monitoring test equipment. Analysis of both
soil and water samples for bromide tracer continued during the quarter. A total
of 3700 bromide samples have been analyzed to date for use in testing and
calibrating the pesticide transport codes PRZM/RUSTIC.
A manuscript entitled "A Method for Testing Whether Model Predictions Fall
within a Prescribed Factor of True Values with Application to Pesticide
33
-------
Leaching", was completed during the quarter and submitted to Water Resources
Research. This work describes a quantitative method for evaluating model
performance at the field level and is viewed as a signifcant new contribution
in the field of model testing. Generally, the technique should be applicable
to a variety of environmental pollutant transport and transformation models.
Plans were developed for a multiagency cooperative field research
project on pesticide leaching at a new field site near Plains, 6A. Three
agencies—EPA, USDA and USGS—will cooperate at the site in an effort
to maxmize efficiency and reduce costs of model testing.
Mr. Charles Smith was appointed as the laboratory representative for the
Environmental Monitoring and Assessment (EMAP) Project Agroecosystem Work Group
and attended the planning workshop held in Chicago, October 24-27, 1988.
Substantial follow-up planning activities also have taken place during the
quarter.
STATUS AND SCHEDULE OF DELIVERABLES;
7661 DUE: 09/30/89 REVISED: COMPLETED:
Final Dougherty Plain Report Including Pesticide Ground Water Threat
Assessment Method
5/88- tille change during FY-89 PPA devel.
7664 DUE: 06/30/89 REVISED: COMPLETED:
Project Report on Soils Data Based for RUSTIC Model (Linked PRZM-Groundwater
Model)
5/88 - title change
8196 DUE: 12/31/90 REVISED: COMPLETED:
Report on Testing RUSTIC Model Using Selected Data Bases
34
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OPP
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: E104 PESTICIDES
ISSUE: D ECOLOGY: TRANSPORT/FATE/FIELD VALIDATION
PPA (L): 08 PREDICTIVE TECHNIQUES FOR ENVIRONMENTAL EXPOSURE
PPA (S): DEVELOP PRED. TECH.
RC: K ERL ATHNS
PROJECT: 14 Pesticide Process Characterzation
PROJECT OFFICER: Arthur W. Garrison PHONE: FTS-250-3145
******************************************
PLANNED START: 10/01/87 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Characterize key environmental processes that lead to transformation or
transport of pesticides in soil, sediment, water and related environments;
apply this information to improve predictive techniques for environmental
exposure.
RATIONALE: Transformation processes such as redox reactions in anoxic
environments (some sediments, subsurface zones), photolysis on soil and plant
surfaces and in the vapor state above application areas, and sorption,
especially of irrigable pesticides, are not characterized to the extent
necessary to account for pesticides loss to the environment. Degradation
products are not identified for many processes.
APPROACH: Laboratory studies using natural waters, soils, sediments, and
reference materials will be conducted to test proposed equations for pesticide
transformation kinetics and sorption equilibria. These studies will provide
rate and equilibrium constants required for exposure predictive models.
Compounds and reaction conditions will be selected to permit generalizations
about changes in molecular structure and environmental conditions. Initially,
photochemical transformations on soil surfaces and sorption of water soluble
(ionizable) pesticides to soils and sediments will be emphasized.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
Studies of the effects of pH on the adsorption of anionic organic
compounds to sediments have been initiated. Titration of a well characterized
sediment using a pH-stat constructed here has shown that, between the ambient pH
value of 7.8 to approximately pH 5.5, hydrogen ion activity can be controlled by
the addition of acid (HC1) to within about 0.5 units. Titration of pentachloro-
phenol (PCP, pKa equal to 4.8) between pH values of 7.8 and 4.0 in EPA 11
sediment (lOg sediment to 200ml water) shows the concentration of pentachloro-
phenol in the aqueous phase to range from 80% of total added (at pH 7.8) to
approximately 4Z (at pH 4.0). Between pH values of 3 and 4, no difference was
35
-------
observed in the partition data for POP in the same pH ranges. Further studies
controlling the pH at higher values with the addition of base (NaOH) are
anticipated, along with titration of other compounds having different
properties. Aqueous phase metals have been measured by ICP to assess the
effects of the pH changes on the dissolution and precipitation of inorganic
species and their possible relationship to organic anion partitioning.
A manuscript, "Reduction of Phorate Sulfoxide in Anaerobic Sediment
Slurries," was submitted to Environmental Toxicology & Chemistry in November
1988. This paper describes hydrolysis and redox processes in sediment and soil
samples. It shows that at temperatures between 25 to 45 degrees C reduction is
the dominant transformation pathway, between 45 and 65 degrees C oxidation
dominates, while above 65 degrees C hydrolysis dominates.
A second paper, "Characterization of Reducing Properties of Anaerobic
Sediment Slurries Using Redox Indicators," also submitted to Environmental
Toxicology & Chemistry in November, provides a basis for using redox indicators
as a tool to describe the redox state of sediments, soils and aquifer
materials.
STATUS AND SCHEDULE OF DELIVERABLES;
8197 DUE» 06/30/90 REVISED: COMPLETED:
Report on Sorption of Water Soluble Ionic Pesticides to Soils and Sediments.
36
-------
PklNT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OPP
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: E104 PESTICIDES
ISSUE: D ECOLOGY: TRANSPORT/FATE/FIELD VALIDATION
PPA (L): 08 PREDICTIVE TECHNIQUES FOR ENVIRONMENTAL EXPOSURE
PPA (S): DEVELOP PRED. TECH.
RC: K ERL ATHNS
PROJECT: 25 Predictive Techniques for Environmental Exposure
PROJECT OFFICER: David S. Brown PHONE: FTS-250-3310
******************************************
PLANNED START: 10/01/81 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Provide long term, short turnaround, or direct single or multimedia
exposure assessment technology assistance to OPP.
RATIONAL: OPP occasionally needs quick turnaround, customized model
development and application assistance for high priority regulatory actions
mandated under FIFRA. This effort provides a focused, coordinated body of
expertise comprised of ORD and OFP agency personnel augmented by extramural
specialists to meet this need on demand. It also provides the expertise to
develop needed long term multimedia, site-specific exposure assessment modeling
techniques.
APPROACH: Develop or assemble single and multimedia pesticide exposure
assessment packages from SOA components and apply them to high priority OPP
regulatory problems. Athens ERL also is responsible for generating needed
agronomic/management scenarios for non-irrigated crop applications and
reporting requirement to OPP. Close coordination with similar exposure/risk
model development activities for OTS and OW are envisioned and required, e.g.
PMN assessments.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Efforts during the quarter focused on completion and documentation of the
code linkages required in assembling the new linked root zone, vadose zone,
saturated zone pesticide transport model RUSTIC. A work assignment for
additional testing of the linked code and beta testing versions was distributed
to three cooperators. So far some differences have been found in the VAX and
Prime versions and these problems are undergoing further investigation.
A series of 40 Pesticide Root Zone Model (PRZM) input scenarios were
developed and provided to CAD West for the Sun Computer Development Project.
Ongoing technical assistance efforts to the PRZM Users Group continued
37
-------
during the quarter. A variety of technical, scientific, and.U',Qmpuflsc-related
questions were handled by phone.
Technical assistance was provided to OPP, as requested %• Gafi-Ssaarita® JEiden,
concerning technical approaches to modeling behavior of pestdJedMksj u*sedt in, ship
paints in the New York, San Diego Bay and Norfolk harbors.
Review, evaluation and testing of the overlay structure; for EG;
implementation of RUSTIC is underway.
STATUS AND SCHEDULE OF DELIVERABLES;
NO DELIVERABLES AVAILABLE
38
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OPP
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: E104 PESTICIDES
ISSUE: I ECOLOGY: ECOTOXICITY AND RISK ASSESSMENT
PPA (L): 13 DEVELOPMENT OF INTEGRATED RISK ASSESSMENT MODELS
PPA (S): INTEGRATED RISK ASS.
RC: K ERL ATHNS
PROJECT: 26 Risk Assessment Methods for FIFRA
PROJECT OFFICER: David S. Brown PHONE: FTS-250-3310
******************************************
PLANNED START: 10/01/85 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Develop, refine and extend existing terrestrial and aquatic fate,
transport and effects models to include hazard impact, subroutines and data for
environmental risk assessments (RA) for the labeled use of pesticides. Results
must be expressed in terms of probability of impact and frequency of occurrence
and duration.
RATIONALE: Proven, operational environmental RA models are needed to evaluate
registration requests for new pesticides and for re-registration and label
changes (e.g, new uses) of existing compounds under FIFRA.
APPROACH: Existing unsaturated/saturated zone soil transport models, proven
runoff-surface water pesticide codes, appropriate ground water codes, and
related air transport models will be combined to produce SOA exposure
assessment model frameworks. These will then be linked with available effects
models to produce defensible RA methodologies for OPP. As completed, the risk
assessment packages will be tested and evaluated, especially in terms of
probabilities and uncertainties associated with real world problems. Close
coordination will be required with CERL, RSKERL, AREAL and the aquatic fate
research at AERL.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Mr. Jeff Scarbrough is developing a ground spray application module for
the new Terrestrial Ecosystem Exposure Assessment Model (TEEAM) and has been
working to eliminate some minor "bugs" discovered in the present aerial spray
application code.
Mr. Mark Cheplick carried out further development and testing of TEEAM
during the quarter and has begun a series of sensitivity tests initiated in the
hope of finding appropriate ways to streamline the code.
A draft report outlining results of initial TEEAM sensitivity tests was
39
-------
completed is vmder review. The report is entitled "Sensitivity Analysis of the
Terrestrial Ecosystem Exposure Assessment Model."
STATUS AND SCHEDULE OF DELIVERABLES;
8129 DUE: 02/28/89 REVISED: COMPLETED:
Users Manual and User Interface Toolkit for Exposure Assessment Models
8130 DUE: 08/31/89 REVISED: COMPLETED:
Report: Sensitivity Analyses and Preliminary Testing of the Terrestrial
Ecosystem Exposure Assessment Model
8131 DUE: 08/31/90 REVISED: COMPLETED:
Users Manual for Updated TEEAM Model
40
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OTS
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: D ECOLOGY: TRANSPORT/FATE/FIELD VALIDATION
PPA (L): 09 DEVELOPMENT OF VALIDATED EXPOSURE ASSESSMENT METHODOLOGIES
PPA (S): EXPOSURE ASSESSMENT
RC: K ERL ATHNS
PROJECT: 12 Development of EcoRisk Exposure Models
PROJECT OFFICER: Craig Barber PHONE: FTS-250-3U7
******************************************
PLANNED START: 10/01/87 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION;
GOAL: Provide modeling approaches for evaluating exchanges of toxic
chemicals between aquatic organisms and their environment.
RATIONALE: The evaluation and prediction of risk from toxicants must be based
on sound methods for assessing the uptake, distribution, and effects in target
organisms. Testing all chemicals would be impossible and models must be
developed that can use readily available chemical parameters to make
predictions.
APPROACH: Exchange models will be developed to provide estimates of body
burdens of representative chemicals. Models will be based on thermodynamic
principles and raorphometric characteristics of organisms as well as on
consideration of route of exposure (water, food, or benthic sediments).
Assessments can then take into account multiple sources of contaminants and
also be extended to include ecological significance or effects. Physiological
response depends on the chemical concentration in the organisms rather than
that in the environment and the exchange models will be linked to toxicokinetic
models to predict effects. Laboratory experiments will be conducted to test
underlying hypotheses, and other factors involved will be identified.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
An article entitled "Modeling Bioaccumulation of Organic Pollutants in
Fish with an Application to PCBs in Great Lake Salmonids" was submitted to
the Canadian Journal of Fisheries and Aquatic Sciences.
Work was begun to extend FGETS' capabilities so that bioaccumulation of
ionizable organic chemicals can be simulated. Because, in the absence of
specific transport mechanisms, only the neutral species of an ionizable
chemical is exchanged across biological membranes, it was initially thought
that this extension to FGETS would simply require computational algorithms to
estimate the water concentrations of the exchangeable species. A compilation of
41
-------
a small data set of published studies on the bioaccumulation of various
chlorophenols indicated that this logic was incorrect because uptake rates
predicated by FGETS adjusted for effective concentration were one or two orders
of magnitude lower than observed values. Such underestimation could result
either because the ionized species is also exchanged or because the transport
conductance of the neutral species of an ionizable chemical through the
interlamellar water of a fish's gills is enhanced by the chemical's
dissociation reaction. The latter explanation is currently being investigated
by constructing analytic solutions to the partial differential equations that
describe mass diffusion with forced convection in flat channels under boundary
conditions that are thought to emulate those associated wtih ionizable
chemicals.
Early in December, Dr. David Randall and Dr. Larry Fiddler visited
ERL-Athens to discuss how their studies in fish respiratory physiology might
interface or help support our bioaccumulation modeling. It was clear that their
work on ammonia and carbon dioxide exchange across fish gills was of immediate
importance to our current work involving ionizable chemical because carbon
dioxide excretion alters the pH and hence the concentration of the neutral
species of an ionizable chemical in the interlamellar water of the gill. It
would be desirable and advantageous to foster this continued interaction if
R&D resources are available.
STATUS AND SCHEDULE OF DELIVERABLES;
8135 DUE: 02/28/89 REVISED: COMPLETED:
Research Brief: Modeling bioaccumulation of polar and ionic chemicals by
fish.
42
-------
PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OTS
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
BUDGET SUB- ACTIVITY:
ISSUE:
PPA (L) :
PPA (S):
CODE TITLE
L104 TOXICS
D ECOLOGY: TRANSPORT /FATE /FIELD VALIDATION
09 DEVELOPMENT OF VALIDATED EXPOSURE ASSESSMENT METHODOLOGIES
EXPOSURE ASSESSMENT
RC: K ERL ATHNS
PROJECT: 27 Development of Validated Exposure Assessment Methodologies
PROJECT OFFICER: Thomas Barnwell PHONE: FTS-250-3210
******************************************
PLANNED START: 10/01/79 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Develop, parameterize and evaluate multimedia modeling systems and
continue development and modification of existing models for non-human
exposures.
RATIONALE: OTS wants to upgrade its metals and organics multimedia modeling
capability for PMN activities and comprehensive risk/benefit analyses on the
impacts of regulating existing chemicals /species and to account for potential
toxic effects at the organism and systems levels given various toxics loading
combinations into surface waters and other environmental compartments.
APPROACH: Thermodynamic metal species and chemical reaction models will be
combined with partitioning and bioaccumulation (including plants) models to
produce a process-based aquatic distribution package for metal species. Also,
additional refinements in transport codes (particularly intermedia) and
transformation kinetics of pollutants will be incorporated into multimedia
models to produce more reliable exposure assessment packages for organics of
interest under TSCA and RCRA.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
A standard Fortran-77 computer code of the preliminary 3-D estuary and
lake sediment transport model was completed. The initial code also was
documented. This initial code will be tested at AREAL in the second quarter and
will be implemented for the Green Bay application. To aid early testing, the
University of Florida will maintain a close working relationship to assist
EPA* s model application throughout the study period. During the coming quarter,
the University of Florida will begin additional development of the sediment
dispersion model and testing with Lake Okeechobee data. Processing of the
initial data is continuing.
AScI tested and debugged the hydrodynamics code delivered last quarter.
A preliminary test data set for Green Bay was compiled and the code was put on
43
-------
a faster computer. A bathymetry data set and segmentation scheme was devised as
well as a wind field processor and tidal boundary option.
In the second quarter the preliminary sediment transport code will be
tested followed by testing and documentation of the hydrodynamics code. A
preliminary data set for the Green Bay Application of the Sediment Transport
Model will be developed and additional assistance will be provided to other
Green Bay reseachers by defining the general hydrodynamics and required linkage
to the WASP model.
STATUS AND SCHEDULE OF DELIVERABLES;
8047 DUE: 08/31/89 REVISED: COMPLETED:
Final Report on Monte Carlo Version of MINTEQ
44
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OTS
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS .
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: D ECOLOGY: TRANSPORT/FATE/FIELD VALIDATION
PPA (L): 10 TRANSPORT AND FATE PROCESS DETERMINATION
PPA (S): TRANSPORT AND FATE
RC: K ERL ATHNS
PROJECT: 09 Chemical Process Characterization for Toxics
PROJECT OFFICER: Richard G. Zepp PHONE: FTS-250-3428
******************************************
PLANNED START: 10/01/79 PLANNED END: 09/30/99
******************************************
PROJECT DESCRIPTION;
GOAL: Characterize key chemical processes (direct-indirect photolysis,
hydrolysis, redox reactions, and sorption/desorption) and expand scientific
understanding of sediment-water exchange to improve exposure and risk
assessment models for PMN chemicals.
RATIONALE: The role of inorganics in pollutant transformation by photolysis and
the kinetics of redox reactions are inadequately understood for reliable use in
exposure assessment models. These processes are known to be environmentally
important; for example, some dyes are rapidly degraded in sediment-water
systems.
APPROACH: Laboratory studies using natural waters, sediments and reference
materials will be used to accept or reject proposed equations for the kinetics
and equilibria of transformation and sorption processes. Rate and equilibrium
constants to fit the equations will be provided. Compounds and reaction
conditions will be selected to permit generalizations about changes in
molecular structure and environmental composition. Photochemical studies will
emphasize the role of naturally occurring inorganic species; redox reactions of
abiotic systems, relative to biotic systems, will be studied. Chemical fate
processes of azo and anthroquinone dyes will receive particular attention.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
A draft paper on the homogeneous hydrolysis rate constants for selected
chlorinated methanes, ethanes, ethenes and propanes has been written. This
paper contains alkaline hydrolysis rate constants and activation parameters for
15 chlorinated hydrocarbons. The data will provide a basis for developing a
structure reactivity relationship for estimation of rate constants for other
halogenated hydrocarbons. A draft journal article entitled "Hydrolysis of
Chlorostilbene Oxide II. Hydrolysis in Aquifer Samples and in Sediment-Water
Systems" contains results that provide support for a model that quantitatively
describes abiotic hydrolysis in heterolytic systems.
45
-------
Kinetic studies of the degradation of Solvent Red 1 in anaerobic
sediment-water systems show that the disappearance of the dye followed
pseudo-first-order kinetics over two half-lives. The half-lives in two
sediments were 94.6 and 67.9 hours.
Studies progressed on the degradation of diphenyl- and dialkyl-N-
nitrosoamines in anaerobic sediments. While diphenyl-N-nitrosoamine was
degraded to diphenyl-amine with a half-life of 11.8 hours, diethyl-, dipropyl-,
and dibutyl-N-nitrosoamines were stable over a period of 14 days. Sorption
studies indicate the dialkyl-N-nitrosoamines do not sorb to the sediment and
that the diphenyl-N-nitrosoamine is only weakly sorbed. These results indicate
that the diphenyl-N-nitrosoamines will be persistent and highly mobile in
groundwater environments.
Studies of the effects of pH on the adsorption of anionic organic
compounds to sediments have been initiated. Titration of a well characterized
sediment using a pH-stat constructed here has shown that, between the ambient pH
value of 7.8 to approximately pH 5.5, hydrogen ion activity can be controlled by
the addition of acid (HC1) to within about 0.5 units. Titration of
pentachlorophenol (POP, pKa equal to 4.8) between pH values of 7.8 and 4.0 in
EPA 11 sediment (10 g sediment in 200 ml water) shows the concentration of
pentachlorophenol in the aqueous phase to range from 80Z of total added (at pH
7.8) to approximately 42 (at pH 4.0). Between pH values of 3 and 4, no
difference was observed in the partition coefficient. This is highly consistent
with octanol-water partitioning data for POP in the same pH ranges. Further
studies controlling the pH at higher values with the addition of base (NaOH)
are anticipated, along with titration of other compounds having different
properties.
Research was continued on the influence of light on the oxidation of
organic substrates by manganese oxides. Kinetic studies of the oxidation of
p-chlorophenol were conducted using monochromatic radiation corresponding to
the maximum absorption of manganese dioxide (336 nm). The pH dependence of the
oxidation rate of p-phenylphenol in manganese oxide suspensions exposed to
sunlight also was investigated. Studies of the influence of light on the
oxidation of anilines by manganese oxides were initiated; the oxidation of
p-chloroaniline was examined. Work on the photoredox reactions of copper were
also continued. Quantum yields were determined as a function of pH for the
photoreduction of copper (II) complexed by nitrogen ligands. Kinetic studies
were conducted in sunlight for comparison. Two journal articles were submitted
for publication during the quarter: "Hydrogen Peroxide Decay in Waters with
Suspended Sediments: Evidence for Biologically Mediated Processes" and
"Aquatic Humic Substances as Sources and Sinks of Photochemically Produced
Transient Reactants."
STATUS AND SCHEDULE OF DELIVERABLES:
8137 DUE: 03/30/90 REVISED: COMPLETED:
Internal Report - (Research Brief) - Fate of Dyes in the Environment.
46
-------
PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OTS
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: D ECOLOGY: TRANSPORT/FATE/FIELD VALIDATION
PPA (L): 10 TRANSPORT AND FATE PROCESS DETERMINATION
PPA (S): TRANSPORT AND FATE
RC: K ERL ATHNS
PROJECT: 37 Microbial Transformation Rate Constants
PROJECT OFFICER: William C. Steen PHONE: FTS-250-3776
******************************************
PLANNED START: 10/01/85 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Develop and apply a system that provides, on a timely basis, second
order microbial transformation rate constants for suspended organisms in
aerobic aquatic systems.
RATIONALE: Under the Toxic Substances Control Act, both new and existing
chemicals must be evaluated for potential to pose environmental risk from the
standpoint of toxicity. A major consideration in assessing environmental
exposure is microbial transformation. Second order rate constants provide a
means of evaluating potential for microbial transformation at various
environmental microbial population levels.
APPROACH: Reproducible second order rate constant measurement techniques will
be established to relate all chemicals to the same population conditions.
Second order microbial transformation rate constants will be measured for
selected chemicals representing each important class of chemicals.
Relationships between microbial transformation rate and molecular spectroscopic
properties will be established for base compounds in each chemical class. Rate
constants for additional compounds of interest will be inferred from their
molecular spectroscopic properties, which are easily measured.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
Second order microbial transformation rate constants were completed for
seven substituted amides for use as PNN analogies. They are tabulated below:
k(b) - L per org. per hr.
Propachlor
Proporial
N-methylbenzamide
Monalide
Alachlor
,1 X E-9
,0 X E-10
,0 X E-12
,0 X E-13
3.0 X E-13
47
-------
Pronamide 5.0 X E-14
Niclosamide 2.0 X E-14
Measurements were made using the ERL-Athens protocol for susjsnxfedt enagsmisns in
aerobic systems.
Compilation has begun on vibrational spectra in different:, meddla* Smr t2»e
substituted amides. These data will be used in conjunction wiiflik makmsflalal
degradation data both to extend property-reactivity correlations ('KSBCsJ) asaA to
develop some understanding of the importance of solvent effect^.,
A new approach to PRCs is being investigated that of fen £&e> paaaimEse of
utilizing more of the available spectral information than is used! alt present, in
arriving at correlations. Because more independent data are 3is*?.di,.. G&ursislsctions
should be more reliable.
In conjunction with the PRCs of biolysis rate constants aadl sg:©cttaess*copic
properties mentioned last month, preliminary work is in progress; tto) ttE3?tt tthe
feasibility of direct aqueous injection GC/FT-IR as an altenraaiJve) teas MilfST-TSi.
LC/FT-IR is a much more difficult technique to use, but is gsnafEaCDl'y $ X< E-H| and
benzanilide (2.4 X E-12). These data and the rate constants Eegoaijtifixi! ffirar six
compounds last quarter will be compared with spectroscopic pfjo.p.ear.c-i3es3 fro> assess
PRCs.
Four substituted sulfonyl urea herbicides were selected tasr measurement of
second order microbial rate constants for PRCs.
STATUS AND SCHEDULE OF DELIVERABLESt
8136 DUE: 08/31/90 REVISED: COMPLETED:
Report: Microbial Transformation Rate Constants of Structurally/
Man-made Chemicals.
48
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OTS
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE. TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: D ECOLOGY: TRANSPORT/FATE/FIELD VALIDATION
PPA (L): 11 EVALUATION OF EXPOSURE ASSESSMENT METHODS
PPA (S): MICROCOSM/FIELD
RC: K ERL ATENS
PROJECT: 05 Environmental Transformation and Equilibrium Constants
PROJECT OFFICER: Heinz Kollig PHONE: FTS-250-3770
******************************************
PLANNED START: 10/01/83 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION;
GOAL: Establish and maintain data bases in which data are of known reliability
for use in risk assessments, either as "analogs" or as inputs to exposure
algorithms, and in expert systems for estimating physical, chemical and
microbial constants. Communicate data to the user community.
RATIONALE: Scientifically valid and accurate transformation rate and
equilibrium constants are required as inputs to mathematical models and other
decision tools to assess risk associated with toxic and other hazardous
chemicals.
APPROACH: A data base management system will be established that can meet user
needs. Data will be acquired from the following sources: (1) the literature,
(2) manufacturers' data submissions to EPA, (3) computations made by
technicians, and (A) inhouse laboratory measurements. All data will be screened
for reliability by applying previously established criteria.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
The computerized Coordinated List of Chemicals (CLC) database, which tells
who is studying what chemical in ORD, was compiled into a computer executable
form. The database can now be used on a PC without any additional software.
A prototype computerized quality evaluation system for the water
solubility of pesticides, developed by the Agricultural Research Service, USDA,
was reviewed. The system should be useful in evaluating water solubility data
for any organic chemical.
Work continued on the development of the fate constant database with
FOCUS.
STATUS AND SCHEDULE OF DELIVERABLES;
7905 DUE: 03/31/89 REVISED: COMPLETED:
Report on problems associated with published environmental fate constants
5/88 - title change
49
-------
50
-------
PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OTS
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: D ECOLOGY: TRANSPORT/FATE/FIELD VALIDATION
PPA (L): 11 EVALUATION OF EXPOSURE ASSESSMENT METHODS
PPA (S): MICROCOSM/FIELD
RC: K ERL ATHNS
PROJECT: 16 Evaluation of Exposure Assessment Methods
PROJECT OFFICER: David L. Lewis PHONE: FTS-250-3358
******************************************
PLANNED START: 10/01/79 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION;
GOAL: Develop and apply laboratory and field systems for testing transport and
transformation subroutines, exposure modeling systems, and risk analysis
systems.
RATIONALE: Methodologies for predicting and/or assessing ecological hazard
have not been adequately tested in complex microcosm and field studies.
APPROACH: The use of controlled laboratory ecosystems to evaluate exposure
modeling systems and risk analysis systems increases the probability of
attributing a testing mismatch to the appropriate subroutine. To evaluate
general applicability, microcosm results are compared with field data. Field
and laboratory ecosystems having different physical, chemical, and biological
makeup are developed and used for testing mathematical methods for determining
eco-structure, evaluating ecological hypotheses and modeling assumptions used
for developing generalized predictive models, and testing exposure assessment
and risk assessment models.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
A completed model of the entire surface water system of the Netherlands
was received. Analysis of the model revealed a number of features that will
require correction. Simulation studies of four test chemicals demonstrated that
most of the segments are advection dominated and thus of relatively slight
value in testing process models. The Dutch Laboratory RIVM is assembling a more
detailed dataset that is less advection dominated for process model testing.
Additional chemicals for process model testing will be identified in the coming
quarter via analysis of the Dutch WAKWAL monitoring system.
Inhouse laboratory experiments to test the hypothesis of a threshold
critical aqueous blood concentration of a toxicant at which effects on an
organism occur are continuing using the neutral hydrophobic test chemical
1,2,3,4-tetrachlorobenzene (TCB). These studies are needed to test FGETS and
51
-------
for development of effects models and are not being done anywhere else.
Because of wide ranges in results for plasma and whole body concentrations of
TCB and plasma content of lipid and moisture, a large amount of effort this
quarter has been on quality assurance for all these analyses. We are now
confident the simplified extraction method being used is as efficient and
consistent as the approved sonication method used by Region IV for extraction
of organics. Therefore, the variation in the TCB data is real. Plasma lipid and
moisture determinations have been modified and refined, and we now have
confidence in those parameters.
The hard-to-define endpoints with the narcotic chemical, TCB, are still a
problem. Bluegill sunfish exposed then sampled when near death or dead (24 to
48 hrs) have plasma TCB concentrations of from 128 to 775 mg/kg, whereas
individuals removed at turnover (1 to 2 hrs) have plasma TCB concentrations
within the same range. At this point the hypothesis of a lethal threshold in
the blood for TCB does not seem realistic. Whole body concentations of TCB,
however, do show some correlation with death and both parameters are being
further studied.
Ongoing and future studies include sequential sampling of blood from a
living channel catfish during exposure to TCB to determine uptake into the
blood with time; exposure and sampling of more bluegills to obtain more
complete datasets; and exposure of guppies to compare whole body concentrations
at death with those in a study in the literature by van Hoogen and Opperhuizen.
The project is behind schedule because of very time consuming and specific
analyses, and the large amount of quality assurance work required. New target
date is March 1989.
A report on an Exposure Analysis Modeling System (EXAMS) subroutine for
predicting microbial transformation rates by biofilms (Gattie, Lewis, Newton)
has been written and is being internally reviewed.
STATUS AND SCHEDULE OF DELIVERABLES;
8138 DUE: 07/31/89 REVISED: COMPLETED:
Report: EXAMS subroutines for predicting microbial transformation rates of
aquatic pollutants by attached populations.
52
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OTS
PMS-060
FIRST QUARTER STATUS REPORT ON FY*89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNSt OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: G STRUCTURE ACTIVITY RELATIONSHIPS
PPA (L): 20 STRUCTURE-ACTIVITY RELATIONSHIPS AND ESTIMATION TECHNIQUES
PPA (S): SAR/EST TECHNIQUES
RC: K ERL ATHNS
PROJECT: 10 Predictive Methods for Environmental Exposure Assessments
PROJECT OFFICER: Samuel W. Karickhoff PHONE: FTS-250-3149
******************************************
PLANNED START: 10/01/80 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION;
GOAL: Develop and test concepts for predicting key environmental transport and
transformation processes for exposure and risk assessments of PMN chemicals.
RATIONALE: Computational procedures are needed for estimation of photochemical,
hydrolytic and other transformation rate coefficients used in exposure
assessments. Such computational approaches minimize the amount of measurement
required and provide the only independent assessment of measured values.
APPROACH: Conceptual relationships and equations relating light absorption and
rate/equilibrium constants to molecular structure will be developed for direct
photolytic and hydrolytic transformations and for acidity constants (pKa).
Process rate and equilibrium constants then will be measured in the
laboratory using natural components. Resulting data will be used to evaluate
and/or modify the concepts and resulting equations.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
The pKa's of esters are being catalogued for continued testing of SPARC,
the ERL-Athens expert system for predicting chemical reactivity parameters such
as pKa, hydrolysis rate constants, UV absorption spectra (for photochemical
degradation rate constants), etc. Rearrangement of Prolog code for SPARC into
stand-alone modules has begun, as well as documentation of Prolog code.
Development of an interface for the spectra database (currently for 200
compounds) with SPARC is still in progress.
Three journal articles describing SPARC and its preliminary applications
are now being cleared at ERL-Athens for publication in one issue of
Environmental Toxicology and Chemistry.
STATUS AND SCHEDULE OF DELIVERABLES;
8144 DUE: 08/31/90 REVISED: COMPLETED:
Report documenting application of expert systems for predicting reactivity
parameters for PMN chemicals
53
-------
54
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OTS
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: G STRUCTURE ACTIVITY RELATIONSHIPS
PPA (L)t 20 STRUCTURE-ACTIVITY RELATIONSHIPS AND ESTIMATION TECHNIQUES
PPA (S): SAR/EST TECHNIQUES
RC: K ERL ATHNS
PROJECT: 15 PRC Relationships and Other Estimation Techniques
PROJECT OFFICER: Susan A. Moore PHONE: FTS-250-3469
******************************************
PLANNED START: 05/01/83 PLANNED END: 09/30/99
******************************************
PROJECT DESCRIPTION;
GOAL: Expand data bases for establishing property reactivity correlations
(PRC) and develop quantitative relationships between microbial rate constants
and molecular descriptors.
RATIONALE: There is a need for developing predictive models for fate and
effects based on structure activity relationships /PRC, because resource
limitations preclude laboratory characterization of all chemicals of interest.
APPROACH: Lab studies with natural water samples will be used as a basis for
assessing formulations for the kinetics of processes describing microbial
transformation of toxic chemicals. Emphasis will be placed on measurements of
biomass associated with transformations. A homologous series of compounds will
be used to examine how changes in compound structure influence the raicrobial
rate constants. Product analyses will be used to verify common transformation
mechanisms.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
Changes in river water that occur when it is stored for extended periods
in the laboratory were investigated. The significance is, first, that the
degradative activity of river water may change during storage leading to
inaccurate conclusions about the degradative activity of the natural setting.
The goal, therefore, is to identify conditions in which river water can be
stored in a pristine state. Second, changes in river water that are induced
by varying the storage conditions are likely to mimic or approximate
natural changes due to seasonal and environmental factors, hence identifying
such factors. A second river water sample was collected and previous results
were confirmed and extended. Storage conditions have not yet been found that
maintain river water in its original state, but progress has been made.
Storage of 20 degrees Centigrade river water at 20 degrees Centigrade for 40
days produced no significant change in total cell concentration, but the
frequency of occurrence of cell strains changed markedly (based on visual
55
-------
inspection of agar plates). In contrast, storage at -72 degrees Centigrade
produced a 20-fold decrease in cell concentration after 3 days although the
frequency of cell strains appeared to remain constant up to 40 days. Storage
at 3 and -12 degrees Centigrade produced results that were intermediate between
those at 20 and -72 degrees Centigrade. A rnicroplate assay was initiated to
identify cell strains in river water and better quantitate their frequencies of
occurrence. Cell concentration was measured as both CPU on agar plates and MPN
in liquid medium. Controls ruled out so called "bottle effects" and effects
due to the thickness of agar on agar plates. Rapid freezing and storage in
liquid nitrogen (approximately -200 degrees C) is being tested. It may be
that river water must be reconstituted from stored components in order to
(re)obtain the original state and allow accurate, reproducible laboratory
analysis of biodegradation. The doubling times in rich medium of the fastest
growing cells that were endogenous to river water were measured in a
spectrophotometric assay. Between 10 and 30 degrees Centrigrade, a 10-fold
increase in temperature produced a 2.2-fold increase in cell growth rate.
Theoretical analysis of biodegradation by Michaelis-Menten and Monod kinetics
was continued with a view towards distinguishing between them. Monod kinetics
are likely to represent complete degradation of xenobiotics to C02 in contrast
to the buildup of side products that is typical of Michaelis-Menten kinetics.
Analysis of physical properties was continued on a second sample of river
water. Ultrafiltration was used to separate components by molecular weight,
and methods for routine organic carbon analysis were initiated. Degradation
studies were begun. Three out of ten samples randomly picked but visually
distinct clones of microbes from river water were found to degrade 4-chloro-
aniline within 10 days after inoculation in basal salts medium.
STATUS AND SCHEDULE OF DELIVERABLES;
7916 DUEs 08/31/88 REVISED: 08/31/89 COMPLETED:
Report: Current use of structure activity relationships for predicting
biotransformation of chemicals
5/88- title and due date changed during FY-89 PPA devel.
56
-------
PRINT DATE: 01/30/89 CLIENT OFFICE AA_OPTS_
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: I ECOLOGY: ECTOXICITY AND RISK ASSESSMENT
PPA (L): 26 DEVELOP METHODOLOGIES FOR ECOLOGICAL RISK ASSESSMENT
PPA (S): RISK ASSESSMENT DEV.
RC: K ERL ATHNS
PROJECT: 13 Predictive Techniques for Ecological Risk
PROJECT OFFICER: Ray R. Lassiter PHONE: FTS-250-3208
******************************************
PLANNED START: 10/01/84 PLANNED END: 09/30/90
******************************************
PROJECT DESCRIPTION;
GOAL: Develop modeling approaches for assessment of risk from toxic chemicals
in natural systems.
RATIONALE: Assessing risk from toxic chemicals involves assessments of
concentration distributions in the environment and of expected effects.
APPROACH: Exposure analysis models will be used to provide expected aquatic
environmental concentration distributions. To develop the capability to analyze
for expected effects, it will be necessary, first, to determine what effects
are of concern (population, community, second, ecosystem), and the appropriate
aquatic systems to use to study those effects, and second, to develop the
appropriate models to represent effects at those levels. Models for effects are
adapted from existing models or developed on basic principles, as required.
Finally, exposure analysis models are linked in a computer implementation with
effects models via a user-friendly interface to provide the working risk
analysis modeling system.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
Recruitment was completed for a microbiologist/modeler this quarter.
Selected candidate is Dr. Rochelle Aurajo from Cornell University, who will
report to the project on April 9, 1989.
Work continued this quarter in design of an experimental GIS interface
between biological distribution data and simulation model parameter sets.
Accounts for all project personnel were established on the NCC VAX, and
authorizations were obtained for use of VAX ARC/INFO on the CASTOR (VAXB) node.
The Tektronix 4106 terminal and Tektronix 4105 emulation using PCPLOT+ on the
PC workstations were set up and tested using VAX sample datasets. Integration
of PC ARC/INFO and the NCC VAX version was tested using a sample Digital Line
Graph (DLG) provided by the United States Geological Survey (USGS) on magnetic
tape for the Chattanooga area. A Bailey ecoregion coverage was designed, and a
57
-------
crop capability class mapping from USDA/ARS was located for possible use. These
coverages will be implemented in the second quarter of FY89. The availability
of digital data for potential study sites in Georgia, Alabama, and Louisiana
was evaluated as part of general study design and feasibility exercises.
Steps for planning the 1989 Ecorisk All Investigators Meeting have been
taken. Tentatively the meeting will be held in Athens during the last week of
February. Contact persons at the other Ecorisk laboratories will be contacted
during the first 2 weeks of January to finalize the necessary arrangements.
In December ERL-Athens principals met to evaluate the status and direction
of the Ecorisk Research Program with respect to the integration of existing
Ecorisk databases and models into Ecorisk Assessment tools that can be used by
OTS. Although no definitive decisions were made, several important topics were
addressed. These includet (1) Should the research of the Ecorisk program be
incorporated into a series of assessment softwares or into a single system like
GEMS? (2) Is there duplication of effort in the Ecorisk program, for example,
(a) FGETS and the Erickson/McKim gill model, (b) the ERL-Athens/UGA
physiological/ecological database and the Dutch biological database, and (c)
the Biology Branch's planned EXAMS/FGETS/FIS software system and the existing
CADSWES Sun-based system supported by the Assessment Branch? (3) Should the
integration of existing Ecorisk databases and models be emphasized during the
1989 All Investigators's meeting?
Habitat associations for approximately 40 species (aquatic and
terrestrial) selected from the USFWS Endangered and Threatened Wildlife and
Plants List are still being acquired. Data have come from USFWS publications,
the Endangered Species Information System (ESIS), and the Multi-State Fish and
Wildlife Information System. The BIOTA database will be linked to several data
layers (land use/land cover, hydrography, political boundaries, etc.) currently
under development for a CIS-based management tool to determine species-at-risk
and parameterize exposure and effects models.
The cooperative agreement with Montana State University and the University
of British Columbia is showing good progress. This work is in support of the
Ecorisk modeling efforts. Most of the preliminary studies on the respirometer
itself, introduction of chemicals and their behavior in the respirometer,
determination of the most significant tissues to analyze, and analysis of
1,2,3,4-tetrachlorobenzene (TCB) uptake by rainbow trout have been performed
both under static conditions and in the respirometer under different water
velocities or forced swimming speeds. Uptake of TCB into various tissues
(plasma, adipose, pink muscle, white muscle, liver, brain, heart, kidney,
liver, gut, upper gut, gills, and spleen) has been determined in fish
sacrificed times up to 6 hours. The results indicate that the body burden of
the toxicant increased and oxygen uptake increased with swimming speed. Also
tissue levels of the toxicant showed a constant ratio to the plasma level
independent of both swimming speed and time of exposure.
The competitive cooperative agreement on prediction of the effects of
toxicants on natural aquatic populations and biological communities is
proceeding on schedule. Three preproposals were received and are currently
in the review process.
Ms. Sue Wolf presented the paper "Neutral chemical accumulation in aquatic
58
-------
plant shoots" at the Ninth Annual Meeting of the Society of Environmental Toxi-
cology and Chemistry (SETAC). Dr. Ray Lassiter and Steven Wooten coauthored
the paper. Ms. Wolf was invited by Dr. D. MacKay to present the paper at the
workshop "Human exposure to chemicals" held at the Institute for Environmental
Studies (University of Toronto, Canada). Both presentations were well received.
STATUS AND SCHEDULE OF DELIVERABLES;
7510 DUEt 08/31/88 REVISED: 08/31/90 COMPLETED:
' POPULATION MODEL AND SOFTWARE INCORPORATING LETHAL AND NONLETHAL EFFECTS
ON FEEDING BEHAVIOR FOR CHEMICALS THAT ACT BY REVERSIBLE MODES OF ACTION
2/87- due date revised per Russo memo 2/6/87; 5/87 - due
date revised to 8/90 during FY-88 PPA planning process as a
result of reductions in planned resources
7512 DUE: 08/31/88 REVISED: 08/31/90 COMPLETED:
DOCUMENTATION REPORT ON SPECIFICATIONS FOR INPUT PARAMETERS AND COMPUTER
CODE FOR AQUATIC ECOSYSTEM MODELS
5/87 - due date revised to 8/90 during FY-88 PPA planning
process as a result of reductions in planned resources
7513 DUE: 08/31/90 REVISED: 08/31/92 COMPLETED:
COMPUTER CODE FOR FIRST OPERATIONAL VERSION OF AN ECOLOGICAL EFFECTS MODEL
FOR AQUATIC ECOSYSTEMS
5/87 - due date revised to 8/92 during FY-88 PPA planning
process as a result of reductions to planned resources
7514 DUE: 08/31/91 REVISED: 08/31/93 COMPLETED:
REPORT ON STATISTICAL ANALYSIS OF TESTS OF ECOSYSTEM MODEL
5/87 - due date revised to 8/93 during FY-88 PPA planning
process as a result of reductions in planned resources
8146 DUE: 05/31/89 REVISED: COMPLETED:
Internal Report: Products of the Ecorisk Research Program.
59
-------
60
-------
PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OTS
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: I ECOLOGY: ECTOXICITY AND RISK ASSESSMENT
PPA (L): 26 DEVELOP METHODOLOGIES FOR ECOLOGICAL RISK ASSESSMENT
PPA (S): RISK ASSESSMENT DEV.
RC: K ERL ATHNS
PROJECT: 28 Risk Assessment Methodologies for Toxic Substances
PROJECT OFFICER: Tom Barnwell PHONE: FTS-250-3160
******************************************
PLANNED START: 10/01/85 PLANNED END: 12/31/99
************************ * * ****************
PROJECT DESCRIPTION;
GOAL: Develop computerized risk assessment systems that help OPTS analysts
conduct various tiers of risk assessments efficiently, including methods for
quantifying uncertainty in risk analyses and procedures for optimal use of
laboratory data, field studies, and modeling techniques.
RATIONALE: Risk assessment requires a wide variety of data and analysis
techniques to implement the multi-tiered approaches used by OPTS. Efficient
software can help OPTS analysts bring together appropriate data and analysis
techniques in an appropriate structure for each specific risk assessment.
Present exposure and effects models rarely give the estimates of uncertainty
that are required to reduce total uncertainty while minimizing implementation
costs.
APPROACH: Existing software will be reviewed including GEMS, ANNIE, and the
IIASA-IRIMS system. Related data bases will be assembled and prototype risk
assessment modeling systems will be developed incorporating all submodels,
databases and uncertainty analysis techniques. Protocols will be evaluated in
laboratory and field studies to optimize risk assessment procedures.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
PC-GEMS distribution and full-fledged use began this quarter by the Office
of Toxic Substances, in cooperation with the University of Wisconsin
Continuing Education Program, which began advertising a short course on
PC-GEMS.
Dr. Steve Chapra and Mr. Jim Waterman of the University of Colorado visited
ERL-Athens to present a seminar on progress to date and to discuss further
work. They obtained a copy of the PRZM model to design a new graphics
interface. The PRZM graphics interface will be implemented on a DEC MicroVAX
GPS workstation in order to insure compatibility with ORD hardware.
61
-------
The ANNIE-EMIFE integration is proceeding smoothly. A draft report was
received this quarter and both manual and software were reviewed in depth.
Comments were received from reviewers at the USGS and from inhouse CSC
programmers. The software is currently being used inhouse to develop an
interface for the SARAH model. A short course to teach inhouse staff and other
interested personnel use of the software is tentatively planned for April.
A short course on Exposure and Bioaccumulation Models is tentatively
planned for Athens the week of July 24-28. The course will be similar
to the two courses presented in Washington DC and Boulder CO last summer.
Dr. James Hill has prepared a paper, "Error Analysis of Two Aquatic
Bioaccumulation Models," that will be submitted to a journal in the second
quarter. The paper compares the Thomann-Connolly bioconcentration model to the
EPA Food and Gill Exchange of Toxicants (F6ETS) model.
STATUS AND SCHEDULE OF DELIVERABLES;
7497 DUE: 09/30/88 REVISED: 11/30/89 COMPLETED:
Users Manual for Update Stratified Lake Transport Model for Risk Assessment
to 9/89 as a result of P.O. receiving an OEPER FY-87 2Z Set
Aside Award for a research project; 6/88 - title change and
due date to 11/89 due to delay in hiring qualified modeler
contractor
7499 DUE: 09/30/88 REVISED: 08/31/90 COMPLETED:
General Bed-Water Exchange Model for Risk Assessment
2/87- due date revised to 9/89 per Russo memo 2/6/87; 6/88
due date to 8/90 due to ecorisk research program fund reduc-
tions
7981 DUE: 08/31/89 REVISED: COMPLETED:
Report on Relative Uncertainty of Loading Versus Other Components of Toxic
Substances Models
5/88 - title change
62
-------
PRINT DATE: 01/30/89 CLIENT OFFICE OTS
PMS-060
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: L104 TOXICS
ISSUE: J SUPPORT
PPA (L): 30 TECHNICAL EVALUATION AND ASSESSMENT
PPA (S): TECHNICAL EVALUATION
RC: K ERL ATHNS
PROJECT: 31 Technical Evaluation and Assistance
PROJECT OFFICER: Lee Mulkey PHONE: FTS-250-3160
******************************************
PLANNED START: 10/01/79 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION;
GOAL: Provide technical assistance to OTS and other program offices on complex
problems relating to environmental exposures, system effects, hazards/risks,
and benefit-risk assessments for toxic chemical regulation and control.
RATIONALE: OTS and other offices (e.g., OW, OPP, OSW and OPPE, Regions)
engaged in toxic chemical regulations and assessments require technical
assistance from ORD. This project will maintain the required inhouse and
extramural expertise.
APPROACH: Athens ERL staff will organize and participate in appropriate
consultations, workshops, reviews, special projects, etc., in support of OTS
and other Agency activities, including the review of TSCA documents, position
papers, strategies, etc., as expertise and resources permit. Access to "on
demand" exhouse expertise and assistance for OTS, Regions, States and other
related office activities also will be provided via maintenance of appropriate
contracts and liaison with CERI and other Agency support groups. Support,
consultation, and assistance to "integrated toxics" projects also will be
provided under this project.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
A project was begun to characterize the uncertainty in the estimation of
human inhalation exposure to volatile organic compounds (VOCs) associated with
domestic water use. The objectives of this project are to construct a model of
human inhalation exposure to VOCs from domestic water and to quantify, in a
systematic fashion, the uncertainty associated with the modeling process.
The project was initiated in November 1988 with the following tasks
completed to date:
1. A literature review to determine what experimentally based data and
modeling systems have been developed to date.
63
-------
2. A model of human exposure (via inhalation) to VOCs from domestic water
use (e.g. showers) has been constructed.
3. A Monte Carlo shell (software) has been linked to the model to allow
for multiple executions of the model with randomly selected input
parameter values.
4. A First Order Error Analysis procedure has been designed for use in
the first model.
The project is anticipated to conclude in the coming quarter.
Atmospheric deposition modeling support has been provided for Region V.
The objective of this project is to perform a 'screening level* study to
determine the contribution of atmospheric deposition to the total mass of toxic
pollutants in Lake Michigan. The project was initiated in September 1989
with the following tasks completed during the quarter:
1. Consultation services were provided to Region V to aid in their
efforts to write a workplan for constructing a comprehensive toxic
emission source inventory.
2. Contacts were made with members of the EPA Atmospheric Research
and Exposure Assessment Laboratory (AREAL/Atmospheric Sciences
Modeling Division) to establish a cooperative effort for completing
the project.
3. In conjunction with AREAL personnel, a draft modeling protocol has
been generated.
It is anticipated that the project will continue until the summer of 1989.
STATUS AND SCHEDULE OF DELIVERABLESi
NO DELIVERABLES AVAILABLE
64
-------
>RINT DATE: 01/30/89
PMS-060
CLIENT OFFICE OERR
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY:
ISSUE:
PPA (L):
Y105 SUPERFUND
B EVALUATE TECHNOLOGIES TO MANAGE UNCONTROLLED WASTE SITES
02 Biodegradation Applications to Superfund Site Cleanups
PPA (S): Biodegradation/EPE
RC: K ERL ATHNS
PROJECT: 33 Biodegradation Applications to Superfund Site Cleanups
PROJECT OFFICER: John E. Rogers PHONE: FTS-250-3592
A*****************************************
PLANNED START: 10/01/88 PLANNED END: 09/01/98
******************************************
PROJECT DESCRIPTION;
GOAL: To evaluate naturally occurring and improved microorganisms for the
degradation of hazardous substances under anaerobic and aerobic conditions.
RATIONALE: Increased remedial action activities under the Superfund
reauthorization will cause a wide range of cleanup technologies to be
evaluated. Biodegradation in some cases, may be the method of choice over
chemical and physical remediation. Present knowledge and the availability of
biotechnologies for remediation must be expanded to meet this need.
APPROACH: Pathways and mechanisms for the anaerobic degradation of hazardous
organic chemicals will be characterized and identified in environmental
samples. Anaerobic consortia capable of growth on the hazardous compound will
be enriched from the environment. The key microorganisms in the consortia will
be isolated and identified. Environmental parameters that either enhance or
inhibit the activity of key organisms will be identified. Methods for
moderating or overcoming inhibitory conditions will be developed.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
Pentachlorophenol (PCP) is an environmentally toxic chemical that was
previously considered recalcitrant to dechlorination under anaerobic
conditions. Anaerobic sediments were obtained from a eutrophic lake near
Athens, GA; the East River in New York City; and a eutrophic lake in the Soviet
Union near the Black Sea. PCP was analyzed by extraction with ethanol and
quantitation with HPLC using a CIS reverse phase column.
PCP (20 to 30 ppm) is completely removed within 2 days in sediments
acclimated to dechlorinate 10 ppm 2,4- or 3,4-dichlorophenol. Chlorinated
intermediate products are concomitantly observed being tetra, tri, di, and mono
species with subsequent dechlorination. By contrast, anaerobic freshwater
sediments unacclimated to chlorinated phenols require weeks of exposure to
PCP before significant degradation and removal of PCP (30 ppm) occurs.
65
-------
Respiking sediment with PGP results in increased rates of PGP degradation. All
degradation rates are apparently first order. Continued respiking eventually
results in a slowing of the rate of PGP consumption indicating an inhibitory
process.
An abstract, "Dechlorination of Pentachlorophenol in Anaerobic Freshwater
Sediments" (Bryant, Howard and Rogers), was submitted for the 1989 ASM Meeting
in New Orleans, LA, in May.
STATUS AND SCHEDULE OF DELIVERABLES;
8238 DUE: 10/31/89 REVISED: COMPLETED:
Report: Potential uses of isolated natural organisms to enhance
bioremediation of mixed hazardous wastes.
66
-------
'PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OERR
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: Y105 SUPERFUND
ISSUE: F PROVIDE TECHNICAL SUPPORT TO ENFORCEMENT, PROGRAM & REGIONS
PPA (L): 22 Enforcement and Other Technical Support/EPE
PPA (S): Technical Support
RC: K ERL ATHNS
PROJECT: 04 Enforcement and Other Technical Support/EPE
PROJECT OFFICER: Donald L. Brockway PHONE: FTS-250-3422
******************************************
PLANNED START: 03/30/87 PLANNED END: 12/30/99
******************************************
PROJECT DESCRIPTION;
GOAL: Provide tech. support, expert advice, & new methods to Regions assessing
exposure/risk at CERCLA sites; emphasize hazard ranking process & subsequent
RIFS analysis, particularly ecological risk.
RATIONALE: Exp. assess, and fate multispectral ID techniques for chemicals,
databases for environ, properties, & process transform, descriptions are
completed or under dervelopment. Application to CERCLA ranking & assessment
procedures has been limited. Work with Reg. 4/ATSDR will permit immediate use
of methods, identify knowledge gaps, and focus study of exposure, health, and
environmental assessments.
APPROACH: ERL-Athens, the Regions (via Reg. 4), & ATSDR will identify, develop
and demonstrate improved exposure and risk assessments. Improved ecological
factors for the hazard ranking system (HRS) will be developed. Case studies
will include application of existing ranking methods (HRS), multimedia analysis
models, and ecorisk procedures. Results will be used in evaluating existing
CERCLA protocols, in transferring technology, and in evaluating need for more
research on pollutant fate and exposure/risk assessment.. Occurrence of new
hazardous source chemicals will be reported to OERR.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE:
ERL-Athens conducted for OERR/HQ a technical review of the
document, "Ecological Assessments of Hazardous Waste Sites." This
document was prepared to be a resource to field Superfund personnel involved in
ecological assessments, and includes components on assesment approaches,
endpoints, toxicity testing, biomarkers, and field surveys. As a resource, the
document is thorough but its utility will be limited because of little "how to"
guidance in choosing among, for example, the large population of toxicity
tests. Review of the document also was obtained from the University of Georgia
Institute of Ecology, which is being funded under the Superfund Ecorisk
Technology Support Center at ERL-Athens.
67
-------
The pilot study of results for Tentatively Identified Compounds (TICs)
from Superfund Contract Laboratories (CLPs) continues. All of the sample runs
from Superfund CLPs have been processed, and data analysis is proceeding.
Thirty-five retained extracts and CLP report packages corresponding to many of
these runs also have been obtained through the help of the Superfund Sample
Management Center. Instrumental runs on the extracts, aimed at identifying
those TICs that are of interest, have begun.
STATUS AND SCHEDULE OF DELIVERABLES;
7966 DUE: 02/28/89 REVISED: COMPLETED: 12/31/88
Report on recommendations for improving the ecological factors ot the hazard
ranking system
6/88 - title change
68
-------
PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OWPE
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: Y105 SUPERFUND
ISSUE: F PROVIDE TECHNICAL SUPPORT TO ENFORCEMENT, PROGRAM & REGIONS
PPA (L): 22 Enforcement and Other Technical Support/EPE
PPA (S): Technical Support
RC: K ERL ATHNS
PROJECT: 23 Anaerobic Biotreatraent Development/SF
PROJECT OFFICER: John E. Rogers PHONE: FTS-250-3592
******************************************
PLANNED START: 09/30/87 PLANNED END: 12/31/99
******************************************
PROJECT DESCRIPTION:
GOAL: Characterize and identify basic biological processes that lead to the
anaerobic degradation or detoxification of hazardous wastes in contaminated
sites.
RATIONALE: A reliable approach is needed for selecting and using biotreatment
processes in the remediation of contaminated hazardous waste sites.
APPROACH: Pathways and mechanisms for the anaerobic degradation of hazardous
organic chemicals will be characterized and identified in environmental
samples. Physical and chemical processes affecting the rates also will be
characterized. Computer subroutines will be developed to model the processes
and effects. The subroutines then will be incorporated into larger computer
models for estimating the efficacy of proposed bioremediation processes.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
Information required to adequately evaluate biological treatment
proposals targeted for the remediation of hazardous waste sites was defined at
a workshop sponsored by the Office of Solid Waste at the Environmental Research
Laboratory - Athens on December 13 - 15. Products of the workshop were: (1)
a summary of the types of information that would be needed to evaluate the
efficiency of a treatment scenario, (2) a list of methods or protocols that
could be used for developing the appropriate data, and (3) a list of EPA
scientists who could provide assistance to those responsible for evaluating
treatment scenarios. Presentations were made by EPA scientists, Dr. J.E.
Rogers, ERL-Athens, Dr. J.A. Glaser, RREL-Cincinnati, and Dr. P.H. Pritchard,
ERL-Gulf Breeze, and by three university and two industry scientistss. EPA
attendees came from OSW, OWPE, ORD, and Regions 4, 7, 8, and 10.
Georgia pond sediment enrichments on p-Cresol (pCr) were examined
under methanogenic, denitrifying, acetogenic (BESA) and sulfidogenic
conditions. Loss of pCr (1 mM) took from three to four weeks in all four
69
-------
systems. Rate of parent substrate loss in methanogenic cultures was slower
than that in denitrifying and acetogenic cultures. Under sulfate reducing
conditions pCr was metabolized coincident with 3.3 raM net loss of sulfate, 78Z
of the theoretical amount. Percent conversion of substrate carbon to gas in
methanogenic cultures was 67.7% with 53.9Z as CHA. Cumulative raraol of CH4
generated was 89Z of the theoretical. Inhibition of CH4 formation in BESA
cultures was incomplete. Acetate was detected only in BESA inhibited cultures.
Under denitrifying conditions, stoichiometric conversion to gaseous end
products was observed (92.8% of N03 was found as N2 and 5.4% as N20). A
transient intermediate, p-hydroxybenzoate was detected, suggesting that pCr
metabolism under NO/-3/- reducing conditions proceeds through p-hydroxybenzoate
and is mediated by a pCr methylhydroxylase as previously shown. These
results indicate that pCr is susceptible to degradation under a wide variety of
anaerobic conditions. An abstract, "Anaerobic biodegradation of p-Cresol
under four reducing conditions" (Rivera, Bossert, Haggbloin, Rogers, and Young)
was submitted for the 1989 ASM Annual Meeting to be held in New Orleans in May.
STATUS AND SCHEDULE OF DELIVERABLES!
NO DELIVERABLES AVAILABLE
70
-------
•PRINT DATE: 01/30/89
PMS-060
CLIENT OFFICE
OERR
FIRST QUARTER STATUS REPORT ON FY'89 PROJECT DESCRIPTIONS
Office of Environmental Processes and Effects Research
ERL ATHNS: OCTOBER - DECEMBER 1988
******************************************
CODE TITLE
BUDGET SUB-ACTIVITY: Y105 SUPERFUND
ISSUE: F PROVIDE TECHNICAL SUPPORT TO ENFORCEMENT, PROGRAM & REGIONS
PPA (L): 22 Enforcement and Other Technical Support/EPE
PPA (S): Technical Support
RC: K ERL ATHNS
PROJECT: 29 Center for Exposure Assessment Modeling
PROJECT OFFICER: Robert Ambrose PHONE: FTS-250-3160
******************************************
PLANNED START: 08/01/87 PLANNED END: 12/30/99
******************************************
PROJECT DESCRIPTION:
GOAL: Provide regional technical support, expert advice, specialized training,
and new methods to conduct exposure assessment modeling for CERCLA sites. To
meet ecological impact needs, risk assessment assistance will be provided.
Emphasis is on site-specific modeling support and review.
RATIONALE: Exposure assessment modeling technology for human and ecological
risk is under development, or completed. Application and transfer of this
technology has been limited because the required highly specialized expertise
has not been available or accessible to the Regions and their consultants.
Providing a dedicated, operational center for modeling technology will promote
existing programs and provide feedback to ongoing research programs.
APPROACH: The Agency's Center for Expsoure Assessment Modeling (CEAM) will work
with the regions and ATSDR to identify support needs, conduct site-specific
assessments, and provide continued technical support. Modeling software, users
manuals, data bases, and procedural handbooks will be developed, distributed,
maintained and supported. Case studies will be conducted with emphasis on
multi-media assessments and associated uncertainties. Results will be used for
technology transfer and as a basis for additional research.
PROJECT STATUS AND ACCOMPLISHMENTS TO DATE;
The ORD Center for Exposure Assessment Modeling (CEAM) staff gave several
presentations on Superfund projects this quarter. Mr. Ambrose presented
"Modeling the Loading, Exposure,and Acute Toxicity of Copper and Zinc in the
Upper Clark Fork River"(SETAC);Dr. James Martin presented "Modeling of Confined
Disposal Facilities" (SETAC); Dr. Zia Hosseinipour presented "Ground Water
Management at Waste Impoundment Sites" (International Conference on Advances in
Groundwater Hydrology); Mr. Ambrose presented "Fate and Transport Modeling of
Wood Preserving Contaminants in Surface Water" (Forum on Remediation of Wood
Preserving Sites); Mr. Ambrose presented a review of CEAM Superfund activities
at the Superfund Technology Support Project's fall General Meeting; and
71
-------
Dr. Martin participated in expert panel review of the Hyde Park/Lake Ontario
dioxin modeling study.
Clark Fork River Superfund Site—Developed model network and input data to
simulate hydrodynamics and mass transport of metals in Clark Fork River between
the Berkeley Pit and Deer Lodge. Prepared and submitted an abstract that
discusses the hydraulic model and surface water transport model applications of
the Clark Fork River Project to the June 27-30, 1989 Missoula MT,
Symposium on Headwaters Hydrology.
Modeling of Confined Disposal Facilities—Completed review and modeling report
of the proposed Waukegan Harbor Confined Disposal Facility and submitted to
Region 5. Attended meeting November 3 in Grosse lie MI to present
results to state agency and plan for Saginaw Bay studies. Completed literature
review of sorption of PCBs on sand filters. Initiated work on revising methods
for computing dike transport.
Great Lakes Modeling Activities—Completed review of revised report on modeling
of dioxin in Lake Ontario as part of Region II study. Reviewed first draft of
dioxin study report by the Large Lakes Research Station and participated in
teleconference with other members of expert panel of Hyde Park/Lake Ontario
study. Review incldued verifying model selected computations and predictions.
EcoRisk Support--FCHAIN and FGETS models. Reviewed relevant literature on
ecological risk assessment.
Technical Assistance—Provided Robert Hayzen, NJDEP, assistance investigating
the problem of on-site human exposure to hexavalent chromium at about 100
hazardous waste sites in New Jersey. Provided Bonnie Eleder, Region V Remedial
Project Manager, with a review of the Sheboygan Harbor and River, Wisconsin
Remedial Investigation/Feasibility Study Project. Introduced Laura Mazanti,
Jeff Stone, Ron Landy, and Judy Sophianapoulos EPA Region IV, to PRZM. Gave
demonstration of how to develop input sequence and what parameters are
required. Provided Dave Hill, Region IV, advice on use of MINTEQ in predicting
lead solubility and speciation at battery cracking superfund sites--Kassouf
Kimberling and Flowood. Provided Dave Hill, Region IV, general information and
advice on soil cleanup levels targeted for the CSX train wreck site. Provided
John Prince, Region II Super RPM for Myers Property Site, NJ, information on
potential dioxin risks to humans from contaminated soil and drinking water.
Provided Stephen Cipot, Region II, information on the RUSTIC model and training
course for possible use at two superfund dry cleaning sites.
Model Distribution—The CEAM Electronic Bulletin Board System (BBS) continued
to be well used. Seventy new users registered this quarter, making a total of
389 users. 477 calls were placed to the BBS, and 14 datasets uploaded from
users for debugging by CEAM staff. The following exposure models were
distributed:
Model Diskette BBS Tape
WASP4 27 16 0
HSPF9 23 03
MINTEQA1 57 31
EXAMSII 20 32
72
-------
PRZM 16 11 3
LC50 5 60
SARAH 9 10
FGETS 13 10
Model Support—Continued development, testing, and support of WASP,
PRODEF/MINTEQ, and Multimedia models. Began quality assurance/quality control
checks and tests of WASP model and support programs and documentation for
release of version 4.14 for VAX and PC system implementation, execution, and
documentation. Continued migration of CEAM model distribution and registered
user data base from VAX to PC environment.
STATUS AND SCHEDULE OF DELIVERABLES;
8167 DUE: 08/31/89 REVISED: COMPLETED:
Training Courses for Regional Superfund Staff on Exposure Assessment
Modeling
8168 DUE: 07/31/89 REVISED: COMPLETED:
Research Brief on Exposure and EcoRisk Assessments Performed by Center for
Exposure Assessment Modeling
8169 DUE: 08/31/90 REVISED: COMPLETED:
Training Courses for Regional Superfund Staff on Exposure Assessment
Modeling
8170 DUE: 07/31/90 REVISED: COMPLETED:
Research Brief on Exposure and EcoRisk Assessments Performed by Center for
Exposure Assessment Modeling
73
------- |