ENVIRONMENTAL RISK ASSESSMENT SESSION

DEVELOPMENT OF GENOMIC RESOURCES FOR MEASURING ENVIRONMENTAL CHALLENGES. Joseph R. Shaw, Celia Y. Chen, Jennifer C. Davey, Carol L. Folt, and Joshua W. Hamilton. Dartmouth College, Hanover, NH.

Until recently, an enormous effort was needed to apply genetic tools to environmental problems. An important consequence of the large-scale genome programs of recent years has been the technological advancements that extend these abilities beyond a limited number of traditional model organisms. There is growing awareness for the need to rapidly develop genomic and other molecular tools for application in key environmental sentinel species. A recent SETAC workshop addressed these issues and highlighted the importance of partnerships in this effort. This is the purpose of the Daphnia Genomics Consortium (DGC) a growing multidisciplinary effort currently comprising over 30 researchers worldwide whose goal is "to develop the Daphnia system to the same depth of molecular, cell and developmental biological understanding as other model systems, but with the added advantage of being able to interpret observations in the context of natural and anthropogenic environmental challenges." Daphnia are well suited for genomic characterization. The clonal nature of the organism provides an exceptional opportunity for separating genetic (among-clone) responses to ecological challenges from environmental noise (within-clone). In addition, the past products of evolution can be evaluated against their current descendants in a controlled setting by means of resting eggs. These eggs are produced by Daphnia and stored viably in sediments for up to a century where they can be harvested and hatched in the laboratory providing access in many cases to original (i.e., before pollution) “control populations”. The DGC has provided an organizational framework to coordinate efforts to develop the Daphnia genomic toolbox; facilitate collaborative research; and develop bioinformatics strategies for organizing the rapidly growing database. Since its formation, members of the DGC have characterized over 1500 microsatellite loci for genetic mapping; developed a fully arrayed cosmid library for efficient isolation of full-length gene sequences; and identified over 500 genes. In addition, funding has been secured to produce BAC libraries; develop cDNA libraries under different conditions (e.g., metal exposure, temperature, hypoxia, predators); sequence the majority of the transcribed genome; and produce cDNA microarrays. Experimental work is underway to characterize gene-expression patterns specific to ecologically relevant levels of toxicological stress. Applications of these tools to current and past Daphnia populations with varied exposure histories should begin to separate the influence of physiological acclimation from genetic adaptation and characterize these changes as both a function of toxicological outcome and ecological fitness.

DEVELOPMENT AND APPLICATION OF AN OIL TOXICITY AND EXPOSURE MODEL, OILTOXEX. D.P. French McCay. Applied Science Associates, Narragansett, RI

An oil toxicity and exposure model (OilToxEx) was developed and validated for estimation of impacts to aquatic organisms resulting from acute exposure to spilled oil. Because oil exposure is shorter than the time required for equilibrium between the organism and the water to be reached, the time and temperature dependence of toxicity is addressed. Oil toxicity is a function of aromatic composition and the toxicity of individual aromatics in the mixture. LC50 (Lethal Concentration to 50% of exposed organisms), as a function of octanol-water partition coefficient (Kow), and an additive model are used to estimate the toxicity of monoaromatic and polycyclic aromatic hydrocarbon mixtures in water-soluble fractions (WSF) and oil-in-water dispersions (OWD) of oil. The toxicity model was verified by comparison with oil bioassay data where the exposure concentrations of aromatics were measured. The observed toxicity in the bioassays could be accounted for by the additive narcotic effects of the dissolved aromatics in the exposure media. Predicted LC50s were compared to those calculated from measured concentrations after spills to verify the exposure model for field conditions. These results indicate that the additive toxicity and exposure model may be used to estimate toxicity of untested oils and spill conditions. A combined fate and effects model has been developed and verified for quantifying oil toxicity after spills. This model has been used for estimating injuries as part of natural resource damage assessments and for estimating potential exposure and toxicity as part of ecological risk assessments.


RECALCULATION OF THE 1986 NATIONAL SALTWATER AQUATIC LIFE CRITERIA FOR NICKEL. P.F. Smith and G.M. DeGraeve. Great Lakes Environmental Center, Traverse City, MI, and T.K. Linton, Great Lakes Environmental Center, Columbus, OH.

A literature search was conducted to update and revise the saltwater aquatic life criteria for nickel to accurately reflect the latest scientific knowledge. The data search and review was conducted using the selection criteria set forth in The Guidelines for Deriving Numerical National Water Quality Criteria for the Protection of Aquatic Organisms and Their Uses, and yielded acute nickel toxicity data for six saltwater genera and chronic nickel toxicity data for three saltwater genera which were not utilized in the 1986 criteria document. The final acute-chronic ratio (FACR) used to calculate the criterion continuous concentration (CCC) in the 1986 nickel criteria document (17.99) included one saltwater species and two freshwater species, since only one saltwater species acute-chronic ratio (ACR) was available at that time. The addition of three new saltwater ACRs allows for a recalculated CCC using exclusively saltwater genera. The addition of the more recent saltwater nickel data slightly lowers the CMC and raises the CCC by almost a factor of three. Thus, the more recently published data for saltwater organisms has implications for changes in the total maximum daily loads (TMDLs) and the saltwater state/tribal and national water quality criteria for nickel.


UTILIZING MAMMALIAN PHARMACOLOGY AND SAFETY DATA TO PRIORITIZE ENVIRONMENTAL SAFETY INITIATIVES ASSOCIATED WITH HUMAN PHARMACEUTICALS. D.B. Huggett, J.C. Cook, J.F. Ericson, and R.T. Williams. Pfizer Inc., Groton, CT 06340.

Due to the potential for long-term, low-level exposure of environmental species to pharmaceuticals in the environment, concerns over chronic ecotoxicity have been raised. Pharmaceuticals typically have specific enzyme and receptor-based modes of action, which are extensively studied in mammals during drug development. A survey of the literature demonstrated that there is conservation of many enzyme/receptor systems between mammalian and teleost systems. Based on this conservation of enzyme/receptor systems across species, a model has been developed to utilize the information from mammalian pharmacological and toxicological studies to evaluate the potential for chronic receptor mediated responses in fish. In this model, a measured human therapeutic plasma concentration (HTPC) is compared to a predicted steady state plasma concentration (FSSPC) in fish, and an effect ratio (ER = HTPC / FSSPC) is computed. The lower the ER, the greater the potential for a pharmacological response in fish. The model was applied to twenty-eight drugs representing 15 therapeutic classes. ER values ranged from ≤ 1 to ≥ 10,000, with the category that represented an ER ≥ 10,000 containing the largest number of compounds (12 of 28). The two compounds with an ER ≤ 1 (17B-Estradiol and 17α-Ethinyl Estradiol) have previously been identified in chronic ecotoxicity evaluations as being active in fish. Chronic fish response data on fluoxetine and propranolol showed good agreement with the model, further supporting the notion that this model is a viable tool for prioritizing environmental safety initiatives associated with pharmaceuticals.


HORMESIS: OCCURRENCE, GENERALIZABILITY AND APPLICATIONS TO TOXICOLOGY AND RISK ASSESSMENT. Edward Calabrese. University of Massachusetts. Amherst, MA.

Hormesis, a dose-response relationship phenomenon characterized by low-dose stimulation and high-dose inhibition, has been frequently observed in properly designed studies and is broadly generalizable as being independent of chemical/physical agent, biological model, and endpoint measured. This under-recognized and-appreciated concept has the potential to profoundly change toxicology and its related disciplines with respect to study design, animal model selection, endpoint selection, risk assessment methods, and numerous other aspects, including chemotherapeutics. This presentation indicates that as a result of hormesis, fundamental changes in the concept and conduct of toxicology and risk assessment should be made, including (a) the definition of toxicology, (b) the process of hazard (e.g., including study design, selection of biological model, dose number and distribution, endpoint measured, and temporal sequence) and risk assessment [e.g., concept of NOAEL (no observed adverse effect level), low dose modeling, recognition of beneficial as well as harmful responses] for all agents, and (c) the harmonization of cancer and noncancer risk assessment.


SPILL HAZARD EVALUATION FOR CHEMICALS SHIPPED IN BULK USING MODELING. D.P. French McCay, N. Whittier, M. Ward, and C. Santos. Applied Science Associates, Narragansett, RI.

A wide variety of chemicals are shipped in bulk raising ecological and human health concerns. Questions that have been posed and addressed here are: (1) What is the expected fate and concentrations of chemical in water resulting from a spill? (2) What are the ecological hazards to aquatic biota? A screening analysis was performed using a hypothetical spill site in Narragansett Bay (Rhode Island, USA) as a representative large estuary.

The chemical spill model, CHEMMAP, was used to predict the fate of a representative sample of chemical products. The model uses physical-chemical properties to simulate fate processes, including: (1) slick spreading, transport, and entrainment of floating materials, (2) transport of dissolved and particulate materials in three dimensions, (3) evaporation and volatilization, (4) dissolution and adsorption, (5) sedimentation and resuspension, (6) and degradation. The chemical fates model estimates the distribution of chemical (as mass and concentrations) on the water surface, on shorelines, in the water column, in the sediments, and in the lower atmosphere over time.

Chemicals typically shipped in bulk were classified into groups based on physical-chemical characteristics. Multiple model runs were simulated with a randomly sampled range of tidal current and wind conditions. Maximum predicted environmental concentrations of representative chemicals for each group were mapped in terms of hazard quotients (HQ). The area where the HQ>1 was calculated for each model run. The mean and standard deviation within a scenario describes the expected hazard and its variability from varying wind and current conditions at the time of the spill.

GREEN CHEMISTRY SESSION

GREEN CHEMISTRY AND INDUSTRY. Berkeley W. Cue, Jr. Ph.D. Pfizer Inc, Groton CT.

This presentation will describe a strong relationship between the twelve principles of green chemistry articulated in “Green Chemistry, Theory and Practice,” with the strategies employed in developing manufacturing processes for Pfizer’s medicines. These strategies evolve from our corporate environmental, health and safety policy, form the operational model for Chemical R&D, and are integrated into the goals of our development chemists.

Specific examples of drug synthesis development programs for a Phase 2 clinical candidate and a commercial product (sertraline hydrochloride, the active ingredient in Zoloft) are presented to illustrate these concepts.

KEYNOTE ADDRESS

GREEN CHEMISTRY: CURRENT STATUS AND FUTURE CHALLENGES
Paul T. Anastas, White House Office of Science and Technology Policy, Washington, D.C.

In its essence, green chemistry is a science-based, non-regulatory and economically driven approach to achieving the goals of environmental protection and sustainable development. The approach has been utilized in a number of industrialized and developing nations. The results in these countries have been that of extremely positive results in terms of both protection to human health and the environment as well as significant economic benefit to the industrial interests involved.

While very broadly applicable, Green chemistry has a very specific and well-defined scope. Green chemistry is chemistry for pollution prevention, which strives to reduce or eliminate the use and generation of hazardous substances. This scope explicitly does not include approaches such as waste treatment, waste control or re-mediation even though these elements are recognized as important, but separate, elements of an environmental protection programs. While many countries have those elements capable of reacting to environmental problems once they are formed, there is a need for the introduction and focus on initiatives that design products and processes such that these environmental problems never occur. This is the focus of green chemistry.

The range of green chemistry includes products and processes. This means that not only the structures of a final product can be designed to be non-hazardous but also each of the transformations along the way to manufacture of a product are designed so that they don’t use or generate hazardous substances. There is an implicit consideration life cycle impacts with the scope of sustainable chemistry. Although traditionally pollution prevention was thought to focus on waste reduction and waste minimization sustainable chemistry includes and expands this focus to all stages of the life cycle. The importance of this expansion is seen through commonly reported achievements from industry where the greatest economic benefits as well as the greatest environmental benefits are being realized as much in the early stages of the process or product life cycle as they are in the latter stages.

The green chemistry programs implemented by government industry and academia on a voluntary basis have achieved success in reducing risk through the reduction of intrinsic hazard at the molecular level. The types of hazards that can and are being addressed by scientific and industrial concerns include physical hazards, toxicological hazards (both human & ecotox, and global hazards), all of which are effected by proper and innovative molecular design.

As we review the success of green chemistry thus far, it is as important to keep an eye on the challenges of the future and identify the scientific challenges confronting green chemistry and especially the role of catalysis in Green Chemistry. Questions such as “What is the role of nanoscience on green chemical catalysis?” “Can we use energy in the place of matter to effectively carry out transformations catalytically on a commercial scale?” “Are the reaction types we use currently in chemical manufacturing the one’s we should be using in the next ten, twenty years?” If we are to meet the challenges of sustainability, it will require that we address the problem at the molecular level as one part of the solution.


THE INTEGRATION OF GREEN CHEMISTRY INTO RESEARCH AND EDUCATION. Professor John Warner. University of Massachusetts, Boston, MA.

The current training, both in the research laboratory as well as the classroom that is provided to our molecular scientists, is not adequate for industry to take advantage of the opportunity that Green Chemistry is elucidating. With government providing funding for this new area of research, academia needs to work in partnership with industry both to train the next generation of scientists as well as discover the next generation of products and processes. In examples ranging from photovoltaics to new polymers, the Green Chemistry Laboratories at the University of Massachusetts are working with the U.S. Green Chemistry Program and industry to develop models for how research and education must be combined in the pursuit of economic and environmental prosperity. Real-world examples of Green Chemistry from the research lab to industrial implementation will be presented.


GREEN CHEMISTRY INTEGRATION: ACADEMIA, INDUSTRY, AND GOVERNMENT. A Panel Presentation: Paul T Anastas, John C Warner and Berkeley Cue.

GEOGRAPHIC INFORMATION SYSTEMS (GIS) SESSION

GIS AND CONSERVATION PLANNING. Dr. Peter V. August. Director, Coastal Resources Institute, University of Rhode Island, Kingston, RI.

The fundamental mission of land trusts and local conservation organizations is to preserve land of conservation interest, generally through the acquisition of fee title or conservation easements, and to ensure that the land's habitat, natural resources, and aesthetic values are protected forever. Land acquisition occurs in two ways, opportunistic and targeted acquisitions. Opportunistic acquisitions occur when landowners donate their land or development rights to their land to conservation organizations. Targeted acquisition occurs when specific lands are identified for purchase in order to protect natural, cultural, or aesthetic resources that are found on or near the property. The purpose of this research is to identify the critical data and procedures required to locate important regions of the landscape that might be the focus of targeted land acquisition strategies. We utilized geographic information systems (GIS) and the Rhode Island GIS database to define priority areas. Analyses were done using ArcView and Spatial Analyst software (Environmental Systems Research Institute). We assembled significant natural resource data for each community and prepared maps showing the location of individual classes of resources and a composite of all critical lands. The maps are designed to be used to target and prioritizing areas for conservation. They can also be used as a public education tool.


GIS AT THE MUNICIPAL LEVEL: APPLICATIONS AND ISSUES. Carol Baker. GIS Administrator, Towns of South Kingstown and New Shoreham, Wakefield, R.I.

The Town of South Kingstown, Rhode Island, is a coastal community in southern Rhode Island. The Town implemented a Geographic Information System in 1997, and has developed and maintains a detailed GIS database including parcels, protected open space, infrastructure and environmental data layers. Ongoing database development and maintenance include the parcel and open space layers, and stormwater and sewer mapping. The Town currently maintains its tax maps in the GIS, prepares maps and performs geographic analyses for numerous Town departments. The GIS has also proven invaluable in many planning functions such as build-out analysis and comprehensive plan updates. Additionally, the Town sells maps and distributes its GIS database to the public. Future plans include making maps and data available on the Internet and public access to the data in Town Hall. This presentation will present an overview of database development, GIS applications and issues involved in public access to the data.


GEOGRAPHIC INFORMATION SYSTEMS FOR UNDERWATER ARCHAEOLOGY. Dr. Rod Mather. Department of History, University of Rhode Island, Kingston, RI.

The spatial relationships between artifacts, features and/or sites are at the heart of archaeology. The traditional way for archaeologists to recover, represent and store spatially-referenced data is through analog (printed) maps and site plans, which use lines, polygons, points, color, shading patterns, symbols, a scale and a key to preserve and present the information. Although archaeological data is ideally suited for the application of GIS, archaeologists in general, and underwater archeologists in particular, are only just beginning to recognize the potential of computer-based spatial databases. This paper illustrates some ways that underwater archaeologists have started to use GIS to facilitate both research and management of submerged cultural resources. Both site-specific and regional-based projects are considered.


ASSESSING AND MONITORING OUR NATION'S ESTUARIES: THE PAST, PRESENT AND FUTURE OF GIS APPLICATIONS?  J. W. Hollister, University of Rhode Island, Kingston, RI, 02881; J. F. Paul, U. S. EPA, National Health and Environmental Effects Research Laboratory, Research Triangle Park, North Carolina 27711; J. Copeland, Computer Sciences Corporation, Narragansett, RI 02882.

The use of computers and Geographic information systems (GIS) tools has grown considerably in the last several decades and these technologies are now considered integral to many of the environmental sciences. One area that has seen a significant increase in the use of GIS has been the monitoring and assessment of our nation's estuaries. In the past, GIS has supported many estuarine assessment and monitoring activities in the Northeast region of the United States and has contributed to the success of sampling activities of the U.S. EPA'S Environmental Monitoring and Assessment Program (i.e., sample site selection, support for field sampling activities), quality assurance of monitoring and assessment data, spatial display of geographically referenced information, quantitative spatial analysis of data, and communication of results. The integral role that GIS has played in these past activities promises the continued, successful use of GIS in current and future estuarine assessment and monitoring applications. For example, GIS applications are currently being developed to model the spatial distribution of estuarine condition within the Northeastern United States. These types of models, along with applications yet to be conceived, will aid in the successful management and maintenance of estuarine health.

MONITORING SESSION

HISTORICAL RECONSTRUCTION OF CONTAMINANT AND ECOLOGICAL CONDITIONS IN AN URBAN HARBOR. W.S. Boothman, C.E. Pesch, and J.S. Latimer. U.S. EPA Atlantic Ecology Division, Narragansett RI, USA, 02882, G.L. Chmura, V. Pospelova, Z. Spasojevic, McGill University, Montreal, QC, Canada.

One problem encountered when trying to establish goals for remediation or restoration of contaminated waterways is the determination of appropriate reference conditions. As an alternative to comparison of reference sites with contaminated waterways, historical reconstruction of past ecological conditions from geochemical and fossil records contained in sediment cores from the waterways themselves can provide both a baseline for contaminant and ecological conditions and determination of the level of contamination associated with extent of impact in a system. During the last 350 years, New Bedford Harbor and surroundings have experienced a series of overlapping socioeconomic periods defined by the principal activities and industries within the harbor and its watershed, e.g., agricultural, whaling, textile, and post-textile. Shifts in the harbor's physical, social, and industrial surroundings have left geochemical and ecological imprints preserved in its sedimentary record. We present here the geochemical record of both preindustrial background conditions and subsequent industrialization of the harbor area and demonstrate alterations in ecological conditions through variations in fossil records of dinoflagellate cyst assemblages and diatom production in New Bedford Harbor and a nearby, nonindustrialized harbor. Through examination of the chronological record of anthropogenic alterations in the harbor and concomitant ecological effects, we may assess the extent to which the ecological integrity of the harbor has been affected by human activities.


HISTORIC MERCURY INPUTS AND MODERN SPATIAL PATTERNS IN FISH TISSUE MERCURY CONCENTRATIONS IN MASSACHUSETTS. M.S. Hutcheson, J. Rose, Office of Research and Standards, Massachusetts Department of Environmental Protection, Boston, MA 02108; B. Eddy, Wall Experiment Station, Massachusetts Department of Environmental Protection, Lawrence, MA 01843-1398; Gordon Wallace, Darryl Luce and Melissa Ferraro, Environmental, Coastal and Ocean Studies Department, University of Massachusetts Boston, Boston, MA 02125.

Northeastern Massachusetts was the site of major industrialization (textiles, shoes) in the late 19th and early 20th centuries. Today its major towns are still relatively densely populated. High recent atmospheric mercury inputs in this region have been predicted by modeling. Detailed analyses of dated sediment cores from one lake in and one outside of the region document increases in sedimentary mercury inputs through the twentieth century and a differentially high deposition in this region. The edible tissue mercury concentrations of largemouth bass (Micropterus salmoides) taken from twenty-six lakes in the region were in the top quartile of mercury concentrations of this species from more rural parts of the state. Those of yellow perch (Perca flavescens) were slightly higher than the rural fish concentrations. There was no geographical pattern in fish tissue mercury concentrations in the northeast with respect to the recent locations of the major point sources of atmospheric mercury. The observed urban/rural differences for M. salmoides contrast with patterns reported from other states (Connecticut and Minnesota). Potential reasons for these differing patterns include differential atmospheric mercury deposition patterns, differing surficial geology, and differing in-lake degrees of mercury biomethylation.


FIELD VALIDATION OF SEDIMENT TOXICITY IDENTIFICATION AND EVALUATION METHODS. K. T. Ho¹, M. L. Gielazyn² R. M. Burgess¹, M.C. Pelletier¹, J.R. Serbst¹, S.A. Ryba¹, M. M. Perron³, and M. Cantwell¹.  ¹US EPA Atlantic Ecology Division, Narragansett, RI 02882;  ²NOAA c/o USEPA, Region IV, Waste Management Division, Atlanta, GA. 30303; and ³University of Rhode Island, Kingston, RI 02881.

Sediment toxicity is a widely recognized problem in many regions of the world. Frequently, however, the cause of toxicity is not known. The ability to identify the cause(s) of toxicity in sediments allows managers to determine sources of continuing contamination to support selection of management strategies, and to make informed decisions on appropriate alternatives for remediation and disposal of toxic dredged material. We have recently developed sediment Toxicity Identification and Evaluation (TIE) methods to aid in the toxicant identification process; however, the question of field validation of these methods still remains. We report on preliminary efforts to link our results in the laboratory with effects in the field. Field endpoints investigated include benthic community condition, sediment chemistry, and evidence of effects to organisms in the field. Specifically, we used contaminated sediment from the Elizabeth River, VA, and compared field endpoints with observed toxicity in preliminary TIE toxicity tests using the bivalve clam Mercenaria merceneria. Preliminary results indicate that toxicity was correlated with positive COMET assay (DNA damage) results in deployed Merceneria and evidence of an impaired benthic community.


RAPID DETECTION OF FECAL CONTAMINATION IN RECREATIONAL WATERS. C.P. Koerting, C. P. Anderson, C. G. Green, J.R. Jadamec, and S. A. Jakubielski. Marine Sciences Dept., University Of Connecticut Groton, CT. 06340; R.T. Vinopal, Department Of Molecular and Cell Biology, University Of Connecticut, Storrs, CT. 06269.

The Coastal Environmental Research Laboratory (University of Connecticut, Marine Sciences Dept.) is applying its patented fluorometric method (U.S. Patent 5,968,762) to the detection of fecal indicator bacteria in recreational waters. We will report on a test that introduces a rapid (4-5 hours) new way to read the results of modified versions of standard, approved, and reliable test kits that, at present, require a day or longer for results. The dual wavelength method simultaneously monitors the emission of both the uncleaved fluorogenic substrate and the released fluorophore. The ratio of the intensities of these two wavelengths is calculated. Monitoring the rate of ratio change allows the rapid estimation of bacteria concentration in the sample. Presently, the ratiometric method can indicate the presence of Enterococcus faecalis in seawater at concentrations of 61 CFU per 100 ml within 4.5 hours. This method works for both marine and freshwater samples. Preliminary results for the application of this method for the detection of total coliforms and Escherichia coli in freshwater using the fluorometric method will also be discussed.


PCB ANALYSIS: HOMOLOGS AND CONGENERS BY GC/MS. P. J. Kane and C. Mosher. Woods Hole Group Environmental Laboratories, Woods Hole, MA.

PCBs analyzed by mass spectrometry can remove ambiguity in identification and quantification that arise using GC/ECD methods. PCBs that are heavily weathered in the environment or metabolically converted may not be identifiable as an aroclor, and go undetected as PCBs in a sample or have significant error in the quantitative analysis. Data presented here uses mass spectrometry to quantify the PCBs by their homolog groupings. Along with the homologs, individual congeners can be analyzed as well, for the monitoring of long term PCB degradation. The congener analysis can distinguish the Dioxin like co-planar isomers from the background congeners. Specific examples of environmentally impacted samples are examined by GC/ECD and GC/MS. This side-by-side comparison brings the qualitative and quantitative issues to light by examining the same sample extract by the two analytical approaches. The mass spectrometer, which is operated in the selected ion-monitoring mode, will meet or exceed the detection limits of the ECD.


THE USE OF FIELD PORTABLE XRF FOR RISK ASSESSMENT OF CONTAMINATED SOILS. Vince Rose. NITON LLC, Billerica, MA 01821.

Laboratory analysis of contaminated metals in soils has intrinsically limited approaches to risk assessment. Recent advances in field portable technologies capable of real-time measurements provide rapid feedback allowing dynamic approaches optimized to site-specific conditions. Examples of several projects will be discussed. Advantages and practical limitations will be analyzed.


HISTORICAL ANALYSIS AS A MONITORING TOOL IN IDENTIFYING PAH SOURCES IN PRINCE WILLIAM SOUND, ALASKA SEDIMENTS. D.S. Page, Bowdoin College, Brunswick ME 04011, P.D. Boehm, J.S. Brown, Battelle, Waltham, MA 02451, A.E. Bence, ExxonMobil Upstream Research Co., Houston, TX 77027, W.A. Burns, WA Burns Consulting Services, Houston, TX 77079, G.S. Douglas, Battelle, Duxbury, MA 02332.

A holistic approach to monitoring and injury assessment requires the consideration of all potential sources of pollutant stress. Historical analyses of past human activities in study areas can be combined with organic geochemistry data to identify baseline pollutant sources that can cause environmental stress. Prince William Sound (PWS) has a complex history of hydrocarbon inputs of which the 1989 oil spill is one component. PWS hydrocarbon sources include a regional background of natural petrogenic hydrocarbons from sources east of PWS, point source inputs of pyrogenic and petrogenic PAH to subtidal sediments at numerous sites of past and present human activities including abandoned settlements, canneries, sawmills, and mines, and recent oil spills. A holistic approach to fingerprinting and quantifying hydrocarbon contributions from multiple sources in a sediment sample involves identification of potential sources through historical analysis, collection of representative samples, and accurate quantification of a suite of diagnostic PAH analytes and chemical biomarker compounds in the source and sediment samples. A constrained iterative least-squares method was used to allocate the contribution of hydrocarbon sources contributing to subtidal sediments collected in PWS embayments in 1991, 1999 and 2000. Natural petrogenic background hydrocarbons are present in all embayment sediments; pyrogenic hydrocarbons including combustion products of diesel are important at sites of human activity; and residues of Monterey (CA) petroleum, widely used as fuel prior to development of the Cook Inlet and North Slope fields, are found at certain locations. Seafloor sediments collected in 1999 and 2000 from some spill-path embayments have low levels (TPAH range from traces to <50 ng/g sediment (dry weight)) of highly degraded Alaska North Slope crude oil residues attributable to the Exxon Valdez spill. An understanding of the history of past human and industrial activity in a spill zone is a necessary tool for the identification of probable sources of hydrocarbon contamination not related to the spill. Misattribution of spill effects is likely when hydrocarbon sources are not fully understood.


EFFECTS OF SULFATE PARTICLES ON DIRECT RADIATIVE FORCING. Scot T. Martin. Associate Professor of Environmental Chemistry, Division of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138.

Whether tropospheric particles are aqueous or crystalline affects the magnitude of global aerosol direct radiative forcing. Exposed to increasing relative humidity (RH), crystalline particles remain so until RH exceeds the deliquescence RH (DRH). Similarly, for decreasing RH, aqueous particles remain so until RH is less than the crystallization RH (CRH). Because CRH and DRH are not equal, the physical state of the particle depends on its initial condition and the direction of RH change, i.e., there is a hysteresis effect. Crystalline particles, losing both H₂O and semivolatile NH₄NO₃(s) to the gas-phase, have smaller diameters than their aqueous counterparts and thus have lower particle scattering efficiencies.

Laboratory studies to quantify these effects will be presented.

We also employ a global 3D model of atmospheric aerosols and chemistry (GEOS-CHEM) to obtain prognostic results of aerosol mass on a global grid. There is a 15-20% change in global aerosol direct radiative forcing between assumptions of aqueous versus crystalline sulfate particles. In this talk we will report on our work on the global effect as well as regional effects, which can be much more significant over regions such as North America, Europe, and China having large column optical depths.

POSTER PRESENTATION ABSTRACTS

EFFECTS OF MARINE PCB CONTAMINATION ON SEABIRDS AT SAGLEK, LABRADOR. N.M. Burgess, Canadian Wildlife Service, Mount Pearl, NL; Z.A. Kuzyk, and J.P. Stow. Environmental Sciences Group, Royal Military College, Kingston, ON; G.A. Fox, Canadian Wildlife Service, Ottawa, ON; K.A. Grasman and M.E. Reaves, Dept. of Biological Sciences, Wright State University, Dayton, OH.

Soil and marine sediments were contaminated by PCBs at a military radar site at Saglek, Labrador. We studied PCB effects in black guillemots (Cepphus grylle), a fish-eating seabird. Our objective was to determine if PCB exposure was associated with changes in immune function, development, and various biochemical and endocrine endpoints in guillemot chicks. Thirty-one chicks were collected in late August 1999. Liver PCB concentrations in the chicks ranged from 14 - 6200 ng/g (wet wt). Liver concentrations of other organochlorines and metals were low. Chicks were divided geographically into three PCB-exposure groups: Reference (geometric mean liver [PCB]: 25 ng/g), Islands (73 ng/g), and Beach (830 ng/g). T-cell-mediated immune response was strongly suppressed by PCB exposure. Mean thymus mass of Beach chicks was 28% lower than that of Reference chicks. Plasma estradiol concentrations increased with PCB exposure. Testicular abnormalities were found in 25% of the Beach and Islands males but not in the Reference males. In females, there was a trend to smaller ovary mass (relative to body mass) with higher PCB exposure. Livers of Beach chicks were enlarged, compared to Reference chicks. Liver EROD activities increased while liver retinol concentrations decreased with PCB exposure. Retinyl palmitate concentrations were reduced but only in females. Our findings indicate that guillemot chicks are affected by PCB exposures as low as 73 ng/g (wet wt) in liver, which corresponds to approximately 1 ug/g (wet wt) in guillemot eggs. These findings suggest that seabirds may be adversely affected by lower PCB exposures than previously thought.


EFFECTS OF STEROIDAL ESTROGEN EXPOSURE ON CUNNER EXTRAPOLATED TO THE POPULATION LEVEL. RE Gutjahr-Gobell, GE Zaroogian, DJ Borsay Horowitz, TR Gleason, and LJ Mills. U.S.EPA, Atlantic Ecology Division, Narragansett, RI.

Endocrine disrupting chemicals (EDCs) in the environment may disturb the population growth rate of wildlife by affecting reproductive output and early life survival of organisms. Cunner (Tautogolabrus adspersus) inhabit marine areas where sewage treatment and contaminant discharges containing estrogens are likely. Additionally, cunner have proven suitable for conducting laboratory experiments with reproductive endpoints. We developed an age-structured matrix population model using published survival and fecundity estimates. By incorporating response data from laboratory exposures, the model was used to evaluate whether EDCs (17-estradiol (E₂), estrone (E₄) and 17-ethynylestradiol (EE₂)) would impact cunner population growth rate (8). Reproductively active cunner were exposed in three experiments (E₂, E₄ or EE₂) by implanting estrogens subcutaneously in a slow-release matrix. Treatments included control and three nominal concentrations (0.05, 0.5 and 2.5 mg/kg). Egg production was determined daily. Results showed E₂ exposure enhanced fecundity over 50% in low and medium treatments, increasing 8, but impaired fecundity 28% in the high treatment, decreasing 8. E₄ exposure impaired fecundity 28% in the medium and 49% in the high treatments, decreasing 8. Likewise, EE₂ impaired fecundity 25% and 70% in the medium and high EE₂ treatments, decreasing 8. Fecundity was unaffected at the low treatment of E₄ and EE₂. A matrix modeling approach using laboratory-generated EDC data may be useful to predict the potential effects on growth rate of wild populations.


MERCURY STUDIES. INFLUENCES OF: FISH SIZE/AGE, TISSUE MOISTURE CONTENT, SEX, REPRODUCTIVE CONDITION, SAMPLE SIZE. M.S. Hutcheson and J.A. Rose. Office of Research and Standards, Massachusetts Department of Environmental Protection, Boston, MA. 02108; B. Eddy, Wall Experiment Station, Massachusetts Department of Environmental Protection, Lawrence, MA 01843-1398.

In the study of the bioaccumulation of mercury in fish, it is often desirable to compare the mercury concentrations of fish populations at different times, locations or with health-based tissue exposure criteria. We will identify several potential contributors to variation in the data (size/age, tissue moisture content, sex, reproductive condition, sample size), which the researcher should consider controlling or adjusting to make more meaningful inferences regarding comparisons being made. In this presentation, we will present data primarily from largemouth bass and yellow perch collected in Massachusetts illustrating the magnitude of variance associated with these variables and provide suggestions for controlling for these sources of variation and improving the ability to discriminate differences between samples. This practical presentation is intended to highlight tools for improving the utility and statistical validity of fish tissue mercury studies.


MODELING ESTUARINE CONDITION: DO LANDSCAPE-SAMPLING UNITS ALTER PREDICTION ACCURACY?  J. W. Hollister, University of Rhode Island, Kingston, RI, 02881; J. L. Copeland, Computer Sciences Corporation, Narragansett, RI 02882; P. V. August, University of Rhode Island, Kingston, RI, 02881; J. F. Paul, U. S. EPA, National Health and Environmental Effects Research Laboratory, Research Triangle Park, NC 27711.

Landscape structure metrics are often used to predict water and sediment quality of lakes, streams, and estuaries; however, sampling units used to generate these landscape metrics are either too large (i.e., an entire watershed) or somewhat arbitrary (i.e., 10 km buffer around a sampling station) and can result in inaccurate predictions. We generated watersheds, Euclidean buffers clipped to the watershed, and hydrologically defined buffers for selected sampling stations from the USEPA's Mid-Atlantic Integrated Assessment. Hydrologic buffers were generated from flow length calculations derived from the National Elevation Dataset. For each sampling unit we calculated percent urban from the National Land Cover Dataset and used this to predict levels of zinc and copper in estuarine sediments. We withheld a portion of the sampling stations and calculated the Root Mean Square Error (RMSE) between predicted and actual sediment contamination values and found that full watersheds had an RMSE nearly three times greater for zinc and two times greater for copper than either the Euclidean or hydrologic buffers. Using full watersheds as a landscape-sampling unit may result in poor predictions of metals concentrations in estuarine sediments. Furthermore, little difference was seen between the predictions of the models using Euclidean and hydrologic buffers, suggesting that the effort spent to compute hydrologically defined buffers might be unnecessary.


EFFECTS OF GENISTEIN ON GROWTH AND DEVELOPMENT OF AQUATIC VERTEBRATES. R.R. Ingham, E.D. Clotfelter, and C.R. Toth. Department of Biology, Providence College, Providence, RI 02918.

Genistein is an isoflavone compound found in some plants. It is weakly estrogenic and a known tyrosine kinase inhibitor. Most research on genistein utilizes rodent models to test for health effects of human consumption of soy-based foods. Genistein is also found in some tree species and is released in effluent from wood pulp and paper mills, yet its role as an environmental contaminant remains largely unexplored. We studied the effects of genistein on the survival, growth and development of two aquatic vertebrates, the fathead minnow (Pimephales promelas) and the African clawed frog (Xenopus laevis). Test organisms were exposed to waterborne genistein at concentrations ranging from 10 to 1280 g/L. Fathead minnows were exposed to genistein for 96 hours; then monitored for eight weeks. We found only slight declines in growth and survival of juvenile minnows (>60 days) due to genistein exposure. We also found no effects on developmental symmetry of three bilateral traits. In our Xenopus experiments we exposed embryos to genistein for 48 hours after fertilization. Gastrulation was severely disrupted at the highest concentration. At intermediate concentrations, anterior/posterior abnormalities were evident at the tadpole stage. These results suggest that genistein is a potentially significant contaminant that can interfere with normal development of aquatic organisms. We are currently conducting similar tests with minnow eggs, as well as investigating sublethal effects in both minnows and frogs.


RISK ASSESSMENT OF MULTIPLE STRESSORS AND SPATIO-TEMPORAL HABITAT MODEL DEVELOPMENT FOR THE COMMON LOON (GAVIA IMMER) IN NORTHEASTERN UNITED STATES AND CANADA. A. Kuhn, Jane Copeland, Matthew Nicholson, Matthew Mitro, Diane Nacci and D. Borsay Horowitz. U.S. EPA, Atlantic Ecology Division, Narragansett, RI 02882.

Mercury (Hg) contamination remains a high priority issue for several EPA program offices and regions because of widespread atmospheric deposition and concerns of accumulation through aquatic food webs. Although there is evidence of reduced productivity in some piscivorous birds and widespread reports of wildlife tissue mercury concentrations exceeding levels associated with adverse effects in controlled studies, it is unclear what impact this has on the viability of populations of piscivorous wildlife. Also, mercury contamination exists within a patchwork of other co-occurring stressors to wildlife populations, and the relative risks are poorly understood. Because Hg bioaccumulates in the aquatic food web, this research focuses on the risks of Hg to top-level predators (piscivorous birds), in particular, common loons (Gavia immer), associated with mercury exposure in the environment. Given the heterogeneous distribution of stressors (e.g., dietary methylmercury, habitat degradation, acidification, human disturbance), this research attempts to identify the spatial relationships among stressors, the potential interactions among stressor impacts, and the relative risks among stressors to populations of loons at various spatial scales. Research to date has focused on five major areas: 1) the landscape characterization including the spatial and temporal distribution of stressors and available habitat for the Common loon; 2) stressor-response relationships especially for endpoints related to survival and fecundity rates; 3) development, evaluation and field verification of a common loon habitat model; 4) an age-classified matrix population models incorporating stressor-response relationships for loons; 5) population dynamics assessed across heterogeneous landscapes where variable stressor levels and habitat qualities influence the distribution of populations.


A GEOCHEMICAL ASSESSMENT OF POTTERS COVE, NARRAGANSETT BAY, RHODE ISLAND. E.L. Laliberte, J.W. King, and J.G. Quinn, Graduate School of Oceanography, University of Rhode Island, Narragansett, RI 02882.

A geochemical assessment of Potters Cove in Narragansett Bay has been performed to examine chemical (trace metal and organic contaminant) and nutrient changes over a variety of time scales. Cores were collected and analyzed for trace metals (cadmium, copper, lead, nickel and zinc), organic contaminants (PCBs, DDTs, PAHs, TPHs) and nutrients (carbon, nitrogen). An age model for the core was developed using Pb210 analysis with a constant rate of supply model. In general, the nutrients and trace metals show increasing trends towards the surface whereas the organic contaminants have subsurface peaks. Sediment trap studies performed over a two-year period indicate that trace metal (Cd, Cu, Pb, Zn) concentrations in suspended sediment are higher in the spring and lower in the summer whereas the nutrient (C, N) concentrations showed the opposite trend. Seasonal trends were not apparent in the organic contaminants in the sediment traps. Water quality parameters (temperature and dissolved oxygen) were measured by Narragansett Bay National Estuarine Research Reserve personnel. Sediment acid volatile sulfide (AVS) concentrations showed a positive correlation to water temperature and a negative correlation to dissolved oxygen concentration. AVS-Simultaneously Extracted Metals (SEM) studies indicated that the AVS concentration was significantly higher than the sum of the SEMs indicating that the trace metals are not bioavailable.


ENVIRONMENTAL RESTORATION AND PROTECTION STRATEGIES AT MULTIPLE SCALES IN RHODE ISLAND WATERSHEDS. S.M. Lussier¹, H. Walker¹, G.G. Pesch¹, W. Galloway¹; R. Adler²; and R. Comeleo³, J. Copeland³. ¹U.S. EPA, Atlantic Ecology Division, Narragansett, RI 02882, ²U.S. EPA, Region I, Boston, MA 02203, ³OAO Corporation, Corvallis, OR and Narragansett, RI 02882.

Public concerns for the environment are often the basis for environmental regulations. The Clean Water Act seeks to ensure that water quality and quantity fully support aquatic life and human health. The legislative requirements help focus limited resources on areas where problems are apparent or anticipated. An additional approach has been adopted by EPA New England to identify areas of healthy natural resources in the New England states. This “New England Resource Protection” approach represents a change of focus from remediating areas not sustaining aquatic life or human use to protecting healthy ecosystems. Diverse stakeholders are involved in an open process designed to identify and characterize healthy ecosystems in both a human health and ecosystem context. This approach facilitates clear communication concerning environmental conditions and threats to healthy ecosystems and promotes public stewardship for the environment. Public concerns can then be translated into a set of specific questions that can be answered through research. The issues and concerns of stakeholders differ at each spatial scale. At the state level, the resources protection process helps identify relatively pristine areas that may benefit from additional protection. At the subbasin scale, areas of specific nonattainment can be identified and probable causes determined. In our Rhode Island case study, we use the Geographic Information System to illustrate how public concerns, Clean Water Act reporting, and New England Resources Protection can be integrated to identify different types of environmental assessment questions and research issues at state, watershed, and subbasin scales.


MERCURY IN THE WHEATON VERNAL POOL. T. Morgan, R. Fontaine, and J. Benoit. Wheaton College, Norton, MA 02766.

Vernal pools are seasonally inundated wetlands that provide important reproductive habitat for amphibians. Although the wet/dry cycle in vernal pools may be conducive to MeHg accumulation, little is known about Hg cycling in these ecosystems. As a first step in studying Hg biogeochemistry in the vernal pool on the Wheaton College campus, soil cores were taken from three sites in May 2002. Total Hg (THg) concentrations ranged from 100 to 300 ng gdw-1, with down-core profiles displaying subsurface maxima at two of the sites (B and C). The third site (A) showed a modest decrease in THg with depth, and THg was correlated with organic matter content. MeHg in the top 2-4 cm ranged from 1.5 to 3.6 ng gdw-1, with higher MeHg concentration and percent MeHg at sites B and C. Site A remained wet in August, despite an extremely dry summer, while sites B and C had dried completely and supported terrestrial vegetation. The wet-dry cycle of the vernal pool seems to be a major factor controlling the distribution of mercury in its soil. Future studies will elucidate the dynamics of MeHg production after spring flooding.



SOURCES OF POLYCYCLIC AROMATIC HYDROCARBONS RELATED TO BIOMARKER LEVELS IN FISH FROM PRINCE WILLIAM SOUND AND THE GULF OF ALASKA. D.S. Page, Bowdoin College, Brunswick, ME.; R.J. Huggett, Michigan State University, East Lansing, MI.; J.J. Stegeman and B. Woodin, Woods Hole Oceanographic Institution, Woods Hole, MA.; K.R. Parker, Data Analysis Group, Cloverdale, CA.; J.S. Brown, Battelle, Waltham, MA.; and A.E. Bence, Exxonmobil Upstream Research Co., Houston, TX.

A study of biomarkers in five fish species from Prince William Sound (PWS) and two of those species from the Gulf of Alaska (GOA) shows evidence of pervasive exposure to low levels of polycyclic aromatic hydrocarbons (PAH) at all site categories in 1999-2000. Site categories refer to GOA sites to the east of PWS and three categories of PWS sites, including non-spill path (NSP), spill path oiled (SPO) and spill path not-oiled (SPNO). Rockfish, rock sole and kelp greenling were collected at near shore locations (~50-500 meters offshore); Pacific halibut and cod were collected further offshore (~500-7000 meters). Seafloor sediments collected at each site were analyzed for PAH, terpanes, steranes, and triaromatic steroids. Partial least-squares analysis of the sediment chemistry using 83 compounds and 16 potential sources revealed hydrocarbon inputs from four principal sources. These are: 1) regional petrogenic sources including oil seeps and eroding sedimentary rocks introduced to GOA waters along a ~300 km long segment of the eastern GOA coastline, 2) combustion products derived from ongoing and historical human activities, 3) residues of Monterey (CA) oil released into PWS during the 1964 Alaskan earthquake, and 4) residues of Exxon Valdez spill oil. GOA sites contain only regional petrogenic hydrocarbons. PAH compounds from the regional petrogenic sources are the probable cause of the low levels of biomarkers measured in the Pacific halibut and cod from GOA sites. PWS sites contain varying proportions of regional petrogenic PAH and combustion-product derived PAH. Individual fish (kelp greenling, rockfish, rock sole) from embayments in PWS, where the sediments have high concentrations of combustion product PAH (up to 7000 ppb), had elevated levels of biomarkers relative to other fish of the same species from those sites. Although low levels (<5-100 ppb PAH) of Exxon Valdez spill oil residues were detected at some nearshore SPO sites, biomarker levels in fish caught at those sites were not elevated with respect to other sites in PWS.


AN AUTOMATED METHOD FOR ANALYSIS OF INORGANIC ARSENIC SPECIES IN SEDIMENTS AND TISSUES BY HGAA. Leonard C. Pitts. Woods Hole Group Environmental Laboratories, 375 Paramount Dr. Suite 2, Raynham, MA 02767.

Measurement of arsenic species is becoming increasingly important in environmental studies due to the varying toxicity of the different arsenic compounds. LD50 studies indicate that the inorganic arsenic species, arsenite (ASIII) and arsenate (AsV) are far more toxic than the organic arsenic species such as monomethyl and dimethyl arsenic. Current methods such as HG-CT-GC-AA or HPLC-ICP MS are labor intensive or require very expensive equipment. Methods are presented here to determine inorganic arsenic in tissues and arsenite and arsenate in sediments utilizing an automated Perkin Elmer FIMS 100 Flow Injection Hydride System with atomic absorption detection. Inorganic arsenic is leached from homogenized tissue samples prepared by cryogenic cell disruption and pulverization followed by extraction in 2 M HCl. An intercalibration study on fish tissue utilizing HG-CT-GC-AAS gave similar results and good matrix spike recoveries were observed. ASIII and AsV are selectively leached from sediments with 0.1 M H₃PO₄ and 0.1 M Na₃PO₄ respectively. Sediments and tissues are leached in an ultrasonic bath for 24 hours and centrifuged prior to reduction and analysis. A reporting limit of 0.01 mg/kg wet weight is achieved for each matrix. Organic arsenic compounds, which can from volatile hydrides, are removed from the analysis with a trap containing graphitized carbon black. Sample analysis time is about 3 minutes.