Oil spills and the environment: A review of chemical fate and biological effects of petroleum
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This chapter has three principal objectives: (1) to summarize the present chemical composition of North American surface waters and point out any discernible trends with time; (2) to review chemical and biochemical principles and processes that control natural water composition, and the ways in which these may be involved in attaining the particular chemical compositions and trends that we can observe; and (3) to point out some of the more important factors that must be considered in collecting surface-water-quality data. This discussion is concerned principally with inorganic chemistry and geochemistry. However, biochemical processes in river and lake water influence their chemical composition extensively, and specific effects are pointed out. Aquatic biology is discussed in another chapter. The physical processes occurring in lakes also have very important effects on water chemistry; these aspects of limnology are covered more fully in a separate chapter. Data on which this chapter is based relate mostly to waters of Canada, the United States, and Mexico. For most of Central America, very little water-quality information is available. Tables 1 through 3 contain analytical data for river waters that illustrate some of the principles discussed, and summarize major features of the chemical composition of North American surface waters. To a certain extent, at least, one would expect the average concentrations of dissolved elements in surface fresh water to reflect the relative abundance of the elements in the crustal rocks exposed at and near the land surface.
Nonnative crayfish are an immediate and pervasive threat to aquatic environments and their biodiversity. Crayfish control can be achieved by physical methods, water chemistry modification, biological methods, biocidal application, and application of crayfish physiology modifiers. The purpose of this report is to identify suitable candidates for potential control of nonnative crayfish through a comprehensive literature review. This review focuses on control methods, specifically on the available data to support registration of a crayfish pesticide. The literature search resulted in 28,058 documents, which were searched to determine if they contained information on physical, chemical, biological, and (or) biocidal approaches to control crayfish. Pesticides directly toxic to crayfish in this literature review include: pyrethroids (natural pyrethrins and synthetic), fipronil, mirex, antimycin-A, and rotenone. Some chemicals, such as diflubenzuron and emamectin benzoate, alter crayfish physiology resulting in a lower pesticide dose needed to control crayfish. Environmental damage, application rate, exposure duration, nontarget effects, environmental persistence, and registration data gaps were used as criteria to define which pesticides are potentially selective to crayfish, along with which have the greatest amount of data to support registration by the U.S. Environmental Protection Agency. Synthetic pyrethroids were identified as the most likely candidate to be developed into a crayfish pesticide. A type-2 synthetic pyrethroid, cyfluthrin, has the greatest potential for eradicating nonnative crayfish. Although other invertebrate species will be negatively affected at the concentrations required for crayfish control, compared with other pyrethroids and other potential control chemicals, cyfluthrin offers rapid ecosystem recovery due to being more selective, having fewer effects on native fish, and having a short aquatic persistence. Cyfluthrin also has few data gaps for U.S. Environmental Protection Agency registration purposes.
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A literature review of bioaccumulation and biotransformation of organic chemicals in birds was undertaken, aiming to support scoping and prioritization of future research. The objectives were to characterize available bioaccumulation/biotransformation data, identify knowledge gaps, determine how extant data can be used, and explore the strategy and steps forward. An intermediate approach balanced between expediency and rigor was taken given the vastness of the literature. Following a critical review of > 500 peer-reviewed studies, > 25,000 data entries and 2 million information bytes were compiled on > 700 organic compounds for ~ 320 wild species and 60 domestic breeds of birds. These data were organized into themed databases on bioaccumulation and biotransformation , field survey , microsomal enzyme activity , metabolic pathway , and bird taxonomy and diet . Significant data gaps were identified in all databases at multiple levels. Biotransformation characterization was largely fragmented over metabolite/pathway identification and characterization of enzyme activity or biotransformation kinetics. Limited biotransformation kinetic data constrained development of an avian biotransformation model. A substantial shortage of in vivo biotransformation kinetics has been observed as most reported rate constants were derived in vitro. No metric comprehensively captured all key contaminant classes or chemical groups to support broad-scope modeling of bioaccumulation or biotransformation. However, metrics such as biota-feed accumulation factor, maximum transfer factor, and total elimination rate constant were more readily usable for modeling or benchmarking than other reviewed parameters. Analysis demonstrated the lack of bioaccumulation/biotransformation characterization of shorebirds, seabirds, and raptors. In the study of bioaccumulation and biotransformation of organic chemicals in birds, this review revealed the need for greater chemical and avian species diversity, chemical measurements in environmental media, basic biometrics and exposure conditions, multiple tissues/matrices sampling, and further exploration on biotransformation. Limitations of classical bioaccumulation metrics and current research strategies used in bird studies were also discussed. Forward-looking research strategies were proposed: adopting a chemical roadmap for future investigations, integrating existing biomonitoring data, gap-filling with non-testing approaches, improving data reporting practices, expanding field sampling scopes, bridging existing models and theories, exploring biotransformation via avian genomics, and establishing an online data repository.
A computer application called Chemical Help was developed to facilitate review of reports for the National Highway Runoff Water-Quality Data and Methodology Synthesis (NDAMS). The application provides a tool to quickly find a proper classification for any constituent in the NDAMS review sheets. Chemical Help contents include the name of each water-quality property, constituent, or parameter, the section number within the NDAMS review sheet, the organizational levels within a classification hierarchy, the database number, and where appropriate, the chemical formula, the Chemical Abstract Service number, and a list of synonyms (for the organic chemicals). Therefore, Chemical Help provides information necessary to research available reference data for the water-quality properties and constituents of potential interest in stormwater studies. Chemical Help is implemented in the Microsoft help-system interface. (Computer files for the use and documentation of Chemical Help are included on an accompanying diskette.)
Review of: Handbook of drugs and chemicals used in the treatment and control of fish diseases. N. Herwig; 1979; Charles C. Thomas, Co., Springfield, Illinois.
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Aquatic ecosystems around the world are contaminated with a wide range of anthropogenic chemicals, including metals and organic pollutants, that originate from point and nonpoint sources. Many of these chemical contaminants have complex environmental cycles, are persistent and bioavailable, can be incorporated into aquatic food webs, and pose a threat to the health of wildlife and humans. Identifying appropriate sentinels that reflect bioavailability is critical to assessing and managing aquatic ecosystems impacted by contaminants. The objective of the present study is to review research on riparian spiders as sentinels of persistent and bioavailable chemical contaminants in aquatic ecosystems. Our review of the literature on riparian spiders as sentinels suggests that significant progress has been made during the last two decades of research. We identified 55 published studies conducted around the world in which riparian spiders (primarily of the families Tetragnathidae, Araneidae, Lycosidae, and Pisauridae) were used as sentinels of chemical contamination of lotic, lentic, and estuarine systems. For several contaminants, such as polychlorinated biphenyls (PCBs), Hg, and Se, it is now clear that riparian spiders are appropriate sentinels. However, many contaminants and factors that could impact chemical concentrations in riparian spiders have not been well characterized. Further study of riparian spiders and their potential role as sentinels is critical because it would allow for development of national-scale programs that utilize riparian spiders as sentinels to monitor chemical contaminants in aquatic ecosystems. A riparian spider sentinel program in the United States would be complementary to existing national sentinel programs, including those for fish and immature dragonflies.
The study of coastal groundwater has recently surfaced as an active interdisciplinary area of research, driven foremost by its importance as a poorly quantified pathway for subsurface material transport into coastal ecosystems. Key issue in coastal groundwater research include a complete geochemical characterization of the groundwater(s); quantification of the kinetics of subsurface transport, including rock-water interactions; determination of groundwater ages; tracing of groundwater discharge into coastal waters using radiochemical fingerprints; and an assessment of the potential ecological impact of such subsurface flow to a reviving water body. For such applications, the isotopic systemics of select naturally occurring radionucludes in the U/Th series has proven to be particularly useful. These radionuclides (e.g., U, Th, Ram and Rn) are ubiquitous in all groundwaters ad are represented by several isotopes with widely different half-lives and chemistries (Figure 1). As a result, varied biogeochemical processes occurring over a broad range of time scales can be studied. In source rock, most U/Th series isotopes in secular equilibrium; that is, the rate of decay of a daughter isotope is equal to that of it radiogenic parent, and so will have equal activities (in this context, the specific activity is simply a measure of the amount of radioactivity per unit amount). In contrast, these nuclides exhibit strong fractionations within the surrounding groundwaters because of their respective physiochemical differences. Disequilibria in U/Th series radionuclides can thus be used to identify distinct water masses, quantify release rates from source rocks, assess groundwater migration rates, and assess groundwater discharge rates in coastal waters., Large isotopic variations also have the potential for providing precise fingerprints for groundwaters from specific aquifers and have been explored as a means for calculating groundwater ages and estuarine water mass transit times. The highly fractionated nature of U/Th series nuclides in groundwater is illustrated by the range in some measured activities. highest activities are typically observed for 222 Rn, reflecting the inert nature of this noble gas. Groundwater 222 Rn (t 1/2 =3.8) activities are thus controlled only by rapid in situ decay (Table 1) and production within host rocks, without the added complications of reversible removal via absorption or precipitation. Uranium, which is soluble as U(VI) in oxidizing waters, is present in intermediate activities in groundwaters that are moderated by redox-initiated removal onto aquifer rocks. The alkaline earth Ra and, to a greater extent, the less soluble actinide Th are readily removed from groundwater by water -- rock interactions and so are strongly depleted. Both of these elements have very short-lived as well as longer-lived isotopes, and so isotopes compositions reflect processes over a range of time scales. Many studies have evaluated and behavior of select radionuclides in groundwater and surface water systems. Recent advances in high-=precision mass spectrometry have opted new possibilities for more subtle interpretations in select long-lived U/Th series isotopes, such as U, Ra, Pa, and Th. However, these techniques have yet to be fully developed, ahns as a consequence, such data remain largely scarce and underutilized. Although many different approaches have been developed to study radionucluide behavior in groundwater, all are based on principles of radioactive production and decay and knowledge of source terms from weathering and recoil processes, as well as removal terms from the interaction with aquifer host rock surface by sorption and precipitation. This review is structured to present first a brief description of the background, driving forces, scales, and ecological significance of submarine groundwater discharge. Following this, a description of the geochemistry and behavior of select radionuclides in groundwater will be presented, and their application to tracing submarine groundwater discharge will be discussed.
This review compiles and evaluates existing scientific information on the use, limitations, and procedural considerations for EROD activity (a catalytic measurement of cytochrome P4501A induction) as a biomarker in fish. A multitude of chemicals induce EROD activity in a variety of fish species, the most potent inducers being structural analogs of 2,3,7,8-tetracholordibenzo- p -dioxin. Although certain chemicals may inhibit EROD induction/activity, this interference is generally not a drawback to the use of EROD induction as a biomarker. The various methods of EROD analysis currently in use yield comparable results, particularly when data are expressed as relative rates of EROD activity. EROD induction in fish is well characterized, the most important modifying factors being fish species, reproductive status and age, all of which can be controlled through proper study design. Good candidate species for biomonitoring should have a wide range between basal and induced EROD activity (e.g., common carp, channel catfish, and mummichog). EROD activity has proven value as a biomarker in a number of field investigations of bleached kraft mill and industrial effluents, contaminated sediments, and chemical spills. Research on mechanisms of CYP1A-induced toxicity suggests that EROD activity may not only indicate chemical exposure, but also may also precede effects at various levels of biological organization. A current research need is the development of chemical exposure-response relationships for EROD activity in fish. In addition, routine reporting in the literature of EROD activity in standard positive and negative control material will enhance confidence in comparing results from different studies using this biomarker.
Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.
Review of: Epiphytic lichen diversity and its dependence on chemical site factors in differently elevated dieback-affected spruce stands of the Harz Mountains. (Dissertationes Botanicae, Band 354). Volker Hesse. 2002. 191 pages, 66 figures, 49 tables, 23x14cm, 390 g. ISBN 978-3-443-64266-2.
Increasing demand on the limited supplies of freshwater in the desert Southwest, as well as other parts of the United States, has increased the level of interest in saline-water resources. Saline ground water has long been recognized as a potentially important contributor to water supply in the Southwest, as demonstrated by the number of hydrologic, geologic, and engineering studies on the distribution of saline water and the feasibility of desalination. Potential future study needs include investigating and documenting the three-dimensional distribution of salinity and chemical composition of saline-water resources and the hydraulic properties of aquifers containing these saline-water resources, assessing the chemical suitability of saline water for use with existing and anticipated desalination technologies, simulating the effect of withdrawal of saline ground water on water levels and water composition in saline and adjoining or overlying freshwater aquifers, and determining the suitability of target geologic formations for injection of desalination-generated waste.
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This chapter focuses on the physic-chemical processes affecting copper, zinc, and tin toxicity to algae. Both Cu and Zn are essential algal micronutrients, cofactors in numerous biochemical processes. The availability of a nutrient or toxic substance can be significantly affected by precipitation. Methods for modeling the effects of adsorption–desorption reactions have been previously reviewed. Useful predictions of algal response require an understanding of the relative importance of these interactions (both magnitude and time dependence). Photoreduction and dissolution of Mn oxides by dissolved humic substances has been proposed as an important factor regulating dissolved Mn distribution in seawater. Photodegradation of iron (Fe) chelates also enhances Fe uptake by algae. Anderson et al. observed that Fe uptake by Thalassiosira weissflogii in a chemically defined medium dominated by FeEDTA complexation doubled in the presence of light.
At the request of the U.S. Environmental Protection Agency (EPA) Office of Research and Development, a subcommittee of the Board of Scientific Counselors Executive Committee conducted an independent and open peer review of the Endocrine Disrupting Chemicals Research Program (EDC Research Program) of the U.S. EPA. The subcommittee was charged with reviewing the design, relevance, progress, scientific leadership, and resources of the program. The subcommittee found that the long-term goals and science questions in the EDC Program are appropriate and represent an understandable and solid framework for setting research priorities, representing a combination of problem-driven and core research. Long-term goal (LTG) 1, dealing with the underlying science surrounding endocrine disruptors, provides a solid scientific foundation for conducting risk assessments and making risk management decisions. LTG 2, dealing with defining the extent of the impact of endocrine-disrupting chemicals (EDCs), has shown greater progress on ecologic effects of EDCs compared with that on human health effects. LTG 3, which involves support of the Endocrine Disruptor Screening and Testing Program of the U.S. EPA, has two mammalian tests already through a validation program and soon available for use. Despite good progress, we recommend that the U.S. EPA a ) strengthen their expertise in wildlife toxicology, b ) expedite validation of the Endocrine Disruptors Screening and Testing Advisory Committee tests, c ) continue dependable funding for the EDC Research Program, d ) take a leadership role in the application of “omics” technologies to address many of the science questions critical for evaluating environmental and human health effects of EDCs, and e ) continue to sponsor multidisciplinary intramural research and interagency collaborations.