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Effects on fish and wildlife of chemical treatments of large areas

Summary: The history of field investigations of the effects of DDT on wildlife is reviewed briefly, from the initial studies in 1945 through the more recent studies of the effects of the large-scale programs for spruce-budworm control and gypsy-moth eradication. DDT dosages and procedures that are recommended for protection of wildlife are reviewed. Effects of aldrin, heptachlor, and toxaphene are discussed in connection with the grasshopper and Mormon cricket control programs. Delayed and indirect effects of chemical treatments are emphasized as an important current problem. Cited in this connection are fish losses in the Yellowstone and Miramichi rivers and losses of wildlife from eating earthworms a year after treatment of the area with DDT. Currently recommended procedures to safeguard wildlife in pesticidal programs are listed.

Journal of Forestry

Applications of mineral surface chemistry to environmental problems

Environmental surface chemistry involves processes that occur at the interface between the regolith, hydrosphere and atmosphere. The more limited scope of the present review addresses natural and anthropogenically-induced inorganic geochemical reactions between solutes in surface and ground waters and soil and aquifer substrates. Important surficial reactions include sorption, ion exchange, dissolution, precipitation and heterogeneous oxidation/reduction processes occurring at the solid/aqueous interface. Recent research advances in this field have addressed, both directly and indirectly, societal issues related to water quality, pollution, biogeochemical cycling, nutrient budgets and chemical weathering related to long term global climate change. This review will include recent advances in the fundamental and theoretical understanding of these surficial processes, breakthroughs in experimental and instrumental surface characterization, and development of methodologies for field applications.

Reviews of Geophysics

Sediment oxygen demand: A review of in situ methods

Sediment oxygen demand (SOD) plays a fundamental role in biological and chemical processes within the benthic layer of a water body. Land use, including agricultural land use, can affect SOD. However, a wide variety of approaches have been used for in situ SOD chamber construction and data collection, and modelers frequently use SOD values from the literature, without consideration of the differences in methods. Here, we review existing literature on SOD chambers (32 papers, 1974–2016), compare the differences between in situ and laboratory methods, evaluate the effects of in situ chamber mixing, and discuss common challenges associated with deployment. A cohesive in situ sealed chamber design for use with a multiparameter water-quality instrument is presented as an effort toward standardizing SOD methodology, an important consideration that may facilitate integration of SOD data sets among multiple research efforts.

Journal of Environmental Quality

Terrestrial population models for ecological risk assessment: A state-of-the-art review

Few attempts have been made to formulate models for predicting impacts of xenobiotic chemicals on wildlife populations. However, considerable effort has been invested in wildlife optimal exploitation models. Because death from intoxication has a similar effect on population dynamics as death by harvesting, these management models are applicable to ecological risk assessment. An underlying Leslie-matrix bookkeeping formulation is widely applicable to vertebrate wildlife populations. Unfortunately, however, the various submodels that track birth, death, and dispersal rates as functions of the physical, chemical, and biotic environment are by their nature almost inevitably highly species- and locale-specific. Short-term prediction of one-time chemical applications requires only information on mortality before and after contamination. In such cases a simple matrix formulation may be adequate for risk assessment. But generally, risk must be projected over periods of a generation or more. This precludes generic protocols for risk assessment and also the ready and inexpensive predictions of a chemical's influence on a given population. When designing and applying models for ecological risk assessment at the population level, the endpoints (output) of concern must be carefully and rigorously defined. The most easily accessible and appropriate endpoints are (1) pseudoextinction (the frequency or probability of a population falling below a prespecified density), and (2) temporal mean population density. Spatial and temporal extent of predicted changes must be clearly specified a priori to avoid apparent contradictions and confusion.

Environmental Toxicology and Chemistry

Methods for control of tick vectors of Lyme Borreliosis

During the IVth International Conference on Lyme Borreliosis in Stockholm, 1990, a workshop on control of Lyme disease vectors briefly reviewed: basic ecological principles for tick control; biocontrol of ticks; chemical control, including the use of repellents and use of permethrin-treated rodent nest material; tick control by habitat modification; and reduction of tick host availability. It was concluded that, although much research work remains, Lyme borreliosis is to a large extent a preventable infection. Avoidance of heavily tick-infested areas, personal protection using proper clothing, and prompt removal of attached ticks remain the most effective protective measures. Many other prophylactic measures are available and could be efficiently integrated into schemes to reduce the abundance of vectors. However, since the ecology of the infection varies greatly between different localities it may be necessary to apply different combinations of control methods in different endemic regions.

Scandinavian Journal of Infectious Diseases

What are gas hydrates?

The English chemistry pioneer Sir Humphry Davy first combined gas and water to produce a solid substance in his lab in 1810. For more than a century after that landmark moment, a small number of scientists catalogued various solid “hydrates” formed by combining water with an assortment of gases and liquids. Sloan and Koh (2007) review this early research, which was aimed at discerning the chemical structures of gas hydrates (Fig. 1.1), as well as the pressures and temperatures at which they are stable. Because no practical applications were found for these synthetic gas hydrates, they remained an academic curiosity.

Book chapter

Agricultural sources of contaminants of emerging concern and adverse health effects on freshwater fish

Agricultural contaminants of emerging concern (CECs) are generally thought of as certain classes of chemicals associated with animal feeding and production facilities. Veterinary pharmaceuticals used in animal food production systems represent one of the largest groups of CECs. In our review, we discuss the extensive increase in use of antibiotics in animal feeding operations (AFOs) around the world. AFOs are a major consumer of antibiotics and other veterinary pharmaceuticals and over the past decade there has been growing information on the occurrence, release, and fate of CECs from animal food production operations, including the application of pharmaceutical-containing manure to agricultural fields and releases from waste lagoons. Concentrations of CECs in surface and ground water in proximity to AFOs correspond to their presence in the AFO wastes. In many cases, the environmental concentrations of agriculturally-derived CECs are below toxicity thresholds. Hormones and hormone replacement compounds are a notable exception, where chemical concentrations near AFOs can exceed concentrations known to cause adverse effects on endocrine-related functions in fish. In addition, some agricultural pesticides, once thought to be safe to non-target organisms, have demonstrated endocrine-related effects that may pose threats to fish populations in agricultural regions. That is, we have pesticides with emerging concerns, thus, the concern is emerging and not necessarily the chemical. In this light, one must consider certain agricultural pesticides to be included in the list of CECs. Even though agricultural pesticides are routinely evaluated in regulatory testing schemes which have been used for decades, the potential hazards of some pesticides have only recently been emerging. Emerging concerns of pesticides in fish include interference with hormone signaling pathways; additive (or more than additive) effects from pesticide mixtures; and adverse population-level effects at concentrations below predicted toxicity thresholds. Consequently, there is a need to evaluate the environmental concerns related to pesticide exposures to fish populations based on current biological and toxicological techniques. This presentation reviews some of the agricultural chemicals that have emerged as contaminants of concern and potentially threaten fish populations in agricultural watersheds.

Conference Paper

Molybdenum Hazards to Fish, Wildlife, and Invertebrates: A Synoptic Review

Ecological and toxicological aspects of molybdenum (Mo) in the environment are briefly reviewed, with emphasis on fish and wildlife. Subtopics include sources and uses, chemical properties, mode of action, background concentrations in biological and nonbiological samples, and lethal and sublethal effects on terrestrial plants and invertebrates, aquatic organisms, birds, and mammals. Current recommendations for Mo and the protection of sensitive living resources are presented.

Contaminant Hazard Reviews

Rodentia and lagomorpha

This comprehensive review examines the extensive literature on wild rodents and lagomorphs as biomonitors of environmental contamination. This chapter covers studies dealing with exposure and effects of environmental contaminants on rodent and lagomorph species, including pesticides (organochlorines, organophosphorus and carbamate compounds, herbicides, plant growth regulators, fungicides, and rodenticides), other organic chemicals, metals, radionuclides, and other miscellaneous contaminants. Many research needs become evident when reviewing ecotoxicological data for rodents and lagomorphs, the most striking being the paucity of information on rodent families other than Muridae (mice and rats). While our ability to qualitatively extrapolate effects observed in laboratory studies to field situations is good for a variety of contaminants, quantitative predictions of dose-response relationships are poor because inter-specific variation and differences in exposure patterns between laboratory and wild species to toxicants are for the most part unknown. More sophisticated comparative toxicity studies need to be undertaken that build on previous work in order to develop a database of information, to account for and model differences in exposure pathways, to document interactions among multiple stressors, to generate data establishing thresholds, critical concentrations, and diagnostic guidelines, and even to develop physiologically-based toxicokinetic models. Such efforts may enhance our ability to predict effects on wild populations, including threatened and endangered species.

Book chapter

Making ‘chemical cocktails’ – Evolution of urban geochemical processes across the periodic table of elements

Urbanization contributes to the formation of novel elemental combinations and signatures in terrestrial and aquatic watersheds, also known as ‘chemical cocktails.’ The composition of chemical cocktails evolves across space and time due to: (1) elevated concentrations from anthropogenic sources, (2) accelerated weathering and corrosion of the built environment, (3) increased drainage density and intensification of urban water conveyance systems, and (4) enhanced rates of geochemical transformations due to changes in temperature, ionic strength, pH, and redox potentials. Characterizing chemical cocktails and underlying geochemical processes is necessary for: (1) tracking pollution sources using complex chemical mixtures instead of individual elements or compounds; (2) developing new strategies for co-managing groups of contaminants; (3) identifying proxies for predicting transport of chemical mixtures using continuous sensor data; and (4) determining whether interactive effects of chemical cocktails produce ecosystem-scale impacts greater than the sum of individual chemical stressors. First, we discuss some unique urban geochemical processes which form chemical cocktails, such as urban soil formation, human-accelerated weathering, urban acidification-alkalinization, and Freshwater Salinization Syndrome. Second, we review and synthesize global patterns in concentrations of major ions, carbon and nutrients, and trace elements in urban streams across different world regions and make comparisons with reference conditions. In addition to our global analysis, we highlight examples from watersheds in the Baltimore-Washington DC area, USA, which show increased transport of major ions, trace metals, and nutrients across streams draining a well-defined land-use gradient. Urbanization increased the concentrations of multiple major and trace elements in streams draining human-dominated watersheds compared to reference conditions. Chemical cocktails of major and trace elements were formed over diurnal cycles coinciding with changes in streamflow, dissolved oxygen, pH, and other variables measured by high-frequency sensors. Some chemical cocktails of major and trace elements were also significantly related to specific conductance (p < 0.05), which can be measured by sensors. Concentrations of major and trace elements increased, peaked, or decreased longitudinally along streams as watershed urbanization increased, which is consistent with distinct shifts in chemical mixtures upstream and downstream of other major cities in the world. Our global analysis of urban streams shows that concentrations of multiple elements along the periodic table significantly increase when compared with reference conditions. Furthermore, similar biogeochemical patterns and processes can be grouped among distinct mixtures of elements of major ions, dissolved organic matter, nutrients, and trace elements as chemical cocktails. Chemical cocktails form in urban waters over diurnal cycles, decades, and throughout drainage basins. We conclude our global review and synthesis by proposing strategies for monitoring and managing chemical cocktails using source control, ecosystem restoration, and green infrastructure. We discuss future research directions applying the watershed chemical cocktail approach to diagnose and manage environmental problems. Ultimately, a chemical cocktail approach targeting sources, transport, and transformations of different and distinct elemental combinations is beneficial to more holistically monitor and manage the emerging impacts of chemical mixtures in the world's fresh waters.

Applied Geochemistry

Gas hydrates in sustainable chemistry

Gas hydrates have received considerable attention due to their important role in flow assurance for the oil and gas industry, their extensive natural occurrence on Earth and extraterrestrial planets, and their significant applications in sustainable technologies including but not limited to gas and energy storage, gas separation, and water desalination. Given not only their inherent structural flexibility depending on the type of guest gas molecules and formation conditions, but also the synthetic effects of a wide range of chemical additives on their properties, these variabilities could be exploited to optimise the role of gas hydrates. This includes increasing their industrial applications, understanding and utilising their role in Nature, identifying potential methods for safely extracting natural gases stored in naturally occurring hydrates within the Earth, and for developing green technologies. This review summarizes the different properties of gas hydrates as well as their formation and dissociation kinetics and then reviews the fast-growing literature reporting their role and applications in the aforementioned fields, mainly concentrating on advances during the last decade. Challenges, limitations, and future perspectives of each field are briefly discussed. The overall objective of this review is to provide readers with an extensive overview of gas hydrates that we hope will stimulate further work on this riveting field.

Chemical Society Reviews

Chemical analyses in the World Coal Quality Inventory

The main objective of the World Coal Quality Inventory (WoCQI) was to collect and analyze a global set of samples of mined coal during a time period from about 1995 to 2006 (Finkelman and Lovern, 2001). Coal samples were collected by foreign collaborators and submitted to country specialists in the U.S. Geological Survey (USGS) Energy Program. However, samples from certain countries, such as Afghanistan, India, and Kyrgyzstan, were collected collaboratively in the field with USGS personnel. Samples were subsequently analyzed at two laboratories: the USGS Inorganic Geochemistry Laboratory located in Denver, CO and a commercial laboratory (Geochemical Testing, Inc.) located in Somerset, PA. Thus the dataset, which is in Excel (2003) format and includes 1,580 samples from 57 countries, does not have the inter-laboratory variability that is present in many compilations. Major-, minor-, and trace-element analyses from the USGS laboratory, calculated to a consistent analytical basis (dry, whole-coal) and presented with available sample identification information, are sorted alphabetically by country name. About 70 percent of the samples also have data from the commercial laboratory, which are presented on an as-received analytical basis. The USGS initiated a laboratory review of quality assurance in 2008, covering quality control and methodology used in inorganic chemical analyses of coal, coal power plant ash, water, and sediment samples. This quality control review found that data generated by the USGS Inorganic Geochemistry Laboratory from 1996 through 2006 were characterized by quality practices that did not meet USGS requirements commonly in use at the time. The most serious shortcomings were (1) the adjustment of raw sample data to standards when the instrument values for those standards exceeded acceptable limits or (2) the insufficient use of multiple standards to provide adequate quality assurance. In general, adjustment of raw data to account for instrument 'drift' is an acceptable practice within strictly defined limits. During the denoted period, USGS required that the maximum adjustment of instrument values, guided by calibration standards, was not allowed to exceed 10 percent. However, in some cases, the Inorganic Geochemistry Laboratory released data that were adjusted by more than 10 percent and (or) were not constrained by an adequate number of control standards. Original instrument values no longer exist for about 80 percent of the analyses during this period; therefore, the acceptability of drift corrections for most of the samples analyzed cannot be determined. For these reasons, the WoCQI data from the USGS Inorganic Geochemistry Laboratory should be used with care. For more information, individuals may contact laboratory management at EnergyLabs@usgs.gov with specific questions about particular datasets or analytical attributes. Standard USGS sampling methods were provided and recommended to collaborators, but the analyzed samples may or may not be representative of their locale; for some samples, only limited information is available concerning sample provenance. Single samples cannot represent spatial or temporal variability within a coal area. Geochemical datasets of U.S. coals can be found in the COALQUAL database (Bragg and others, 1997) and the National Coal Quality Inventory (Hatch and others, 2006), as only non-U.S. sample data are presented in the WoCQI. Although the WoCQI does not contain worldwide coverage of coal deposits, it is truly a unique and valuable compilation. The information in the WoCQI should prove useful for identifying possible areas for future global coal research.

Open-File Report

Xenobiotic-induced apoptosis: significance and potential application as a general biomarker of response

The process of apoptosis, often coined programmed cell death, involves cell injury induced by a variety of stimuli including xenobiotics and is morphologically, biochemically, and physiologically distinct from necrosis. Apoptotic death is characterized by cellular changes such as cytoplasm shrinkage, chromatin condensation, and plasma membrane asymmetry. This form of cell suicide is appealing as a general biomarker of response in that it is expressed in multiple cell systems (e.g. immune, neuronal, hepatal, intestinal, dermal, reproductive), is conserved phylogenetically (e.g. fish, rodents, birds, sheep, amphibians, roundworms, plants, humans), is modulated by environmentally relevant levels of chemical contaminants, and indicates a state of stress of the organism. Further, apoptosis is useful as a biomarker as it serves as a molecular control point and hence may provide mechanistic information on xenobiotic stress. Studies reviewed here suggest that apoptosis is a sensitive and early indicator of acute and chronic chemical stress, loss of cellular function and structure, and organismal health. Examples are provided of the application of this methodology in studies of health of lake trout (Salvelinus namaycush) in the Laurentian Great Lakes.

Biomarkers

Formulations for aircraft and airfield deicing and anti-icing: aquatic toxicity and biochemical oxygen demand

The Airport Cooperative Research Program (ACRP) has sponsored research on environmental characteristics of aircraft and pavement deicers and anti-icers focusing primarily on biochemical oxygen demand (BOD) and aquatic toxicity of formulated products and individual chemical components of formulations. This report presents a background of issues leading to this research, objectives of this document, and a description of the efforts and findings of this research. Except when the distinction among products is necessary for clarity, &ldquo;deicer&rdquo; will refer to aircraft-deicing fluids (ADFs), aircraft anti-icing fluids (AAFs), and pavement-deicing materials (PDMs) generally. The efforts of this project have included the following: A review of regulations and specifications related to the performance and environmental characteristics of deicer formulations A review of issues related to the impact that deicers have on aquatic systems and causes of those impacts Laboratory testing of current-use deicers to establish benchmark values for aquatic toxicity, BOD, and chemical oxygen demand (COD) A review of deicer formulations under development and their relevant performanceand environmental-related characteristics A review of operational and infrastructure considerations A synopsis of current analytical methods used in environmental characterization of airport deicing runoff A toxicity-based investigation of current-use deicers to determine components responsible for toxicity and identify component classes to focus a search for alternative components Identification of gaps in knowledge and data pertaining to the above topics

Report

Improvements in the use of aquatic herbicides and establishment of future research directions

Peer-reviewed literature over the past 20 years identifies significant changes and improvements in chemical control strategies used to manage nuisance submersed vegetation. The invasive exotic plants hydrilla (Hydrilla verticillata L.f. Royle) and Eurasian watermilfoil (Myriophyllum spicatum L.) continue to spread and remain the plant species of greatest concern for aquatic resource managers at the national scale. Emerging exotic weeds of regional concern such as egeria (Egeria densa Planch.), curlyleaf pondweed (Potamogeton crispus L.), and hygrophila (Hygrophila polysperma (Roxb.) T. Anders), as well as native plants such as variable watermilfoil (Myriophyllum heterophyllum Michx), and cabomba (Cabomba caroliniana Gray) are invasive outside their home ranges. In addition, there is always the threat of new plant introductions such as African elodea (Lagarosiphon major (Ridley) Moss) or narrow-leaf anacharis (Egeria najas Planchon). The registration of the bleaching herbicide fluridone in the mid 1980s for whole-lake and large-scale management stimulated numerous lines of research involving reduction of use rates, plant selectivity, residue monitoring, and impacts on fisheries. In addition to numerous advances, the specificity of fluridone for a single plant enzyme led to the first documented case of herbicide resistance in aquatic plant management. The resistance of hydrilla to fluridone has stimulated a renewed interest by industry and others in the registration of alternative modes of action for aquatic use. These newer chemistries tend to be enzyme-specific compounds with favorable non-target toxicity profiles. Registration efforts have been facilitated by increased cooperation between key federal government agencies that have aquatic weed control and research responsibilities, and regulators within the U.S. Environmental Protection Agency (USEPA). We reviewed past and current research efforts to identify areas in need of further investigation and to establish priorities for future research directions in chemical management of submersed plants. The priorities we identified include: (A) improving methods for evaluating non-target impacts of herbicides with an emphasis on threatened and endangered species, or species of special concern; (B) improving herbicide performance in flowing-water environments, including irrigation canals; (C) screening and developing new herbicides to supplement fluridone for large-scale or whole-lake management approaches; (D) screening and developing new organic algaecides to supplement the use of copper-based compounds; (E) developing risk assessment tools to educate the public on the risks of invasive species and chemical management options; (F) increasing cooperative research with ecologists and fisheries scientists to evaluate the long-term impacts of invasive species introductions and herbicide programs on native plant assemblages, water quality, and fish populations; and (G) improving the integration of chemical control technology with other aquatic plant management disciplines. While circumstances may dictate setting new priorities or dropping current ones, the list we have generated represents our vision of the needs that will require the greatest focus over the next several years.

Conference Paper

Toxicity, sublethal effects, and potential modes of action of select fungicides on freshwater fish and invertebrates

Despite decades of agricultural and urban use of fungicides and widespread detection of these pesticides in surface waters, relatively few data are available on the effects of fungicides on fish and invertebrates in the aquatic environment. Nine fungicides are reviewed in this report: azoxystrobin, boscalid, chlorothalonil, fludioxonil, myclobutanil, fenarimol, pyraclostrobin, pyrimethanil, and zoxamide. These fungicides were identified as emerging chemicals of concern because of their high or increasing global use rates, detection frequency in surface waters, or likely persistence in the environment. A review of the literature revealed significant sublethal effects of fungicides on fish, aquatic invertebrates, and ecosystems, including zooplankton and fish reproduction, fish immune function, zooplankton community composition, metabolic enzymes, and ecosystem processes, such as leaf decomposition in streams, among other biological effects. Some of these effects can occur at fungicide concentrations well below single-species acute lethality values (48- or 96-hour concentration that effects a response in 50 percent of the organisms, that is, effective concentration killing 50 percent of the organisms in 48 or 96 hours) and chronic sublethal values (for example, 21-day no observed adverse effects concentration), indicating that single-species toxicity values may dramatically underestimate the toxic potency of some fungicides. Fungicide modes of toxic action in fungi can sometimes reflect the biochemical and (or) physiological effects of fungicides observed in vertebrates and invertebrates; however, far more studies are needed to explore the potential to predict effects in nontarget organisms based on specific fungicide modes of toxic action. Fungicides can also have additive and (or) synergistic effects when used with other fungicides and insecticides, highlighting the need to study pesticide mixtures that occur in surface waters. For fungicides that partition to organic matter in sediment and soils, it is particularly important to determine their effects on freshwater mussels and other freshwater benthic invertebrates in contact with sediments, as available toxicity studies with pelagic species, mainly Daphnia magna , may not be representative of these benthic organisms. Finally, there is a critical need for studies of the chronic effects of fungicides on reproduction, immunocompetence, and ecosystem function; sublethal endpoints with population and community-level relevance.

Open-File Report

Acute toxicity of the lampricides TFM and niclosamide: Effects on a vascular plant and a chironomid species

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and niclosamide have been used for about 60 years to control sea lamprey (Petromyzon marinus) in the Great Lakes Basin and Lake Champlain. To register these chemicals as pesticides in North America, their environmental effects must be reviewed on a periodic basis. As a part of this effort, toxicity of TFM and niclosamide to duckweed (Lemna gibba), and of niclosamide to aquatic midge (Chironomus tentans), was assessed. Results of these studies suggest that for both lampricides, the no-observable and lowest observable effects concentrations (NOEC and LOEC) exceed expected environmental concentrations, with effects only in the highest concentrations tested and the longest exposure times. Duckweed exposed to TFM indicated 7-day LOECs ≥ 4.88 mg/L for average specific growth rate and yield, with the EC50 > 9.74 mg/L. For duckweed exposed to niclosamide, 7-day LOECs for average specific growth rate and yield ranged from 0.271 to 0.569 mg/L, with the IC50 0.725 mg/L or greater depending on the parameter measured. For midge larvae exposed to niclosamide-dosed sediment, the LOEC values based on survival and growth were 26.2 mg/kg and > 82.1 mg/kg, respectively, and the EC50 based on survival was 49.6 mg/kg. Based on these data, deleterious effects on aquatic plants and benthic invertebrates are unlikely to result from use of TFM and niclosamide for lamprey control, given that the effect concentrations are in excess of the expected environmental concentrations.

Great Lakes Basin, Lake Champlain

Zinc hazards to plants and animals with emphasis on fishery and wildlife resources

Ecological and toxicological aspects of zinc in the environment are reviewed with emphasis on natural resources. Subtopics include sources and uses; chemical and biochemical properties; carcinogenicity, mutagenicity, teratogenicity; background concentrations in biological and nonbiological compartments; effects of zinc deficiency; toxic and sublethal effects on terrestrial plants and invertebrates, aquatic organisms, birds, and mammals; and recommendations for the protection of sensitive resources.

Book chapter