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

Diflubenzuron (1(4chlorophenyl)3(2,6difluorobenzoyl)urea), also known as dimilin, is a potent broad spectrum insect growth regulator that interferes with chitin synthesis at time of molting and is effective in controlling immature stages of insects. Diflubenzuron was approved for domestic use in 1976 to control gypsy moth (Lymantria dispar), and in 1979 against the cotton boll weevil (Anthonomus grandis). By 1989 this compound was also registered for domestic use against mosquitos, forest Lepidoptera, mushroom flies, and leaf-eating insect pests of citrus, woody ornamentals, vegetables, and fruit. Diflubenzuron seldom persists for more than a few days in soil and water. When used properly in forest management, it is unlikely to be leached into ground water from the application site. Degradation in water and soil is most rapid when small particle formulations are applied; microorganisms are abundant; and at elevated pH, temperature, and organic loading. Chemical and biological processes initially yield 2,6difluorobenzoic acid and 4chlorophenylurea.

Contaminant Hazard Reviews

Model structure of the stream salmonid simulator (S3)—A dynamic model for simulating growth, movement, and survival of juvenile salmonids

Fisheries and water managers often use population models to aid in understanding the effect of alternative water management or restoration actions on anadromous fish populations. We developed the Stream Salmonid Simulator (S3) to help resource managers evaluate the effect of management alternatives on juvenile salmonid populations. S3 is a deterministic stage-structured population model that tracks daily growth, movement, and survival of juvenile salmon. A key theme of the model is that river flow affects habitat availability and capacity, which in turn drives density dependent population dynamics. To explicitly link population dynamics to habitat quality and quantity, the river environment is constructed as a one-dimensional series of linked habitat units, each of which has an associated daily time series of discharge, water temperature, and usable habitat area or carrying capacity. The physical characteristics of each habitat unit and the number of fish occupying each unit, in turn, drive survival and growth within each habitat unit and movement of fish among habitat units. The purpose of this report is to outline the underlying general structure of the S3 model that is common among different applications of the model. We have developed applications of the S3 model for juvenile fall Chinook salmon ( Oncorhynchus tshawytscha ) in the lower Klamath River. Thus, this report is a companion to current application of the S3 model to the Trinity River (in review). The general S3 model structure provides a biological and physical framework for the salmonid freshwater life cycle. This framework captures important demographics of juvenile salmonids aimed at translating management alternatives into simulated population responses. Although the S3 model is built on this common framework, the model has been constructed to allow much flexibility in application of the model to specific river systems. The ability for practitioners to include system-specific information for the physical stream structure, survival, growth, and movement processes ensures that simulations provide results that are relevant to the questions asked about the population under study.

Open-File Report

Approaches to modeling weathered regolith

Sustainable soils are a requirement for maintaining human civilizations ( Carter and Dale 1974 ; Lal 1989 ). However, as the “most complicated biomaterial on the planet” ( Young and Crawford 2004 ), soils represent one of the most difficult systems to understand and model with respect to chemical, physical, and biological coupling over time (Fig. 1 ). Despite the complexity of these interactions, certain patterns in soil properties and development are universally observed and have been used in soil science as a means for classification. Elemental, mineralogical, or isotopic concentrations in soils plotted versus depth beneath the land surface comprise such patterns. Soil depth profiles are often reported for solid soil materials, and, less frequently, for solutes in soil pore waters. These profiles cross a large range in spatial scales that traditionally have been studied by different disciplines. For example, shallow, biologically active horizons are commonly defined as the soil zone in agronomic studies whereas the mobile layer of the regolith is referred to as soil in geomorphological studies. In contrast, many geochemical studies target chemical weathering to tens or even hundreds of meters in depth, sometimes extending the definition of “soils” to include the entire regolith down to parent bedrock or alluvium. Soil profiles also exhibit a large range in temporal scales ( Amundson 2004 ; Brantley 2008b ). Solid-state profiles document chemical and mineralogical changes integrated over the time scales of evolution of regolith from protolith. This “geologic time” can vary from tens to hundreds of years for weathered material developed on moraines deposited by active glaciers ( Anderson et al. 1997 ), to millions or possibly hundreds of millions of years of regolith evolution as documented in laterites and bauxites on stable cratons ( Nahon 1986 ). In contrast, solute profiles reflect much shorter time scales corresponding to the residence time of the soil water which commonly ranges from days to decades ( Stonestrom et al. 1998 ). Factors impacting soil minerals can therefore be related to geologically old processes while those impacting pore waters are related to contemporary processes. We first discuss a geochemical frame work for modeling soil profiles, including a simple scheme that depends on the extent of enrichment or depletion. Such profiles are comprised of reaction fronts affected by chemical, hydrologic, geologic and biologic processes that control soil evolution. We then present a hierarchy of models that have been used to interpret both solid state and solute compositions in regolith. The more simple approaches to model depletion in soils, using analytical models, are first described. The most elementary of these is a linear model that calculates rate constants from the slopes of either solid or solute weathering gradients: these rate constants represent lumped parameters that describe weathering in terms of an integrated reaction rate. Two other analytical models are then presented that have been used to fit solid state elemental profiles with exponential and sigmoidal functions. All of these analytical approaches are derived for models of soils as containing a limited number of components, phases, and species. At a more complex level, numerical models are then presented to elucidate how kinetic and transport parameters as well as chemical, hydrologic, and physical soil data can be incorporated. We consider two forms of these models, first relatively simple spreadsheet calculators and then more sophisticated multi-component, multi-phase reactive-transport numerical codes. Our treatment of reactive transport modeling is relatively cursory, in recognition of the treatment in the chapter by Steefel and Maher (2009 , this volume). Because these models incorporate more phases, components, and species than the other approaches and explicitly model the more fundamental reaction mechanisms involved, they generally have a greater need for parameterization. In our conclusion section, we discuss how this hierarchy of approaches can yield generalizations about soils that are often complementary.

Reviews in Mineralogy and Geochemistry

Hydrologic, sediment, and biological data associated with irrigation drainage in the middle Green River basin, Utah and Colorado, water years 1991-2000

Hydrologic, sediment, and biological data were collected in the middle Green River basin in eastern Utah from 1991 to 2000 in an effort to monitor the effects of irrigation drainage on wetland areas and streams, aid in the development of remediation plans, and evaluate the effectiveness of selenium remediation efforts at Stewart Lake Waterfowl Management Area (WMA). Data consist primarily of selenium concentrations in surface water, ground water, bottom sediment, and biological samples. Supporting hydrologic data include field measurements of temperature, pH, specific conductance, water levels in wells, and discharge at surface-water sites. Selected water samples also were analyzed for major ions, trace elements, nutrients, and gross alpha and beta radiation. The concentration of selected selenium species is reported for several bottom-sediment samples from Stewart Lake WMA and the concentration of total selenium in suspended-sediment samples from the area are included. Well logs for six wells installed at Stewart Lake WMA are presented along with trace-element data for several biological samples collected at selected sites throughout the middle Green River basin.

Colorado, Utah, Wyoming

Avian Species Inventory at Manzanar National Historic Site, California - Final Report to the National Park Service

We conducted a baseline inventory for avian species at Manzanar National Historic Site, Inyo County, Calif., from 2002 to 2005. Under the guidelines of the Mojave Network Biological Inventory Program, the primary objectives for this study were to (1) inventory and document the occurrence of avian species at Manzanar, with the goal of documenting at least 90 percent of the species present; (2) provide a geographic information system (GIS)-referenced list of sensitive species occurring at Manzanar that are rare, on Federal or State lists, or otherwise worthy of special consideration; and (3) enter all species data into the National Park Service NPSpecies database. Survey methods included general area searches, variable circular plot point-count censusing, nocturnal surveys, and nest searching. During 13 year-round survey sessions, we documented the occurrence of 132 bird species at Manzanar and confirmed breeding by 19 of these. Based on our findings, as well as review of the literature and searches for records of species occurrence, we estimate inventory completeness for regularly occurring bird species at Manzanar to be near 90 percent. No sensitive species on Federal or State lists were found. The distribution and relative abundance of common bird species at this site is now well enough known to begin development of a monitoring protocol for this group.

Open-File Report

Potential effects of energy development on environmental resources of the Williston Basin in Montana, North Dakota, and South Dakota—Species of conservation concern

The ecosystems of the Williston Basin provide direct and indirect benefits to society. These benefits include carbon sequestration, flood control, nutrient rich soils for agricultural productivity, and habitat for wildlife. This chapter’s main focus is on the effects of energy development on species that occupy the ecosystems in the Williston Basin. We compiled a list of documented species of conservation concern that are of most interest to Federal regulators and resource managers. Species of concern were either listed as endangered or threatened under the Endangered Species Act or listed by States as species of concern in Natural Heritage Program checklists or State Wildlife Action Plans. All told, we determined that 357 species of concern likely occupy the Williston Basin. These species represented seven different taxonomic groups: plants (native and nonnative), terrestrial invertebrates, birds, mammals, reptiles and amphibians, and fish and mussels. We reviewed the existing scientific information pertaining to potential effects of energy development on these taxonomic groups. Currently, little is known about the abundance and distribution of many of these species. But some information exists that may be useful in predicting the potential effects of energy development on certain taxonomic groups. Most of this information has been developed through scientific research focused on effects to mammal and bird populations. Effects to other taxonomic groups seems to be understudied. In general, it seems that disturbances and modifications associated with development have the potential to negatively affect a wide range of species; however, many studies produce uncertain results because they are not designed to compare populations before and after energy development takes place. Most of these studies also do not monitor resources over multiple years and thus cannot detect population trends. Likewise, there are few examples of landscape-scale assessments of the cumulative effects of energy development that could be used for species or habitat management purposes. We suggest that more research needs to be completed to measure potential effects to a broad range of species in multiple taxonomic groups. This may require also developing some understanding about the basic ecology of many of the species covered in this report. In concert with this more basic research, we also suggest that more comprehensive assessments of potential negative cumulative effects across the Williston Basin should be developed in an effort to guide more strategic management of biological resources.

Montana, North Dakota, South Dakota

Development and application of indices to assess the condition of benthic algal communities in U.S. streams and rivers

Multi-metric indices (MMIs) are a measure of a combination of characteristics of biological communities and are used as indicators of water quality and ecological health. Although MMIs for algal communities have been developed for specific regions of the United States, none of the indices have national applicability. The MMIs described in this report were developed by the National Water-Quality Assessment Program of the U.S. Geological Survey to assess the overall health of benthic algal communities in U.S. streams and rivers within five geographic regions that encompass the conterminous United States.The traditional procedure for developing MMIs (also referred to as indices of biological integrity) is to select individual metrics that, separately, can distinguish between undisturbed sites (selected for this study as reference sites) and predetermined disturbed sites. The metrics are then combined into a single index. In addition to traditional approaches for selecting individual metrics, the current study used stepwise logistic regressions to select sets of metrics that best predicted whether sites were in an undisturbed or a disturbed condition. Multi-metric indices and logistic regression models were developed for five regions of the United States using calibration datasets and were evaluated using independent validation datasets.

Open-File Report

Water-quality, streambed-sediment, and biological data from the Clark Fork-Pend Oreille and Spokane River basins, Montana, Idaho, and Washington, 1998-2001

Water-quality, streambed-sediment, and biological data were collected in the Clark Fork-Pend Oreille and Spokane River basins as part of the U.S. Geological Survey's National Water-Quality Assessment Program and are presented in this report. These river basins compose the Northern Rockies Intermontane Basins study unit which was selected to include a river system that has a mixture of forested, agricultural, urban, and developing areas. Waterquality samples were collected from 28 surface-water sites and 86 ground-water sites from June 1998 to September 2001. Data collected included measurements of physical properties and chemical analyses of concentrations of major ions, trace elements, nutrients, organic carbon, pesticides, volatile organic compounds, and radiochemical constituents. Streambed-sediment and biological tissue samples were collected from 41 sites and analyzed for trace elements and organochlorine compounds. Benthic algae were collected to determine chlorophyll concentration and areal density.

Idaho, Montana, Washington

Water-quality assessment of the upper Illinois River Basin in Illinois, Indiana, and Wisconsin: Major and trace elements in water, sediment, and biota, 1978-90

The distribution of 22 major and trace elements was examined in water, sediment, and biota in the upper Illinois River Basin in Illinois, Indiana, and Wisconsin as part of a pilot National Water-Quality Assessment project done by the U.S. Geological Survey from 1987 through 1990. The 22 elements are aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, chromium, cobalt, copper, iron, lead, manganese, mercury, molybdenum, nickel, phosphorus, selenium, silver, strontium, vanadium, and zinc. Concentrations of U.S. Environmental Protection Agency (USEPA) priority pollutants among the 22 elements were elevated in the Chicago area in all three aquatic components (water, sediment, and biota). Further, some of the priority pollutants also were found at elevated concentrations in biota in agricultural areas in the basin. Cadmium, chromium, copper, iron, lead, mercury, silver, and zinc concentrations in water exceeded USEPA acute or chronic water-quality criteria at several sites in the Chicago area. Correlations among concentrations of elements in water, sediment, and biota were found, but the correlation analysis was hindered by the large proportion of observations less than the minimum reporting level in water. Those sites where water-quality criteria were sometimes exceeded were not always the same sites where concentrations in biota were the largest. This relation indicates that accumulation of these pollutants in biota is confounded by complex geochemical and biological processes that differ throughout the upper Illinois River Basin.

Illinois, Indiana, Wisconsin

Risk-based prioritization of organic chemicals and locations of ecological concern in sediment from Great Lakes tributaries

With improved analytical techniques, environmental monitoring studies are increasingly able to report the occurrence of tens or hundreds of chemicals per site, making it difficult to identify the most relevant chemicals from a biological standpoint. For this study, organic chemical occurrence was examined, individually and as mixtures, in the context of potential biological effects. Sediment was collected at 71 Great Lakes tributary sites and analyzed for 87 chemicals. Multiple risk-based lines of evidence were used to prioritize chemicals and locations, including comparing sediment concentrations and estimated porewater concentrations to established whole-organism benchmarks (i.e., sediment and water quality criteria and screening values) and to high-throughput toxicity screening data from the U.S. Environmental Protection Agency's ToxCast database, estimating additive effects of chemical mixtures on common ToxCast endpoints, and estimating toxic equivalencies for mixtures of alkylphenols and polycyclic aromatic hydrocarbons (PAHs). This multiple-lines-of-evidence approach enabled the screening of more chemicals, mitigated the uncertainties of individual approaches, and strengthened common conclusions. Collectively, at least one benchmark/screening value was exceeded for 54 of the 87 chemicals, with exceedances observed at all 71 of the monitoring sites. Chemicals with the greatest potential for biological effects, both individually and as mixture components, were bisphenol A, 4-nonylphenol, indole, carbazole, and several polycyclic aromatic hydrocarbons (PAHs). Potential adverse outcomes based on ToxCast gene targets and putative adverse outcome pathways relevant to individual chemicals and chemical mixtures included tumors, skewed sex ratios, reproductive dysfunction, hepatic steatosis, and early mortality, among others. Results provide a screening level prioritization of chemicals with the greatest potential for adverse biological effects and an indication of sites where they are most likely to occur.

Illinois, Indiana, Michigan, Minnesota, New York,

Food, beverage, and feedstock processing facility wastewater: A unique and underappreciated source of contaminants to U.S. streams

Process wastewaters from food, beverage, and feedstock facilities, although regulated, are an under-investigated environmental contaminant source. Food process wastewaters (FPWWs) from 23 facilities in 17 U.S. states were sampled and documented for a plethora of chemical and microbial contaminants. Of the 576 analyzed organics, 184 (32%) were detected at least once, with concentrations as large as 143 μg L –1 (6:2 fluorotelomer sulfonic acid), and as many as 47 were detected in a single FPWW sample. Cumulative per/polyfluoroalkyl substance concentrations up to 185 μg L –1 and large pesticide transformation product concentrations (e.g., methomyl oxime, 40 μg L –1 ; clothianidin TMG, 2.02 μg L –1 ) were observed. Despite 48% of FPWW undergoing disinfection treatment prior to discharge, bacteria resistant to third-generation antibiotics were found in each facility type, and multiple bacterial groups were detected in all samples, including total coliforms. The exposure–activity ratios and toxicity quotients exceeded 1.0 in 13 and 22% of samples, respectively, indicating potential biological effects and toxicity to vertebrates and invertebrates associated with the discharge of FPWW. Organic contaminant profiles of FPWW differed from previously reported contaminant profiles of municipal effluents and urban storm water, indicating that FPWW is another important source of chemical and microbial contaminant mixtures discharged into receiving surface waters.

Alabama, Arkansas, California, Idaho, Illinois, Io