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Biomarker similarities between the saline lacustrine Eocene Green River and the Paleoproterozoic Barney Creek Formations

The Paleoproterozoic Barney Creek Formation, which is currently interpreted as a restricted, deep marine paleoenvironment, plays a disproportionate role in our understanding of Proterozoic ocean chemistry and the rise of complex life. The Barney Creek Formation hosts several unusual biomarker features, specifically its methylhopane and carotenoid signatures. Herein, we demonstrate that the saline lacustrine Eocene Green River Formation shares a similar distribution of methylhopanes and carotenoids, which is characteristic of saline lacustrine organic matter more generally. These distinct methylhopane and carotenoid patterns are not observed together in marine organic matter of any geologic age. These results imply a saline lacustrine depositional environment for the Barney Creek Formation, which agrees with earlier but now abandoned depositional models of this formation. As a result, models of Proterozoic ocean chemistry and emergence of complex life that rely on a marine Barney Creek Formation should be re-examined. Alternatively, if Paleoproterozoic marine biomarker signatures resemble those of younger saline lacustrine systems, then this must be recognized to accurately interpret geologic biomarker and paleoenvironmental records.

Colorado, Utah

Management intensity alters decomposition via biological pathways

Current conceptual models predict that changes in plant litter chemistry during decomposition are primarily regulated by both initial litter chemistry and the stage-or extent-of mass loss. Far less is known about how variations in decomposer community structure (e.g., resulting from different ecosystem management types) could influence litter chemistry during decomposition. Given the recent agricultural intensification occurring globally and the importance of litter chemistry in regulating soil organic matter storage, our objectives were to determine the potential effects of agricultural management on plant litter chemistry and decomposition rates, and to investigate possible links between ecosystem management, litter chemistry and decomposition, and decomposer community composition and activity. We measured decomposition rates, changes in litter chemistry, extracellular enzyme activity, microarthropod communities, and bacterial versus fungal relative abundance in replicated conventional-till, no-till, and old field agricultural sites for both corn and grass litter. After one growing season, litter decomposition under conventional-till was 20% greater than in old field communities. However, decomposition rates in no-till were not significantly different from those in old field or conventional-till sites. After decomposition, grass residue in both conventional- and no-till systems was enriched in total polysaccharides relative to initial litter, while grass litter decomposed in old fields was enriched in nitrogen-bearing compounds and lipids. These differences corresponded with differences in decomposer communities, which also exhibited strong responses to both litter and management type. Overall, our results indicate that agricultural intensification can increase litter decomposition rates, alter decomposer communities, and influence litter chemistry in ways that could have important and long-term effects on soil organic matter dynamics. We suggest that future efforts to more accurately predict soil carbon dynamics under different management regimes may need to explicitly consider how changes in litter chemistry during decomposition are influenced by the specific metabolic capabilities of the extant decomposer communities.

Biogeochemistry

Reactive-transport simulation of phosphorus in the sewage plume at the Massachusetts Military Reservation, Cape Cod, Massachusetts

The subsurface transport of phosphorus introduced by the disposal of treated sewage effluent to ground-infiltration disposal beds at the Massachusetts Military Reservation on western Cape Cod was simulated with a three-dimensional reactive-transport model. The simulations were used to estimate the load of phosphorus transported to Ashumet Pond during operation of the sewage-treatment plant from 1936 to 1995 and for 60 years following cessation of sewage disposal. The model accounted for spatial and temporal changes in water discharge from the sewage-treatment plant, ground-water flow, transport of associated chemical constituents, and a set of chemical reactions, including phosphorus sorption on aquifer materials, dissolution and precipitation of iron- and manganese-oxyhydroxide and iron phosphate minerals, organic carbon sorption and decomposition, cation sorption, and irreversible denitrification. The flow and transport in the aquifer were simulated by using parameters consistent with those used in previous flow models of this area of Cape Cod, except that numerical dispersion was much larger than the physical dispersion estimated in previous studies. Sorption parameters were fit to data derived from phosphorus sorption and desorption laboratory column experiments. Rates of organic carbon decomposition were adjusted to match the location of iron concentrations in an anoxic iron zone within the sewage plume. The sensitivity of the simulated load of phosphorus transported to Ashumet Pond was calculated for a variety of processes and input parameters. Model limitations included large uncertainties associated with the loading of the sewage beds, the flow system, and the chemistry and sorption characteristics in the aquifer. The results of current model simulations indicate a small load of phosphorus transported to Ashumet Pond during 1965-85, but this small load was particularly sensitive to model parameters that specify flow conditions and the chemical process by which non-desorbable phosphorus is incorporated in the sediments. The uncertainties were large enough to make it difficult to determine whether loads of phosphorus transported to Ashumet Pond in the 1990s were greater or less than loads during the previous two decades. The model simulations indicate substantial discharge of phosphorus to Ashumet Pond after about 1965. After the period 2000-10 the simulations indicate that the load of phosphorus transported to Ashumet Pond decreases continuously, but the load of phosphorus remains substantial for many decades. The current simulations indicate a peak in phosphorus discharge to Ashumet Pond of about 1,000 kilograms per year during the 1990s; however, comparisons of simulated phosphorus concentrations with measured concentrations in 1993 indicate that the peak in phosphorus load transported to Ashumet Pond may be larger and moving more quickly in the model simulations than in the aquifer. The results of the three-dimensional reactive-transport simulations are consistent with the loading history, experimental laboratory data, and field measurements. The results of the simulations adequately reproduce the spatial distribution of phosphorus concentrations measured in 1993, the magnitude of changes in phosphorus concentration with time in a profile near the disposal beds following cessation of sewage disposal, the observed iron zone in the sewage plume, the approximate flow of treated sewage effluent into Ashumet Valley, and laboratory-column data for phosphorus sorption and desorption.

Massachusetts

The interacting roles of climate, soils, and plant production on soil microbial communities at a continental scale

Soil microbial communities control critical ecosystem processes such as decomposition, nutrient cycling, and soil organic matter formation. Continental scale patterns in the composition and functioning of microbial communities are related to climatic, biotic, and edaphic factors such as temperature and precipitation, plant community composition, and soil carbon, nitrogen, and pH. Although these relationships have been well explored individually, the examination of the factors that may act directly on microbial communities vs. those that may act indirectly through other ecosystem properties has not been well developed. To further such understanding, we utilized structural equation modeling (SEM) to evaluate a set of hypotheses about the direct and indirect effects of climatic, biotic, and edaphic variables on microbial communities across the continental United States. The primary goals of this work were to test our current understanding of the interactions among climate, soils, and plants in affecting microbial community composition, and to examine whether variation in the composition of the microbial community affects potential rates of soil enzymatic activities. A model of interacting factors created through SEM shows several expected patterns. Distal factors such as climate had indirect effects on microbial communities by influencing plant productivity, soil mineralogy, and soil pH, but factors related to soil organic matter chemistry had the most direct influence on community composition. We observed that both plant productivity and soil mineral composition were important indirect influences on community composition at the continental scale, both interacting to affect organic matter content and microbial biomass and ultimately community composition. Although soil hydrolytic enzymes were related to the moisture regime and soil carbon, oxidative enzymes were also affected by community composition, reflected in the abundance of soil fungi. These results highlight that soil microbial communities can be modeled within the context of multiple interacting ecosystem properties acting both directly and indirectly on their composition and function, and this provides a rich and informative context with which to examine communities. This work also highlights that variation in climate, microbial biomass, and microbial community composition can affect maximum rates of soil enzyme activities, potentially influencing rates of decomposition and nutrient mineralization in soils.

Ecology

Acute toxicity of sodium bicarbonate, a major component of coal bed natural gas produced waters, to 13 aquatic species as defined in the laboratory

Water produced during coal bed natural gas (CBNG) extraction in the Powder River Structural Basin of Wyoming and Montana (USA) may contain concentrations of sodium bicarbonate (NaHCO 3 ) of more than 3000 mg/L. The authors evaluated the acute toxicity of NaHCO 3 , also expressed as bicarbonate (HCO 3 − ), to 13 aquatic organisms. Of the 13 species tested, 7 had a median lethal concentration (LC50) less than 2000 mg/L NaHCO 3 , or 1300 mg/L HCO 3 − . The most sensitive species were Ceriodaphnia dubia, freshwater mussels (Lampsilis siliquoidea), pallid sturgeon (Scaphirhynchus albus), and shovelnose sturgeon (Scaphirhynchus platorynchus). The respective LC50s were 989 mg/L, 1120 mg/L, 1249 mg/L, and 1430 mg/L NaHCO 3 , or 699 mg/L, 844 mg/L, 831 mg/L, and 1038 mg/L HCO 3 − . Age affected the sensitivity of fathead minnows, even within life stage. Two days posthatch, fathead minnows were more sensitive to NaHCO 3 and HCO 3 − compared with 4-d-old fish, even though fish up to 14 d old are commonly used for toxicity evaluations. The authors recommend that ion toxicity exposures be conducted with organisms less than 24 h posthatch to ensure that experiments document the most sensitive stage of development. The results of the present study, along with historical and current research regarding the toxicity of bicarbonate, may be useful to establish regulatory standards for HCO 3 − .

Environmental Toxicology and Chemistry

Biological conditions in streams of Johnson County, Kansas, and nearby Missouri, 2003 and 2004

Johnson County is one of the fastest growing and most populated counties in Kansas. Urban development affects streams by altering stream hydrology, geomorphology, water chemistry, and habitat, which then can lead to adverse effects on fish and macroinvertebrate communities. In addition, increasing sources of contaminants in urbanizing streams results in public-health concerns associated with exposure to and consumption of contaminated water. Biological assessments, or surveys of organisms living in aquatic environments, are crucial components of water-quality programs because they provide an indication of how well water bodies support aquatic life. This fact sheet describes current biological conditions of Johnson County streams and characterizes stream biology relative to urban development. Biological conditions were evaluated by collecting macroinvertebrate samples from 15 stream sites in Johnson County, Kansas, in 2003 and 2004 (fig. 1). Data from seven additional sites, collected as part of a separate study with similar objectives in Kansas and Missouri (Wilkison and others, 2005), were evaluated to provide a more comprehensive assessment of watersheds that cross State boundaries. Land-use and water- and streambed-sediment-quality data also were used to evaluate factors that may affect macroinvertebrate communities. Metrics are indices used to measure, or evaluate, macroinvertebrate response to various factors such as human disturbance. Multimetric scores, which integrated 10 different metrics that measure various aspects of macroinvertebrate communities, including organism diversity, composition, tolerance, and feeding characteristics, were used to evaluate and compare biological health of Johnson County streams. This information is useful to city and county officials for defining current biological conditions, evaluating conditions relative to State biological criteria, evaluating effects of urbanization, developing effective water-quality management plans, and documenting changes in biological conditions and water quality.

Kansas, Missouri

Influence of sediment chemistry and sediment toxicity on macroinvertebrate communities across 99 wadable streams of the Midwestern USA

Simultaneous assessment of sediment chemistry, sediment toxicity, and macroinvertebrate communities can provide multiple lines of evidence when investigating relations between sediment contaminants and ecological degradation. These three measures were evaluated at 99 wadable stream sites across 11 states in the Midwestern United States during the summer of 2013 to assess sediment pollution across a large agricultural landscape. This evaluation considers an extensive suite of sediment chemistry totaling 274 analytes (polycyclic aromatic hydrocarbons, organochlorine compounds, polychlorinated biphenyls, polybrominated diphenyl ethers, trace elements, and current-use pesticides) and a mixture assessment based on the ratios of detected compounds to available effects-based benchmarks. The sediments were tested for toxicity with the amphipod Hyalella azteca (28-d exposure), the midge Chironomus dilutus (10-d), and, at a few sites, with the freshwater mussel Lampsilis siliquoidea (28-d). Sediment concentrations, normalized to organic carbon content, infrequently exceeded benchmarks for aquatic health, which was generally consistent with low rates of observed toxicity. However, the benchmark-based mixture score and the pyrethroid insecticide bifenthrin were significantly related to observed sediment toxicity. The sediment mixture score and bifenthrin were also significant predictors of the upper limits of several univariate measures of the macroinvertebrate community (EPT percent, MMI (Macroinvertebrate Multimetric Index) Score, Ephemeroptera and Trichoptera richness) using quantile regression. Multivariate pattern matching (Mantel-like tests) of macroinvertebrate species per site to identified contaminant metrics and sediment toxicity also indicate that the sediment mixture score and bifenthrin have weak, albeit significant, influence on the observed invertebrate community composition. Together, these three lines of evidence (toxicity tests, univariate metrics, and multivariate community analysis) suggest that elevated contaminant concentrations in sediments, in particular bifenthrin, is limiting macroinvertebrate communities in several of these Midwest streams.

Science of the Total Environment

Chapter 21 Western phosphate field - Depositional and economic deposit models

The Western Phosphate Field (WPF), composed of Permian marine sedimentary strata that cover over 300,000 km 2 in the middle Rocky Mountains of Idaho, Montana, Utah, and Wyoming in the United States, contains vast resources of phosphate mined for fertilizer and a range of other industrial applications. The richest deposits of phosphate in the WPF occur in the Meade Peak Phosphatic Shale Member of the Phosphoria Formation in southeast Idaho. Phosphate is an essential and even limiting nutrient of algal production, which occurs at the bottom of the marine food web in the oceanic photic zone. The high concentrations of phosphate and trace elements in the Phosphoria Formation reflect a low accumulation rate of diluting phases, such as terrigenous siliciclastic debris and carbonate, rather than an unusually high level of primary productivity at the time of deposition. Indeed, the mean rate of accumulation of PO 4 3 required a continuous flux of PO 4 3 into the basin and the photic zone of the water column, but only at a moderate level. This flux was maintained by upwelling of nutrient-rich seawater, imported at depth from the open ocean. Although only a fraction of the organic matter that hosted the PO 4 3 and other nutrients (NO 3 , Cd, Cu, Mo, Ni, and Zn) actually escaped oxidation in the water column, their rate of accu- mulation on the sea floor defined the basin hydrography. Rates of accumulation of Cr, U, V, and rare-earth elements by precipitation and adsorp- tion reactions identify redox conditions in the bottom water as having been denitrifying, maintained by a balance between the rate of oxidation of organic matter settling through the water column and the flux of open-ocean seawater at depth. Atmospheric mixing maintained oxygen respiration in the uppermost several tens of meters of the water column. This hydrography and seawater chemistry are present in several sedimentary envi- ronments in the ocean today. In the WPF, there is an estimated surface mineable reserve base and subeconomic resource of 7.6 billion mt, at an average grade of 24% P 2 O 5 ; a subeconomic underground- mineable resource of 17 billion mt, at a grade of 28%; and 507 billion mt of subresource- grade phosphatic material that underlie the WPF at a depth greater than 305 m. The relationship between phosphate-ore specifications and weathering suggests that significant changes in processing, with associated cost increases, will be required to extend recovery of ore below the relatively strongly weathered zone near the surface. Four open pit mines currently extract phosphate from two moderately to steeply dipping ore zones that typically contain between 20% and 35% P 2 O 5 . Although the shales are enriched in trace elements, especially As, Cd, Cr, Cu, Mo, Se, U, V, Zn, and rare-earth elements, the relative concentration of organic carbon and selected major element oxides determines the suitability of phosphate-rich rock for feed to processing plants and its other applications. Selected specifications from the four operating mines include the following: minimum P 2 O 5 of 18-20% and average of 26-27%; maximum A1 2 O 3 of 1.6-5.0%; maximum MgO of 0.3-0.6%; a CaO/P 2 O 5 ratio of 1.5-1.6; and total carbon content of 4%-5%. Weathering to a depth of as much as 100 m significantly enhances ore quality by decreasing the proportions of calcite, dolomite, and organic matter relative to carbonate fluorapatite, the primary ore mineral

Colorado, Idaho, Montana, Nebraska, North Dakota,

Evaluation of numerical sediment quality targets for the St. Louis River Area of Concern

Numerical sediment quality targets (SQTs) for the protection of sediment-dwelling organisms have been established for the St. Louis River Area of Concern (AOC), 1 of 42 current AOCs in the Great Lakes basin. The two types of SQTs were established primarily from consensus-based sediment quality guidelines. Level I SQTs are intended to identify contaminant concentrations below which harmful effects on sediment-dwelling organisms are unlikely to be observed. Level II SQTs are intended to identify contaminant concentrations above which harmful effects on sediment-dwelling organisms are likely to be observed. The predictive ability of the numerical SQTs was evaluated using the matching sediment chemistry and toxicity data set for the St. Louis River AOC. This evaluation involved determination of the incidence of toxicity to amphipods (Hyalella azteca) and midges (Chironomus tentans) within five ranges of Level II SQT quotients (i.e., mean probable effect concentration quotients [PEC-Qs]). The incidence of toxicity was determined based on the results of 10-day toxicity tests with amphipods (endpoints: survival and growth) and 10-day toxicity tests with midges (endpoints: survival and growth). For both toxicity tests, the incidence of toxicity increased as the mean PEC-Q ranges increased. The incidence of toxicity observed in these tests was also compared to that for other geographic areas in the Great Lakes region and in North America for 10- to 14-day amphipod (H. azteca) and 10- to 14-day midge (C. tentans or C. riparius) toxicity tests. In general, the predictive ability of the mean PEC-Qs was similar across geographic areas. The results of these predictive ability evaluations indicate that collectively the mean PEC-Qs provide a reliable basis for classifying sediments as toxic or not toxic in the St. Louis River AOC, in the larger geographic areas of the Great Lakes, and elsewhere in North America.

Archives of Environmental Contamination and Toxico

Restoration of Circum-Arctic Upper Jurassic source rock paleolatitude based on crude oil geochemistry

Tectonic geochemical paleolatitude (TGP) models were developed to predict the paleolatitude of petroleum source rock from the geochemical composition of crude oil. The results validate studies designed to reconstruct ancient source rock depositional environments using oil chemistry and tectonic reconstruction of paleogeography from coordinates of the present day collection site. TGP models can also be used to corroborate tectonic paleolatitude in cases where the predicted paleogeography conflicts with the depositional setting predicted by the oil chemistry, or to predict paleolatitude when the present day collection locality is far removed from the source rock, as might occur due to long distance subsurface migration or transport of tarballs by ocean currents. Biomarker and stable carbon isotope ratios were measured for 496 crude oil samples inferred to originate from Upper Jurassic source rock in West Siberia, the North Sea and offshore Labrador. First, a unique, multi-tiered chemometric (multivariate statistics) decision tree was used to classify these samples into seven oil families and infer the type of organic matter, lithology and depositional environment of each organofacies of source rock [Peters, K.E., Ramos, L.S., Zumberge, J.E., Valin, Z.C., Scotese, C.R., Gautier, D.L., 2007. Circum-Arctic petroleum systems identified using decision-tree chemometrics. American Association of Petroleum Geologists Bulletin 91, 877-913]. Second, present day geographic locations for each sample were used to restore the tectonic paleolatitude of the source rock during Late Jurassic time (???150 Ma). Third, partial least squares regression (PLSR) was used to construct linear TGP models that relate tectonic and geochemical paleolatitude, where the latter is based on 19 source-related biomarker and isotope ratios for each oil family. The TGP models were calibrated using 70% of the samples in each family and the remaining 30% of samples were used for model validation. Positive relationships exist between tectonic and geochemical paleolatitude for each family. Standard error of prediction for geochemical paleolatitude ranges from 0.9?? to 2.6?? of tectonic paleolatitude, which translates to a relative standard error of prediction in the range 1.5-4.8%. The results suggest that the observed effect of source rock paleolatitude on crude oil composition is caused by (i) stable carbon isotope fractionation during photosynthetic fixation of carbon and (ii) species diversity at different latitudes during Late Jurassic time. ?? 2008 Elsevier Ltd. All rights reserved.

Organic Geochemistry

Geochemical modeling of water-rock interactions in mining environments

Geochemical modeling is a powerful tool for evaluating geochemical processes in mining environments. Properly constrained and judiciously applied, modeling can provide valuable insights into processes controlling the release, transport, and fate of contaminants in mine drainage. This chapter contains 1) an overview of geochemical modeling, 2) discussion of the types of models and computer programs used, 3) description of a procedure for screening water analyses for modeling input, and 4) examples of the application of modeling for interpreting geochemical processes in mining environments. Three general strategies in current use to interpret water-rock interactions are statistical analysis, “inverse” modeling, and “forward” modeling. Multivariate correlation analysis, factor analysis, cluster analysis, and other statistical techniques can group water-chemistry data into sets that may relate to hydrogeochemical processes (Drever, 1988; Puckett and Bricker, 1992). In the field of geochemical exploration, statistical analysis is used widely to treat large data sets of rock and sediment chemistry (e.g., Garrett, 1989). No physical or chemical principles are involved directly in these statistical treatments, hence they are not considered further in this chapter. Nevertheless, statistical analysis can be a useful tool in organizing complex geochemical data for interpretation.

Book chapter

Long-term trends in Arctic riverine chemistry signal multi-faceted northern change

Rivers integrate processes occurring throughout their watersheds and are therefore sentinels of change across broad spatial scales. River chemistry also regulates ecosystem function across Earth’s land–ocean continuum, exerting control from the micro- (for example, local food web) to the macro- (for example, global carbon cycle) scale. In the rapidly warming Arctic, a wide range of processes—from permafrost thaw to biological uptake and transformation—might reasonably alter river water chemistry. Here we use data from major rivers that collectively drain two-thirds of the Arctic Ocean watershed to assess widespread change in biogeochemical function within the pan-Arctic basin from 2003 to 2019. While the oceanward flux of alkalinity and associated ions increased markedly over this time frame, nitrate and other inorganic nutrient fluxes declined. Fluxes of dissolved organic carbon showed no overall trend. This divergence in response indicates the perturbation of multiple processes on land, with implications for biogeochemical cycling in the coastal ocean. We anticipate that these findings will facilitate refinement of conceptual and numerical models of current and future functioning of Arctic coastal ecosystems and spur research on scale-dependent change across the river-integrated Arctic domain.

Arctic

CO 2 mitigation via accelerated limestone weathering

We evaluate accelerated weathering of limestone (AWL: CO 2 + CaCO 3 + H 2 O=> Ca 2+ + 2HCO 3 - ) as a low-tech, inexpensive, high-capacity, environmentally-friendly CO 2 capture and sequestration technology. With access to seawater and limestone being essential to this approach, significant limestone resources are close to most CO 2 -emitting power plants along the coastal US. Waste fines, representing more than 20% of current US crushed limestone production (>10 9 tonnes/yr), could be used as an inexpensive source of AWL carbonate. Under such circumstances CO 2 mitigation cost could be as low as $3-$4/tonne. More broadly, 10-20% of US point-source CO 2 emissions could be treated at $20-$30/tonne CO 2 . AWL end-solution disposal in the ocean would significantly reduce effects on ocean pH and carbonate chemistry relative to those caused by direct atmospheric or ocean CO 2 disposal. Indeed, the increase in ocean Ca 2+ and bicarbonate offered by AWL should enhance growth of corals and other calcifying marine organisms.

Conference Paper

Arsenic concentration and selected geochemical characteristics for ground water and aquifer materials in southeastern Michigan

Fifty-six private wells, 20 public wells and 38 monitoring wells in ten counties in southeastern Michigan were sampled to determine the concentration of naturally-occurring arsenic and specific geochemical parameters. The majority of ground water samples were analyzed for pH, dissolved oxygen, oxidation/reduction potential, specific conductance, major ions, dissolved and suspended organic carbon, and arsenic. Selected samples were analyzed for minor elements, nutrients, the isotope ratio of carbon and the concentration of tritium. The Mississippian Marshall Sandstone comprises a major aquifer in southeastern Michigan. To compare the lithology of the Marshall Aquifer to water chemistry, two new wells were drilled through the Marshall Sandstone to the underlying Coldwater Shale. Depth-specific bedrock and water samples were collected from these wells. For public and private drinking-water wells, the lowest concentration detected by USGS analysis was <1 microgram per liter and the highest was 220 micrograms per liter. Arsenic concentrations near or exceeding the current USEPA standard of 50 micrograms per liter occurred in ground water from each of the major aquifers in the study area. In the two newly-drilled wells, the lowest concentration detected by the USGS was <1 microgram per liter at about 350 ft below land surface and the highest concentration of 140 micrograms per liter was detected at around 50 ft below land surface. The data from this study may be used to indicate well characteristics and water chemistry factors that are related to arsenic in ground water in southeastern Michigan.

Michigan

Geochemical studies of the Green River Formation in the Piceance Basin, Colorado: I. Major, minor, and trace elements

The Eocene Green River Formation contains the largest oil shale deposits in the world and is a welldocumented example of a lacustrine depositional system. In addition, mineral resources associated with oil shale in the Piceance Basin nahcolite [NaHCO3] and dawsonite [NaAl(CO3)(OH)2)] are of current and potential economic value, respectively. Detailed geochemical analysis across the basin can aid in the understanding of the depositional environment, sedimentary processes, and water-chemistry evolution in this system. Quantitative geochemical data for Green River oil shale from the Piceance Basin of Colorado were collected by inductively coupled plasma optical emission spectroscopy and mass spectrometry as part of this study. The basin margin is represented by samples from exposures at Douglas Pass (Garfield County) and the basin center area is characterized by core samples from two drilled wells: the Shell 23X-2 and John Savage 24-1 (Rio Blanco County). Major elements and groups of elements are used as proxies for clastic influx (Si, Al, K, Ti), carbonate deposition (Ca, Mg), salinity (Na), paleo-productivity (P), and redox state (Fe, S), respectively. Minor and trace elements reinforce observations based on major elements, including Rb, Zr, Nb for clastic influx and Mn, Sr for carbonate. Trace elements are used to characterize redox conditions (As, Mo, U, V, Co, Ni, Cu, Zn) and salinity (Rb/K, B/Ga). Chemical distinctions between the basin margin and the basin center, in terms of these components and total organic carbon concentrations, support the model of a permanently stratified lake through most of the depositional interval. A primary purpose of the study was to conduct more extensive sampling to confirm conclusions of a previous reconnaissance study. Geochemical data from this study indicates elevated Na around the basin margin occurring earlier than in the deeper basin. Early in the history of Lake Uinta, the salinity may have been elevated first in the shallower marginal waters, due to increased evaporation, which then led to elevated salinity in the basin center through transport of saline density currents. Other indicators of salinity (Rb/K, B/Ga) do not track Na content in intervals where clay minerals are absent due to diagenetic alteration under hypersaline conditions but may be used to indicate the salinities at which authigenic Na-bearing minerals begin to form. Most Na-rich samples show high proportions of clastic constituents (Si, Al, K, Ti) compared to conventional carbonate constituents (Ca, Mg). Redox-sensitive period IV transition metal elements (V, Co, Ni, Cu, Zn) show only local occurrence of significant enrichment relative to average shale abundances. Analysis of Fe/Al ratios for this dataset suggests that the depletion of these elements may be related to source rocks depleted in mafic constituents, with apparent redox-related enrichments subdued by this effect. The basin margin samples reflect generally oxic bottom waters, with some intervals deposited under more reducing, possibly dysoxic to anoxic conditions. The basin center results indicate more reducing conditions, with Mo and U enrichment factors suggesting operation of a particulate shuttle mechanism that scavenged Mo on Fe/Mn-oxyhydroxides that redissolved at depth, with Mo precipitating along with sulfides and/or organic matter at or near the sediment/water interface.

Colorado

Critical review: Grand challenges in assessing the adverse effects of contaminants of emerging concern on aquatic food webs

Much progress has been made in the past few decades in understanding the sources, transport, fate, and biological effects of contaminants of emerging concern (CECs) in aquatic ecosystems. Despite these advancements, significant obstacles still prevent comprehensive assessments of the environmental risks associated with the presence of CECs. Many of these obstacles center around the extrapolation of effects of single chemicals observed in the laboratory or effects found in individual organisms or species in the field to impacts of multiple stressors on aquatic food webs. In the present review, we identify 5 challenges that must be addressed to promote studies of CECs from singular exposure events to multispecies aquatic food web interactions. There needs to be: 1) more detailed information on the complexity of mixtures of CECs in the aquatic environment, 2) a greater understanding of the sublethal effects of CECs on a wide range of aquatic organisms, 3) an ascertaining of the biological consequences of variable duration CEC exposures within and across generations in aquatic species, 4) a linkage of multiple stressors with CEC exposure in aquatic systems, and 5) a documenting of the trophic consequences of CEC exposure across aquatic food webs. We examine the current literature to show how these challenges can be addressed to fill knowledge gaps.

Environmental Toxicology and Chemistry

Environmental persistence and toxicity of weathered wildland fire retardants to rainbow trout

Long-term fire retardants are employed to combat and control wildfires by altering the way fuels burn, and they continue to decrease fire intensity after water in the retardant solution has evaporated. After application, fire retardants may persist on dry stream beds or in riparian habitats before precipitation events flush the retardant into intermittent streams. We exposed juvenile (30–60 days post swim-up) rainbow trout ( Oncorhynchus mykiss ) to fire retardants weathered for 7–56 days on different substrates (duff, gravel, high organic content soil, and low organic content soil) under static conditions for 96 h to evaluate the potential toxicity of two current-use long-term fire-retardant (LC95A-R and MVP-Fx) products. Trout mortality was greater in LC95A-R treatments compared to MVP-Fx due to higher concentrations of LC95A-R in the applied product than MVP-Fx at the same application rate. Underlying substrate affected fire-retardant toxicity, with 31% higher average mortality for products applied to duff and gravel compared to soil. Differences in mortality across substrates and products after weathering may be attributed to differences in the mix ratio of applied product and interactions of product chemistries with underlying substrate. These interactions resulted in elevated ionic concentrations of the overlying water in duff and gravel treatments. Trout mortality decreased 15% for products weathered 56 days compared to 7 days. Our results suggest that long-term fire retardants may persist in the environment and that underlying substrate may alter the toxicity of these products upon entrance into an intermittent stream.

Archives of Environmental Contamination and Toxico

Suppressing bullfrog larvae with carbon dioxide

Current management strategies for the control and suppression of the American Bullfrog ( Lithobates catesbeianus = Rana catesbeiana Shaw) and other invasive amphibians have had minimal effect on their abundance and distribution. This study evaluates the effects of carbon dioxide (CO 2 ) on pre- and prometamorphic Bullfrog larvae. Bullfrogs are a model organism for evaluating potential suppression agents because they are a successful invader worldwide. From experimental trials we estimated that the 24-h 50% and 99% lethal concentration (LC 50 and LC 99 ) values for Bullfrog larvae were 371 and 549 mg CO 2 /L, respectively. Overall, larvae that succumbed to experimental conditions had a lower body condition index than those that survived. We also documented sublethal changes in blood chemistry during prolonged exposure to elevated CO 2 . Specifically, blood pH decreased by more than 0.5 pH units after 9 h of exposure and both blood partial pressure of CO 2 (pCO 2 ) and blood glucose increased. These findings suggest that CO 2 treatments can be lethal to Bullfrog larvae under controlled laboratory conditions. We believe this work represents the necessary foundation for further consideration of CO 2 as a potential suppression agent for one of the most harmful invaders to freshwater ecosystems.

Journal of Herpetology