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Supercritical fluid carbon dioxide extraction and liquid chromatographic separation with electrochemical detection of methylmercury from biological samples

Using the coupled methods presented in this paper, methylmercury can be accurately and rapidly extracted from biological samples by modified supercritical fluid carbon dioxide and quantitated using liquid chromatography with reductive electrochemical detection. Supercritical fluid carbon dioxide modified with methanol effectively extracts underivatized methylmercury from certified reference materials Dorm-1 (dogfish muscle) and Dolt-2 (dogfish liver). Calcium chloride and water, with a ratio of 5:2 (by weight), provide the acid environment required for extracting methylmercury from sample matrices. Methylmercury chloride is separated from other organomercury chloride compounds using HPLC. The acidic eluent, containing 0.06 mol L-1 NaCl, insures the presence of methylmercury chloride and facilitates the reduction of mercury on a glassy carbon electrode. If dual glassy carbon electrodes are used, a positive peak is observed at -0.65 to -0.70 V and a negative peak is observed at -0.90V with the organomercury compounds that were tested. The practical detection limit for methylmercury is 5 X 10-8 mol L-1 (1 X 10-12 tool injected) when a 20 ??L injection loop is used.

International Journal of Environmental Analytical ↗

Methylmercury in subarctic amphibians: Environmental gradients, bioaccumulation, and estimated flux

Rapid warming in polar regions is causing large changes to ecosystems, including altering environmentally available mercury (Hg). Although subarctic freshwater systems have simple vertebrate communities, Hg in amphibians remains unexplored. We measured total Hg (THg) in wetland sediments and methylmercury (MeHg) in multiple life-stages (eggs to adults) of wood frogs ( Rana sylvatica ) and larval boreal chorus frogs ( Pseudacris maculata ) from up to 25 wetlands near Churchill, Manitoba (Canada), during the summers of 2018–2019. We used egg mass counts for wood frogs from 24 wetlands (2015–2019) and per-ovum MeHg concentrations to estimate site-level MeHg flux by metamorphs from wetlands to the terrestrial environment. Total Hg in wetland sediment was unrelated to MeHg concentrations of amphibian larvae, but sediment THg increased with from coastal tundra vegetation to inland boreal forests. Methylmercury concentrations of wood frog eggs (geometric mean = 35.9; range: 6.7–77.9 ng/g dry wt) exceeded previous reports for amphibians, including from sites contaminated by industrial sources of Hg. Methylmercury concentrations of adult wood frogs (298.9 ng/g dry wt) were also higher than that for frogs included in a recent assessment of MeHg in amphibians across the contiguous United States. Within wetlands, MeHg concentrations of wood frog larvae were strongly correlated with MeHg concentrations in eggs earlier in the summer, and concentrations increased with each life stage. We estimate there would have been 1,971.8–3,286.4 ng MeHg exported from wetlands by wood frog metamorphs, which is 3.4–5.6 times more MeHg than inputted by eggs. Collectively, these data provide an initial assessment of Hg concentrations, body burdens, and dynamics in subarctic food webs that are expected to experience large changes from climate warming.

Manitoba↗

Acute Toxicity of 4-hydroxydiphenylamine (4-HDPA) and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone (6PPDQ), transformation products of 6PPD, to early instars of the mayfly, Neocloeon triangulifer

Our analysis of water samples collected during a rain event from two urban rivers in the Greater Toronto area, Ontario, Canada, indicated that selected transformation products (TPs) of the tire antioxidant, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), including 6PPD-quinone (6PPDQ) and 4-hydroxydiphenylamine (4-HDPA), were present at concentrations >1 µg/L. In acute (96-hr) toxicity tests with aquatic larvae of the mayfly Neocloeon triangulifer , 6PPDQ did not cause mortalities at the highest test concentration, which was just below the limit of solubility. In toxicity tests with 4-HDPA, a calculated 96-hr median lethal concentration of 339 µg/L is above environmentally relevant concentrations. However, in toxicity tests with 6PPD, there was evidence that the degradation of this tire wear compound produced unknown TPs that caused mortalities in exposed mayfly larvae. Additional work could identify other TPs of 6PPD that could be a hazard to aquatic invertebrates exposed to tire wear compounds transported into surface waters from transportation corridors.

Ontario↗

Ground-water contamination by organic bases derived from coal-tar wastes

A fluid sample from a shallow aquifer contaminated by coal-tar wastes was analyzed for organic bases. The sample consisted of a mixture of aqueous and oily-tar phases. The phases were separated by centrifugation and filtration. Organic bases were isolated from each phase by pH adjustment and solvent extraction. Organic bases in the oily-tar phase were further purified by neutral-alumina, micro-column adsorption chromatography. Separation and identification of the organic bases in each phase were achieved by using capillary gas chromatography-mass spectrometry-computer (GC-MS-COM) and probe distillation-high resolution mass spectrometry (PD-HRMS) techniques. Organic bases present in the aqueous phase included primary aromatic amines (such as aniline, alkylated anilines, and naphthylamines) as well as azaarenes (such as alkylated pyridines, quinolines, acridine, and benzoquinolines). The oily-tar phase contained acridine, benzacridines, dibenzacridines, and numerous other azaarenes, the elemental compositions of which were determined by PD-HRMS. Azaarenes in the oily-tar phase, varying in size from 6 to 12 rings, are reported for the first time. The origin and environmental significance of these compounds are discussed.

Environmental Toxicology and Chemistry↗

Simulation of branched serial first-order decay of atrazine and metabolites in adapted and nonadapted soils

In the present study a branched serial first-order decay (BSFOD) model is presented and used to derive transformation rates describing the decay of a common herbicide, atrazine, and its metabolites observed in unsaturated soils adapted to previous atrazine applications and in soils with no history of atrazine applications. Calibration of BSFOD models for soils throughout the country can reduce the uncertainty, relative to that of traditional models, in predicting the fate and transport of pesticides and their metabolites and thus support improved agricultural management schemes for reducing threats to the environment. Results from application of the BSFOD model to better understand the degradation of atrazine supports two previously reported conclusions: atrazine (6-chloro- N -ethyl- N ′-(1-methylethyl)-1,3,5-triazine-2,4-diamine) and its primary metabolites are less persistent in adapted soils than in nonadapted soils; and hydroxyatrazine was the dominant primary metabolite in most of the soils tested. In addition, a method to simulate BSFOD in a one-dimensional solute-transport unsaturated zone model is also presented.

Environmental Toxicology and Chemistry↗

Effects of hardness and alkalinity in culture and test waters on reproduction of Ceriodaphnia dubia

Ceriodaphnia dubia were cultured in four reconstituted water formulations with hardness and alkalinity concentrations ranging from soft to the moderately hard water that is required by whole-effluent toxicity (WET) testing methods for culturing test organisms. The effects of these culture formulations alone and in combination with two levels of Cl-, SO42, and HCO3- on reproduction of C. dubia were evaluated with the standard three-brood test. Reproduction was significantly reduced when test waters had lower hardness than culture waters. However, reproduction was not significantly different when animals cultured in low-hardness waters were exposed to moderately hard waters. The hardness of the culture water did not significantly affect the sensitivity of C. dubia to the three anions. Conversely, increased hardness in test waters significantly reduced the toxicities of Cl- and SO42-, with HCO3- toxicity following the same pattern. Alkalinity exhibited no consistent effect on Cl- and SO42- toxicity. The physiological stress of placing animals cultured in moderately hard water into softer test waters might contribute to marginal failures of otherwise nontoxic effluents. The standard WET protocol should be revised to allow the culture of C. dubia under lower hardness conditions to better represent local surface water chemistries.

Environmental Toxicology and Chemistry↗

The types of data needed for assessing the environmental and human health impacts of coal

Coal is one of the most important sources of energy. Its worldwide use will continue to expand during the next several decades, particularly in rapidly developing countries such as China and India. Unfortunately, coal use may bring with it environmental and human health costs. Many of the environmental and health problems attributed to coal combustion are due to mobilization of potentially toxic elements. Some of these problems could be minimized or even avoided if comprehensive databases containing appropriate coal quality information were available to decision makers so that informed decisions could be made regarding coal use. Among the coal quality parameters that should be included in these databases are: C, H, N, O, pyritic sulfur, organic sulfur, major, minor, and trace element concentrations, modes of occurrence of environmentally sensitive elements, cleanability, mineralogy, organic chemistry, petrography, and leachability.Coal is one of the most important sources of energy. Its worldwide use will continue to expand during the next several decades, particularly in rapidly developing countries such as China and India. Unfortunately, coal use may bring with it environmental and human health costs. Many of the environmental and health problems attributed to coal combustion are due to mobilization of potentially toxic elements. Some of these problems could be minimized or even avoided if comprehensive databases containing appropriate coal quality information were available to decision makers so that informed decisions could be made regarding coal use. Among the coal quality parameters that should be included in these databases are: C, H, N, O, pyritic sulfur, organic sulfur, major, minor, and trace element concentrations, modes of occurrence of environmentally sensitive elements, cleanability, mineralogy, organic chemistry, petrography, and leachability.

International Journal of Coal Geology↗

Environmental characteristics and benthic invertebrate assemblages in Colorado mountain lakes

Twenty-two high-elevation lakes (>3000 m) in Rocky Mountain National Park and Indian Peaks Wilderness Area, Colorado, were surveyed during summer 1998 to explore relationships among benthic invertebrates, water chemistry (particularly nitrate concentrations), and other environmental variables. Water samples were collected from the deepest portion of each lake and analyzed for ions and other water chemistry parameters. Benthic invertebrates were collected from the littoral zone using both a sweep net and Hess sampler. Physical and geographical measurements were derived from maps. Relationships among benthic invertebrate assemblages and environmental variables were examined using canonical correspondence analysis, and the importance of sampling methodology and taxonomie resolution on these relationships was evaluated. Choice of sampling methodology strongly influenced the outcome of statistical analyses, whereas taxonomie resolution did not. Presence/absence of benthic invertebrate taxa among the study lakes was best explained by elevation and presence of fish. Relative abundance and density of benthic invertebrate taxa were more strongly influenced by sampling date and water chemistry. Nitrate (NO₃⁻) concentration, potentially on the rise due to regional nitrogen deposition, was unrelated to benthic invertebrate distribution regardless of sampling method or taxonomie resolution.

Western North American Naturalist↗

Choosing indicators of natural resource condition: A case study in Arches National Park, Utah, USA

Heavy visitor use in many areas of the world have necessitated development of ways to assess visitation impacts. Arches National Park recently completed a Visitor Experience and Resource Protection (VERP) plan. Integral to this plan was developing a method to identify biological indicators that would both measure visitor impacts and response to management actions. The process used in Arches for indicator selection is outlined here as a model applicable to many areas facing similar challenges. The steps were: (1) Vegetation types most used by visitors were identified. Impacted and unimpacted areas in these types were sampled, comparing vegetation and soil factors. (2) Variables found to differ significantly between compared sites were used as potential indicators. (3) Site-specific criteria for indicators were developed, and potential indicators evaluated using these criteria. (4) Chosen indicators were further researched for ecological relevancy. (5) Final indicators were chosen, field tested, and monitoring sites designated. In Arches, indicators were chosen for monitoring annually (soil crust index, soil compaction, number of used social trails and soil aggregate stability) and every five years (vegetation cover and frequency; ground cover; soil chemistry; and plant tissue chemistry).

Environmental Management↗

Temporal change in biological community structure in the Fountain Creek basin, Colorado, 2001-2008

In 2001, the U.S. Geological Survey, in cooperation with Colorado Springs City Engineering, began a study to better understand the relations between environmental characteristics and biological communities in the Fountain Creek basin in order to aide water-resource management and guide future monitoring activities. To accomplish this task, environmental (streamflow, habitat, and water chemistry) and biological (fish and macroinvertebrate) data were collected annually at 24 sites over a 6- or 8-year period (fish, 2003 to 2008; macroinvertebrates, 2001 to 2008). For this report, these data were first analyzed to determine the presence of temporal change in macroinvertebrate and fish community structure among years using nonparametric multivariate statistics. Where temporal change in the biological communities was found, these data were further analyzed using additional nonparametric multivariate techniques to determine which subset of selected streamflow, habitat, or water-chemistry variables best described site-specific changes in community structure relative to a gradient of urbanization. This study identified significant directional patterns of temporal change in macroinvertebrate and fish community structure at 15 of 24 sites in the Fountain Creek basin. At four of these sites, changes in environmental variables were significantly correlated with the concurrent temporal change identified in macroinvertebrate and fish community structure (Monument Creek above Woodmen Road at Colorado Springs, Colo.; Monument Creek at Bijou Street at Colorado Springs, Colo.; Bear Creek near Colorado Springs, Colo.; Fountain Creek at Security, Colo.). Combinations of environmental variables describing directional temporal change in the biota appeared to be site specific as no single variable dominated the results; however, substrate composition variables (percent substrate composition composed of sand, gravel, or cobble) collectively were present in 80 percent of the environmental variable subsets that were significantly correlated with temporal change in the macroinvertebrate and fish community structure. Other important environmental variables related to temporal change in the biological community structure included those describing channel form (streambank height) and streamflow (normalized annual mean daily flow, high flood-pulse count). Site-specific results from this study were derived from a relatively small number of observations (6 or 8 years of data); therefore, additional years of data may reveal other sites with temporal change in biological community structure, or could define stronger and more consistent linkages between environmental variables and observed temporal change. Likewise current variable subsets could become weaker. Nonetheless, there were several sites where temporal change was detected in this study that could not be explained by the available environmental variables studied herein. Modification of current data-collection activities may be necessary to better understand site-specific temporal relations between biological communities and environmental variables.

Scientific Investigations Report↗

Genotoxicity in native fish associated with agricultural runoff events

The primary objective of the present study was to test whether agricultural chemical runoff was associated with in-stream genotoxicity in native fish. Using Sacramento sucker (Catostomus occidentalis), we combined field-caging experiments in an agriculturally dominated watershed with controlled laboratory exposures to field-collected water samples, and we coupled genotoxicity biomarker measurements in fish with bacterial mutagenicity analysis of water samples. We selected DNA strand breakage as a genotoxicity biomarker and Ames Salmonella mutagenicity tests as a second, supporting indicator of genotoxicity. Data from experiments conducted during rainfall runoff events following winter application of pesticides in 2000 and 2001 indicated that DNA strand breaks were significantly elevated in fish exposed to San Joaquin River (CA, USA) water (38.8, 28.4, and 53.6% DNA strand breakage in year 2000 field, year 2000 lab, and year 2001 field exposures, respectively) compared with a nearby reference site (15.4, 8.7, and 12.6% DNA strand breakage in year 2000 field, year 2000 lab, and year 2001 field exposures, respectively). Time-course measurements in field experiments supported a linkage between induction of DNA strand breakage and the timing of agricultural runoff. San Joaquin River water also caused significant reversion mutation in two Ames Salmonella tester strains. Salmonella mutagenicity corroborated in-stream effects, further strengthening a causal relationship between runoff events and genotoxicity. Potentially responsible agents are discussed in the context of timing of runoff events in the field, concordance between laboratory and field exposures, pesticide application patterns in the drainage, and analytical chemistry data.

Environmental Toxicology and Chemistry↗

Water quality in the vicinity of Mosquito Creek Lake, Trumbull County, Ohio, in relation to the chemistry of locally occurring oil, natural gas, and brine

Environmental samples collected in the Mosquito Creek Lake area were used to characterize water quality in relation to the chemistry of locally occurring oil, natural gas, and brine and to establish baseline water quality. Mosquito Creek Lake (a manmade reservoir) and the shallow bedrock aquifers near the lake are major sources of potable water in central Trumbull County. The city of Warren relies on the lake as a sole source of potable water. Some of the lake bottom may be in direct hydraulic connection with the underlying aquifers. The city of Cortland, along the southeastern shore of the lake, relies on the Cussewago Sandstone aquifer as a sole source of potable water. This aquifer subcrops beneath the glacio-fluvial sediments that underlie the lake. Nearly all residential homes around the lake, with the exception of homes in the city of Cortland, rely on domestic supply wells as a source of potable water. Oil and natural gas exploration and production have been ongoing in the Mosquito Creek Lakearea since the discovery of the historic Mecca Oil Pool in the Mississippian Berea and Cussewago Sandstones in 1860. Since the late 1970' s, the major drilling objective and zone of production is the Lower Silurian Clinton sandstone. The oil and natural gas resources of the Mosquito Creek Lake area, including reservoir pressure, production history, and engineering and abandonment practices are described in this report. The chemical and isotopic characteristics of the historic Mecca oil and natural gas are very different than those of the Clinton sandstone oil and natural gas. Gas chromatograms show that Mecca oil samples are extensively altered by biodegradation, whereas Clinton sandstone oils are not. Extensive alteration of Mecca oil is consistent with their occurrence at very shallow depths (less than 100 ft below land surface) where microbial activity can affect their composition. Also, the carbon-isotope composition of dissolved methane gas from Berea and Cussewago Sandstone water samples indicates that the gas is microbially generated, whereas the Clinton sandstone gases are thermogenically generated. Methane gas, in addition to crude oil, occurs naturally in the shallow Berea and Cussewago Sandstone aquifers in the Mosquito Creek Lake area and concentrations of dissolved methane are significant in the city of Cortland public-supply wells and in the domestic-supply wells near the southern shore of the lake. Water associated with oil and gas in the Clinton sandstone is a brine with high concentrations of chloride. Water from the Berea and Cussewago Sandstones, however, is fresh and potable. The contrasting geochemical characteristics are important for addressing water-quality issues that relate to oil and natural gas development in the Mosquito Creek area. A reexamination of the geologic framework and results of a subsurface-gas survey show that crude oil in the historic Mecca Oil Pool probably does not seep into Mosquito Creek Lake. Environmental samples show no evidence of any measurable release of oil, gas, or brine from the deeper Clinton sandstone oil and gas wells to the shallow aquifers, the lake, or lake tributaries. Brine is not associated with the hydrocarbons in the shallow Berea-Cussewago aquifer system and therefore cannot be a source of brine contamination. A mixing diagram constructed for dissolved bromide and chloride in surface water and water-supply wells shows no demonstrable mixing of these water resources with brine from the Clinton sandstone. There is some notable salinity in surface waters; however, the water is bromide poor, and a mixing diagram indicates that some local ground waters are influenced by halite solutions, presumably derived from leaching of road salt or from septic effluent.

Ohio↗

Identifying biotic integrity and water chemistry relations in nonwadeable rivers of Wisconsin: Toward the development of nutrient criteria

We sampled 41 sites on 34 nonwadeable rivers that represent the types of rivers in Wisconsin, and the kinds and intensities of nutrient and other anthropogenic stressors upon each river type. Sites covered much of United States Environmental Protection Agency national nutrient ecoregions VII-Mostly Glaciated Dairy Region, and VIII-Nutrient Poor, Largely Glaciated upper Midwest. Fish, macroinvertebrates, and three categories of environmental variables including nutrients, other water chemistry, and watershed features were collected using standard protocols. We summarized fish assemblages by index of biotic integrity (IBI) and its 10 component measures, and macroinvertebrates by 2 organic pollution tolerance and 12 proportional richness measures. All biotic and environmental variables represented a wide range of conditions, with biotic measures ranging from poor to excellent status, despite nutrient concentrations being consistently higher than reference concentrations reported for the regions. Regression tree analyses of nutrients on a suite of biotic measures identified breakpoints in total phosphorus (~0.06 mg/l) and total nitrogen (~0.64 mg/l) concentrations at which biotic assemblages were consistently impaired. Redundancy analyses (RDA) were used to identify the most important variables within each of the three environmental variable categories, which were then used to determine the relative influence of each variable category on the biota. Nutrient measures, suspended chlorophyll a, water clarity, and watershed land cover type (forest or row-crop agriculture) were the most important variables and they explained significant amounts of variation within the macroinvertebrate (R 2 = 60.6%) and fish (R 2 = 43.6%) assemblages. The environmental variables selected in the macroinvertebrate model were correlated to such an extent that partial RDA analyses could not attribute variation explained to individual environmental categories, assigning 89% of the explained variation to interactions among the categories. In contrast, partial RDA attributed much of the explained variation to the nutrient (25%) and other water chemistry (38%) categories for the fish model. Our analyses suggest that it would be beneficial to develop criteria based upon a suite of biotic and nutrient variables simultaneously to deem waters as not meeting their designated uses. ?? 2007 Springer Science+Business Media, LLC.

Environmental Management↗

Adaptations of indigenous bacteria to fuel contamination in karst aquifers in south-central Kentucky

The karst aquifer systems in southern Kentucky can be dynamic and quick to change. Microorganisms that live in these unpredictable aquifers are constantly faced with environmental changes. Their survival depends upon adaptations to changes in water chemistry, taking advantage of positive stimuli and avoiding negative environmental conditions. The U.S. Geological Survey conducted a study in 2001 to determine the capability of bacteria to adapt in two distinct regions of water quality in a karst aquifer, an area of clean, oxygenated groundwater and an area where the groundwater was oxygen depleted and contaminated by jet fuel. Water samples containing bacteria were collected from one clean well and two jet fuel contaminated wells in a conduit-dominated karst aquifer. Bacterial concentrations, enumerated through direct count, ranged from 500,000 to 2.7 million bacteria per mL in the clean portion of the aquifer, and 200,000 to 3.2 million bacteria per mL in the contaminated portion of the aquifer over a twelve month period. Bacteria from the clean well ranged in size from 0.2 to 2.5 mm, whereas bacteria from one fuel-contaminated well were generally larger, ranging in size from 0.2 to 3.9 mm. Also, bacteria collected from the clean well had a higher density and, consequently, were more inclined to sink than bacteria collected from contaminated wells. Bacteria collected from the clean portion of the karst aquifer were predominantly (,95%) Gram-negative and more likely to have flagella present than bacteria collected from the contaminated wells, which included a substantial fraction (,30%) of Gram-positive varieties. The ability of the bacteria from the clean portion of the karst aquifer to biodegrade benzene and toluene was studied under aerobic and anaerobic conditions in laboratory microcosms. The rate of fuel biodegradation in laboratory studies was approximately 50 times faster under aerobic conditions as compared to anaerobic, sulfur-reducing conditions. The optimum pH for fuel biodegradation ranged from 6 to 7. These findings suggest that bacteria have adapted to water-saturated karst systems with a variety of active and passive transport mechanisms.

Kentucky↗

Integrated assessment of runoff from livestock farming operations: analytical chemistry, in vitro bioassays, and in vivo fish exposures

Animal waste from livestock farming operations can contain varying levels of natural and synthetic androgens and/or estrogens, which can contaminate surrounding waterways. In the present study, surface stream water was collected from 6 basins containing livestock farming operations. Aqueous concentrations of 12 hormones were determined via chemical analyses. Relative androgenic and estrogenic activity was measured using in vitro cell assays (MDA-kb2 and T47D-Kbluc assays, respectively). In parallel, 48-h static-renewal in vivo exposures were conducted to examine potential endocrine-disrupting effects in fathead minnows. Mature fish were exposed to surface water dilutions (0%, 25%, 50%, and 100%) and 10-ng/L of 17α-ethynylestradiol or 50-ng/L of 17β-trenbolone as positive controls. Hepatic expression of vitellogenin and estrogen receptor α mRNA, gonadal ex vivo testosterone and 17β-estradiol production, and plasma vitellogenin concentrations were examined. Potentially estrogenic and androgenic steroids were detected at low nanogram per liter concentrations. In vitro estrogenic activity was detected in all samples, whereas androgenic activity was detected in only 1 sample. In vivo exposures to the surface water had no significant dose-dependent effect on any of the biological endpoints, with the exception of increased male testosterone production in 1 exposure. The present study, which combines analytical chemistry measurements, in vitro bioassays, and in vivo fish exposures, highlights the integrated value and future use of a combination of techniques to obtain a comprehensive characterization of an environmental chemical mixture.

Arkansas, Iowa, Kentucky, New York, Wisconsin↗

Role of edaphic, hydrologic, and land cover variables in determining dissolved organic carbon in Missouri (USA) reservoirs and streams

In Missouri, distinct geophysical gradients influence statewide patterns in water quality. Here, we quantify the spatiotemporal variability of dissolved organic carbon (DOC) in reservoirs and streams and the edaphic, hydrologic, and land cover variables that account for cross-system variation. Datasets included statewide inventories collected over decades and studies with greater temporal resolution ( n = >6350 DOC measurements). Among reservoirs, the smallest DOC concentration was measured in a spring-fed system within a forested watershed, and the largest was where agricultural biosolids were applied to the land (range 1.0–15.9 mg/L, overall mean 5.8 mg/L). Reservoir values increased from the southern forested Highlands (mean 4.7 mg/L) to the northern agricultural Plains (mean 7.0 mg/L). Stream DOC was similar to reservoir values (overall mean in streams 6.3 mg/L; Highlands mean 4.0 mg/L; Plains mean 6.6 mg/L), despite differences in study design and collection period. Reservoir DOC increased in spring, indicative of allochthonous loading, with small autochthonous additions during a broad summer peak. Temporal variability in DOC was low relative to macronutrients and chlorophyll in both reservoirs and streams, indicating DOC may be a sensitive and readily detected indicator of temporal change in these systems. In regression analyses, watershed features accounted for more than 60% of overall cross-system variability in DOC in both reservoirs and streams. Driver-response relations, however, differed between regions. This analysis extends our understanding of environmental influences on surface water chemistry in Missouri and indicates DOC is nearly as predictable as macronutrients using landscape-level features.

Missouri↗

Understanding ocean acidification impacts on organismal to ecological scales

Ocean acidification (OA) research seeks to understand how marine ecosystems and global elemental cycles will respond to changes in seawater carbonate chemistry in combination with other environmental perturbations such as warming, eutrophication, and deoxygenation. Here, we discuss the effectiveness and limitations of current research approaches used to address this goal. A diverse combination of approaches is essential to decipher the consequences of OA to marine organisms, communities, and ecosystems. Consequently, the benefits and limitations of each approach must be considered carefully. Major research challenges involve experimentally addressing the effects of OA in the context of large natural variability in seawater carbonate system parameters and other interactive variables, integrating the results from different research approaches, and scaling results across different temporal and spatial scales.

Oceanography↗

Temporal changes in aquatic-invertebrate and fish assemblages in streams of the north-central and northeastern U.S.

Many management agencies seek to evaluate temporal changes in aquatic assemblages at monitoring sites, but few have sites with ecological time series that are long enough for this purpose. Trends in aquatic-invertebrate and fish assemblage composition were assessed at 27 long-term monitoring sites in the north-central and northeastern United States. Temporal changes were identified using serial trend analysis. Sites with significant serial trends were further evaluated by relating explanatory environmental variables (e.g., streamflow, habitat, and water chemistry) to changes in assemblage composition. Significant trends were found at 19 of 27 study sites; however, differences in the sensitivity of the aquatic fauna to environmental stressors were identified. For example, significant trends in fish assemblages were found at more sites (15 of 27) than for aquatic-invertebrate assemblages (10 of 27 sites). In addition, trends in the invertebrate assemblage were most often explained by changes in streamflow processes (e.g., duration and magnitude of low- and high-flows, streamflow variability, and annual rates of change), whereas trends in the fish assemblage were more related to changes in water chemistry. Results illustrate the value of long-term monitoring for the purpose of assessing temporal trends in aquatic assemblages. The ability to detect trends in assemblage composition and to attribute these changes to environmental factors is necessary to understand mechanistic pathways and to further our understanding of how incremental anthropogenic alterations modify aquatic assemblages over time. Finally, this study's approach to trends analysis can be used to better inform the design of monitoring programs as well as support the ongoing management needs of stakeholders, water-resource agencies, and policy makers.

Connecticut, Illinois, Indiana, Iowa, Massachusett↗