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At least 1,189 records · Page 66Linked to original sources

Binding of polychlorinated biphenyls to aquatic humic substances: The role of substrate and sorbate properties on partitioning

Two ortho- (2,2‘,5 and 2,2‘,5,6‘) and a non-ortho- (3,3‘,4,4‘) substituted polychlorinated biphenyl (PCB) congeners were used to study the effects of sorbate structure in binding processes to two lacustrine fulvic acids. Binding constants were determined by solubility enhancement of the solutes by the fulvic acids. The binding of the ortho-trichlorobiphenyl was significantly less than the non-ortho-substituted tetrachlorobiphenyl to both fulvic acids. Surprisingly, the measured ortho-trichlorobiphenyl binding constant to both fulvic acids was approximately the same as the ortho-substituted tetrachlorobiphenyl. The effect of the chlorines in the ortho position inhibits free rotation around the 1,1‘ carbon bond, thereby making the molecule less able to interact effectively with the fulvic acid substrate relative to its non-ortho-substituted congeners. Finally, binding of all three PCBs to the Great Dismal Swamp fulvic acid was significantly higher than for the Pony Lake sample. This observation is attributable to the former substrate's higher degree of aromaticity and polarizability, which can potentially interact more favorably with the PCBs through an increase in van der Waals type interactions.

Environmental Science & Technology↗

Multi-region assessment of chemical mixture exposures and predicted cumulative effects in USA wadeable urban/agriculture-gradient streams

Chemical-contaminant mixtures are widely reported in large stream reaches in urban/agriculture-developed watersheds, but mixture compositions and aggregate biological effects are less well understood in corresponding smaller headwaters , which comprise most of stream length, riparian connectivity, and spatial biodiversity. During 2014–2017, the U.S. Geological Survey (USGS) measured 389 unique organic analytes (pharmaceutical, pesticide, organic wastewater indicators) in 305 headwater streams within four contiguous United States (US) regions. Potential aquatic biological effects were evaluated for estimated maximum and median exposure conditions using multiple lines of evidence, including occurrence/concentrations of designed-bioactive pesticides and pharmaceuticals and cumulative risk screening based on vertebrate-centric ToxCast™ exposure-response data and on invertebrate and nonvascular plant aquatic life benchmarks. Mixed-contaminant exposures were ubiquitous and varied, with 78% (304) of analytes detected at least once and cumulative maximum concentrations up to more than 156,000 ng/L. Designed bioactives represented 83% of detected analytes. Contaminant summary metrics correlated strong-positive (rho (ρ): 0.569–0.719) to multiple watershed-development metrics, only weak-positive to point-source discharges (ρ: 0.225–353), and moderate- to strong-negative with multiple instream invertebrate metrics (ρ: −0.373 to −0.652). Risk screening indicated common exposures with high probability of vertebrate-centric molecular effects and of acute toxicity to invertebrates, respectively. The results confirm exposures to broad and diverse contaminant mixtures and provide convincing multiple lines of evidence that chemical contaminants contribute substantially to adverse multi-stressor effects in headwater-stream communities.

Science of the Total Environment↗

Nekton density patterns and hurricane recovery in submerged aquatic vegetation, and along non-vegetated natural and created edge habitats

We compared nekton habitat value of submerged aquatic vegetation, flooded non-vegetated natural and man-made edge habitats in mesohaline interior marsh areas in southwest Louisiana using a 1-m 2 throw trap and 3-mm bag seine. When present, SAV habitats supported close to 4 times greater densities and higher species richness of nekton as compared to either natural or man-made edge habitats, which supported similar densities to one another. Three species of concern (bayou killifish, diamond killifish, chain pipefish) were targeted in the analysis, and two of the three were collected almost entirely in SAV habitat. During the course of the study, Hurricanes Ike and Gustav passed directly over the study sites in September 2008. Subsequent analyses indicated significant reductions in resident nekton density 1-mo post hurricanes, and only limited recovery 13-mo post-hurricane. Possible alteration of environmental characteristics such as scouring of SAV habitat, deposition of sediment over SAV, edge erosion and marsh loss, and extended high salinities may explain these lasting impacts

Louisiana↗

Trophodynamics of per- and polyfluoroalkyl substances in the food web of a large Atlantic slope river

Per- and polyfluoroalkyl substances (PFASs) have attracted scientific and regulatory attention due to their persistence, bioaccumulative potential, toxicity, and global distribution. We determined the accumulation and trophic transfer of 14 PFASs (5 short-chain and 9 long-chain) within the food web of the Yadkin-Pee Dee River of North Carolina and South Carolina, US. Food web components and pathways were determined by stable isotope analyses of producers, consumers, and organic matter. Analyses of water, sediment, organic matter, and aquatic biota revealed that PFASs were prevalent in all food web compartments. Biofilm, an aggregation of bacteria, fungi, algae, and protozoans and a basal resource for the aquatic food web, showed high PFAS accumulation (in 10 of 14 compounds), particularly for perfluorooctanoic acid, with the greatest mean concentration of 463.73 ng/g. The food web compartment with the most detections and greatest concentrations of PFASs was aquatic insects; all 14 PFASs were detected in individual aquatic insect samples (range of <limit of detection [<LOD] to 1670.10 ng/g of wet weight [WW]). These findings may suggest a trophic link between biofilm PFASs and aquatic insect PFASs. Individual fish tissue samples ranged from <LOD to 797.00 ng/g of WW, where perfluorooctanesulfonate (PFOS) was the dominant PFAS among all samples (64%). The ova of an imperiled fish, the robust redhorse ( Moxostoma robustum ), had concentrations of 10 PFASs (range of <LOD to 482.88 ng/g of WW) and the highest PFOS concentration (482.88 ng/g of WW), indicating a likely maternal transfer. The trophic magnification factors (TMFs) calculated in this study showed that various taxa accumulated PFAS compounds differently. PFBS, a short-chain PFAS compound that would presumably exhibit lesser TMFs, had nine values among our compartments and organisms >1.0 (range of 0.57 to 2.33); it is possible that an unmeasured PFBS precursor may be accumulating in biota and metabolizing to PFBS, leading to a higher than expected TMFs for this compound. Our findings demonstrate the prevalence of PFASs in a freshwater food web with potential implications for ecological and human health.

North Carolina, South Carolina↗

Lifetime chronicles of selenium exposure linked to deformities in an imperiled migratory fish

Aquatic ecosystems worldwide face growing threats from elevated levels of contaminants from human activities. Toxic levels of selenium (Se) shown to cause deformities in birds, fish, and mammals can transfer from parents to progeny during embryonic development or accumulate through Se-enriched diets. For migratory species that move across landscapes, tracking exposure to elevated Se is vital to mitigating vulnerabilities. Yet, traditional toxicological investigations resolve only recent Se exposure. Here, we use a novel combination of X-ray fluorescence microscopy and depositional chronology in a biomineral to reveal for the first time provenance, life stage, and duration of toxic Se exposure over the lifetime of an organism. Spinal deformities observed in wild Sacramento Splittail ( Pogonichthys macrolepidotus ), an imperiled migratory minnow, were attributed to elevated Se acquired through maternal transfer and juvenile feeding on contaminated prey. This novel approach paves the way for diagnosing sources, pathways, and potential for a cumulative exposure of Se relevant for conservation.

California↗

Wetland drying linked to variations in snowmelt runoff across Grand Teton and Yellowstone national parks

In Grand Teton and Yellowstone national parks wetlands offer critical habitat and play a key role in supporting biological diversity. The shallow depths and small size of many wetlands make them vulnerable to changes in climate compared with larger and deeper aquatic habitats. Here, we use a simple water balance model to generate estimates of biophysical drivers of wetland change. We then examine the relationship between wetland inundation status and four principal drivers (i.e., temperature, precipitation, evapotranspiration, and runoff) spanning varying meteorological conditions over an 8-year time series from Grand Teton and Yellowstone national parks. We found that a higher percentage of surveyed wetlands were dry in years characterized by lower snowmelt runoff. While runoff-based models were most supported, wetland drying was also related to variations in April to June precipitation and temperatures. Our work shows that wetland drying was widespread across both parks, but sub-regional variations were best described at the hydrologic subbasin-level. Documenting the varying responses of wetlands to meteorological drivers is a necessary first step to identifying which subbasins are most sensitive to recent change and contemplating how future change may alter the distribution of wetlands and their dependent taxa.

Idaho, Montana, Wyoming↗

Aquatic concentrations of chemical analytes compared to ecotoxicity estimates

We describe screening level estimates of potential aquatic toxicity posed by 227 chemical analytes that were measured in 25 ambient water samples collected as part of a joint USGS/USEPA drinking water plant study. Measured concentrations were compared to biological effect concentration (EC) estimates, including USEPA aquatic life criteria, effective plasma concentrations of pharmaceuticals, published toxicity data summarized in the USEPA ECOTOX database, and chemical structure-based predictions. Potential dietary exposures were estimated using a generic 3-tiered food web accumulation scenario. For many analytes, few or no measured effect data were found, and for some analytes, reporting limits exceeded EC estimates, limiting the scope of conclusions. Results suggest occasional occurrence above ECs for copper, aluminum, strontium, lead, uranium, and nitrate. Sparse effect data for manganese, antimony, and vanadium suggest that these analytes may occur above ECs, but additional effect data would be desirable to corroborate EC estimates. These conclusions were not affected by bioaccumulation estimates. No organic analyte concentrations were found to exceed EC estimates, but ten analytes had concentrations in excess of 1/10th of their respective EC: triclocarban, norverapamil, progesterone, atrazine, metolachlor, triclosan, para-nonylphenol, ibuprofen, venlafaxine, and amitriptyline, suggesting more detailed characterization of these analytes.

Science of the Total Environment↗

Seasonal differences and grazing pressure alter the fate of gold nanoparticles in a microcosm experiment

Gold nanoparticles (AuNPs) are used as models to track and predict NP fates and effects in ecosystems. Previous work found that aquatic macrophytes and their associated biofilm primarily drove the fate of AuNPs within aquatic ecosystems and that seasonality was an important abiotic factor in the fate of AuNPs. Therefore, the present work aims to study if grazers, by feeding on these interfaces, modify the AuNP fate and if this is altered by seasonal fluctuations. Microcosms were dosed with 44.8 μg/L of AuNP weekly for 4 weeks and maintained in environmental chambers simulating Spring and Fall light and temperature conditions. We discovered that seasonal changes and the presence of grazers significantly altered the fate of Au. Higher temperatures in the warmer season increased dissolved organic carbon (DOC) content in the water column, leading to stabilization of Au in the water column. Additionally, snail grazing on biofilm growing on the Egeria densa surface led to a transfer of Au from macrophytes to the organic matter above the sediments. These results demonstrate that climate and grazers significantly impacted the fate of Au from AuNPs, highlighting the role that grazers might have in a large and biologically more complex ecosystem.

Environmental Science & Technology↗

Success of lake restoration depends on spatial aspects of nutrient loading and hydrology

Many aquatic ecosystems have deteriorated due to human activities and their restoration is often troublesome. It is proposed here that the restoration success of deteriorated lakes critically depends on hitherto largely neglected spatial heterogeneity in nutrient loading and hydrology. A modelling approach is used to study this hypothesis by considering four lake types with contrasting nutrient loading (point versus diffuse) and hydrology (seepage versus drainage). By comparing the longterm effect of common restoration measures (nutrient load reduction, lake flushing or biomanipulation) in these four lake types, we found that restoration through reduction of nutrient loading is effective in all cases. In contrast, biomanipulation only works in seepage lakes with diffuse nutrient inputs, while lake flushing will even be counterproductive in lakes with nutrient point sources. The main conclusion of the presented analysis is that a priori assessment of spatial heterogeneity caused by nutrient loading and hydrology is essential for successful restoration of lake ecosystems.

Science of the Total Environment↗

Urban sprawl leaves its PAH signature

The increasing vehicle traffic associated with urban sprawl in the United States is frequently linked to degradation of air quality, but its effect on aquatic sediment is less well-recognized. This study evaluates trends in PAHs, a group of contaminants with multiple urban sources, in sediment cores from 10 reservoirs and lakes in six U.S. metropolitan areas. The watersheds chosen represent a range in degree and age of urbanization. Concentrations of PAHs in all 10 reservoirs and lakes increased during the past 20-40 years. PAH contamination of the most recently deposited sediment at all sites exceeded sediment-quality guidelines established by Environment Canada, in some cases by several orders of magnitude. These results add a new chapter to the story told by previous coring studies that reported decreasing concentrations of PAHs after reaching highs in the 1950s. Concurrent with the increase in concentrations is a change in the assemblage of PAHs that indicates the increasing trends are driven by combustion sources. The increase in PAH concentrations tracks closely with increases in automobile use, even in watersheds that have not undergone substantial changes in urban land-use levels since the 1970s.The increasing vehicle traffic associated with urban sprawl in the United States is frequently linked to degradation of air quality, but its effect on aquatic sediment is less well-recognized. This study evaluates trends in PAHs, a group of contaminants with multiple urban sources, in sediment cores from 10 reservoirs and lakes in six U.S. metropolitan areas. The watersheds chosen represent a range in degree and age of urbanization. Concentrations of PAHs in all 10 reservoirs and lakes increased during the past 20-40 years. PAH contamination of the most recently deposited sediment at all sites exceeded sediment-quality guidelines established by Environment Canada, in some cases by several orders of magnitude. These results add a new chapter to the story told by previous coring studies that reported decreasing concentrations of PAHs after reaching highs in the 1950s. Concurrent with the increase in concentrations is a change in the assemblage of PAHs that indicates the increasing trends are driven by combustion sources. The increase in PAH concentrations tracks closely with increases in automobile use, even in watersheds that have not undergone substantial changes in urban land-use levels since the 1970s.

Environmental Science & Technology↗

Incorporating projected climate conditions to map future riparian refugia

Identifying areas expected to remain buffered from climate change and maintain biodiversity and ecological function (i.e., climate refugia) is important for climate adaptation planning. As structurally diverse transitional zones between terrestrial and aquatic environments, riparian areas are often biological hotspots and provide critical corridors for species movement, particularly in arid and semi-arid regions. In our study region in the western and central USA, identifying riparian areas that could serve as climate refugia is a priority for wildlife managers. We mapped areas with connected riparian habitats that, based on landscape diversity and projected changes in summer temperatures and landscape runoff, are expected to serve as climate refugia. To incorporate uncertainty and balance the need for near- and long-term planning, we mapped potential refugia for 2 future time periods (2040–2069, 2070–2099) based on 2 climate models that represented divergent but plausible climate outcomes. The approach we developed is not constrained by physiology or behavior of target species and can be used to identify areas expected to fare comparatively well under a wide range of future climate scenarios. Our approach can also be used to identify areas where restoration could increase riparian connectedness and climate resilience.

Colorado, Indiana, Kansas, Montana, North Dakota, ↗

Unifying concepts linking dissolved organic matter composition to persistence in aquatic ecosystems

The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δ 13 C-dissolved organic carbon (DOC) and Δ 14 C-DOC), optical properties (absorbance and fluorescence), and molecular composition (ultrahigh resolution mass spectrometry). Isolates encompassed end-members of allochthonous and autochthonous DOM from sites across the United States, the Pacific Ocean, and Antarctic lakes. Modern Δ 14 C-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA 254 ), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δ 13 C-DOC and optical properties reflecting autochthonous end-members were positively correlated to more aliphatic compounds. Furthermore, the two sets of autochthonous end-members (Pacific Ocean and Antarctic lakes) exhibited distinct molecular composition due to differences in extent of degradation. Across all sites and end-members studied, we find a consistent shift in composition with aging, highlighting the persistence of certain biomolecules concurrent with degradation time.

Environmental Science & Technology↗

High-frequency data reveal deicing salts drive elevated specific conductance and chloride along with pervasive and frequent exceedances of the U.S. Environmental Protection Agency aquatic life criteria for chloride in urban streams

Increasing specific conductance (SC) and chloride concentrations [Cl] negatively affect many stream ecosystems. We characterized spatial variability in SC, [Cl], and exceedances of Environmental Protection Agency [Cl] criteria using nearly 30 million high-frequency observations (2–15 min intervals) for SC and modeled [Cl] from 93 sites across three regions in the eastern United States: Southeast, Mid-Atlantic, and New England. SC and [Cl] increase substantially from south to north and within regions with impervious surface cover (ISC). In the Southeast, [Cl] weakly correlates with ISC, no [Cl] exceedances occur, and [Cl] concentrations are constant with time. In the Mid-Atlantic and New England, [Cl] and [Cl] exceedances strongly correlate with ISC. [Cl] criteria are frequently exceeded at sites with greater than 9–10% ISC and median [Cl] higher than 30–80 mg/L. Tens to hundreds of [Cl] exceedances observed annually at most of these sites help explain previous research where stream ecosystems showed changes at (primarily nonwinter) [Cl] as low as 30–40 mg/L. Mid-Atlantic chronic [Cl] exceedances occur primarily in December–March. In New England, exceedances are common in nonwinter months. [Cl] is increasing at nearly all Mid-Atlantic and New England sites with the largest increases at sites with higher [Cl].

Environmental Science and Technology↗

Declining acidic deposition begins reversal of forest-soil acidification in the northeastern U.S. and eastern Canada

Decreasing trends in acidic deposition levels over the past several decades have led to partial chemical recovery of surface waters. However, depletion of soil Ca from acidic deposition has slowed surface water recovery and led to the impairment of both aquatic and terrestrial ecosystems. Nevertheless, documentation of acidic deposition effects on soils has been limited, and little is known regarding soil responses to ongoing acidic deposition decreases. In this study, resampling of soils in eastern Canada and the northeastern U.S. was done at 27 sites exposed to reductions in wet SO 4 2 &ndash; deposition of 5.7&ndash;76%, over intervals of 8&ndash;24 y. Decreases of exchangeable Al in the O horizon and increases in pH in the O and B horizons were seen at most sites. Among all sites, reductions in SO 4 2 &ndash; deposition were positively correlated with ratios (final sampling/initial sampling) of base saturation ( P < 0.01) and negatively correlated with exchangeable Al ratios ( P < 0.05) in the O horizon. However, base saturation in the B horizon decreased at one-third of the sites, with no increases. These results are unique in showing that the effects of acidic deposition on North American soils have begun to reverse.

Environmental Science & Technology↗

Molecular signature of organic nitrogen in septic-impacted groundwater

Dissolved inorganic and organic nitrogen levels are elevated in aquatic systems due to anthropogenic activities. Dissolved organic nitrogen (DON) arises from various sources, and its impact could be more clearly constrained if specific sources were identified and if the molecular-level composition of DON were better understood. In this work, the pharmaceutical carbamazepine was used to identify septic-impacted groundwater in a coastal watershed. Using ultrahigh resolution mass spectrometry data, the nitrogen-containing features of the dissolved organic matter in septic-impacted and non-impacted samples were compared. The septic-impacted groundwater samples have a larger abundance of nitrogen-containing formulas. Impacted samples have additional DON features in the regions ascribed as ‘protein-like’ and ‘lipid-like’ in van Krevelen space and have more intense nitrogen-containing features in a specific region of a carbon versus mass plot. These features are potential indicators of dissolved organic nitrogen arising from septic effluents, and this work suggests that ultrahigh resolution mass spectrometry is a valuable tool to identify and characterize sources of DON.

Environmental Science: Processes and Impacts↗

Wildfires influence mercury transport, methylation, and bioaccumulation in headwater streams of the Pacific Northwest

The increasing frequency and severity of wildfires are among the most visible impacts of climate change. However, the effects of wildfires on mercury (Hg) transformations and bioaccumulation in stream ecosystems are poorly understood. We sampled soils, water, sediment, in-stream leaf litter, periphyton, and aquatic invertebrates in 36 burned (one-year post fire) and 21 reference headwater streams across the northwestern U.S. to evaluate the effects of wildfire occurrence and severity on total Hg (THg) and methylmercury (MeHg) transport and bioaccumulation. Suspended particulate THg and MeHg concentrations were 89 and 178% greater in burned watersheds compared to unburned watersheds and increased with burn severity, likely associated with increased soil erosion. Concentrations of filter-passing THg were similar in burned and unburned watersheds, but filter-passing MeHg was 51% greater in burned watersheds, and suspended particles in burned watersheds were enriched in MeHg but not THg, suggesting higher MeHg production in burned watersheds. Among invertebrates, MeHg in grazers, filter-feeders, and collectors was 33, 48, and 251% greater in burned watersheds, respectively, but did not differ in shredders or predators. Thus, increasing wildfire frequency and severity may yield increased MeHg production, mobilization, and bioaccumulation in headwaters and increased transport of particulate THg and MeHg to downstream environments.

Idaho, Oregon, Washington↗

Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances

The number- and weight-averaged molecular weights of a number of aquatic fulvic acids, a commercial humic acid, and unfractionated organic matter from four natural water samples were measured by high-pressure size exclusion chromatography (HPSEC). Molecular weights determined in this manner compared favorably with those values reported in the literature. Both recent literature values and our data indicate that these substances are smaller and less polydisperse than previously believed. Moreover, the molecular weights of the organic matter from three of the four natural water samples compared favorably to the fulvic acid samples extracted from similar environments. Bulk spectroscopic properties of the fulvic substances such as molar absorptivity at 280 nm and the E4/E6 ratio were also measured. A strong correlation was observed between molar absorptivity, total aromaticity, and the weight average molecular weights of all the humic substances. This observation suggests that bulk spectroscopic properties can be used to quickly estimate the size of humic substances and their aromatic contents. Both parameters are important with respect to understanding humic substance mobility and their propensity to react with both organic and inorganic pollutants.

Environmental Science & Technology↗

Evaluating early-warning indicators of critical transitions in natural aquatic ecosystems

Ecosystems can show sudden and persistent changes in state despite only incremental changes in drivers. Such critical transitions are difficult to predict, because the state of the system often shows little change before the transition. Early-warning indicators (EWIs) are hypothesized to signal the loss of system resilience and have been shown to precede critical transitions in theoretical models, paleo-climate time series, and in laboratory as well as whole lake experiments. The generalizability of EWIs for detecting critical transitions in empirical time series of natural aquatic ecosystems remains largely untested, however. Here we assessed four commonly used EWIs on long-term datasets of five freshwater ecosystems that have experienced sudden, persistent transitions and for which the relevant ecological mechanisms and drivers are well understood. These case studies were categorized by three mechanisms that can generate critical transitions between alternative states: competition, trophic cascade, and intraguild predation. Although EWIs could be detected in most of the case studies, agreement among the four indicators was low. In some cases, EWIs were detected considerably ahead of the transition. Nonetheless, our results show that at present, EWIs do not provide reliable and consistent signals of impending critical transitions despite using some of the best routinely monitored freshwater ecosystems. Our analysis strongly suggests that a priori knowledge of the underlying mechanisms driving ecosystem transitions is necessary to identify relevant state variables for successfully monitoring EWIs.

Proceedings of the National Academy of Sciences of↗