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Why is metal bioaccumulation so variable? Biodynamics as a unifying concept

Ecological risks from metal contaminants are difficult to document because responses differ among species, threats differ among metals, and environmental influences are complex. Unifying concepts are needed to better tie together such complexities. Here we suggest that a biologically based conceptualization, the biodynamic model, provides the necessary unification for a key aspect in risk: metal bioaccumulation (internal exposure). The model is mechanistically based, but empirically considers geochemical influences, biological differences, and differences among metals. Forecasts from the model agree closely with observations from nature, validating its basic assumptions. The biodynamic metal bioaccumulation model combines targeted, high-quality geochemical analyses from a site of interest with parametrization of key physiological constants for a species from that site. The physiological parameters include metal influx rates from water, influx rates from food, rate constants of loss, and growth rates (when high). We compiled results from 15 publications that forecast species-specific bioaccumulation, and compare the forecasts to bioaccumulation data from the field. These data consider concentrations that cover 7 orders of magnitude. They include 7 metals and 14 species of animals from 3 phyla and 11 marine, estuarine, and freshwater environments. The coefficient of determination ( R 2 ) between forecasts and independently observed bioaccumulation from the field was 0.98. Most forecasts agreed with observations within 2-fold. The agreement suggests that the basic assumptions of the biodynamic model are tenable. A unified explanation of metal bioaccumulation sets the stage for a realistic understanding of toxicity and ecological effects of metals in nature.

Environmental Science & Technology↗

Biogeochemical controls on diel cycling of stable isotopes of dissolved 02 and dissolved inorganic carbon in the Big Hole River, Montana

Rivers with high biological productivity typically show substantial increases in pH and dissolved oxygen (DO) concentration during the day and decreases at night, in response to changes in the relative rates of aquatic photosynthesis and respiration. These changes, coupled with temperature variations, may impart diel (24-h) fluctuations in the concentration of trace metals, nutrients, and other chemical species. A better understanding of diel processes in rivers is needed and will lead to improved methods of data collection for both monitoring and research purposes. Previous studies have used stable isotopes of dissolved oxygen (DO) and dissolved inorganic carbon (DIC) as tracers of geochemical and biological processes in streams, lakes, and marine systems. Although seasonal variation in δ 18 O of DO in rivers and lakes has been documented, no study has investigated diel changes in this parameter. Here, we demonstrate large (up to 13‰) cycles in δ 18 O-DO for two late summer sampling periods in the Big Hole River of southwest Montana and illustrate that these changes are correlated to variations in the DO concentration, the C-isotopic composition of DIC, and the primary productivity of the system. The magnitude of the diel cycle in δ 18 O-DO was greater in August versus September because of the longer photoperiod and warmer water temperatures. This study provides another biogeochemical tool for investigating the O 2 and C budgets in rivers and may also be applicable to lake and groundwater systems.

Montana↗

Anaerobic biotransformation of roxarsone and related N-substituted phenylarsonic acids

Large quantities of arsenic are introduced into the environment through land application of poultry litter containing the organoarsenical feed additive roxarsone (3-nitro-4-hydroxyphenylarsonic acid). The objective of this study was to evaluate the bioconversion of roxarsone and related N-substituted phenylarsonic acid derivatives under anaerobic conditions. The results demonstrate that roxarsone is rapidly transformed in the absence of oxygen to the corresponding aromatic amine, 4-hydroxy-3-aminophenylarsonic acid (HAPA). The formation of HAPA is attributable to the facile reduction of the nitro group. Electron-donating substrates, such as hydrogen gas, glucose, and lactate, stimulated the rate of nitro group reduction, indicating a microbial role. During long-term incubations, HAPA and the closely related 4-aminophenylarsonic acid (4-APA) were slowly biologically eliminated by up to 99% under methanogenic and sulfate-reducing conditions, whereas little or no removal occurred in heat-killed inoculum controls. Arsenite and, to a lesser extent, arsenate were observed as products of the degradation. Freely soluble forms of the inorganic arsenical species accounted for 19-28% of the amino-substituted phenylarsonic acids removed. This constitutes the first report of a biologically catalyzed rupture of the phenylarsonic group under anaerobic conditions. ?? 2006 American Chemical Society.

Environmental Science & Technology↗

Toxicogenomics in regulatory ecotoxicology

Recently, we have witnessed an explosion of different genomic approaches that, through a combination of advanced biological, instrumental, and bioinformatic techniques, can yield a previously unparalleled amount of data concerning the molecular and biochemical status of organisms. Fueled partially by large, well-publicized efforts such as the Human Genome Project, genomic research has become a rapidly growing topical area in multiple biological disciplines. Since 1999, when the term “toxicogenomics” was coined to describe the application of genomics to toxicology (1), a rapid increase in publications on the topic has occurred (Figure 1). The potential utility of toxicogenomics in toxicological research and regulatory activities has been the subject of scientific discussions and, as with any new technology, has evoked a wide range of opinion (2–6).

Environmental Science & Technology↗

Biodegradation and attenuation of steroidal hormones and alkylphenols by stream biofilms and sediments

Biodegradation of select endocrine-disrupting compounds (17&beta;-estradiol, estrone, 17&alpha;-ethynylestradiol, 4-nonylphenol, 4-nonylphenolmonoexthoylate, and 4-nonylphenoldiethoxylate) was evaluated in stream biofilm, sediment, and water matrices collected from locations upstream and downstream from a wastewater treatment plant effluent discharge. Both biologically mediated transformation to intermediate metabolites and biologically mediated mineralization were evaluated in separate time interval experiments. Initial time intervals (0&ndash;7 d) evaluated biodegradation by the microbial community dominant at the time of sampling. Later time intervals (70 and 185 d) evaluated the biodegradation potential as the microbial community adapted to the absence of outside energy sources. The sediment matrix was more effective than the biofilm and water matrices at biodegrading 4-nonylphenol and 17&beta;-estradiol. Biodegradation by the sediment matrix of 17&alpha;-ethynylestradiol occurred at later time intervals (70 and 185 d) and was not observed in the biofilm or water matrices. Stream biofilms play an important role in the attenuation of endocrine-disrupting compounds in surface waters due to both biodegradation and sorption processes. Because sorption to stream biofilms and bed sediments occurs on a faster temporal scale (<1 h) than the potential to biodegrade the target compounds (50% mineralization at >185 d), these compounds can accumulate in stream biofilms and sediments.

Environmental Science & Technology↗

Transcriptomic effects-based monitoring for endocrine active chemicals: Assessing relative contribution of treated wastewater to downstream pollution

The present study investigated whether a combination of targeted analytical chemistry information with unsupervised, data-rich biological methodology (i.e., transcriptomics) could be utilized to evaluate relative contributions of wastewater treatment plant (WWTP) effluents to biological effects. The effects of WWTP effluents on fish exposed to ambient, receiving waters were studied at three locations with distinct WWTP and watershed characteristics. At each location, 4 d exposures of male fathead minnows to the WWTP effluent and upstream and downstream ambient waters were conducted. Transcriptomic analyses were performed on livers using 15 000 feature microarrays, followed by a canonical pathway and gene set enrichment analyses. Enrichment of gene sets indicative of teleost brain–pituitary–gonadal–hepatic (BPGH) axis function indicated that WWTPs serve as an important source of endocrine active chemicals (EACs) that affect the BPGH axis (e.g., cholesterol and steroid metabolism were altered). The results indicated that transcriptomics may even pinpoint pertinent adverse outcomes (i.e., liver vacuolization) and groups of chemicals that preselected chemical analytes may miss. Transcriptomic Effects-Based monitoring was capable of distinguishing sites, and it reflected chemical pollution gradients, thus holding promise for assessment of relative contributions of point sources to pollution and the efficacy of pollution remediation.

Environmental Science & Technology↗

Fate and transport of linear alkylbenzenesulfonate in a sewage- contaminated aquifer: A comparison of natural-gradient pulsed tracer tests

Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of IAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of LAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.

Environmental Science & Technology↗

Relation of climate change to the acidification of surface waters by nitrogen deposition

Abrupt increases and decreases in mean seasonal and annual stream NO3- concentrations during the period of record (1983-1995) at Biscuit Brook, a headwater stream in the Catskill Mountains of New York, have provided an opportunity to study the biogeochemical processes that control NO3- movement through forested watersheds. The Catskills receive the highest rate of NO3- deposition in the New York and New England region of the United States, and many streams have measurable NO3- concentrations throughout the growing season. Correlations between deposition and stream NO3- concentrations are not statistically significant. Stream NO3- concentrations are positively correlated with mean annual air temperature, suggesting that on a year-to-year basis rates of N mineralization and nitrification rather than deposition or vegetation uptake are the primary factors controlling nitrogen leaching from forests where nitrogen in excess of the biological demand is available. Results from nitrification and stable isotope studies are consistent with this conclusion. These data suggest that the release of NO3- to Catskill surface waters and the associated acidification would be enhanced in the short term through increases in mean annual air temperature.Abrupt increases and decreases in mean seasonal and annual stream NO3- concentrations during the period of record (1983-1995) at Biscuit Brook, a headwater stream in the Catskill Mountains of New York, have provided an opportunity to study the biogeochemical processes that control NO3- movement through forested watersheds. The Catskills receive the highest rate of NO3- deposition in the New York and New England region of the United States, and many streams have measurable NO3- concentrations throughout the growing season. Correlations between deposition and stream NO3- concentrations are not statistically significant. Stream NO3- concentrations are positively correlated with mean annual air temperature, suggesting that on a year-to-year basis rates of N mineralization and nitrification rather than deposition or vegetation uptake are the primary factors controlling nitrogen leaching from forests where nitrogen in excess of the biological demand is available. Results from nitrification and stable isotope studies are consistent with this conclusion. These data suggest that the release of NO3- to Catskill surface waters and the associated acidification would be enhanced in the short term through increases in mean annual air temperature.

Environmental Science & Technology↗

Influences of upland and riparian land use patterns on stream biotic integrity

We explored land use, fish assemblage structure, and stream habitat associations in 20 catchments in Opequon Creek watershed, West Virginia. The purpose was to determine the relative importance of urban and agriculture land use on stream biotic integrity, and to evaluate the spatial scale (i.e., whole-catchment vs riparian buffer) at which land use effects were most pronounced. We found that index of biological integrity (IBI) scores were strongly associated with extent of urban land use in individual catchments. Sites that received ratings of poor or very poor based on IBI scores had > 7% of urban land use in their respective catchments. Habitat correlations suggested that urban land use disrupted flow regime, reduced water quality, and altered stream channels. In contrast, we found no meaningful relationship between agricultural land use and IBI at either whole-catchment or riparian scales despite strong correlations between percent agriculture and several important stream habitat measures, including nitrate concentrations, proportion of fine sediments in riffles, and the abundance of fish cover. We also found that variation in gradient (channel slope) influenced responses of fish assemblages to land use. Urban land use was more disruptive to biological integrity in catchments with steeper channel slopes. Based on comparisons of our results in the topographically diverse Opequon Creek watershed with results from watersheds in flatter terrains, we hypothesize that the potential for riparian forests to mitigate effects of deleterious land uses in upland portions of the watershed is inversely related to gradient.

Landscape Ecology↗

A procedure for classifying textural facies in gravel‐bed rivers

Textural patches (i.e., grain‐size facies) are commonly observed in gravel‐bed channels and are of significance for both physical and biological processes at subreach scales. We present a general framework for classifying textural patches that allows modification for particular study goals, while maintaining a basic degree of standardization. Textures are classified using a two‐tier system of ternary diagrams that identifies the relative abundance of major size classes and subcategories of the dominant size. An iterative procedure of visual identification and quantitative grain‐size measurement is used. A field test of our classification indicates that it affords reasonable statistical discrimination of median grain size and variance of bed‐surface textures. We also explore the compromise between classification simplicity and accuracy. We find that statistically meaningful textural discrimination requires use of both tiers of our classification. Furthermore, we find that simplified variants of the two‐tier scheme are less accurate but may be more practical for field studies which do not require a high level of textural discrimination or detailed description of grain‐size distributions. Facies maps provide a natural template for stratifying other physical and biological measurements and produce a retrievable and versatile database that can be used as a component of channel monitoring efforts.

Water Resources Research↗

Ca cycling and isotopic fluxes in forested ecosystems in Hawaii

Biogeochemical processes fractionate Ca isotopes in plants and soils along a 4 million year developmental sequence in the Hawaiian Islands. We observed that plants preferentially take up 40Ca relative to 44Ca, and that biological fractionation and changes in the relative contributions from volcanic and marine sources produce a significant increase in 44Ca in soil exchangeable pools. Our results imply moderate fluxes enriched in 44Ca from strongly nutrient-depleted old soils, in contrast with high 40Ca fluxes in young and little weathered environments. In addition, biological fractionation controls divergent geochemical pathways of Ca and Sr in the plant-soil system. While Ca depletes progressively with increasing soil age, Sr/Ca ratios increase systematically. Sr isotope ratios provide a valuable tracer for provenance studies of alkaline earth elements in forested ecosystems, but its usefulness is limited when deciphering biogeochemical processes involved in the terrestrial Ca cycle. Ca isotopes in combination with Sr/ Ca ratios reveal more complex processes involved in the biogeochemistry of Ca and Sr. Copyright 2005 by the American Geophysical Union.

Geophysical Research Letters↗

Vital effects in coral skeletal composition display strict three-dimensional control

Biological control over coral skeletal composition is poorly understood but critically important to paleoenvironmental reconstructions. We present microanalytical measurements of trace-element abundances as well as oxygen and carbon isotopic compositions of individual skeletal components in the zooxanthellate coral Colpophyllia sp. Our data show that centers of calcification (COC) have higher trace element concentrations and distinctly lighter isotopic compositions than the fibrous components of the skeleton. These observations necessitate that COC and the fibrous skeleton are precipitated by different mechanisms, which are controlled by specialized domains of the calicoblastic cell-layer. Biological processes control the composition of the skeleton even at the ultra-structure level. Copyright 2006 by the American Geophysical Union.

Geophysical Research Letters↗

Numerical models of salt marsh evolution: ecological, geomorphic, and climatic factors

Salt marshes are delicate landforms at the boundary between the sea and land. These ecosystems support a diverse biota that modifies the erosive characteristics of the substrate and mediates sediment transport processes. Here we present a broad overview of recent numerical models that quantify the formation and evolution of salt marshes under different physical and ecological drivers. In particular, we focus on the coupling between geomorphological and ecological processes and on how these feedbacks are included in predictive models of landform evolution. We describe in detail models that simulate fluxes of water, organic matter, and sediments in salt marshes. The interplay between biological and morphological processes often produces a distinct scarp between salt marshes and tidal flats. Numerical models can capture the dynamics of this boundary and the progradation or regression of the marsh in time. Tidal channels are also key features of the marsh landscape, flooding and draining the marsh platform and providing a source of sediments and nutrients to the marsh ecosystem. In recent years, several numerical models have been developed to describe the morphogenesis and long-term dynamics of salt marsh channels. Finally, salt marshes are highly sensitive to the effects of long-term climatic change. We therefore discuss in detail how numerical models have been used to determine salt marsh survival under different scenarios of sea level rise.

Reviews of Geophysics↗

Sedimentary organics in Glen Torridon, Gale Crater, Mars: Results from the SAM instrument suite and supporting laboratory analyses

The Sample Analysis at Mars (SAM) suite instrument on board NASA's Curiosity rover has characterized the inorganic and organic chemical composition of seven samples from the Glen Torridon (GT) clay-bearing unit. A variety of organic molecules were detected with SAM using pyrolysis (up to ∼850°C) and wet chemistry experiments coupled with evolved gas analysis (EGA) and gas chromatography-mass spectrometry. SAM EGA and GCMS analyses revealed a greater diversity and abundance of sulfur-bearing aliphatic and aromatic organic compounds in the sediments of this Gale crater unit than earlier in the mission. We also report the detection of nitrogen-containing, oxygen-containing, and chlorine-containing molecules, as well as polycyclic aromatic hydrocarbons found in GT, although the sources of some of these organics may be related to the presence of chemical reagents in the SAM instrument background. However, sulfur-bearing organics released at high temperature (≥600°C) are likely derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources and consistent with the presence of recalcitrant organic materials in the sample. The SAM measurements of the GT clay-bearing unit expand the inventory of organic matter present in Gale crater and is also consistent with the hypothesis that clay minerals played an important role in the preservation of ancient refractory organic matter on Mars. These findings deepen our understanding of the past habitability and biological potential of Gale crater.

JGR Planets↗

River geomorphology affects biogeochemical responses to hydrologic events in a large river ecosystem

Shifts in the frequency and intensity of high discharge events due to climate change may have important consequences for the hydrology and biogeochemistry of rivers. However, our understanding of event-scale biogeochemical dynamics in large rivers lags that of small streams. To fill this gap, we used high-frequency sensor data collected during four consecutive summers from a main channel and backwater site of the Upper Mississippi River. We identified high discharge events and calculated event concentration-discharge responses for both physical-chemical (nitrate, turbidity, and fluorescent dissolved organic matter) and biological (chlorophyll-a and cyanobacteria) constituents using metrics of hysteresis and slope. We found a range of responses across events, particularly for nitrate. Although fluorescent dissolved organic matter (FDOM) and turbidity exhibited more consistent responses across events, contrasting hysteresis metrics indicated that FDOM was flushed to the river from more distant sources than turbidity. Biological responses (chlorophyll a and cyanobacteria) differed more between sites than physical and chemical constituents. Lastly, we found that the event characteristics best explaining concentration responses differed between sites, with event magnitude more frequently related to responses in the main channel, and antecedent wetness conditions associated with response variation in the backwater. Our results indicate that event responses in large rivers are distinct across the diverse habitats and biogeochemical components of a large floodplain river, which has implications for local and downstream ecosystems as the climate shifts.

Minnesota, Wisconsin↗

Physicochemical properties and bioreactivity of sub-10 µm geogenic particles: Comparison of volcanic ash and desert dust

Exposure to ambient particulate matter (PM) with an aerodynamic diameter of <10 μm (PM 10 ) is a well-established health hazard. There is increasing evidence that geogenic (Earth-derived) particles can induce adverse biological effects upon inhalation, though there is high variability in particle bioreactivity that is associated with particle source and physicochemical properties. In this study, we investigated physicochemical properties and biological reactivity of volcanic ash from the April 2021 eruption of La Soufrière volcano, St. Vincent, and two desert dust samples: a standardized test dust from Arizona and an aeolian Gobi Desert dust sampled in China. We determined particle size, morphology, mineralogy, surface texture and chemistry in sub-10 μm material to investigate associations between particle physicochemical properties and observed bioreactivity. We assessed cellular responses (cytotoxic and pro-inflammatory effects) to acute particle exposures (24 hr) in monocultures at the air-liquid interface using two types of cells of the human airways: BEAS-2B bronchial epithelial cells and A549 alveolar type II epithelial cells. In acellular assays, we also assessed particle oxidative potential and the presence of microorganisms. The results showed that volcanic ash and desert dust exhibit intrinsically different particle morphology, surface textures and chemistry, and variable mineralogical content. We found that Gobi Desert dust is more bioreactive than freshly erupted volcanic ash and Arizona test dust, which is possibly linked to the presence of microorganisms (bacteria) and/or nanoscale elongated silicate minerals (potentially clay such as illite or vermiculite) on particle surfaces.

GeoHealth↗

Bølling-Allerød productivity in the subarctic Pacific driven by seasonal upwelling

The Bølling-Allerød deglacial event is marked by high diatom productivity and opal deposition throughout the subarctic Pacific. This opal could either constitute a strengthened biological pump and thus carbon sequestration, or a weakened biological pump and release of marine-sequestered CO 2 to the atmosphere. We quantify silicic acid supply at IODP Site U1340 in the Bering Sea using biogenic opal and δ 30 Si of Coscinodiscus , a diatom genus. These records, along with diatom environmental indicators, suggest the Bølling-Allerød had high silicic acid availability related to a shift from stratification to seasonal upwelling dynamics. We thus propose the primary cause of the high productivity event was increased macronutrient supply from vertical exchange that injected old, nutrient-rich, CO 2 -rich waters into the surface. Enhanced CO 2 release from the subarctic Pacific may help explain critical intervals of CO 2 rise that occur at the onsets of the Bølling-Allerød and PreBoreal.

Geophysical Research Letters↗

Microbial control of silver mineralization at a sea-floor hydrothermal site on the northern Gorda Ridge

THE Sea Cliff hydrothermal field, on the northern Gorda Ridge, contains mounds and chimneys of hydrothermally precipitated sulphide and sulphate minerals typical of sea-floor hydrothermal vent sites 1 . In addition, large areas of the sea floor are covered by subhorizontal hydrothermal crusts. Samples of the crust recovered by submersible are composed of intensely altered fragments of basalt and basaltic hyaloclastite cemented by amorphous silica and chalcedony with less abundant barite, and minor amounts of base-metal sulphide minerals 2 . Some surfaces of the crust were formerly colonized by bacterial mats, which are locally preserved by replacement and overgrowth of the bacterial filaments by metal sulphide minerals and amorphous silica. The bacterial filaments are selectively replaced by prousite (Ag 3 AsS 3 ), pearceite 3 (Ag 14.7–x Cu 1.3+x As 2 S 11 ), chalcopyrite (CuFeS 2 ) and rarely by galena (PbS). Our observations suggest that bacterially mediated processes selectively precipitate silver, arsenic and copper, and that biological processes may contribute to precious-metal enrichment in some sea-floor hydrothermal base-metal sulphide deposits.

California, Oregon↗