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A. Robin Stewart

Publications and source records attributed to A. Robin Stewart.

At least 19 recordsLinked to original sources

Preparation and analysis methods for fish tissue collected from Lake Koocanusa, Montana

Lake Koocanusa, a reservoir, receives mine wastes from metallurgical coal mines in the Elk River Valley of British Columbia, Canada. Selenium and other elements discharged by the mines into the waters of the United States can pose unknown risks to aquatic life. The U.S. Geological Survey Wyoming-Montana Water Science Center can collaborate with Montana Fish, Wildlife and Parks and other State and Federal agencies to design studies and to collect fish tissues to help fill this knowledge gap. This report describes the processes, techniques, and methods used to collect and analyze fish tissue collected from Lake Koocanusa; and procedures used to review and manage data, including quality assurance and quality control procedures used by the U.S. Geological Survey Wyoming-Montana Water Science Center and supporting analytical laboratories. These fish tissue collections began in 2021.

Montana

Bioaccumulation and trophic transfer of selenium in a large oligotrophic river

In flowing waters with elevated selenium concentrations, fish are often considered to be at risk from selenium toxicity owing to dietary exposure and accumulation in ovary tissues and subsequent deformities in developing larvae. We studied selenium throughout components of the aquatic food webs at geomorphically distinct locations along the oligotrophic Kootenai River (Montana and Idaho, USA), a river with moderately elevated dissolved selenium concentrations (~ 1 µg/L). Components included water, sediment, freshly accrued biofilms, in-situ periphyton, sestonic detritus, aquatic invertebrates, and fish, with spring and fall sampling. Selenium concentrations were similar among the sediment, biofilm, periphyton, and detritus samples with most concentrations ranging between 0.5 to 2.0 (mg/kg dry weight (dw)). Among the aquatic invertebrates, the highest selenium concentrations were observed in Paraleptophlebia sp. mayflies (>15 mg/kg dw) and oligochaetes (>30 mg/kg dw). Selenium in chironomids was higher in the spring than fall, but otherwise, no consistent concentration patterns with season or feeding traits were observed. Fish tissue selenium concentrations were highly variable among species and tissue type. Selenium in fish tissues tended to be highest in livers of rainbow trout and mountain whitefish relative to egg/ovary, muscle, and carcass tissue. With northern pikeminnow, redside shiner, and slimy sculpin, selenium concentrations tended to be highest in ovary tissues. For example, selenium in rainbow trout livers ranged from an average (range) of 37 (4.5 to 151) compared to 8.7 (2.7 to 12.3) in northern pikeminnow livers. Egg/ovary concentrations ranged from a high of 26 (10.7 to 64) in redside shiner in contrast to 12.2 (6.9 to 17) mg/kg dw in slimy sculpin. A drawback of the fish-tissue approach to monitoring and managing selenium risks in freshwaters is the need to kill multiple fish per site and event. Potential alternative monitoring approaches are illustrated using aquatic invertebrates or using the food web monitoring results to derive monitoring targets for selenium in water or invertebrate tissue that could avoid the need to kill fish to assess whether fish protection guidelines are met.

Idaho, Montana

Near-field receiving-water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California—2020

Trace-metal concentrations in sediment and in the clam Limecola petalum (World Register of Marine Species, 2020; formerly reported as Macoma balthica and M. petalum ), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer (km) south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in south San Francisco Bay, California. This report includes the data collected by the U.S. Geological Survey (USGS) for January 2020–December 2020 (Cain and others, 2022). These data append to long-term datasets extending back to 1974. A major focus of the report is an integrated description of the 2020 data within the context of the longer, multidecadal dataset. This dataset supports the City of Palo Alto’s Near-Field Receiving- Water Monitoring Program, initiated in 1994. Silver and copper contamination substantially decreased at the site in the 1980s following the implementation by PARWQCP of advanced wastewater-treatment and source-control measures. Since the 1990s, concentrations of these elements in surface sediments have continued to decrease, although more slowly. For example, from 1994 to 2020, the minimum annual mean silver concentration—0.20 milligram per kilogram (mg/kg)—was observed in multiple years. In 2020, silver concentrations ranged from 0.18 to 0.28 mg/kg. These concentrations are 2 to 3 times higher than the regional background concentration. Presently (2020), sediment-copper concentrations appear to be near the regional background level. Over the same period (1994–2020), sedimentary iron and zinc exhibited modest decreases. Sedimentary aluminum, chromium, mercury, nickel, and selenium have not exhibited any trend. Since 1994, silver and copper concentrations in L. petalum have varied seasonally, apparently in response to a combination of site-specific metal exposures and cyclic growth and reproduction, as reported previously. Seasonal patterns for other elements, including chromium, mercury, nickel, selenium, and zinc, generally were similar in timing and magnitude as those for silver and copper. Downward trends in the silver and zinc concentrations in L. petalum during 1994–2020 were evident and appeared to be related to the general physiological condition of the clam, indicated by a condition index. Biological effects of elevated silver and copper contamination at the Palo Alto site have been interpreted from data collected during and after the recession of these contaminants. Concentrations of both elements in the soft tissues of L. petalum decreased with sedimentary copper and silver. This pattern was associated with changes in the reproductive activity of L. petalum , as well as the structure of the benthic invertebrate community. Reproductive activity of L. petalum increased as metal concentrations in L. petalum decreased (Hornberger and others, 2000), and presently is stable with almost all animals initiating reproduction in the fall and spawning the following spring. Analyses of the benthic community structure indicate that the infaunal invertebrate community has shifted from one dominated by several opportunistic species when silver and copper exposures were highest to one in which the species abundance is more evenly distributed, a pattern that indicates a more stable community that is subjected to fewer stressors. Importantly, this long-term change is unrelated to other metals and other measured environmental factors, including salinity and sediment composition. In addition, two of the opportunistic species ( Ampelisca abdita and Streblospio benedicti ) that brood their young and live on the surface of the sediment in tubes have shown a continual decrease in dominance coincident with the decrease in metals. Both species had short-lived rebounds in abundance in 2008, 2009, and 2010 and showed signs of increasing abundance in 2020. Heteromastus filiformis (a subsurface polychaete worm that lives in the sediment, consumes sediment and organic particles residing in the sediment, and reproduces by laying its eggs on or in the sediment) showed a concurrent increase in dominance and, in the last several years before 2008, showed a stable population. H. filiformis abundance increased slightly from 2011 to 2012 and returned to pre-2011 numbers in 2020. The reproductive mode of most species that were present in 2020 was indicative of species that were capable of movement either as pelagic larvae or as mobile adults. Although oviparous species were lower in number in this group, the authors hypothesize that these species will return slowly as more species move back into the area. The use of functional ecology was highlighted in the 2020 benthic community data, which showed that the animals that have now returned to the mudflat are those that can respond successfully to a physical, nontoxic disturbance. Today, community data show a mix of species that consume the sediment, or filter feed, those that have pelagic larvae that must survive landing on the sediment, and those that brood their young. The long-term recovery observed after the 1970s can be ascribed to the decrease in sediment pollutants.

California

Near-field receiving-water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California—2019

Trace-metal concentrations in sediment and in the clam Limecola petalum (formerly reported as Macoma balthica and M. petalum ), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in south San Francisco Bay, Calif. This report includes the data collected by the U.S. Geological Survey (USGS) for the period January 2019 to December 2019. These data append to long-term datasets extending back to 1974. A major focus of the report is an integrated description of the 2019 data within the context of the longer, multidecadal dataset. This dataset supports the City of Palo Alto’s Near-Field Receiving-Water Monitoring Program, initiated in 1994. Significant reductions in silver and copper contamination occurred at the site in the 1980s following the implementation by PARWQCP of advanced wastewater treatment and source control measures. Since the 1990s, concentrations of these elements in surface sediments have continued to decrease, although more slowly. Silver appears to have stabilized at concentrations about twice the regional background concentration. Presently, sediment copper concentrations appear to be near the regional background level. Over the same period (1994–2019), sedimentary iron and zinc also exhibited modest declines. Sedimentary aluminum, chromium, mercury, nickel, and selenium have not exhibited any trend. Since 1994, concentrations of silver and copper in L. petalum have varied seasonally, apparently in response to a combination of site-specific metal exposures and cyclic growth and reproduction, as reported previously. Seasonal patterns for other elements, including chromium, mercury, nickel, selenium, and zinc, were generally similar in timing and magnitude as those for silver and copper. The annual growth and reproductive cycle explained a small amount of the variance in annual silver and zinc tissue metal concentrations. However, interannual trends are not apparent for any element. Biological effects of elevated silver and copper contamination at the Palo Alto site have been interpreted from data collected during and after the recession of these contaminants. Concentrations of both elements in the soft tissues of L. petalum declined with sedimentary copper and silver. This pattern was associated with changes in the reproductive activity of L. petalum , as well as the structure of the benthic invertebrate community. Reproductive activity of L. petalum increased as metal concentrations in L. petalum declined and presently is stable with almost all animals initiating reproduction in the fall and spawning the following spring. Analyses of the benthic community structure indicate that the infaunal invertebrate community has shifted from one dominated by several opportunistic species when silver and copper exposures were highest to one in which the species abundance is more evenly distributed, a pattern that indicates a more stable community that is subjected to fewer stressors. Importantly, this long-term change is unrelated to other metals and other measured environmental factors, including salinity and sediment composition. In addition, two of the opportunistic species ( Ampelisca abdita and Streblospio benedicti ) that brood their young and live on the surface of the sediment in tubes have shown a continual decline in dominance coincident with the decline in metals. Both species had short-lived rebounds in abundance in 2008, 2009, and 2010 and showed signs of increasing abundance in 2019. Heteromastus filiformis (a subsurface polychaete worm that lives in the sediment, consumes sediment and organic particles residing in the sediment, and reproduces by laying its eggs on or in the sediment) showed a concurrent increase in dominance and, in the last several years before 2008, showed a stable population. H. filiformis abundance increased slightly in 2011–2012 and returned to pre-2011 numbers in 2019. An unidentified disturbance occurred on the mudflat in early 2008 that resulted in the loss of the benthic animals, except for deep-dwelling animals like L. petalum . However, within two months of this event, animals returned to the mudflat. The resilience of the community suggested that the disturbance was not caused by a persistent toxin or anoxia. The reproductive mode of most species that were present in 2019 was indicative of species that were available either as pelagic larvae or as mobile adults. Although oviparous species were lower in number in this group, the authors hypothesize that these species will return slowly as more species move back into the area. The use of functional ecology was highlighted in the 2019 benthic community data, which showed that the animals that have now returned to the mudflat are those that can respond successfully to a physical, nontoxic disturbance. Today, community data show a mix of species that consume the sediment, or filter feed, those that have pelagic larvae that must survive landing on the sediment, and those that brood their young. USGS scientists view the 2008 disturbance event as a response by the infaunal community to an episodic natural stressor (possibly sediment accretion or a pulse of freshwater), in contrast to the long-term recovery from metal contamination. We will compare this recovery to the long-term recovery observed after the 1970s when the decline in sediment pollutants was the dominating factor.

California

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

Resolving selenium exposure risk: Spatial, temporal, and tissue-specific variability of an endemic fish in a large, dynamic estuary

Estuaries provide critical habitat for a vast array of fish and wildlife but are also a nexus for core economic activities that mobilize and concentrate contaminants that can threaten aquatic species. Selenium (Se), an essential element and potent reproductive toxin, is enriched in parts of the San Francisco Estuary (SFE) to levels known to cause toxicity, yet the risk of Se to species that inhabit the SFE is not well understood. We quantified Se concentrations in muscle, liver and ovary of the demersal cyprinid Sacramento Splittail from six regions in the SFE at three time points to evaluate Se exposure risk. Selenium levels exceeded proposed EPA criteria in ovary and thresholds of concern for liver in 15% and 20%, respectively, of fish collected in the fall of 2010, preceding the discovery of juvenile Splittail displaying a high incidence (>40%) of spinal deformities characteristic of Se toxicity, and again in 2011. No exceedances were detected in muscle tissue. Selenium concentrations varied significantly among regions for muscle (F 5,113 = 20.49, p < 0.0001), liver (F 5,113 = 28.4, p < 0.0001) and ovary (F 5,112 = 19.3, p < 0.0001) but did not vary between the wet and dry years, nor were they influenced by foraging trophic level or prey selection. Foraging location along the salinity gradient, defined by δ 34 S values, explained regional Se exposures in Splittail. Relationships between tissues varied among regions for muscle and liver and muscle and ovary, but a single global relationship could be defined for ovary and liver Se concentrations. Our results suggest that the proposed EPA Se criteria for muscle tissue in Splittail may be under-protective as it would not have predicted exceedances in liver or ovary tissue and that the relationship between muscle tissue and ovary and liver may be Se concentration and seasonal dependent.

California

Nutrients mediate the effects of temperature on methylmercury concentrations in freshwater zooplankton

Methylmercury (MeHg) bioaccumulation in freshwater aquatic systems is impacted by anthropogenic stressors, including climate change and nutrient enrichment. The goal of this study was to determine how warmer water temperatures and excess nutrients would alter zooplankton communities and phytoplankton concentrations, and whether those changes would in turn increase or decrease MeHg concentrations in freshwater zooplankton. To test this, we employed a 2x2 factorial experimental design with nutrient and temperature treatments. Mesocosms were filled with ambient water and plankton from Cottage Grove Reservoir, Oregon, U.S.A, a waterbody that has experienced decades of elevated MeHg concentrations and corresponding fish consumption advisories due to run-off from Black Butte Mine tailings, located within the watershed. Treatment combinations of warmer temperature (increased by 0.7°C) and nutrient addition (a single pulse of 10 ambient concentrations of nitrogen and phosphorous), control, and a combination of temperature and nutrients were applied to mesocosms.

Oregon

Near-field receiving-water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California—2017

Trace-metal concentrations in sediment and in the clam Macoma petalum (formerly reported as Macoma balthica ), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in south San Francisco Bay, Calif. This report includes the data collected by U.S. Geological Survey (USGS) scientists for the period January 2017 to December 2017. These append to long-term datasets extending back to 1974. A major focus of the report is an integrated description of the 2017 data within the context of the longer, multi-decadal dataset. This dataset supports the City of Palo Alto’s Near-Field Receiving Water Monitoring Program, initiated in 1994. Significant reductions in silver and copper concentrations in sediment and M. petalum occurred at the site in the 1980s following the implementation by PARWQCP of advanced wastewater treatment and source control measures. Since the 1990s, concentrations of these elements appear to have stabilized at concentrations somewhat above silver (Ag) or near copper (Cu) regional background concentrations. Data for other metals, including chromium (Cr), mercury (Hg), nickel (Ni), selenium (Se), and zinc (Zn), have been collected since 1994. Over this period, concentrations of these elements have remained relatively constant, aside from seasonal variation that is common to all elements. In 2017, concentrations of silver and copper in M. petalum varied seasonally in response to a combination of site-specific metal exposures and annual growth and reproduction, as reported previously. Seasonal patterns for other elements, including Cr, Ni, Zn, Hg, and Se, were generally similar in timing and magnitude as those for Ag and Cu. This record suggests that legacy contamination and regional-scale factors now largely control sedimentary and bioavailable concentrations of silver and copper, as well as other elements of regulatory interest, at the Palo Alto site. Analyses of the benthic community structure of a mudflat in south San Francisco Bay over a 40-year period show that changes in the community have occurred concurrent with reduced concentrations of metals in the sediment and in the tissues of the biosentinel clam, M. petalum , from the same area. Analysis of M. petalum shows increases in reproductive activity concurrent with the decline in metal concentrations in the tissues of this organism. Reproductive activity is presently stable (2017), with almost all animals initiating reproduction in the fall and spawning the following spring. The entire infaunal community has shifted from being dominated by several opportunistic species to a community where the species are more similar in abundance, a pattern that indicates a more stable community that is subjected to fewer stressors. In addition, two of the opportunistic species ( Ampelisca abdita and Streblospio benedicti ) that brood their young and live on the surface of the sediment in tubes have shown a continual decline in dominance coincident with the decline in metals; both species had short-lived rebounds in abundance in 2008, 2009, and 2010 and showed signs of increasing abundance in 2017. Heteromastus filiformis (a subsurface polychaete worm that lives in the sediment, consumes sediment and organic particles residing in the sediment, and reproduces by laying its eggs on or in the sediment) showed a concurrent increase in dominance and, in the last several years before 2008, showed a stable population. H. filiformis abundance increased slightly in 2011–2012 and returned to pre-2011 numbers in 2017. An unidentified disturbance occurred on the mudflat in early 2008 that resulted in the loss of the benthic animals, except for deep-dwelling animals like M. petalum . However, within two months of this event animals returned to the mudflat. The resilience of the community suggested that the disturbance was not due to a persistent toxin or anoxia. The reproductive mode of most species that were present in 2017 is reflective of species that were available either as pelagic larvae or as mobile adults. Although oviparous species were lower in number in this group, the authors hypothesize that these species will return slowly as more species move back into the area. The use of functional ecology was highlighted in the 2017 benthic community data, which showed that the animals that have now returned to the mudflat are those that can respond successfully to a physical, nontoxic disturbance. Today, community data show a mix of species that consume the sediment, or filter feed, have pelagic larvae that must survive landing on the sediment, and those that brood their young. USGS scientists view the 2008 disturbance event as a response by the infaunal community to an episodic natural stressor (possibly sediment accretion or a pulse of freshwater), in contrast to the long-term recovery from metal contamination. We will compare this recovery to the long-term recovery observed after the 1970s when the decline in sediment pollutants was the dominating factor.

California

Near-field receiving water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California; 2016

Trace-metal concentrations in sediment and in the clam Macoma petalum (formerly reported as Macoma balthica ), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in south San Francisco Bay, Calif. This report includes the data collected by U.S. Geological Survey (USGS) scientists for the period January 2014 to December 2016. These append to long-term datasets extending back to 1974. A major focus of the report is an integrated description of the 2016 data within the context of the longer, multi-decadal dataset. This dataset supports the City of Palo Alto’s Near-Field Receiving Water Monitoring Program, initiated in 1994. Significant reductions in silver and copper concentrations in sediment and M. petalum occurred at the site in the 1980s following the implementation by PARWQCP of advanced wastewater treatment and source control measures. Since the 1990s, concentrations of these elements appear to have stabilized at concentrations somewhat above (silver) or near (copper) regional background concentrations Data for other metals, including chromium (Cr), mercury (Hg), nickel (Ni), selenium (Se), and zinc (Zn), have been collected since 1994. Over this period, concentrations of these elements have remained relatively constant, aside from seasonal variation that is common to all elements. In 2016, concentrations of silver and copper in M. petalum varied seasonally in response to a combination of site-specific metal exposures and annual growth and reproduction, as reported previously. Seasonal patterns for other elements, including Cr, Ni, Zn, Hg, and Se, were generally similar in timing and magnitude as those for Ag and Cu. This record suggests that legacy contamination and regional-scale factors now largely control sedimentary and bioavailable concentrations of silver and copper, as well as other elements of regulatory interest, at the Palo Alto site. Analyses of the benthic community structure of a mudflat in south San Francisco Bay over a 40-year period show that changes in the community have occurred concurrent with reduced concentrations of metals in the sediment and in the tissues of the biosentinel clam, M. petalum , from the same area. Analysis of M. petalum shows increases in reproductive activity concurrent with the decline in metal concentrations in the tissues of this organism. Reproductive activity is presently stable (2016), with almost all animals initiating reproduction in the fall and spawning the following spring. The entire infaunal community has shifted from being dominated by several opportunistic species to a community where the species are more similar in abundance, a pattern that indicates a more stable community that is subjected to fewer stressors. In addition, two of the opportunistic species ( Ampelisca abdita and Streblospio benedicti ) that brood their young and live on the surface of the sediment in tubes have shown a continual decline in dominance coincident with the decline in metals; both species had short-lived rebounds in abundance in 2008, 2009, and 2010 and showed signs of increasing abundance in 2016. Heteromastus filiformis (a subsurface polychaete worm that lives in the sediment, consumes sediment and organic particles residing in the sediment, and reproduces by laying its eggs on or in the sediment) showed a concurrent increase in dominance and, in the last several years before 2008, showed a stable population. H. filiformis abundance increased slightly in 2011–2012 and returned to pre-2011 numbers in 2016. An unidentified disturbance occurred on the mudflat in early 2008 that resulted in the loss of the benthic animals, except for deep-dwelling animals like Macoma petalum . However, within two months of this event animals returned to the mudflat. The resilience of the community suggested that the disturbance was not due to a persistent toxin or anoxia. The reproductive mode of most species present in 2016 is reflective of species that were available either as pelagic larvae or as mobile adults. Although oviparous species were lower in number in this group, the authors hypothesize that these species will return slowly as more species move back into the area. The use of functional ecology was highlighted in the 2016 benthic community data, which showed that the animals that have now returned to the mudflat are those that can respond successfully to a physical, nontoxic disturbance. Today, community data show a mix of species that consume the sediment, or filter feed, have pelagic larvae that must survive landing on the sediment, and those that brood their young. USGS scientists view the 2008 disturbance event as a response by the infaunal community to an episodic natural stressor (possibly sediment accretion or a pulse of freshwater), in contrast to the long-term recovery from metal contamination. We will compare this recovery to the long-term recovery observed after the 1970s when the decline in sediment pollutants was the dominating factor.

California

A practical method for the determination of total selenium in environmental samples using isotope dilution-hydride generation-inductively coupled plasma-mass spectrometry

A safe, practical, and accurate method for the determination of selenium (Se) in range of environmental samples was developed. Small sample masses, 5–20 mg, were amended with 82 Se enriched isotope for the isotope dilution (ID), preceding a multi-step wet digestion with nitric acid (HNO 3 ) and hydrogen peroxide (H 2 O 2 ). Samples were incubated in an autoclave for 3 h at 20 psi and 126°C. Digestates were subsequently reduced with concentrated hydrochloric acid to Se(IV) the most favorable valence for hydride generation (HG). The solutions were then analyzed on an ICP-MS equipped with Flow Injection system (FIAS-400). Polyatomic, isobaric, and background interferences were removed through the use of HG and ID with an 82 Se enriched isotope spike. Recoveries for certified reference materials were determined and averaged 96% for biological tissues (NRCC DOLT3, DOLT4, DORM2, TORT2, and TORT3, and NIST 2976) and 108% for estuarine sediment (NRCC PACS2) with an average coefficient of variation for replicate measurements of ∼ 3.5%. Limit of detection was 0.13 ng Se g −1 dry weight or 0.19 ng Se L −1 . This method can be broadly applied to biological tissues, sediments, suspended particulates, and water samples with minimal modifications making this method highly useful for assessing the ecotoxicology of total Se in aquatic ecosystems.

Limnology and Oceanography: Methods

Mercury in western North America: A synthesis of environmental contamination, fluxes, bioaccumulation, and risk to fish and wildlife

Western North America is a region defined by extreme gradients in geomorphology and climate, which support a diverse array of ecological communities and natural resources. The region also has extreme gradients in mercury (Hg) contamination due to a broad distribution of inorganic Hg sources. These diverse Hg sources and a varied landscape create a unique and complex mosaic of ecological risk from Hg impairment associated with differential methylmercury (MeHg) production and bioaccumulation. Understanding the landscape-scale variation in the magnitude and relative importance of processes associated with Hg transport, methylation, and MeHg bioaccumulation requires a multidisciplinary synthesis that transcends small-scale variability. The Western North America Mercury Synthesis compiled, analyzed, and interpreted spatial and temporal patterns and drivers of Hg and MeHg in air, soil, vegetation, sediments, fish, and wildlife across western North America. This collaboration evaluated the potential risk from Hg to fish, and wildlife health, human exposure, and examined resource management activities that influenced the risk of Hg contamination. This paper integrates the key information presented across the individual papers that comprise the synthesis. The compiled information indicates that Hg contamination is widespread, but heterogeneous, across western North America. The storage and transport of inorganic Hg across landscape gradients are largely regulated by climate and land-cover factors such as plant productivity and precipitation. Importantly, there was a striking lack of concordance between pools and sources of inorganic Hg, and MeHg in aquatic food webs. Additionally, water management had a widespread influence on MeHg bioaccumulation in aquatic ecosystems, whereas mining impacts where relatively localized. These results highlight the decoupling of inorganic Hg sources with MeHg production and bioaccumulation. Together the findings indicate that developing efforts to control MeHg production in the West may be particularly beneficial for reducing food web exposure instead of efforts to simply control inorganic Hg sources.

Science of the Total Environment

Near-field receiving water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California; 2015

Trace-metal concentrations in sediment and in the clam Macoma petalum (formerly reported as Macoma balthica ), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in South San Francisco Bay, California. This report includes data collected by U.S. Geological Survey (USGS) scientists for the period from January 2015 to December 2015. These data are appended to long-term datasets extending back to 1974, and serve as the basis for the City of Palo Alto&rsquo;s Near-Field Receiving Water Monitoring Program, initiated in 1994. Following significant reductions in the late 1980s, silver (Ag) and copper (Cu) concentrations in sediment and M. petalum appear to have stabilized. Data for other metals, including chromium (Cr), mercury (Hg), nickel (Ni), selenium (Se), and zinc (Zn), have been collected since 1994. Over this period, concentrations of these elements have remained relatively constant, aside from seasonal variation that is common to all elements. In 2015, concentrations of Ag and Cu in M. petalum varied seasonally in response to a combination of site-specific metal exposures and annual growth and reproduction, as reported previously. Seasonal patterns for other elements, including Cr, Ni, Zn, Hg, and Se, were generally similar in timing and magnitude as those for Ag and Cu. In M. petalum , all observed elements showed annual maxima in January&ndash;February and minima in April, except for Zn, which was lowest in December. In sediments, annual maxima also occurred in January&ndash;February, and minima were measured in June and September. In 2015, metal concentrations in both sediments and clam tissue were among the lowest on record. This record suggests that regional-scale factors now largely control sedimentary and bioavailable concentrations of Ag and Cu, as well as other elements of regulatory interest, at the Palo Alto site. Analyses of the benthic community structure at the same mudflat over a 40-year period show that changes in the community have occurred concurrent with reduced concentrations of metals in the sediment and in the tissues of the biosentinel clam, M. petalum , from the same area. Analysis of M. petalum shows increases in reproductive activity concurrent with the decline in metal concentrations in the tissues of this organism. Reproductive activity is presently stable (2015), with almost all animals initiating reproduction in the fall and spawning the following spring. The entire infaunal community has shifted from being dominated by several opportunistic species to a community where the species are more similar in abundance, a pattern that indicates a more stable community that is subjected to fewer stressors. In addition, two of the opportunistic species ( Ampelisca abdita and Streblospio benedicti ) that brood their young and live on the surface of the sediment in tubes have shown a continual decline in dominance coincident with the decline in metals; both species had short-lived rebounds in abundance in 2008, 2009, and 2010 and showed signs of increasing abundance in 2015. Heteromastus filiformis (a subsurface polychaete worm that lives in the sediment, consumes sediment and organic particles residing in the sediment, and reproduces by laying its eggs on or in the sediment) showed an increase in dominance, concurrent with the decrease in Ag and Cu concentrations, and in the last several years before 2008, showed a stable population. H. filiformis abundance increased slightly in 2011&ndash;2012 and returned to pre-2011 abundance in 2015. An unidentified disturbance occurred on the mudflat in early 2008 that resulted in the loss of the benthic animals, except for deep-dwelling animals like M. petalum . However, within two months of this event animals returned to the mudflat. The resilience of the community suggested that the disturbance was not due to a persistent toxin or to anoxia. The reproductive mode of most species present in 2015 is reflective of species that were available either as pelagic larvae or as mobile adults. Although oviparous (live-birth) species were lower in number in this group, the authors hypothesize that these species will return slowly as more species move back into the area. The use of functional ecology was highlighted in the 2015 benthic community data, which showed that the animals that have now returned to the mudflat are those that can respond successfully to a physical, nontoxic disturbance. Today, community data show a mix of species that consume the sediment, or filter feed, have pelagic larvae that must survive landing on the sediment, and those that brood their young. USGS scientists view the 2008 disturbance event as a response by the infaunal community to an episodic natural stressor (possibly sediment accretion or a pulse of freshwater), in contrast to the long-term recovery from metal contamination. We will compare this recovery to the long-term recovery observed after the 1970s when the decline in sediment pollutants was the dominating factor.

California

Spatial and temporal patterns of mercury concentrations in freshwater fish across the Western United States and Canada

Methylmercury contamination of fish is a global threat to environmental health. Mercury (Hg) monitoring programs are valuable for generating data that can be compiled for spatially broad syntheses to identify emergent ecosystem properties that influence fish Hg bioaccumulation. Fish total Hg (THg) concentrations were evaluated across the Western United States (US) and Canada, a region defined by extreme gradients in habitat structure and water management. A database was compiled with THg concentrations in 96,310 fish that comprised 206 species from 4262 locations, and used to evaluate the spatial distribution of fish THg across the region and effects of species, foraging guilds, habitats, and ecoregions. Areas of elevated THg exposure were identified by developing a relativized estimate of fish mercury concentrations at a watershed scale that accounted for the variability associated with fish species, fish size, and site effects. THg concentrations in fish muscle ranged between 0.001 and 28.4 (&mu;g/g wet weight (ww)) with a geometric mean of 0.17. Overall, 30% of individual fish samples and 17% of means by location exceeded the 0.30 &mu;g/g ww US EPA fish tissue criterion. Fish THg concentrations differed among habitat types, with riverine habitats consistently higher than lacustrine habitats. Importantly, fish THg concentrations were not correlated with sediment THg concentrations at a watershed scale, but were weakly correlated with sediment MeHg concentrations, suggesting that factors influencing MeHg production may be more important than inorganic Hg loading for determining fish MeHg exposure. There was large heterogeneity in fish THg concentrations across the landscape; THg concentrations were generally higher in semi-arid and arid regions such as the Great Basin and Desert Southwest, than in temperate forests. Results suggest that fish mercury exposure is widespread throughout Western US and Canada, and that species, habitat type, and region play an important role in influencing ecological risk of mercury in aquatic ecosystems.

Science of the Total Environment

Near-field receiving water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California: 2014

Trace-metal concentrations in sediment and in the clam Macoma petalum (formerly reported as Macoma balthica ), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer (km) south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in South San Francisco Bay, Calif. This report includes the data collected by U.S. Geological Survey (USGS) scientists for the period January 2014 to December 2014. These append to long-term datasets extending back to 1974, and serve as the basis for the City of Palo Alto&rsquo;s Near-Field Receiving Water Monitoring Program, initiated in 1994. Following significant reductions in the late 1980s, silver (Ag) and copper (Cu) concentrations in sediment and M. petalum appear to have stabilized. Data for other metals, including chromium (Cr), mercury (Hg), nickel (Ni), selenium (Se), and zinc (Zn), have been collected since 1994. Over this period, concentrations of these elements have remained relatively constant, aside from seasonal variation that is common to all elements. In 2014, concentrations of Ag and Cu in M. petalum varied seasonally in response to a combination of site-specific metal exposures and annual growth and reproduction, as reported previously. Seasonal patterns for other elements, including Cr, Ni, Zn, Hg, and Se, were generally similar in timing and magnitude as those for Ag and Cu. In M. petalum , all observed elements showed annual maxima in January&ndash;February and minima in April, except for Zn, which was lowest in December. In sediments, annual maxima also occurred in January&ndash;February, and minima were measured in June and September. In 2014, metal concentrations in both sediments and clam tissue were among the lowest on record. This record suggests that regional-scale factors now largely control sedimentary and bioavailable concentrations of Ag and Cu, as well as other elements of regulatory interest, at the Palo Alto site. Analyses of the benthic community structure of a mudflat in South San Francisco Bay over a 40-year period show that changes in the community have occurred concurrent with reduced concentrations of metals in the sediment and in the tissues of the biosentinel clam, M. petalum , from the same area. Analysis of M. petalum shows increases in reproductive activity concurrent with the decline in metal concentrations in the tissues of this organism. Reproductive activity is presently stable (2014), with almost all animals initiating reproduction in the fall and spawning the following spring. The entire infaunal community has shifted from being dominated by several opportunistic species to a community where the species are more similar in abundance, a pattern that indicates a more stable community that is subjected to fewer stressors. In addition, two of the opportunistic species ( Ampelisca abdita and Streblospio benedicti ) that brood their young and live on the surface of the sediment in tubes have shown a continual decline in dominance coincident with the decline in metals; both species had short-lived rebounds in abundance in 2008, 2009, and 2010. Heteromastus filiformis (a subsurface polychaete worm that lives in the sediment, consumes sediment and organic particles residing in the sediment, and reproduces by laying its eggs on or in the sediment) showed a concurrent increase in dominance and, in the last several years before 2008, showed a stable population. H. filiformis abundance increased slightly in 2011&ndash;2012 and returned to pre-2011 numbers in 2014. An unidentified disturbance occurred on the mudflat in early 2008 that resulted in the loss of the benthic animals, except for deep-dwelling animals like Macoma petalum . However, within two months of this event animals returned to the mudflat. The resilience of the community suggested that the disturbance was not due to a persistent toxin or to anoxia. The reproductive mode of most species present in 2014 is reflective of species that were available either as pelagic larvae or as mobile adults. Although oviparous species were lower in number in this group, the authors hypothesize that these species will return slowly as more species move back into the area. The use of functional ecology was highlighted in the 2014 benthic community data, which showed that the animals that have now returned to the mudflat are those that can respond successfully to a physical, nontoxic disturbance. Today, community data show a mix of species that consume the sediment, or filter feed, have pelagic larvae that must survive landing on the sediment, and those that brood their young. USGS scientists view the 2008 disturbance event as a response by the infaunal community to an episodic natural stressor (possibly sediment accretion or a pulse of freshwater), in contrast to the long-term recovery from metal contamination. We will compare this recovery to the long-term recovery observed after the 1970&rsquo;s when the decline in sediment pollutants was the dominating factor.

California

Ancient fish and recent invaders: white sturgeon Acipenser transmontanus diet response to invasive-species-mediated changes in a benthic prey assemblage

Invasive organisms can have significant impacts on native species, and the San Francisco Estuary (SFE), California, USA, is one of the world's most invaded estuaries. Decline of native white sturgeon Acipenser transmontanus abundance in the SFE has been acknowledged, but underlying mechanisms are poorly understood. Invasion by the overbite clam Potamocorbula amurensis has drastically altered the SFE benthic prey community, yet little is known about how this change has affected sturgeon diets. We investigated changes in the diet of white sturgeon following the overbite clam invasion and subsequent shift in the SFE benthic prey assemblage. Gut content analysis was used to compare white sturgeon prey composition and importance between the pre- and post-invasion periods. Additionally, stable isotope analysis was employed to estimate the assimilation of prey items to sturgeon biomass. Overbite clams dominated diets in the post-invasion period, accounting for 82 to 93% of total volume. Stable isotope analysis confirmed the importance of this prey item, although their assimilated contribution to sturgeon biomass was estimated to be less (70 to 83%) than gut contents indicated. The frequency of fish in white sturgeon guts increased in the post-invasion period, and isotope analysis indicated relatively large contributions of fish to sturgeon biomass (3.7 to 19%). The trophic adaptability of white sturgeon has allowed them to exploit this new prey source (overbite clam). Future conservation and restoration efforts must consider a potentially destabilized food web given the large importance of a single prey item.

Marine Ecology Progress Series

Influence of estuarine processes on spatiotemporal variation in bioavailable selenium

Dynamic processes (physical, chemical and biological) challenge our ability to quantify and manage the ecological risk of chemical contaminants in estuarine environments. Selenium (Se) bioavailability (defined by bioaccumulation), stable isotopes and molar carbon-tonitrogen ratios in the benthic clam Potamocorbula amurensis, an important food source for predators, were determined monthly for 17 yr in northern San Francisco Bay. Se concentrations in the clams ranged from a low of 2 to a high of 22 &mu;g g -1 over space and time. Little of that variability was stochastic, however. Statistical analyses and preliminary hydrodynamic modeling showed that a constant mid-estuarine input of Se, which was dispersed up- and down-estuary by tidal currents, explained the general spatial patterns in accumulated Se among stations. Regression of Se bioavailability against river inflows suggested that processes driven by inflows were the primary driver of seasonal variability. River inflow also appeared to explain interannual variability but within the range of Se enrichment established at each station by source inputs. Evaluation of risks from Se contamination in estuaries requires the consideration of spatial and temporal variability on multiple scales and of the processes that drive that variability.

Marine Ecology Progress Series

Explaining differences between bioaccumulation measurements in laboratory and field data through use of a probabilistic modeling approach

In the regulatory context, bioaccumulation assessment is often hampered by substantial data uncertainty as well as by the poorly understood differences often observed between results from laboratory and field bioaccumulation studies. Bioaccumulation is a complex, multifaceted process, which calls for accurate error analysis. Yet, attempts to quantify and compare propagation of error in bioaccumulation metrics across species and chemicals are rare. Here, we quantitatively assessed the combined influence of physicochemical, physiological, ecological, and environmental parameters known to affect bioaccumulation for 4 species and 2 chemicals, to assess whether uncertainty in these factors can explain the observed differences among laboratory and field studies. The organisms evaluated in simulations including mayfly larvae, deposit-feeding polychaetes, yellow perch, and little owl represented a range of ecological conditions and biotransformation capacity. The chemicals, pyrene and the polychlorinated biphenyl congener PCB-153, represented medium and highly hydrophobic chemicals with different susceptibilities to biotransformation. An existing state of the art probabilistic bioaccumulation model was improved by accounting for bioavailability and absorption efficiency limitations, due to the presence of black carbon in sediment, and was used for probabilistic modeling of variability and propagation of error. Results showed that at lower trophic levels (mayfly and polychaete), variability in bioaccumulation was mainly driven by sediment exposure, sediment composition and chemical partitioning to sediment components, which was in turn dominated by the influence of black carbon. At higher trophic levels (yellow perch and the little owl), food web structure (i.e., diet composition and abundance) and chemical concentration in the diet became more important particularly for the most persistent compound, PCB-153. These results suggest that variation in bioaccumulation assessment is reduced most by improved identification of food sources as well as by accounting for the chemical bioavailability in food components. Improvements in the accuracy of aqueous exposure appear to be less relevant when applied to moderate to highly hydrophobic compounds, because this route contributes only marginally to total uptake. The determination of chemical bioavailability and the increase in understanding and qualifying the role of sediment components (black carbon, labile organic matter, and the like) on chemical absorption efficiencies has been identified as a key next steps.

Integrated Environmental Assessment and Management

Selenium concentrations and stable isotopic compositions of carbon and nitrogen in the benthic clam Corbula amurensis from northern San Francisco Bay, California: May 1995–February 2010

The clam-based food webs of San Francisco Bay, California efficiently bioaccumlate selenium and thus provide pathways for exposure to predators important to the estuary. This study documents changes in monthly selenium concentrations for the clam Corbula amurensis , a keystone species of the estuary, at five locations in northern San Francisco Bay from 1995 through 2010. Samples were collected from designated U.S. Geological Survey stations and prepared and analyzed by U.S. Geological Survey methods. Stable isotopes of carbon and nitrogen in soft tissues of clams also were measured as an indicator of sources of selenium for the clams. These monitoring data indicate that clam selenium concentrations ranged from a low of 2 to a high of 22 micrograms per gram dry weight with strong spatial and seasonal variation over the period of study.

California