Multi-scale trend analysis of water quality using error propagation of generalized additive models.

Effective stewardship of ecosystems to sustain current ecological status or mitigate impacts requires nuanced understanding of how conditions have changed over time in response to anthropogenic pressures and natural variability. Detecting and appropriately characterizing changes requires accurate and flexible trend assessment methods that can be readily applied to environmental monitoring datasets. A key requirement is complete propagation of uncertainty through the analysis. However, this is difficult when there are mismatches between sampling frequency, period of record, and trends of interest. Here, we propose a novel application of generalized additive models (GAMs) for characterizing multi-decadal changes in water quality indicators and demonstrate its utility by analyzing a 30-year record of biweekly-to-monthly chlorophyll-a concentrations in the San Francisco Estuary. GAMs have shown promise in water quality trend analysis to separate long-term (i.e., annual or decadal) trends from seasonal variation. Our proposed methods estimate seasonal averages in a response variable with GAMs, extract uncertainty measures for the seasonal estimates, and then use the uncertainty measures with mixed-effects meta-analysis regression to quantify inter-annual trends that account for full propagation of error across methods. We first demonstrate that nearly identical descriptions of temporal changes can be obtained using different smoothing spline formulations of the original time series. We then extract seasonal averages and their standard errors for an a priori time period within each year from the GAM results. Finally, we demonstrate how across-year trends in seasonal averages can be modeled with mixed-effects meta-analysis regression that propagates uncertainties from the GAM fits to the across-year analysis. Overall, this approach leverages GAMs to smooth data with missing observations or varying sample effort across years to estimate seasonal averages and meta-analysis to estimate trends across years. Methods are provided in the wqtrends R package.

Four decades of water quality change in the upper San Francisco Estuary.

Quantitative descriptions of chemical, physical, and biological characteristics of estuaries are critical for developing an ecological understanding of drivers of change. Historical trends and relationships between key species of dissolved inorganic nitrogen (ammonium, nitrate/nitrite, total) from the Delta region of the San Francisco Estuary were modeled with an estuarine adaptation of the Weighted Regressions on Time, Discharge, and Season (WRTDS). Analysis of flow-normalized data revealed trends that were different from those in the observed time-series. Flow-normalized data exhibited changes in magnitude and even reversal of trends relative to the observed data. Modelled trends demonstrated that nutrient concentrations were on average higher in the last twenty years relative to the earlier periods of observation, although concentrations have been slowly declining since the mid-1990s and early 2000s. We further describe mechanisms of change with two case studies that evaluated 1) downstream changes in nitrogen following upgrades at a wastewater treatment plant, and 2) interactions between biological invaders, chlorophyll, macro-nutrients (nitrogen and silica), and flow in Suisun Bay. WRTDS results for ammonium trends showed a distinct signal as a result of upstream wastewater treatment plant upgrades, with specific reductions observed in the winter months during low-flow conditions. Results for Suisun Bay showed that chlorophyll a production in early years was directly stimulated by flow, whereas the relationship with flow in later years was indirect and influenced by grazing pressure. Although these trends and potential causes of change have been described in the literature, results from WRTDS provided an approach to test alternative hypotheses of spatiotemporal drivers of nutrient dynamics in the Delta.

Blurred lines: Multiple freshwater and marine algal toxins at the land-sea interface of San Francisco Bay, California.

San Francisco Bay (SFB) is a eutrophic estuary that harbors both freshwater and marine toxigenic organisms that are responsible for harmful algal blooms. While there are few commercial fishery harvests within SFB, recreational and subsistence harvesting for shellfish is common. Coastal shellfish are monitored for domoic acid and paralytic shellfish toxins (PSTs), but within SFB there is no routine monitoring for either toxin. Dinophysis shellfish toxins (DSTs) and freshwater microcystins are also present within SFB, but not routinely monitored. Acute exposure to any of these toxin groups has severe consequences for marine organisms and humans, but chronic exposure to sub-lethal doses, or synergistic effects from multiple toxins, are poorly understood and rarely addressed. This study documents the occurrence of domoic acid and microcystins in SFB from 2011 to 2016, and identifies domoic acid, microcystins, DSTs, and PSTs in marine mussels within SFB in 2012, 2014, and 2015. At least one toxin was detected in 99% of mussel samples, and all four toxin suites were identified in 37% of mussels. The presence of these toxins in marine mussels indicates that wildlife and humans who consume them are exposed to toxins at both sub-lethal and acute levels. As such, there are potential deleterious impacts for marine organisms and humans and these effects are unlikely to be documented. These results demonstrate the need for regular monitoring of marine and freshwater toxins in SFB, and suggest that co-occurrence of multiple toxins is a potential threat in other ecosystems where freshwater and seawater mix.

Sources and fates of heavy metals in a mining-impacted stream: temporal variability and the role of iron oxides.

Heavy metal contamination of surface waters at mining sites often involves complex interactions of multiple sources and varying biogeochemical conditions. We compared surface and subsurface metal loading from mine waste pile runoff and mine drainage discharge and characterized the influence of iron oxides on metal fate along a 0.9-km stretch of Tar Creek (Oklahoma, USA), which drains an abandoned Zn/Pb mining area. The importance of each source varied by metal; mine waste pile runoff contributed 70% of Cd, while mine drainage contributed 90% of Pb, and both sources contributed similarly to Zn loading. Subsurface inputs accounted for 40% of flow and 40-70% of metal loading along this stretch. Streambed iron oxide aggregate material contained highly elevated Zn (up to 27,000 µg g(-1)), Pb (up to 550 µg g(-1)) and Cd (up to 200 µg g(-1)) and was characterized as a heterogeneous mixture of iron oxides, fine-grain mine waste, and organic material. Sequential extractions confirmed preferential sequestration of Pb by iron oxides, as well as substantial concentrations of Zn and Cd in iron oxide fractions, with additional accumulation of Zn, Pb, and Cd during downstream transport. Comparisons with historical data show that while metal concentrations in mine drainage have decreased by more than an order of magnitude in recent decades, the chemical composition of mine waste pile runoff has remained relatively constant, indicating less attenuation and increased relative importance of pile runoff. These results highlight the importance of monitoring temporal changes at contaminated sites associated with evolving speciation and simultaneously addressing surface and subsurface contamination from both mine waste piles and mine drainage.

Prioritizing environmental risk of prescription pharmaceuticals.

Low levels of pharmaceutical compounds have been detected in aquatic environments worldwide, but their human and ecological health risks associated with low dose environmental exposure is largely unknown due to the large number of these compounds and a lack of information. Therefore prioritization and ranking methods are needed for screening target compounds for research and risk assessment. Previous efforts to rank pharmaceutical compounds have often focused on occurrence data and have paid less attention to removal mechanisms such as human metabolism. This study proposes a simple prioritization approach based on number of prescriptions and toxicity information, accounting for metabolism and wastewater treatment removal, and can be applied to unmeasured compounds. The approach was performed on the 200 most-prescribed drugs in the US in 2009. Our results showed that under-studied compounds such as levothyroxine and montelukast sodium received the highest scores, suggesting the importance of removal mechanisms in influencing the ranking, and the need for future environmental research to include other less-studied but potentially harmful pharmaceutical compounds.

Spatial heterogeneity of methane ebullition in a large tropical reservoir.

Tropical reservoirs have been identified as important methane (CH(4)) sources to the atmosphere, primarily through turbine and downstream degassing. However, the importance of ebullition (gas bubbling) remains unclear. We hypothesized that ebullition is a disproportionately large CH(4) source from reservoirs with dendritic littoral zones because of ebullition hot spots occurring where rivers supply allochthonous organic material. We explored this hypothesis in Lake Kariba (Zambia/Zimbabwe; surface area >5000 km(2)) by surveying ebullition in bays with and without river inputs using an echosounder and traditional surface chambers. The two techniques yielded similar results, and revealed substantially higher fluxes in river deltas (∼10(3) mg CH(4) m(-2) d(-1)) compared to nonriver bays (<100 mg CH(4) m(-2) d(-1)). Hydroacoustic measurements resolved at 5 m intervals showed that flux events varied over several orders of magnitude (up to 10(5) mg CH(4) m(-2) d(-1)), and also identified strong differences in ebullition frequency. Both factors contributed to emission differences between all sites. A CH(4) mass balance for the deepest basin of Lake Kariba indicated that hot spot ebullition was the largest atmospheric emission pathway, suggesting that future greenhouse gas budgets for tropical reservoirs should include a spatially well-resolved analysis of ebullition hot spots.

Fish consumption and mercury exposure among Louisiana recreational anglers.

BACKGROUND: Methylmercury (MeHg) exposure assessments among average fish consumers in the United States may underestimate exposures among U.S. subpopulations with high intakes of regionally specific fish. OBJECTIVES: We examined relationships among fish consumption, estimated mercury (Hg) intake, and measured Hg exposure within one such potentially highly exposed group, recreational anglers in the state of Louisiana, USA. METHODS: We surveyed 534 anglers in 2006 using interviews at boat launches and fishing tournaments combined with an Internet-based survey method. Hair samples from 402 of these anglers were collected and analyzed for total Hg. Questionnaires provided information on species-specific fish consumption during the 3 months before the survey. RESULTS: Anglers' median hair Hg concentration was 0.81 µg/g (n = 398; range, 0.02-10.7 µg/g); 40% of participants had levels >1 µg/g, which approximately corresponds to the U.S. Environmental Protection Agency's reference dose. Fish consumption and Hg intake were significantly positively associated with hair Hg. Participants reported consuming nearly 80 different fish types, many of which are specific to the region. Unlike the general U.S. population, which acquires most of its Hg from commercial seafood sources, approximately 64% of participants' fish meals and 74% of their estimated Hg intake came from recreationally caught seafood. CONCLUSIONS: Study participants had relatively elevated hair Hg concentrations and reported consumption of a wide variety of fish, particularly locally caught fish. This group represents a highly exposed subpopulation with an exposure profile that differs from fish consumers in other regions of the United States, suggesting a need for more regionally specific exposure estimates and public health advisories.

Stable isotope (N, C, Hg) study of methylmercury sources and trophic transfer in the northern gulf of Mexico.

We combined N, C, and Hg stable isotope measurements to identify the most important factors that influence MeHg accumulation in fish from the northern Gulf of Mexico (nGOM), and to determine if coastal species residing in the Mississippi River (MR) plume and migratory oceanic species derive their MeHg from the same, or different, sources. In six coastal species and two oceanic species (blackfin and yellowfin tuna), trophic position as measured by delta(15)N explained most of the variance in log[MeHg] (r(2) approximately 0.8), but coastal species and tuna fell along distinct, nearly parallel lines with significantly different intercepts. The tuna also had significantly higher delta(202)Hg (0.2-0.5 per thousand) and Delta(201)Hg ( approximately 1.5 per thousand) than the coastal fish (delta(202)Hg = 0 to -1.0 per thousand; Delta(201)Hg approximately 0.4 per thousand). The observations can be best explained by largely disconnected food webs rooted in different baseline delta(15)N signatures (MR-plume vs oceanic) and isotopically distinct MeHg sources, with oceanic MeHg having undergone substantial photodegradation ( approximately 50%) before entering the base of the food web. Given the MR's large, productive footprint in the nGOM and the potential for exporting prey and MeHg to the adjacent oligotrophic GOM, the disconnected food webs and different MeHg sources are consistent with recent evidence in other systems of important oceanic MeHg sources.

Relative importance of atmospheric and riverine mercury sources to the northern Gulf of Mexico.

A box model was developed to quantify the major sources and dominant fates of inorganic mercury (Hg) in the Mississippi River-influenced area of the northern Gulf of Mexico (nGOM). Riverine (75%) and direct atmospheric deposition (25%) deliver 9.7 t Hg y(-1) to this productive fishery; most (80%) accumulates in bottom sediments where it can be methylated and enter foodwebs. Although riverine inputs dominate atmospheric deposition, 75% of the riverine sediment-associated Hg accumulates in only approximately 8% of the study area. Atmospheric deposition can explain most of the Hg accumulating in sediments of the remaining area. Considering the differences in temporal responsiveness of riverine (centuries) and atmospheric (years) Hg inputs to anthropogenic emissions changes, the spatial limits of the riverine Hg source andthe potential dominance of atmospheric deposition over large areas could have implications for the timing of benefits from policies reducing anthropogenic Hg emissions.

Mercury bioaccumulation and trophic transfer in sympatric snapper species from the Gulf of Mexico.

Consumption of marine fish is a major route of toxic methyl mercury (MeHg) exposure to ocean apex predators and human populations. Here we explore the influence of trophic structure on total mercury (Hg) accumulation in red snapper (RS, Lutjanus campechanus) and gray snapper (GS, Lutjanus griseus) from the coastal Louisiana region of the Gulf of Mexico, west of the Mississippi River. The objectives of this investigation were to: (1) determine the effectiveness of the use of offshore recreational fishing charter boats and marinas as sources of fish samples and (2) compare species differences in Hg bioaccumulation, trophic position, and carbon sources. Our data show that length-normalized Hg concentrations (> or = 97% as MeHg in tissue of both species) were 230% greater in GS in comparison to RS collected from the same general area. Stable C and N isotope signatures (delta15N and delta13C) indicate that GS occupy a slightly higher trophic position (approximately 30% of one trophic position higher) on the Gulf food web in comparison to RS and that GS appear to incorporate higher trophic positioned prey, continually and at smaller sizes. Mercury was strongly correlated with combined delta15N and delta13C in pooled species data, arguing that most of the substantial difference in Hg bioaccumulation between RS and GS can be explained by modest differences in their trophic position and, to a lesser degree, carbon sources, which had low variation and high overlap among species. These observations demonstrate that even minor to moderate differences in trophic position and food habits in sympatric species can create relatively large differences in bioaccumulation regimes and underscores the importance of quantitative characterization of trophic structure in marine MeHg bioaccumulation studies.

Characterization of zinc, lead, and cadmium in mine waste: implications for transport, exposure, and bioavailability.

We characterized the lability and bioaccessibility of Zn, Pb, and Cd in size-fractionated mine waste at the Tar Creek Superfund Site (Oklahoma) to assess the potential for metal transport, exposure, and subsequent bioavailability. Bulk mine waste samples contained elevated Zn (9100 +/- 2500 ppm), Pb (650 +/- 360 ppm), and Cd (42 +/- 10 ppm), while particles with the greatest potential for windborne transport and inhalation (< 10 microm) contained substantially higher concentrations, up to 220 000 ppm Zn, 16 000 ppm Pb, and 530 ppm Cd in particles < 1 microm. Although the mined ore at Tar Creek primarily consisted of refractory metal sulfides with low bioavailability, sequential extractions and physiologically based extractions indicate that physical and chemical weathering have shifted metals into relatively labile and bioaccessible mineral phases. In < 37 microm mine waste particles, 50-65% of Zn, Pb, and Cd were present in the "exchangeable" and "carbonate" sequential extraction fractions, and 60-80% of Zn, Pb, and Cd were mobilized in synthetic gastric fluid, while ZnS and PbS exhibited minimal solubility in these solutions. Our results demonstrate the importance of site-specific characterization of size-fractionated contemporary mine waste when assessing the lability and bioavailability of metals at mine-waste impacted sites.

Long-term fate of a pulse arsenic input to a eutrophic lake.

The long-term fate of a 30-year-old pulse arsenic input to a eutrophic lake was studied to determine if As has become effectively trapped in sediments or remains in active exchange with the water column. Legacy As was readily mobilized from sediments of Spy Pond (Arlington, MA), a eutrophic kettle-hole lake that was treated with 1000s kg As in the 1960s to manage excessive aquatic macrophyte growth. Arsenic was mobilized from hypolimnetic sediments during bottom-water anoxia in spring, summer, and fall, and As accumulated to maximum concentrations of 2100 nM. Mobilization of As from epilimnetic sediments was the largest source of As to the water column on a mass basis (145 mol), despite the fact that the epilimnion remains oxic year-round. Sediment cores revealed that surficial sediments contained As at 30-50 times background levels and suggested that there is contemporary As loading to hypolimnetic sediments (590 mol y(-1)). Mass balance estimates indicate that <5% of the contemporary As load comes from external inputs and that the remainder can be explained by mobilization and redistribution of legacy As, both through the water column and by vertical migration of dissolved As within sediments. These findings demonstrate that, decades after As inputs cease, As in contaminated sediments may remain labile and be mobilized to both anoxic and oxic water columns and accumulate to levels near the sediment surface and in the water column that may pose ongoing risks to ecological health.

Acceleration of amyloid beta-peptide aggregation by physiological concentrations of calcium.

Alzheimer disease is characterized by the accumulation of aggregated amyloid beta-peptide (Abeta) in the brain. The physiological mechanisms and factors that predispose to Abeta aggregation and deposition are not well understood. In this report, we show that calcium can predispose to Abeta aggregation and fibril formation. Calcium increased the aggregation of early forming protofibrillar structures and markedly increased conversion of protofibrils to mature amyloid fibrils. This occurred at levels 20-fold below the calcium concentration in the extracellular space of the brain, the site at which amyloid plaque deposition occurs. In the absence of calcium, protofibrils can remain stable in vitro for several days. Using this approach, we directly compared the neurotoxicity of protofibrils and mature amyloid fibrils and demonstrate that both species are inherently toxic to neurons in culture. Thus, calcium may be an important predisposing factor for Abeta aggregation and toxicity. The high extracellular concentration of calcium in the brain, together with impaired intraneuronal calcium regulation in the aging brain and Alzheimer disease, may play an important role in the onset of amyloid-related pathology.

Equilibrium-based sampler for determining Cu2+ concentrations in aquatic ecosystems.

The bioavailability of potentially toxic metals in aquatic systems is frequently related to the dissolved free metal ion (M2+) concentration. However, typical methods used to determine M2+ are labor intensive or require sophisticated equipment. We developed an inexpensive, in situ sampling device--the "gellyfish"--that simplifies Cu2+ determinations in seawater. The gellyfish is a thin disk of polyacrylamide gel embedded with iminodiacetate (Id) groups bound to immobile beads. The sampler operates on the principle that the immobilized Id groups equilibrate with the Cu2+ concentration of the surrounding solution. Cu is then back-extracted into a known volume of 10% HNO3 and measured by inductively coupled plasma mass spectrometry (ICP-MS). In laboratory tests, we varied Cu2+ concentrations between 10(-12) and 10(-8) M and salinity between 5 and 35 ppt. Id-bound Cu (CuId(measured)) did not respond to changes in total Cu. However, CuId(measured) does increase in a predictable manner with increasing Cu2+, and prototype gellyfish precision (average coefficient of variation = 10%) is sufficient to resolve small differences in Cu2+ (+/-30%). Modeled Cu uptake, based on thermodynamic equilibrium speciation of Id within gellyfish, is a good predictor of CuId(measured) (r2 = 0.96 and n = 45).

Particulate arsenic and iron during anoxia in a eutrophic, urban lake.

The bioavailability and transport of particle-reactive pollutants are influenced by their partitioning between dissolved and particulate phases. We explored the importance of particle complexation to the arsenic cycle in an urban lake (Upper Mystic Lake, eastern MA, USA) that experiences arsenic remobilization from contaminated sediments during seasonal hypolimnetic anoxia. Particle size distributions were measured using a new in situ serial filtration system that excludes oxygen and filters at low flow rates to minimize filtration artifacts. Despite anoxia, the majority of remobilized As was present as As(V), and typically 85 to 95% of total As was particle complexed, with 25 to 50% found in the size fraction between 0.4 and 0.05 microm. Iron was distributed similarly among these size classes (>95% of total Fe associated with particles larger than 0.05 microm, 30 to 50% between 0.4 microm and 0.05 microm), contrary to conventional expectation that the majority of Fe should be present as soluble Fe(II) in anoxic waters. By classical filtration (i.e., through a 0.4-microm filter), the colloidal fractions of both Fe and As would have been inaccurately classified as dissolved. Correlations between depth profiles of total As and particulate Fe as well as comparisons of measured arsenic sorption (i.e., total As > 0.05 microm) against predictions by surface complexation modeling of As on amorphous Fe(III) oxides argue that arsenic sorbed on Fe(III) oxides was the major As species present in this lake's hypolimnion throughout several months of anoxia.

Antimony: an unlikely confounder in the relationship between well water arsenic and health outcomes in Bangladesh.

Recent in vitro studies have suggested a potential role for antimony as a confounder in human health studies related to arsenic in drinking water. We measured tube-well water concentrations of antimony and arsenic in the Pabna region of Bangladesh, where arsenic concentrations are known to be elevated and the concentrations of antimony have not yet been thoroughly documented. Two hundred forty-five tube-well water samples were collected from various regions in Pabna, Bangladesh, as part of an ongoing case-control study. Water samples were analyzed for arsenic and antimony concentrations by inductively coupled plasma-mass spectrometry using U.S. Environmental Protection Agency method 200.8. The arsenic concentrations in the tube-well water samples ranged from < 1 microg/L to 747 microg/L. All 245 water samples had antimony concentrations < 1 microg/L. Based on consideration of the concentrations used the in vitro studies compared with field-observed concentrations, our results do not support the hypothesis that antimony would be a significant confounder in observed relationships between arsenic exposure through drinking water and potential health outcomes in Pabna, Bangladesh.

Nitrate controls on iron and arsenic in an urban lake.

Aquatic ecosystems are often contaminated by multiple substances. Nitrate, a common aquatic pollutant, strongly influenced the cycling of arsenic (As) under anoxic conditions in urban Upper Mystic Lake (Massachusetts, USA) by oxidizing ferrous iron [Fe(II)] to produce As-sorbing particulate hydrous ferric oxides and causing the more oxidized As(V), which is more particle-reactive than As(III) under these conditions, to dominate. This process is likely to be important in many natural waters.