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.

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.

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.

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.

Alzheimer disease is characterized by the accumulation of aggregated amyloid ␤-peptide (A␤) in the brain. The physiological mechanisms and factors that predispose to A␤ aggregation and deposition are not well understood. In this report, we show that calcium can predispose to A␤ 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 A␤ 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.Amyloid ␤-peptide (A␤) 2 is the primary constituent of amyloid plaques in Alzheimer disease (AD). Cleavage of the amyloid ␤ precursor protein leads to the production of A␤ peptides of varying lengths, of which the 40-amino acid peptide is the major species (A␤ 1-40 ) (1). Mutations that cause familial Alzheimer disease generally lead to an increase in the level of the more fibrillogenic 42-amino acid peptide A␤ 1-42 (1, 2). The aggregation of A␤ into mature amyloid fibrils occurs through a number of intermediate structural forms, variously referred to as oligomers or protofibrils. Soluble oligomeric species and protofibrillar structures may affect neuronal function and viability (3-5), and mature amyloid fibrils are toxic to neurons in vitro and in vivo (6, 7). Identifying factors that promote A␤ aggregation may thus be important for understanding the pathophysiology of AD and developing therapeutic strategies.The mechanism by which A␤ aggregates in the brain is not fully understood, although there is increasing evidence that metal ions may play a role. Physiological levels of copper and zinc have been shown to accelerate A␤ aggregation (8 -10), and trace levels of copper and zinc may initiate seeding and oligomerization of A␤ (11). It has also been suggested that the binding of A␤ to the membrane sialoglycolipid GM1 ganglioside can lead to a conformational change in A␤ and seeding of aggregation (12). Recent evidence suggests that A␤ 1-42 is the A␤ species required for the seeding of amyloid fibril formation and plaque deposition in vivo, as mice overexpressing only A␤ 1-42 developed amyloid plaques, whereas mice overexpressing only A␤ 1-40 did not (13). In this report we show that calcium can accelerate aggregation of A␤ 1-42 , with marked effects on the formation of early protofibrillar structures, as well as the protofibril t...

[1] Large dams can have major ecological and biogeochemical impacts on downstream ecosystems such as wetlands and riparian habitats. We examined sediment removal and carbon (C), nitrogen (N), and phosphorus (P) cycling in Itezhi-Tezhi Reservoir (ITT; area ¼ 364 km 2 , hydraulic residence time ¼ 0.7 yr), which is located directly upstream of a high ecological value floodplain ecosystem (Kafue Flats) in the Zambezi River Basin. Field investigations (sediment cores, sediment traps, water column samples), mass balance estimates, and a numerical biogeochemical reservoir model were combined to estimate N, P, C, and sediment removal, organic C mineralization, primary production, and N fixation. ), and significant N-fixation ($30% for the total primary production) was required to support primary production due to marginal inputs of inorganic N. Model simulations indicate that future hydropower development in the reservoir, involving the installation of turbines driven by hypolimnetic water, will likely result in the delivery of low-oxygen waters to downstream ecosystems and increased outputs of dissolved inorganic N and P by a factor of $4 and $2 compared to current dam management, respectively.

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.

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.