David B. Senn

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 MRs 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.

Acceleration of Amyloid β-Peptide Aggregation by Physiological Concentrations of Calcium

Alzheimer disease is characterized by the accumulation of aggregated amyloid β-peptide (Aβ) in the brain. The physiological mechanisms and factors that predispose to Aβ aggregation and deposition are not well understood. In this report, we show that calcium can predispose to Aβ 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 Aβ 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.

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.

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.

Impact of a large tropical reservoir on riverine transport of sediment, carbon, and nutrients to downstream wetlands

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 = 364 km(2), hydraulic residence time = 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. Since dam completion in 1978, 330 x 10(3) tons (t) of sediment and 16 x 10(3), 1.5 x 10(3), 200 t of C, N, and P, respectively, have accumulated annually in ITT sediments. Approximately 50% of N inputs and 60% of P inputs are removed by the reservoir, illustrating its potential in decreasing nutrients to the downstream Kafue Flats floodplain. The biogeochemical model predicted substantial primary production in ITT (similar to 280 g C m(-2) yr(-1)), and significant N-fixation (similar to 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 similar to 4 and similar to 2 compared to current dam management, respectively.

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.

Sediment accumulation and carbon, nitrogen, and phosphorus deposition in the large tropical reservoir Lake Kariba (Zambia/Zimbabwe)

Large dams affect the aquatic continuum from land to ocean by accumulating particles and nutrients in their reservoirs. We examined sediment cores to quantify sediment, organic carbon (OC), nitrogen (N), and phosphorous (P) accumulation, and to examine historic changes and spatial variability in the sedimentation pattern in Lake Kariba, the largest hydropower reservoir in the Zambezi River Basin (ZRB). Sediment characteristics (concentrations of OC, N, P; delta(13)C and delta(15)N; wet bulk density) showed large variability both with sediment depth and between cores. While organic matter (OM) in river deltas was primarily allochthonous in origin, OM characteristics (delta(13)C, C:N) in lacustrine sediments suggest that autochthonous sources account for >45% of the OM that accumulates over large areas of the lake. At the same time, the relative contribution of allochthonous material within individual layers of lacustrine cores varied considerably with depth due to discrete flood deposits. The overall sediment accumulation rate in Lake Kariba is on the order of 4 x 10(6) t yr(-1), and the estimated OC accumulation of 120 x 10(3) t C yr(-1) accounts for similar to 1% of globally buried OC in reservoirs. In addition, mass balance calculations revealed that approximately 70% and 90% of incoming total N and P, respectively, are eliminated from the water column by sedimentation (N, P) and denitrification (N). Since Lake Kariba attenuates flow from similar to 50% of the ZRB, these OC, N, and P removals represent a drastic reduction in nutrient loadings to downstream riparian ecosystems and to the coastal Indian Ocean.

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.

Disturbance impacts on mercury dynamics in northern Gulf of Mexico sediments

A 0 2), 210 Pb levels are consistent with the episodic deposition of >10 cm of sediments. These surface sediments (0–10 cm) at A 0 2 had the highest %MeHg of all stations and all dates, suggesting that the disturbance resulted initially in increased net methylation. While the observed disturbances elsewhere could not in all cases be definitively linked to hurricane activities, the substantial thickness of deposits (>10 cm) at multiple sites is consistent with a major event, and the similarity in the deposits’ chemical fingerprint across all impacted sites suggests similar sources or processes. We estimate that the two hurricanes redistributed approximately 5 times the annual Hg input from the Mississippi-Atchafalaya River system and atmospheric deposition. These observations highlight the need to consider the effects of major disturbances on the biogeochemical cycling of Hg in coastal systems.

Spatial heterogeneity of benthic methane dynamics in the subaquatic canyons of the Rhone River Delta (Lake Geneva)

Abstract Heterogeneous benthic methane (CH4) dynamics from river deltas with important organic matter accumulation have been recently reported in various aquatic and marine environments. The spatial heterogeneity of dissolved CH4 concentrations and associated production and diffusion rates were investigated in the Rhone River Delta of Lake Geneva (Switzerland/France) using sediment cores taken as part of the éLEMO Project. Benthic CH4 dynamics within the complex subaquatic canyon structure of the Rhone Delta were compared (1) between three canyons of different sedimentation regimes, (2) along a longitudinal transect of the ‘active’ canyon most influenced by the Rhone River, and (3) laterally across a canyon. Results indicated higher CH4 diffusion and production rates in the ‘active’ compared to the other canyons, explained by more allochthonous carbon deposition. Within the active canyon, the highest diffusion and production rates were found at intermediate sites further along the canyon. Stronger resuspension of sediments directly in front of the river inflow was likely the cause for the variable emission rates found there. Evidence also suggests more CH4 production occurs on the levees (shoulders) of canyons due to preferred sedimentation in those locations. Our results from the heterogeneous Rhone delta in Lake Geneva further support the concept that high sedimentary CH4 concentrations should be expected in depositional environments with high inputs of allochthonous organic carbon.