Evidence that Pacific tuna mercury levels are driven by marine methylmercury production and anthropogenic inputs.

Pacific Ocean tuna is among the most-consumed seafood products but contains relatively high levels of the neurotoxin methylmercury. Limited observations suggest tuna mercury levels vary in space and time, yet the drivers are not well understood. Here, we map mercury concentrations in skipjack tuna across the Pacific Ocean and build generalized additive models to quantify the anthropogenic, ecological, and biogeochemical drivers. Skipjack mercury levels display a fivefold spatial gradient, with maximum concentrations in the northwest near Asia, intermediate values in the east, and the lowest levels in the west, southwest, and central Pacific. Large spatial differences can be explained by the depth of the seawater methylmercury peak near low-oxygen zones, leading to enhanced tuna mercury concentrations in regions where oxygen depletion is shallow. Despite this natural biogeochemical control, the mercury hotspot in tuna caught near Asia is explained by elevated atmospheric mercury concentrations and/or mercury river inputs to the coastal shelf. While we cannot ignore the legacy mercury contribution from other regions to the Pacific Ocean (e.g., North America and Europe), our results suggest that recent anthropogenic mercury release, which is currently largest in Asia, contributes directly to present-day human mercury exposure.

Accumulation of Marcellus Formation Oil and Gas Wastewater Metals in Freshwater Mussel Shells.

For several decades, high-salinity water brought to the surface during oil and gas (O&G) production has been treated and discharged to waterways under National Pollutant Discharge Elimination System (NPDES) permits. In Pennsylvania, USA, a portion of the treated O&G wastewater discharged to streams from 2008 to 2011 originated from unconventional (Marcellus) wells. We collected freshwater mussels, Elliptio dilatata and Elliptio complanata, both upstream and downstream of a NPDES-permitted facility, and for comparison, we also collected mussels from the Juniata and Delaware Rivers that have no reported O&G discharge. We observed changes in both the Sr/Cashell and 87Sr/86Srshell in shell samples collected downstream of the facility that corresponded to the time period of greatest Marcellus wastewater disposal (2009-2011). Importantly, the changes in Sr/Cashell and 87Sr/86Srshell shifted toward values characteristic of O&G wastewater produced from the Marcellus Formation. Conversely, shells collected upstream of the discharge and from waterways without treatment facilities showed lower variability and no trend in either Sr/Cashell or 87Sr/86Srshell with time (2008-2015). These findings suggest that (1) freshwater mussels may be used to monitor changes in water chemistry through time and help identify specific pollutant sources and (2) O&G contaminants likely bioaccumulated in areas of surface water disposal.

Mercury concentrations in tuna blood and muscle mirror seawater methylmercury in the Western and Central Pacific Ocean.

Understanding the relationship between mercury in seafood and the distribution of oceanic methylmercury is key to understand human mercury exposure. Here, we determined mercury concentrations in muscle and blood of bigeye and yellowfin tunas from the Western and Central Pacific. Results showed similar latitudinal patterns in tuna blood and muscle, indicating that both tissues are good candidates for mercury monitoring. Complementary tuna species analyses indicated species- and tissue- specific mercury patterns, highlighting differences in physiologic processes of mercury uptake and accumulation associated with tuna vertical habitat. Tuna mercury content was correlated to ambient seawater methylmercury concentrations, with blood being enriched at a higher rate than muscle with increasing habitat depth. The consideration of a significant uptake of dissolved methylmercury from seawater in tuna, in addition to assimilation from food, might be interesting to test in models to represent the spatiotemporal evolutions of mercury in tuna under different mercury emission scenarios.

Stable mercury concentrations of tropical tuna in the south western Pacific ocean: An 18-year monitoring study.

Global anthropogenic mercury (Hg) emissions to the atmosphere since industrialization are widely considered to be responsible for a significant increase in surface ocean Hg concentrations. Still unclear is how those inputs are converted into toxic methylmercury (MeHg) then transferred and biomagnified in oceanic food webs. We used a unique long-term and continuous dataset to explore the temporal Hg trend and variability of three tropical tuna species (yellowfin, bigeye, and skipjack) from the southwestern Pacific Ocean between 2001 and 2018 (n = 590). Temporal trends of muscle nitrogen (δ15N) and carbon (δ13C) stable isotope ratios, amino acid (AA) δ15N values and oceanographic variables were also investigated to examine the potential influence of trophic, biogeochemical and physical processes on the temporal variability of tuna Hg concentrations. For the three species, we detected significant inter-annual variability but no significant long-term trend for Hg concentrations. Inter-annual variability was related to the variability in tuna sampled lengths among years and to tuna muscle δ15N and δ13C values. Complementary AA- and model-estimated phytoplankton δ15N values suggested the influence of baseline processes with enhanced tuna Hg concentrations observed when dinitrogen fixers prevail, possibly fuelling baseline Hg methylation and/or MeHg bioavailability at the base of the food web. Our results show that MeHg trends in top predators do not necessary capture the increasing Hg concentrations in surface waters suspected at the global oceanic scale due to the complex and variable processes governing Hg deposition, methylation, bioavailability and biomagnification. This illustrates the need for long-term standardized monitoring programs of marine biota worldwide.

Forensic tracers of exposure to produced water in freshwater mussels: a preliminary assessment of Ba, Sr, and cyclic hydrocarbons.

Hydraulic fracturing is often criticized due in part to the potential degradation of ground and surface water quality by high-salinity produced water generated during well stimulation and production. This preliminary study evaluated the response of the freshwater mussel, Elliptio complanata, after exposure to produced water. A limited number of adult mussels were grown over an 8-week period in tanks dosed with produced water collected from a hydraulically fractured well. The fatty tissue and carbonate shells were assessed for accumulation of both inorganic and organic pollutants. Ba, Sr, and cyclic hydrocarbons indicated the potential to accumulate in the soft tissue of freshwater mussels following exposure to diluted oil and gas produced water. Exposed mussels showed accumulation of Ba in the soft tissue several hundred times above background water concentrations and increased concentrations of Sr. Cyclic hydrocarbons were detected in dosed mussels and principle component analysis of gas chromatograph time-of-flight mass spectrometer results could be a novel tool to help identify areas where aquatic organisms are impacted by oil and gas produced water, but larger studies with greater replication are necessary to confirm these results.

Seabirds supply nitrogen to reef-building corals on remote Pacific islets.

Seabirds concentrate nutrients from large marine areas on their nesting islands playing an important ecological role in nutrient transfer between marine and terrestrial ecosystems. Here we investigate the role of guano on corals reefs across scales by analyzing the stable nitrogen isotopic (δ15N) values of the scleractinian coral Pocillopora damicornis on fringing reefs around two Pacific remote islets with large seabird colonies. Marine stations closest to the seabird colonies had higher nitrate + nitrite concentrations compared to more distant stations. Coral and zooxanthellae δ15N values were also higher at these sites, suggesting that guano-derived nitrogen is assimilated into corals and contributes to their nitrogen requirements. The spatial extent of guano influence was however restricted to a local scale. Our results demonstrate that seabird-derived nutrients not only spread across the terrestrial ecosystem, but also affect components of the adjacent marine ecosystem. Further studies are now needed to assess if this nutrient input has a positive or negative effect for corals. Such studies on remote islets also open fresh perspectives to understand how nutrients affect coral reefs isolated from other anthropogenic stressors.

Inter- and intra-annual variations of Pb/Ca ratios in clam shells (Mercenaria mercenaria): a record of anthropogenic lead pollution?

In this study, we re-assess the use of bivalve shells as a proxy of lead pollution. Previous studies have stressed that shells display little variability compared to soft tissues and thus are better for pollution biomonitoring. However, in this manuscript we illustrate that there is large inter- and intra-annual Pb variability between shells of the clam Mercenaria mercenaria collected in North Carolina, USA. Therefore, year to year, as well as intra-annual variations in Pb/Ca ratios should be interpreted with caution. Despite this variability, we were able to obtain an annual Pb chronology from 1949 to 2002 using 11 shells collected at different times which clearly exhibited the late 1970's peak in Pb from leaded gasoline use. This indicates that when enough specimens are pooled together, bivalve shells can be used to reconstruct large, long term changes in environmental Pb concentrations. Our data compare well with other studies of aragonite clams from sites with low regional lead pollution. From this we conclude that the Cape Lookout region of North Carolina has not received extensive pollution over the 1949-2002 period. The Pb concentration in shells growing in the 1949-1976 period was not significantly different from those growing in the 1982-2002 period, although other proxies suggest that the 1949-1976 period should be considerably higher. Therefore, our data suggest that there is still a modern low-level source of Pb in the coastal North Carolina environment.

Do freshwater mussel shells record road-salt pollution?

Road-salt pollution in streams in the Northeastern United States has become a major concern, but historical data are scarce. Freshwater bivalve shells have the ability to record past environmental information, and may act as archives of road-salt pollution. We sampled Elliptio complanata shells from four streams, as well as specimens collected in 1877. Average [Na/Ca]shell was highest in modern shells from the stream with the highest sodium concentrations, and low in shells collected from this same stream in 1877 as well as in the shells from other streams, suggesting that [Na/Ca]shell serves as a proxy for road-salt pollution. We expected higher [Na/Ca]shell in winter and spring. However, high-resolution [Na/Ca]shell analyses along the growth axis of one shell did not reveal any clear subannual patterns, which could be the result of shell growth cessation in winter and/or during periods of high stream sodium concentrations. Therefore, bulk [Na/Ca]shell analysis from multiple shells can be used as a proxy of large changes in stream sodium concentrations, but high-resolution variations in stream sodium concentrations do not seem to be recorded in the shells.

Contrasting biogeochemical characteristics of the Oubangui River and tributaries (Congo River basin).

The Oubangui is a major tributary of the Congo River. We describe the biogeochemistry of contrasting tributaries within its central catchment, with watershed vegetation ranging from wooded savannahs to humid rainforest. Compared to a 2-year monitoring record on the mainstem Oubangui, these tributaries show a wide range of biogeochemical signatures, from highly diluted blackwaters (low turbidity, pH, conductivity, and total alkalinity) in rainforests to those more typical for savannah systems. Spectral analyses of chromophoric dissolved organic matter showed wide temporal variations in the Oubangui compared to spatio-temporal variations in the tributaries, and confirm that different pools of dissolved organic carbon are mobilized during different hydrological stages. δ(13)C of dissolved inorganic carbon ranged between -28.1‰ and -5.8‰, and was strongly correlated to both partial pressure of CO2 and to the estimated contribution of carbonate weathering to total alkalinity, suggesting an important control of the weathering regime on CO2 fluxes. All tributaries were oversaturated in dissolved greenhouse gases (CH4, N2O, CO2), with highest levels in rivers draining rainforest. The high diversity observed underscores the importance of sampling that covers the variability in subcatchment characteristics, to improve our understanding of biogeochemical cycling in the Congo Basin.