Solubilization of particulate Cu by different solutions, mimicking digestive fluids of deposit-feeders, was quantified in stable isotope ⁶⁵Cu-spiked sediments (with 3 days-2 months Cu-sediment contact time or aging). Copper solubilization generally decreased with prolonged aging. However, such decrease became less evident after 1 month and equilibrium of Cu in sediments could be reached after 2 months. Aging effects on Cu solubilization can be explained by the changes in Cu geochemical fractionation with aging: Cu generally transferred from more mobile phases (carbonate and Fe–Mn associated) to more refractory phases (organic associated and residual phase). Besides Cu geochemical fractionation, digestive fluid composition and different Cu solubilization pathways involved, as well as sedimentary organic content, could all affect the digestive solubilization of Cu and its change with aging. Our results emphasize the necessity of considering Cu aging in laboratory sediment toxicity experiments, and in risk assessment of Cu contaminated sediments.

Seasonal variation in mercury (Hg) concentrations and food web structure was assessed for eastern Lake Ontario. Hg concentrations, measured in 6 species of invertebrates and 8 species of fishes, tended to be highest in the spring and lowest in the summer for most biota. Yellow perch (Perca flavescens) exhibited significant ontogenetic shifts in diet and Hg, although such patterns were not evident for other species. Food web structure, as indicated by stable isotope values (δ¹⁵N, δ¹³C) was not static. Log-transformed Hg data were strongly and consistently correlated with δ¹⁵N values for the whole food web in each of the three seasons (slopes, 0.17–0.24) and across the entire year (slope, 0.2). While significantly different between seasons, the regression slope values are still consistent with published global Hg biomagnification rates. Our results indicate that the assessment of Hg trends in Great Lakes must take into account seasonal patterns and time of sampling.

Coral cores were collected along an environmental and water quality gradient through the Whitsunday Island group, Great Barrier Reef (Australia), for trace element and stable isotope analysis. The primary aim of the study was to examine if this gradient could be detected in coral records and, if so, whether the gradient has changed over time with changing land use in the adjacent river catchments. Y/Ca was the trace element ratio which varied spatially across the gradient, with concentrations progressively decreasing away from the river mouths. The Ba/Ca and Y/Ca ratios were the only indicators of change in the gradient through time, increasing shortly after European settlement. The Mn/Ca ratio responded to local disturbance related to the construction of tourism infrastructure. Nitrogen isotope ratios showed no apparent trend over time. This study highlights the importance of site selection when using coral records to record regional environmental signals.

In the present work, fat, skin, liver and muscle samples from Leptonychotes weddellii (Weddell seal, n=2 individuals), Lobodon carcinophagus (crabeater seal, n=2), Arctocephalus gazella (Antarctic fur seal, n=3) and Mirounga leonina (southern elephant seal, n=1) were collected from King George Island, Antarctica, and analysed for POPs (PCBs, organochlorine pesticides and PBDEs) and stable isotopes (δ¹³C and δ¹⁵N in all tissues but fat). PBDEs could be found in only one sample (L. weddellii fat). Generally, PCBs (from 74 to 523ngg⁻¹lw), DDTs (from 14 to 168ngg⁻¹lw) and chlordanes (from 9 to 78ngg⁻¹lw) were the prevailing compounds. Results showed a clear stratification in accordance with ecological data. Nonetheless, stable isotope analyses provide a deeper insight into fluctuations due to migrations and nutritional stress. Correlation between δ¹⁵N and pollutants suggests, to some degree, a considerable ability to metabolize and/or excrete the majority of them.

Atoll lagoons display a high diversity of trophic states due mainly to their specific geomorphology, and probably to their level and mode of human exploitation. We investigated the functioning of the Ahe atoll lagoon, utilized for pearl oyster farming, through estimations of photosynthetic parameters (pulse amplitude modulation fluorometry) and primary production (¹³C incorporation) measurements of the size structured phytoplankton biomass (<2μm and >2μm). Spatial and temporal scales of variability were surveyed during four seasons, over 16months, at four sites within the lagoon. While primary production (P) was dominated by the picophytoplankton, its biomass specific primary productivity (Pᴮ) was lower than in other atoll lagoons. The variables size fraction of the phytoplankton, water temperature, season, the interaction term station*fraction and site, explained significantly the variance of the data set using redundancy analysis. No significant trends over depth were observed in the range of 0–20m. A clear spatial pattern was found which was persistent over the seasons: south and north sites were different from the two central stations for most of the measured variables. This pattern could possibly be explained by the existence of water cells showing different water residence time within the lagoon. Photoacclimation strategies of the two size fractions differed through their light saturation coefficient (higher for picophytoplankton), but not through their maximum photosynthetic capacity (ETRₘₐₓ). Positive linear relationships between photosynthetic parameters indicated that their dynamic was independent of light availability in this ecosystem, but most probably dependent on nutrient availability and/or rapid changes in the community structure. Spatial and temporal patterns of the measured processes are then further discussed in the context of nutrient availability and the possible role of cultured oysters in nutrient recycling.

Biocovers are an alternative for mitigating fugitive and residual emissions of methane from landfills. In this study, we evaluated the performance of two experimental passive methane oxidation biocovers (PMOBs) constructed within the existing final cover of the St-Nicéphore landfill (Quebec, Canada). The biocovers were fed in a controlled manner with raw biogas and surface fluxes were obtained using static chambers. This enabled calculating mass balances of CH₄ and oxidation efficiencies (f ₒ_MB). Most of the time, f ₒ_MB ≥ 92 % were obtained for loadings as high as 818 g CH₄ m⁻² day⁻¹ (PMOB-2) and 290 g CH₄ m⁻² day⁻¹ (PMOB-3B). The lowest efficiencies (f ₒ_MB = 45.5 % and 34.0 %, respectively) were obtained during cold days (air temperature ~0 °C). Efficiencies were also calculated using stable isotopes (f ₒ_SI); the highest f ₒ_SI were 66.4 % for PMOB-2 and 87.3 % for PMOB-3B; whereas the lowest were 18.8 % and 23.1 %, respectively. However, f ₒ_SI values reflect CH₄ oxidation up to a depth of 0.10 m, which may partly explain the difference in regards to mass balance-derived efficiencies. Indeed, it is expected that a significant fraction of the total CH₄ oxidation occurs within the zone near the surface, where there is greater O₂ availability. The influence of the values of fractionation factors α ₒₓ and α ₜᵣₐₙₛ were also evaluated in this paper.

We assessed the suitability of two nonnative poeciliid fishes—western mosquitofish (Gambusia affinis) and sailfin mollies (Poecilia latipinna)—for monitoring selenium exposure in desert pupfish (Cyprinodon macularius). Our investigation was prompted by a need to avoid lethal take of an endangered species (pupfish) when sampling fish for chemical analysis. Total selenium (SeTot) concentrations in both poeciliids were highly correlated with SeTot concentrations in pupfish. However, mean SeTot concentrations varied among fish species, with higher concentrations measured in mosquitofish than in mollies and pupfish from one of three sampled agricultural drains. Moreover, regression equations describing the relationship of selenomethionine to SeTot differed between mosquitofish and pupfish, but not between mollies and pupfish. Because selenium accumulates in animals primarily through dietary exposure, we examined fish trophic relationships by measuring stable isotopes (δ 13C and δ 15N) and gut contents. According to δ 13C measurements, the trophic pathway leading to mosquitofish was more carbon-depleted than trophic pathways leading to mollies and pupfish, suggesting that energy flow to mosquitofish originated from allochthonous sources (terrestrial vegetation, emergent macrophytes, or both), whereas energy flow to mollies and pupfish originated from autochthonous sources (filamentous algae, submerged macrophytes, or both). The δ 15N measurements indicated that mosquitofish and mollies occupied similar trophic levels, whereas pupfish occupied a slightly higher trophic level. Analysis of gut contents showed that mosquitofish consumed mostly winged insects (an indication of terrestrial taxa), whereas mollies and pupfish consumed mostly organic detritus. Judging from our results, only mollies (not mosquitofish) are suitable for monitoring selenium exposure in pupfish.

Past mining and processing of uranium ore at a former uranium mining site near Monument Valley, AZ has resulted in nitrate contamination of groundwater. The objective of this study was to investigate the potential of ethanol addition for enhancing the reduction of nitrate in groundwater. The results of two pilot-scale field tests showed that the concentration of nitrate decreased, while the concentration of nitrous oxide (a product of denitrification) increased. In addition, changes in aqueous concentrations of sulfate, iron, and manganese indicated that the ethanol amendment caused a change in prevailing redox conditions. The results of compound-specific stable isotope analysis for nitrate–nitrogen indicated that the nitrate concentration reductions were biologically mediated. Denitrification rate coefficients estimated for the pilot tests were approximately 50 times larger than resident-condition (non-enhanced) values obtained from prior characterization studies conducted at the site. The nitrate concentrations in the injection zone have remained at levels three orders of magnitude below the initial values for many months, indicating that the ethanol amendments had a long-term impact on the local subsurface environment.

INTRODUCTION: Five liver samples of two different ray species (Gymnura altavela and Zapteryx brevirostris) off the coast of Rio de Janeiro, Brazil, were analyzed for their pollution with anthropogenic and naturally occurring organohalogen compounds. MATERIAL AND METHODS: The samples were extracted with accelerated solvent extraction, and after a clean-up procedure, organohalogen compounds were separated by a modified group separation on activated silica. Subsequent analyses were done by targeted and non-targeted gas chromatography–mass spectrometry in the electron capture negative ion mode. RESULTS AND DISCUSSION: “Classic” organohalogen compounds such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and technical 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane (DDT) were detected and quantified. PCBs generally exceeded the parts per million level and represented up to 90% of the total contamination of the ray livers. High concentrations were also detected for p,p′-DDE. Non-targeted full scan investigations lead to the detection of an abundant trichlorinated compound which was identified as a new DDT metabolite in biota. Different PBDE congeners and several halogenated natural products were quantified as well. In addition, polychlorinated terphenyls were identified and analyzed in the two species. Moreover, both ray species showed different fatty acid patterns and stable carbon isotope signatures. CONCLUSIONS: The two ray species showed high concentrations of organohalogen compounds in their liver tissue. Varied δ 13C values by up to 3.1‰ indicated that the two ray species were living in different habitats.