peer reviewed | Mercury (Hg) concentrations have significantly increased in oceans during the last century. This element accumulates in marine fauna and can reach toxic levels. Seafood consumption is the main pathway of methylmercury (MeHg) toxicity in humans. Here, we analyzed total Hg (T-Hg) concentrations in two oceanic squid species (Ommastrephes bartramii and Thysanoteuthis rhombus) of an increasing commercial interest off Martinique, French West Indies. Stable isotope ratios reveal a negative linear relationship between δ15N or δ13C in diamondback squid samples. No significant trend was observed between δ34S values and T-Hg concentrations, contrasting with the sulfate availability and sulfide abundance hypotheses. This adds to a growing body of evidence suggesting Hg methylation via sulfate-reducing bacteria is not the main mechanism driving Hg bioavailability in mesopelagic organisms. All squid samples present T-Hg levels below the maximum safe consumption limit (0.5 ppm), deeming the establishment of a commercial squid fishery in the region safe for human consumption.

It is widely recognized that green infrastructures in urban ecosystems provides important ecosystem services, including air purification. The potential absorption of nitrogen oxides (NOₓ) by urban trees has not been fully quantified, although it is important for air pollution mitigation and the well-being of urban residents. In this study, four common tree species (Sophora japonica L., Fraxinus chinensis Roxb., Populus tomentosa Carrière, Sabina chinensis (L.)) in Beijing, China, were studied. The dual stable isotopes (¹⁵N and ¹⁸O) and a Bayesian isotope mixing model were applied to estimate the sources contributions of potential nitrogen sources to the roadside trees based on leaf and soil sampling in urban regions. The following order of sources contributions was determined: soil > dry deposition > traffic-related NOₓ. The capacity of urban trees for NOₓ removal in the city was estimated using a remote sensing and GIS approach, and the removal capacity was found to range from 0.79 to 1.11 g m⁻² a⁻¹ across administrative regions, indicating that 1304 tons of NOₓ could be potentially removed by urban trees in 2019. Our finding qualified the potential NOₓ removal by urban trees in terms of atmospheric pollution mitigation, highlighting the role of green infrastructure in air purification, which should be taken into account by stakeholders to manage green infrastructure as the basis of a nature-based approach.

Applying mineral phosphorus (P) fertilizers introduces a considerable input of the toxic heavy metal cadmium (Cd) into arable soils. This study investigates the fate of P fertilizer derived Cd (Cddff) in soil-wheat systems using a novel combination of enriched stable Cd isotope mass balances, sequential extractions, and Bayesian isotope mixing models. We applied an enriched ¹¹¹Cd labeled mineral P fertilizer to arable soils from two long-term field trials with distinct soil properties (a strongly acidic pH and a neutral pH) and distinct past mineral P fertilizer application rates. We then cultivated wheat in a pot trial on these two soils. In the neutral soil, Cd concentrations in the soil and the wheat increased with increasing past mineral P fertilizer application rates. This was not the case in the strongly acidic soil. Less than 2.3% of freshly applied Cddff was taken up by the whole wheat plant. Most of the Cddff remained in the soil and was predominantly (>95% of freshly applied Cddff) partitioned into the easily mobilizable acetic acid soluble fraction (F1) and the potentially mobile reducible fraction (F2). Soil pH was the determining factor for the partitioning of Cddff into F1, as revealed through a recovery of about 40% of freshly applied Cddff in F1 in the neutral pH soil compared with about 60% in the strongly acidic soil. Isotope mixing models showed that F1 was the predominant source of Cd for wheat on both soils and that it contributed to over 80% of the Cd that was taken up by wheat. By tracing the fate of Cddff in entire soil-plant systems using different isotope source tracing approaches, we show that the majority of Cddff remains mobilizable and is potentially plant available in the subsequent crop cycle.

Initial Cadmium (Cd) isotope fractionation studies in cereals ascribed the retention of Cd and its light isotopes to the binding of Cd to sulfur (S). To better understand the relation of Cd binding to S and Cd isotope fractionation in soils and plants, we combined isotope and XAS speciation analyses in soil-rice systems that were rich in Cd and S. The systems included distinct water management (flooded vs. non-flooded) and rice accessions with (excluder) and without (non-excluder) functional membrane transporter OsHMA3 that transports Cd into root vacuoles. Initially, 13% of Cd in the soil was bound to S. Through soil flooding, the proportion of Cd bound to S increased to 100%. Soil flooding enriched the rice plants towards heavy isotopes (δ¹¹⁴/¹¹⁰Cd = −0.37 to −0.39%) compared to the plants that grew on non-flooded soils (δ¹¹⁴/¹¹⁰Cd = −0.45 to −0.56%) suggesting that preferentially light Cd isotopes precipitated into Cd sulfides. Isotope compositions in CaCl₂ root extracts indicated that the root surface contributed to the isotope shift between soil and plant during soil flooding. In rice roots, Cd was fully bound to S in all treatments. The roots in the excluder rice strongly retained Cd and its lights isotopes while heavy isotopes were transported to the shoots (Δ¹¹⁴/¹¹⁰Cdₛₕₒₒₜ₋ᵣₒₒₜ 0.16–0.19‰). The non-excluder rice accumulated Cd in shoots and the apparent difference in isotope composition between roots and shoots was smaller than that of the excluder rice (Δ¹¹⁴/¹¹⁰Cdₛₕₒₒₜ₋ᵣₒₒₜ −0.02 to 0.08‰). We ascribe the retention of light Cd isotopes in the roots of the excluder rice to the membrane transport of Cd by OsHMA3 and/or chelating Cd–S complexes in the vacuole. Cd–S was the major binding form in flooded soils and rice roots and partly contributed to the immobilization of Cd and its light isotopes in soil-rice systems.

The Yellow River is the second largest river in China. Carbon transport by the Yellow River has significant influence on riverine carbon cycles in Asia. During the wet season, the riverine carbon was mainly found in dissolved form, i.e., dissolved organic carbon (DOC), along the entire course of the river. The distinct spatial variations of DOC concentration were observed at different reaches of the mainstream (p < 0.01), while the highest mean DOC concentration was generally observed at midstream (4.13 ± 0.91 mg/L). Carbon stable isotope analysis δ¹³C and C: N ratio of DOC, evidenced the sources of DOC in headwater and upstream were primarily the terrestrial plants (94% and 61%), but it was changed to soil organic matter (SOM) in mid- and downstream (36% and 37%), and the contribution of sewage to DOC were also increased to 17% and 18%. In the whole mainstream of the Yellow River, water temperature (WT) had a significant impact on DOC concentration, and it could explain 67% of the DOC variance. However, in a large catchment, the driving mechanisms on the DOC variations in headwaters will not necessarily be those controlling DOC trends in downstream. The study firstly quantified, in headwater and upstream, the natural factors explained as much as 65% and 73% of the DOC variations, respectively. In mid- and downstream areas, DOC was significantly influenced by the amount of wastewater discharged by the industry and the use of chemical fertilizers (p < 0.05). These findings may facilitate a better assessment of global riverine carbon cycling and may help to reveal the importance of the balance between development and environmental sustainability with the changing DOC transport features in the Yellow River due to human disturbances.

Metal release into the environment from anthropogenic activities may endanger ecosystems and human health. However, identifying and quantifying anthropogenic metal bioaccumulation in organisms remain a challenging task. In this work, we assess Cu isotopes in Pacific oysters (C. gigas) as a new tool for monitoring anthropogenic Cu bioaccumulation into marine environments. Arcachon Bay was taken as a natural laboratory due to its increasing contamination by Cu, and its relevance as a prominent shellfish production area. Here, we transplanted 18-month old oysters reared in an oceanic neighbor area into two Arcachon Bay mariculture sites under different exposure levels to continental Cu inputs. At the end of their 12-month long transplantation period, the oysters’ Cu body burdens had increased, and was shifted toward more positive δ⁶⁵Cu values. The gradient of Cu isotope compositions observed for oysters sampling stations was consistent with relative geographic distance and exposure intensities to unknown continental Cu sources. A binary isotope mixing model based on experimental data allowed to estimate the Cu continental fraction bioaccumulated in the transplanted oysters. The positive δ⁶⁵Cu values and high bioaccumulated levels of Cu in transplanted oysters support that continental emissions are dominantly anthropogenic. However, identifying specific pollutant coastal source remained unelucidated mostly due to their broader and overlapping isotope signatures and potential post-depositional Cu isotope fractionation processes. Further investigations on isotope fractionation of Cu-based compounds in an aqueous medium may improve Cu source discrimination. Thus, using Cu as an example, this work combines for the first time a well-known caged bivalve approach with metal stable isotope techniques for monitoring and quantifying the bioaccumulation of anthropogenic metal into marine environments. Also, it states the main challenges to pinpoint specific coastal anthropogenic sources utilizing this approach and provides the perspectives for further studies to overcome them.

Mercury (Hg) concentrations in fishes from the NW Atlantic Ocean pose concern due to the importance of this region to U.S. fisheries harvest. In this study, total Hg (THg) concentrations and nitrogen stable isotope (δ¹⁵N) values were quantified in muscle tissues sampled from Golden (Lopholatilus chamaeleonticeps) and Blueline (Caulolatilus microps) Tilefish collected during a fishery-independent survey conducted in the NW Atlantic to compare bioaccumulation patterns between these species. Total Hg concentrations averaged (±SD) 0.4 ± 0.4 μg/g dry weight (d.w.) for L. chamaeleonticeps and 1.1 ± 0.7 μg/g d.w. for C. microps with <2% of all sampled fish, those >70 cm fork length, exceeding the most restrictive USEPA regulatory guidelines for human consumption (THg > 0.46 μg/g w.w.), when converted to wet weight concentrations. The THg concentrations reported here for individuals from the NW Atlantic stock are comparable to those reported for similarly sized individuals collected from the SW Atlantic stock but notably lower than those reported for Gulf of Mexico L. chamaeleonticeps, indicating different Hg exposure and assimilation kinetics for fish from the NW Atlantic, and highlights the broad geographic variability of Hg bioaccumulation among Tilefish stocks. Caulolatilus microps had higher δ¹⁵N values relative to L. chamaeleonticeps and a pattern of decreasing THg concentrations was also present from south to north across the study range. It is concluded that this trophic difference and spatial pattern in Tilefish THg concentrations emphasizes the habitat and resource partitioning mechanisms described for these sympatric species that permits their coexistence in the continental shelf environment. Importantly, regional variability in THg concentrations accentuate the possible roles of fine-scale biotic and abiotic processes that can act to regulate Hg bioaccumulation among individuals and species.

Hg accumulation in marine organisms depends strongly on in situ water or sediment biogeochemistry and levels of Hg pollution. To predict the rates of Hg exposure in human communities, it is important to understand Hg assimilation and processing within commercially harvested marine fish, like the European seabass Dicentrarchus labrax. Previously, values of Δ¹⁹⁹Hg and δ²⁰²Hg in muscle tissue successfully discriminated between seven populations of European seabass. In the present study, a multi-tissue approach was developed to assess the underlying processes behind such discrimination.We determined total Hg content (THg), the proportion of monomethyl-Hg (%MeHg), and Hg isotopic composition (e.g. Δ¹⁹⁹Hg and δ²⁰²Hg) in seabass liver. We compared this to the previously published data on muscle tissue and local anthropogenic Hg inputs.The first important finding of this study showed an increase of both %MeHg and δ²⁰²Hg values in muscle compared to liver in all populations, suggesting the occurrence of internal MeHg demethylation in seabass. This is the first evidence of such a process occurring in this species. Values for mass-dependent (MDF, δ²⁰²Hg) and mass-independent (MIF, Δ¹⁹⁹Hg) isotopic fractionation in liver and muscle accorded with data observed in estuarine fish (MDF, 0–1‰ and MIF, 0–0.7‰). Black Sea seabass stood out from other regions, presenting higher MIF values (≈1.5‰) in muscle and very low MDF (≈-1‰) in liver. This second finding suggests that under low Hg bioaccumulation, Hg isotopic composition may allow the detection of a shift in the habitat use of juvenile fish, such as for first-year Black Sea seabass.Our study supports the multi-tissue approach as a valid tool for refining the analysis of Hg sourcing and metabolism in a marine fish. The study’s major outcome indicates that Hg levels of pollution and fish foraging location are the main factors influencing Hg species accumulation and isotopic fractionation in the organisms.

Long term monitoring of atmospheric wet and dry depositions and associated nutrients fluxes was conducted on the coast of Japan facing the East China Sea continuously for 1 year and 2 months, with the origin of air mass investigated based on isotope analyses (Sr, Nd, and NO₃). During the same period, intensive observations of ocean conditions and the chemical composition of sinking particles collected using sediment traps were conducted to investigate the effects of atmospheric deposition-derived nutrients on phytoplankton blooms. Dry-deposition-derived nutrient inputs to the surface ocean were larger during autumn to spring than in summer due to the effect of continental air mass occasionally carrying Asian dust (yellow sand). However, these nutrients fluxes were limited (1.1–1.5 mg-N m⁻² day⁻¹ on average) and didn't appear to cause phytoplankton blooms through the year. Although average dissolved inorganic nitrogen (DIN) concentrations in rainwater were lower in oceanic air masses compared to continental air masses, wet-deposition-derived nutrient inputs to the surface ocean on rainy days during the summer (26.0 mg-N m⁻² day⁻¹ on average) were large due to higher precipitation from oceanic air masses. Wet-deposition-derived nutrients significantly increased nutrient concentrations in the surface ocean and seemed to cause phytoplankton blooms in the warm rainy season when nutrients in the surface were depleted due to increased stratification. The increase in phytoplankton biomass was reflected in increased particle sinking into the bottom layer, as well as changing chemical characteristics. The supply of flesh phytoplankton-derived labile organic matter into the bottom layer could be expected to promote rapid bacterial decomposition and contribute to the formation of hypoxic water masses in early summer when the ocean was strongly stratified. Atmospheric deposition-derived nutrients in East Asia will have important impacts on not only the oligotrophic outer ocean but also surrounding coastal areas in the warm rainy season.

Fish embryos, as an endogenous system, strictly regulate an energy metabolism that is particularly sensitive to environmental pressure. This study used orange-spotted grouper embryos and stable isotope ⁶⁷Zn to test the hypothesis that waterborne Zn exposure had a significant effect on energy metabolism in embryos. The fish embryos were exposed to a gradient level of waterborne ⁶⁷Zn, and then sampled to quantify ⁶⁷Zn bioaccumulation and mRNA expressions of key genes involved glucose metabolism. The results indicated that the bioaccumulated ⁶⁷Zn generally increased with increasing waterborne ⁶⁷Zn concentrations, while it tended to be saturated at waterborne ⁶⁷Zn > 0.7 mg L⁻¹. As we hypothesized, the expression of PK and PFK gene involved glycolysis pathway was significantly up-regulated under waterborne ⁶⁷Zn exposure >4 mg L⁻¹. Waterborne ⁶⁷Zn exposure >2 mg L⁻¹ significantly suppressed PCK and G6PC gene expression involved gluconeogenesis pathway, and also inhibited the AKT2, GSK-3beta and GLUT4 genes involved Akt signaling pathway. Our findings first characterized developmental stage-dependent Zn uptake and genotoxicity in fish embryos. We suggest fish embryos, as a small-scale modeling biosystem, have a large potential and wide applicability for determining cytotoxicity/genotoxicity of waterborne metal in aquatic ecosystem.