Volatile organic compounds identification and specific stable isotopic analysis (δ13C) in microplastics by purge and trap gas chromatography coupled to mass spectrometry and combustion isotope ratio mass spectrometry (PT-GC-MS-C-IRMS).

Microplastics (MPs) have become one of the major global environmental issues in recent decades due to their ubiquity in the environment. Understanding MPs source origin and reactivity is urgently needed to better constrain their fate and budget. Despite improvements in analytical methods to characterize MPs, new tools are needed to help understand their sources and reactivity in a complex environment. In this work, we developed and applied an original Purge-&-Trap system coupled to a GC-MS-C-IRMS to explore the δ13C compound-specific stable isotope analysis (CSIA) of volatile organic compounds (VOC) embedded in MPs. The method consists of heating and purging MP samples, with VOCs being cryo-trapped on a Tenax sorbent, followed by GC-MS-C-IRMS analysis. The method was developed using a polystyrene plastic material showing that sample mass and heating temperature increased the sensitivity while not influencing VOC δ13C values. This robust, precise, and accurate methodology allows VOC identification and δ13C CSIA in plastic materials in the low nanogram concentration range. Results show that the monomer styrene displays a different δ13C value (- 22.2 ± 0.2‰), compared to the δ13C value of the bulk polymer sample (- 27.8 ± 0.2‰). This difference could be related to the synthesis procedure and/or diffusion processes. The analysis of complementary plastic materials such as polyethylene terephthalate, and polylactic acid displayed unique VOC δ13C patterns, with toluene showing specific δ13C values for polystyrene (- 25.9 ± 0.1‰), polyethylene terephthalate (- 28.4 ± 0.5‰), and polylactic acid (- 38.7 ± 0.5‰). These results illustrate the potential of VOC δ13C CSIA in MP research to fingerprint plastic materials, and to improve our understanding of their source cycle. Further studies in the laboratory are needed to determine the main mechanisms responsible for MPs VOC stable isotopic fractionation.

Sensitive determination of methylmercury δ13C compound specific stable isotopic analysis by purge and trap gas chromatography combustion isotope ratio mass spectrometry.

Despite several decades of mercury research, answering fundamental questions on where and how methylmercury (CH3Hg) toxin is naturally produced in aquatic ecosystems, is still highly challenging. Investigating complex and/or coupled processes in the context of global changes requires new high-resolution analytical tools. The purpose of the compound specific carbon stable isotopic analysis (δ13C-CSIA) of the methyl group of methylmercury (CH3Hg), is to explore how the carbon cycle contributes to CH3Hg sources and formation pathways. The main problem associated with recent CH3Hg δ13C-CSIA methods is the limited sensitivity when using Liquid Injection (LI)-GC-C-IRMS techniques, requiring several micrograms of CH3Hg (as Hg). In this work, we present the development and application of an original Purge-&-Trap system (PT) coupled to a GC-C-IRMS with the purpose of transferring and analyzing the total amount of CH3Hg available in a sample vial in the low nanogram range. The new PT-GC-C-IRMS system enhance the sensitivity by a factor better than 200, relative to LI-GC-C-IRMS, by minimizing the sample mass requirements. The δ13CCH3Hg values obtained, following the same sample derivatization approach coupled to PT-GC-C-IRMS (-53.5 ± 1.9 ‰), were in good agreement with the ones obtained in a previous study (-53.8 ± 1.1 ‰). The standard solution was prepared from the same salt, requesting only 25-200 ng of CH3Hg (as Hg). This new methodology represents a milestone towards the analysis of large array of biological samples displaying CH3Hg concentrations in the low-mid ng g-1 range, in order to explore the meaning of the carbon stable isotopic signature of CH3Hg in the environment.

A Model of Mercury Distribution in Tuna from the Western and Central Pacific Ocean: Influence of Physiology, Ecology and Environmental Factors.

Information on ocean scale drivers of methylmercury levels and variability in tuna is scarce, yet crucial in the context of anthropogenic mercury (Hg) inputs and potential threats to human health. Here we assess Hg concentrations in three commercial tuna species (bigeye, yellowfin, and albacore, n = 1000) from the Western and Central Pacific Ocean (WCPO). Models were developed to map regional Hg variance and understand the main drivers. Mercury concentrations are enriched in southern latitudes (10°S-20°S) relative to the equator (0°-10°S) for each species, with bigeye exhibiting the strongest spatial gradients. Fish size is the primary factor explaining Hg variance but physical oceanography also contributes, with higher Hg concentrations in regions exhibiting deeper thermoclines. Tuna trophic position and oceanic primary productivity were of weaker importance. Predictive models perform well in the Central Equatorial Pacific and Hawaii, but underestimate Hg concentrations in the Eastern Pacific. A literature review from the global ocean indicates that size tends to govern tuna Hg concentrations, however regional information on vertical habitats, methylmercury production, and/or Hg inputs are needed to understand Hg distribution at a broader scale. Finally, this study establishes a geographical context of Hg levels to weigh the risks and benefits of tuna consumption in the WCPO.

Quantifying the impacts of artisanal gold mining on a tropical river system using mercury isotopes.

In some locations, artisanal and small-scale gold-mining (ASGM) represents a significant source of anthropogenic Hg to freshwater environments. The Hg released from ASGM can contaminate aquatic fauna and pose health risks to downstream populations. Total Hg (THg) concentrations, speciation, and isotopic compositions were analyzed in water, suspended particulate matter, soil, and bottom sediment samples from pristine areas and in places of active and legacy gold mining along the Oyapock River (French Guiana) and its tributaries. Mass-independent fractionation (MIF) of even Hg isotopes in top soils (Δ200Hg = -0.06 ±â€¯0.02‰, n = 10) implied the uptake of gaseous Hg(0) by plants, rather than wet deposition, as the primary Hg source. Odd isotope MIF was lower in deep soils (Δ199Hg = -0.75 ±â€¯0.03‰, n = 7) than in top soils (Δ199Hg = -0.55 ±â€¯0.15‰, n = 3). This variation could be attributed to differences between the isotopic signatures of modern and pre-industrial atmospheric Hg. Combining a Hg-isotope binary mixing model with a multiple linear regression based on physico-chemical parameters measured in the sediment samples, we determined that active mined creek sediments are contaminated by ASGM activities, with up to 78% of THg being anthropogenic. Of this anthropogenic Hg, more than half (66-74%) originates from liquid Hg(0) that is released during ASGM. The remaining anthropogenic Hg comes from the ASGM-driven erosion of Hg-rich soils into the river. The isotope signatures of anthropogenic Hg in bottom sediments were no longer traceable in formerly mined rivers and creeks.

Mercury Isotope Signatures of Methylmercury in Rice Samples from the Wanshan Mercury Mining Area, China: Environmental Implications.

Rice consumption is the primary pathway of methylmercury (MeHg) exposure for residents in mercury-mining areas of Guizhou Province, China. In this study, compound-specific stable isotope analysis (CSIA) of MeHg was performed on rice samples collected in the Wanshan mercury mining area. An enrichment of 2.25‰ in total Hg (THg) δ202Hg was observed between rice and human hair, and THg Δ199Hg in hair was 0.12‰ higher than the value in rice. Rice and human hair samples in this study show distinct Hg isotope signatures compared to those of fish and human hair of fish consumers collected in China and other areas. Distinct Hg isotope signatures were observed between IHg and MeHg in rice samples (in mean ± standard deviation: δ202HgIHg at -2.30‰ ± 0.49‰, Δ199HgIHg at -0.08‰ ± 0.04‰, n = 7; δ202HgMeHg at -0.80‰ ± 0.25‰, Δ199HgMeHg at 0.08‰ ± 0.04‰, n = 7). Using a binary mixing model, it is estimated that the atmospheric Hg contributed 31% ± 16% of IHg and 17% ± 11% of THg in the rice samples and the IHg in soil caused by past mining activities contributed to the remaining Hg. This study demonstrated that Hg stable isotopes are good tracers of human MeHg exposure to fish and rice consumption, and the isotope data can be used for identifying the sources of IHg and MeHg in rice.

Amazon River dissolved load: temporal dynamics and annual budget from the Andes to the ocean.

The aim of the present study is to estimate the export fluxes of major dissolved species at the scale of the Amazon basin, to identify the main parameters controlling their spatial distribution and to identify the role of discharge variability in the variability of the total dissolved solid (TDS) flux through the hydrological cycle. Data are compiled from the monthly hydrochemistry and daily discharge database of the "Programa Climatologico y Hidrologico de la Cuenca Amazonica de Bolivia" (PHICAB) and the HYBAM observatories from 34 stations distributed over the Amazon basin (for the 1983-1992 and 2000-2012 periods, respectively). This paper consists of a first global observation of the fluxes and temporal dynamics of each geomorphological domain of the Amazon basin. Based on mean interannual monthly flux calculations, we estimated that the Amazon basin delivered approximately 272 × 10(6) t year(-1) (263-278) of TDS during the 2003-2012 period, which represents approximately 7 % of the continental inputs to the oceans. This flux is mainly made up by HCO3, Ca and SiO2, reflecting the preferential contributions of carbonate and silicate chemical weathering to the Amazon River Basin. The main tributaries contributing to the TDS flux are the Marañon and Ucayali Rivers (approximately 50 % of the TDS production over 14 % of the Amazon basin area) due to the weathering of carbonates and evaporites drained by their Andean tributaries. An Andes-sedimentary area-shield TDS flux (and specific flux) gradient is observed throughout the basin and is first explained by the TDS concentration contrast between these domains, rather than variability in runoff. This observation highlights that, under tropical context, the weathering flux repartition is primarily controlled by the geomorphological/geological setting and confirms that sedimentary areas are currently active in terms of the production of dissolved load. The log relationships of concentration vs discharge have been characterized over all the studied stations and for all elements. The analysis of the slope of the relationship within the selected contexts reveals that the variability in TDS flux is mainly controlled by the discharge variability throughout the hydrological year. At the outlet of the basin, a clockwise hysteresis is observed for TDS concentration and is mainly controlled by Ca and HCO3 hysteresis, highlighting the need for a sampling strategy with a monthly frequency to accurately determine the TDS fluxes of the basin. The evaporite dissolution flux tends to be constant, whereas dissolved load fluxes released from other sources (silicate weathering, carbonate weathering, biological and/or atmospheric inputs) are mainly driven by variability in discharge. These results suggest that past and further climate variability had or will have a direct impact on the variability of dissolved fluxes in the Amazon. Further studies need to be performed to better understand the processes controlling the dynamics of weathering fluxes and their applicability to present-day concentration-discharge relationships at longer timescales.

Shallow methylmercury production in the marginal sea ice zone of the central Arctic Ocean.

Methylmercury (MeHg) is a neurotoxic compound that threatens wildlife and human health across the Arctic region. Though much is known about the source and dynamics of its inorganic mercury (Hg) precursor, the exact origin of the high MeHg concentrations in Arctic biota remains uncertain. Arctic coastal sediments, coastal marine waters and surface snow are known sites for MeHg production. Observations on marine Hg dynamics, however, have been restricted to the Canadian Archipelago and the Beaufort Sea (<79 °N). Here we present the first central Arctic Ocean (79-90 °N) profiles for total mercury (tHg) and MeHg. We find elevated tHg and MeHg concentrations in the marginal sea ice zone (81-85 °N). Similar to other open ocean basins, Arctic MeHg concentration maxima also occur in the pycnocline waters, but at much shallower depths (150-200 m). The shallow MeHg maxima just below the productive surface layer possibly result in enhanced biological uptake at the base of the Arctic marine food web and may explain the elevated MeHg concentrations in Arctic biota. We suggest that Arctic warming, through thinning sea ice, extension of the seasonal sea ice zone, intensified surface ocean stratification and shifts in plankton ecodynamics, will likely lead to higher marine MeHg production.