Identification and Quantification of Microplastics in the Marine Environment Using the Laser Direct Infrared (LDIR) Technique.

Here, we evaluate for the first time the performances of the newly developed laser direct infrared (LDIR) technique and propose an optimization of the initial protocol for marine microplastics (MPs) analysis. Our results show that an 8 µm porosity polycarbonate filter placed on a Kevley slide enables preconcentration and efficient quantification of MPs, as well as polymer and size determination of reference plastic pellets of polypropylene (PP), polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET), with recoveries ranging from 80-100% and negligible blank values for particle sizes ranging from 200 to 500 µm. A spiked experiment using seawater, sediment, mussels, and fish stomach samples showed that the method responded linearly with significant slopes (R2 ranging from 0.93-1.0; p < 0.001, p < 0.01). Overall, 11 polymer types were identified with limited handling and an analysis time of ca. 3 h for most samples and 6 h for complex samples. Application of this technique to Mediterranean marine samples (seawater, sediment, fish stomachs and mussels) indicated MP concentrations and size distribution consistent with the literature. A high predominance of PVC (sediment, fish stomachs) and PE and PP (seawater, mussels) was observed in the analyzed samples.

Persistent Organic Pollutants Burden, Trophic Magnification and Risk in a Pelagic Food Web from Coastal NW Mediterranean Sea.

The storage capacity, trophic magnification and risk of sixty-two POPs have been evaluated in a well-characterized pelagic food web (including phytoplankton, zooplankton, six fish, and two cephalopods species) from an impacted area in NW Mediterranean Sea. Our results show the high capacity of the planktonic compartment for the storage of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), consistent with their estimated low trophic magnification factors (TMF) of 0.2-2.0 (PBDEs) and of 0.3-1.1 (PCDD/Fs). ∑PBDEs dominated in the zooplankton size-class 200-1000 µm (∼330 ng g-1 lw, median), whereas ∑PCDD/Fs accumulated preferentially in phytoplankton size-class 0.7-200 µm (875 pg g-1 lw, median). In contrast, polychlorinated biphenyls (PCBs) were preferentially bioaccumulated in the higher trophic levels (six fish species and two cephalopods) with TMFs = 0.8-3.9, reaching median concentrations of 4270 and 3140 ng g-1 lw (∑PCBs) in Atlantic bonito (Sarda sarda) and chub mackerel (Scomber colias), respectively. For these edible species, the estimated weekly intakes of dioxin-like POPs for humans based on national consumption standards overpassed the EU tolerable weekly intake. Moreover, the concentrations of nondioxin-like PCBs in S. sarda were above the EU maximum levels in foodstuffs, pointing to a risk. No risk evidence was found due to consumption of all other edible species studied, neither for PBDEs. The integrated burden of POPs in the food web reached ∼18 µg g-1 lw, representing a dynamic stock of toxic organic chemicals in the study area. We show that the characterized food web could be a useful and comprehensive "bioindicator" of the chemical pollution status of the study area, opening new perspectives for the monitoring of toxic chemicals in Mediterranean coastal waters.

Phthalate Release from Plastic Fragments and Degradation in Seawater.

Plastic debris in the environment contains plasticizers, such as phthalates (PAEs), that can be released during plastic aging. Here, two common plastic materials, an insulation layer of electric cables (polyvinyl chloride, PVC-cables) and plastic garbage bag (polyethylene, PE-bags), were incubated in natural seawater under laboratory conditions, and the PAE migration to the seawater phase was studied with varying light and bacterial conditions over a 90-day time course. Free PAEs diluted in seawater were also studied for bacterial degradation. Our results showed that, within the first month of incubation, both plastic materials significantly leached out PAEs into the surrounding water. We found that di-isobutyl phthalate (DiBP) and di- n-butyl phthalate (DnBP) were the main PAEs released from the PE-bags, with the highest values of 83.4 ± 12.5 and 120.1 ± 18.0 ng g-1 of plastic, respectively. Furthermore, dimethyl phthalate (DMP) and diethyl phthalate (DEP) were the main PAEs released from PVC-cables, with mass fractions as high as 9.5 ± 1.4 and 68.9 ± 10.3 ng g-1, respectively. Additionally, we found that light and bacterial exposure increased the total amount of PAEs released from PVC-cables by a factor of up to 5, whereas they had no influence in the case of PE-bags.

The Amazon River: A Major Source of Organic Plastic Additives to the Tropical North Atlantic?

The release of emerging organic contaminants is identified among the most critical hazards to the marine environment, and plastic additives have received growing attention due to their worldwide distribution and potential deleterious effects. Here, we report dissolved surface water concentrations of two important families of plastic additives (organophosphate esters (OPEs) and bisphenols) and other related organic compounds (perfluorinated chemicals) measured in the North Atlantic from Cape Verde to the West Indies. We found that OPEs were the most abundant contaminants, reaching remarkably high concentrations in open ocean waters (1200 km offshore of the American Coast, at the location of the Amazon river plume during the sampling period), with up to 1.3 µg L-1 (Σ9OPEs). A Lagrangian analysis confirmed that these high concentrations of contaminants originated from the Amazon River plume and were transported more than 3000 km by the North Brazil Current and its retroflection. We thus consider the Amazon River as a major source of organic contaminants of emerging concern to the tropical North Atlantic Ocean and suggest that medium-/long-range contaminant transport occurs, most certainly facilitated by the highly stratified conditions offered by the river plume.

Occurrence, Loading, and Exposure of Atmospheric Particle-Bound POPs at the African and European Edges of the Western Mediterranean Sea.

A comparative study for 62 toxic chemicals based on the simultaneous monthly collection of aerosol samples during 2015-2016 in two coastal cities at both the African (Bizerte, Tunisia) and European (Marseille, France) edges of the Western Mediterranean basin is presented. Legacy polychlorinated biphenyls (∑18PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (∑17PCDD/Fs) show generally higher median levels at the African edge (2.1 and 0.2 pg m-3, respectively) compared to the European coastal site (1.0 and 0.08 pg m-3, respectively). Contrarily, the "emerging" polybrominated diphenyl ethers' (∑27PBDEs) median concentrations were higher in Marseille (∼9.0 pg m-3) compared to Bizerte (∼6.0 pg m-3). Different past usages and current emission patterns were found at both edges of the Western Mediterranean, most probably linked to the respective different regulatory frameworks for toxic chemicals. Our results indicate that the total organic carbon (TOC) and/or the elemental carbon (EC) contents in the atmospheric aerosol may have a stronger effect than the total suspended particle (TSP) content as a whole on the spatial-temporal variability and the long-range atmospheric transport potential of the studied POPs. A "jumping" of the PBDE local atmospheric stocks from the Northwestern European Mediterranean edge to the Northwestern African coast seems to be possible under favorable conditions at present. While a higher PBDE median loading is estimated for the Marseille area (∼550 ng m-2 y-1) compared to Bizerte (∼400 ng m-2 y-1), the median PCB and PCDD/F dry deposition fluxes were higher at the African site, resulting in a 3-fold higher toxic equivalent (TEQ) loading of dioxin-like pollutants (400 pg TEQ m-2 y-1) compared to Marseille (∼140 pg TEQ m-2 y-1), with potential implications for aquatic organisms. However, the inhalation exposure assessment points to a minimum risk for human health at both sites.

Occurrence, fate, behavior and ecotoxicological state of phthalates in different environmental matrices.

Because of their large and widespread application, phthalates or phthalic acid esters (PAEs) are ubiquitous in all the environmental compartements. They have been widely detected throughout the worldwide environment. Indoor air where people spend 65-90% of their time is also highly contaminated by various PAEs released from plastics, consumer products as well as ambient suspended particulate matter. Because of their widespread application, PAEs are the most common chemicals that humans are in contact with daily. Based on various exposure mechanisms, including the ingestion of food, drinking water, dust/soil, air inhalation and dermal exposure the daily intake of PAEs may reach values as high as 70 µg/kg/day. PAEs are involved in endocrine disrupting effects, namely, upon reproductive physiology in different species of fish and mammals. They also present a variety of additional toxic effects for many other species including terrestrial and aquatic fauna and flora. Therefore, their presence in the environment has attracted considerable attention due to their potential impacts on ecosystem functioning and on public health. This paper is a synthesis of the extensive literature data on behavior, transport, fate and ecotoxicological state of PAEs in environmental matrices: air, water, sediment, sludge, wastewater, soil, and biota. First, the origins and physicochemical properties of PAEs that control the behavior, transport and fate in the environment are reviewed. Second, the compilation of data on transport and fate, adverse environmental and human health effects, legislation, restrictions, and ecotoxicological state of the environment based on PAEs is presented.

Temporal trends of plastic additive contents in sediment cores of three French rivers (Loire, Meuse and Moselle) over the last decades.

Sediment cores from three major French watersheds (Loire, Meuse and Moselle) have been dated by 137Cs and 210Pbxs from 1910 (Loire), 1947 (Meuse) and 1930 (Moselle) until the present in order to reconstruct trajectories of plastic additive contaminants including nine phthalate esters (PAEs) and seven organophosphate esters (OPEs), measured by gas chromatography-mass spectrometer (GC-MS-MS). Historical levels of ∑PAEs were higher than those of ∑OPEs in the Loire and the Moselle sediments, while ∑PAEs and ∑OPEs contents were of the same order of magnitude in the Meuse sediments. Although increases in concentrations do not evolve linearly, our results clearly indicate an increase in OPEs and PAEs concentrations from the 1950-1970 period onwards, compared with the first half of the 20th century. Our results show that, ∑OPE contents increase gradually over time in the Loire and Meuse rivers but evolve more randomly in the Moselle River. Trajectories of ∑PAEs depend on the river and no generality can be established, suggesting sedimentary reworking and/or local contamination. Data from this study allowed comparisons of contents of ∑OPEs and ∑PAEs between rivers, with ∑OPE concentrations in the Moselle River > Meuse River > Loire River, and concentrations of ∑PAEs in the Loire River > Moselle River > Meuse River. Among all PAEs, di(2-ethylhexyl) phthalate (DEHP) was the most abundant in all sediment samples, followed by diisobutyl phthalate (DiBP). Tris (2-chloroisopropyl) phosphate (TCPP) was the most abundant OPE in sediments of the three rivers. In addition, strong positive Pearson correlations were observed between organic matter (OM) parameters and OPE concentrations, and to a lesser extent, between OM parameters and PAE concentrations. This is particularly true for the Moselle River and for the Loire River, but less so for the Meuse River.

Temporal evolution of plastic additive contents over the last decades in two major European rivers (Rhone and Rhine) from sediment cores analyses.

Although global plastic distribution is at the heart of 21st century environmental concerns, little information is available concerning how organic plastic additives contaminate freshwater sediments, which are often subject to strong anthropogenic pressure. Here, sediment core samples were collected in the Rhone and the Rhine watersheds (France), dated using 137Cs and 210Pbxs methods and analysed for nine phthalates (PAEs) and seven organophosphate esters (OPEs). The distribution of these organic contaminants was used to establish a chronological archive of plastic additive pollution from 1860 (Rhine) and 1930 (Rhone) until today. Sediment grain size and parameters related to organic matter (OM) were also measured as potential factors that may affect the temporal distribution of OPEs and PAEs in sediments. Our results show that OPE and PAE levels increased continuously in Rhone and Rhine sediments since the first records. In both rivers, ∑PAEs levels (from 9.1 ± 1.7 to 487.3 ± 27.0 ng g-1 dry weight (dw) ± standard deviation and from 4.6 ± 1.3 to 65.2 ± 11.2 ng g-1 dw, for the Rhine and the Rhone rivers, respectively) were higher than ∑OPEs levels (from 0.1 ± 0.1 to 79.1 ± 13.7 ng g-1 dw and from 0.6 ± 0.1 to 17.8 ± 2.3 ng g-1 dw, for Rhine and Rhone rivers, respectively). In both rivers, di(2-ethylhexyl) phthalate (DEHP) was the most abundant PAE, followed by diisobutyl phthalate (DiBP), while tris (2-chloroisopropyl) phosphate (TCPP) was the most abundant OPE. No relationship was found between granulometry and additives concentrations, while organic matter helps explain the vertical distribution of PAEs and OPEs in the sediment cores. This study thus establishes a temporal trajectory of PAEs and OPEs contents over the last decades, leading to a better understanding of historical pollution in these two Western European rivers.

Comparative analysis of microplastics detection methods applied to marine sediments: A case study in the Bay of Marseille.

An intercomparison exercise on "microplastics in sediment" was carried out by five laboratories using samples collected in the Bay of Marseille in September 2021. The results from different extraction and identification methods varied depending on the type and size classes of MPs, and was better than 80 % for the size class >300 µm and for the fragments. The variability in recovery rates can be attributed to the choice of reagents and extraction protocols. Recovery rates per laboratory were between 47 % and 113 % and the use of ZnCl2 and NaI increased recovery rates by an average of 70 %. The lowest recovery rates (47 and 53 %) were attributed to the reference methods (FTIR and LDIR), conversely the highest (80 and 87 %) were attributed to identification by Nile Red. The average ranged between 23 and 53 items /50 g d.w. with decreases offshore and at greater depth.

Temporal trajectories of artificial radiocaesium 137Cs in French rivers over the nuclear era reconstructed from sediment cores.

137Cs is a long-lived man-made radionuclide introduced in the environment worldwide at the early beginning of the nuclear Era during atmospheric nuclear testing's followed by the civil use of nuclear energy. Atmospheric fallout deposition of this major artificial radionuclide was reconstructed at the scale of French large river basins since 1945, and trajectories in French nuclearized rivers were established using sediment coring. Our results show that 137Cs contents in sediments of the studied rivers display a large spatial and temporal variability in response to the various anthropogenic pressures exerted on their catchment. The Loire, Rhone, and Rhine rivers were the most affected by atmospheric fallout from the global deposition from nuclear tests. Rhine and Rhone also received significant fallout from the Chernobyl accident in 1986 and recorded significant 137Cs concentrations in their sediments over the 1970-1985 period due to the regulatory releases from the nuclear industries. The Meuse River was notably impacted in the early 1970s by industrial releases. In contrast, the Seine River display the lowest 137Cs concentrations regardless of the period. All the rivers responded similarly over time to atmospheric fallout on their catchment, underlying a rather homogeneous resilience capacity of these river systems to this source of contamination.

Photochemical production and behavior of hydroperoxyacids in heterotrophic bacteria attached to senescent phytoplanktonic cells.

The photooxidation of cellular monounsaturated fatty acids was investigated in senescent phytoplanktonic cells (Emiliania huxleyi) and in their attached bacteria under laboratory controlled conditions. Our results indicated that UV-visible irradiation of phytodetritus induced the photooxidation of oleic (produced by phytoplankton and bacteria) and cis-vaccenic (specifically produced by bacteria) acids. These experiments confirmed the involvement of a substantial singlet oxygen transfer from senescent phytoplanktonic cells to attached bacteria, and revealed a significant correlation between the concentration of chlorophyll, a photosensitizer, in the phytodetritus and the photodegradation state of bacteria. Hydroperoxyacids (fatty acid photoproducts) appeared to be quickly degraded to ketoacids and hydroxyacids in bacteria and in phytoplanktonic cells. This degradation involves homolytic cleavage (most likely induced by UV and/or transition metal ions) and peroxygenase activity (yielding epoxy acids).

The role of mesopelagic fishes as microplastics vectors across the deep-sea layers from the Southwestern Tropical Atlantic.

Microplastics (MPs; <5 mm) are a macro issue recognised worldwide as a threat to biodiversity and ecosystems. Widely distributed in marine ecosystems, MPs have already been found in the deep-sea environment. However, there is little information on ecological mechanisms driving MP uptake by deep-sea species. For the first time, this study generates data on MP contamination in mesopelagic fishes from the Southwestern Tropical Atlantic (SWTA) to help understand the deep-sea contamination patterns. An alkaline digestion protocol was applied to extract MPs from the digestive tract of four mesopelagic fish species: Argyropelecus sladeni, Sternoptyx diaphana (Sternoptychidae), Diaphus brachycephalus, and Hygophum taaningi (Myctophidae). A total of 213 particles were recovered from 170 specimens, and MPs were found in 67% of the specimens. Fibres were the most common shape found in all species, whereas polyamide, polyethylene, and polyethylene terephthalate were the most frequent polymers. The most contaminated species was A. sladeni (93%), and the least contaminated was S. diaphana (45%). Interestingly, individuals caught in the lower mesopelagic zone (500-1000 m depth) were less contaminated with MPs than those captured in the upper mesopelagic layer (200-500 m). Our results highlight significant contamination levels and reveal the influence of mesopelagic fishes on MPs transport in the deep waters of the SWTA.

Microplastics in Asian freshwater ecosystems: Current knowledge and perspectives.

Plastic pollution in freshwater ecosystems, including microplastics (MPs) smaller than 5 mm, has become an emerging global concern. Asia is considered a "hot spot" for plastic pollution due to rapid economic and demographic growth, together with rapid urbanization. Here, we provide an overview of the current knowledge on MP abundance, sources, fate, and transfer in Asian freshwater ecosystems based on publications from January 2014 to May 2021. MP contamination in freshwater compartments, including water, sediment, and biota, was found to vary strongly. In water, it ranged from 0.004 items m-3 in a moderately urbanized region to more than 500,000 items m-3 in a dumping river in a highly populated watershed. In the sediment, MP abundance ranged from 1 to more than 30,000 items kg-1 dry weight. Polyethylene (PE) and polypropylene (PP) were predominant in both water and sediment compartments. MP was detected in biota samples from all the studied species, but their abundance depended on the locations and species studied. Overall, MP characteristics (form, size, color, and polymer type) depended on sources and natural constraints (mainly hydrodynamics). This study also revealed that MP in Asian freshwater ecosystems mainly originated from domestic wastewater/runoff, followed by industrial emissions, fisheries and aquaculture wastewater. Plastic waste is not efficiently recycled or incinerated in Asia, leading to MP transfer and accumulation in the aquatic environment, and, more importantly, to ingestion by low to high trophic level organisms. This work highlights several knowledge gaps to guides future research to improve MP pollution management for the sustainable development of highly populated regions such as Asia.

Phthalates and organophosphate esters in surface water, sediments and zooplankton of the NW Mediterranean Sea: Exploring links with microplastic abundance and accumulation in the marine food web.

In this study, surface seawater, sediment and zooplankton samples were collected from three different sampling stations in Marseille Bay (NW Mediterranean Sea) and were analyzed for both microplastics and organic plastic additives including seven phthalates (PAEs) and nine organophosphate esters (OPEs). PAE concentrations ranged from 100 to 527 ng L-1 (mean 191 ± 123 ng L-1) in seawater, 12-610 ng g-1 dw (mean 194 ± 193 ng g-1 dw) in sediment and 0.9-47 µg g-1 dw (mean 7.2 ± 10 µg g-1 dw) in zooplankton, whereas OPE concentrations varied between 9 and 1013 ng L-1 (mean 243 ± 327 ng L-1) in seawater, 13-49 ng g-1 dw (mean 25 ± 11 ng g-1 dw) in sediment and 0.4-4.6 µg g-1 dw (mean 1.6 ± 1.0 µg g-1 dw) in zooplankton. Microplastic counts in seawater ranged from 0 to 0.3 items m-3 (mean 0.05 ± 0.05 items m-3). We observed high fluctuations in contaminant concentrations in zooplankton between different sampling events. However, the smallest zooplankton size class generally exhibited the highest PAE and OPE concentrations. Field-derived bioconcentration factors (BCFs) showed that certain compounds are prone to bioaccumulate in zooplankton, including some of the most widely used chlorinated OPEs, but with different intensity depending on the zooplankton size-class. The concentration of plastic additives in surface waters and the abundance of microplastic particles were not correlated, implying that they are not necessarily good indicators for each other in this compartment. This is the first comprehensive study on the occurrence and temporal variability of PAEs and OPEs in the coastal Mediterranean based on the parallel collection of water, sediment and differently sized zooplankton samples.

Environmental occurrence of phthalate and organophosphate esters in sediments across the Gulf of Lion (NW Mediterranean Sea).

Seven phthalate (PAEs) and nine organophosphate esters (OPEs) were measured in surface sediments across the Gulf of Lion (NW Mediterranean Sea) at twelve stations characterized by different anthropogenic signatures. ∑PAEs and ∑OPEs concentrations ranged from 2 to 766 ng/g DW (av. 196 ng/g DW) and from 4 to 227 ng/g DW (av. 54 ng/g DW), respectively. Our analysis of the potential sources of these organic plastic additives in sediments of the Gulf of Lion suggests that the dominant factors affecting their occurrence and environmental distribution are port-based industrial activities and urban pressures. Indeed, the highest ∑PAEs and ∑OPEs concentrations were found close to the ports of Toulon and Marseille (Estaque) and at the sites impacted by the Marseille metropolitan area (i.e. at the outlets of the waste water treatment plant at Cortiou and at the mouth of the Huveaune River). The lowest levels were generally found in protected areas (e.g. Port-Cros) and at sites relatively far from the coast. DEHP was seen to be the most abundant PAE while TDCP, TEHP and TiBP were the most abundant OPEs in the area. Our results also expose the contribution of additives entering the Gulf of Lion via sedimentary material from the Rhône River, with positive correlations between the total organic carbon (TOC) content in the sediment and the ∑PAEs and ∑OPEs concentrations. However, additive concentrations decreased from shore to offshore in the Rhône River discharge area, indicating an efficient dilution of the contaminants accumulated at the river mouth area.

Organic additive release from plastic to seawater is lower under deep-sea conditions.

Plastic garbage patches at the ocean surface are symptomatic of a wider pollution affecting the whole marine environment. Sinking of plastic debris increasingly appears to be an important process in the global fate of plastic in the ocean. However, there is insufficient knowledge about the processes affecting plastic distributions and degradation and how this influences the release of additives under varying environmental conditions, especially in deep-sea environments. Here we show that in abiotic conditions increasing hydrostatic pressure inhibits the leaching of the heaviest organic additives such as tris(2-ethylhexyl) phosphate and diisononyl phthalate from polyethylene and polyvinylchloride materials, whereas deep-sea and surface marine prokaryotes promote the release of all targeted additives (phthalates, bisphenols, organophosphate esters). This study provides empirical evidences for more efficient additive release at the ocean surface than in deep seawater, where the major plastic burden is supposed to transit through before reaching the sediment compartment.

Occurrence of organic plastic additives in surface waters of the Rhône River (France).

We present here a comprehensive study (1-year regular sampling) on the occurrence of major families of organic plastic additives in the Rhône River surface waters. Potential sources and contaminant export are also discussed. A total of 22 dissolved phase samples were analyzed for 22 organic additives mainly used in the plastic industry, including organophosphate esters (OPEs), phthalates (PAEs) and bisphenols (BPs). Our results indicate that PAEs were the most abundant class, with concentrations ranging from 97 to 541 ng L-1, followed by OPEs (85-265 ng L-1) and BPs (4-21 ng L-1). Among PAEs, diethylhexyl phthalate (DEHP) was the most abundant compound, whereas TCPP (Tris(1-chloro-2-propyl) phosphate) and TnBP (Tri(n-butyl)phosphate) were the predominant OPEs. Bisphenol S was the only BP detected. 5-54 metric tons year-1 of dissolved organic plastic additives of emerging concern are estimated to be exported to the Gulf of Lion by the Rhône River, which is the main freshwater source of the Mediterranean Sea.

Macro-litter in surface waters from the Rhone River: Plastic pollution and loading to the NW Mediterranean Sea.

We present here the first estimates of floating macro-litter in surface waters from the Rhone River, based on monthly visual observations during 1-year period (2016-2017). Plastic represented 77% of the identified items, confirming its predominance in riverine floating litter. Fragments (2.5-50 cm) and Single Use Plastics (i.e. bags, bottles and cover/packaging) were among the most abundant items. Frequent non-plastic floating litter were paper items such as packaging material and newspapers, and metal items (mostly cans), representing 14% and 5% of total litter, respectively. A lower-end estimate resulted in ∼223,000 plastic items (∼0.7 t of plastic) transported annually by the Rhone surface waters to the Gulf of Lion (NW Mediterranean Sea). Floating macro-plastics are only a fraction of the total plastic export by the Rhone. Our study highlights the current discrepancy between field observations and theoretical estimations. Improvements are needed to harmonize data collection methodologies for field studies and model validation.

Occurrence of perfluoroalkyl substances in the Bay of Marseille (NW Mediterranean Sea) and the Rhône River.

Four perfluoroalkyl substances (PFAS) were analyzed in 62 duplicate surface water samples from the Rhône River and Marseille Bay (France; NW Mediterranean Sea). Perfluorooctane sulfonate (PFOS) was detected in all samples and exceeded the European Environmental Quality Standard (EQS) values in over 80% of the cases. The most contaminated samples were from the Rhône River (up to 200 ng L-1 ∑4 PFAS), as well as those collected near a wastewater treatment plant outlet in Marseille Bay (up to 9 ng L-1 ∑4 PFAS). While PFOS was the predominant PFAS in Marseille Bay, remarkably high concentrations of perfluorohexanoic acid (PFHxA) were measured in the Rhône River (8-193 ng L-1). The relative abundances of individual compounds differed thus significantly between the Rhône River and Marseille Bay, indicating different sources. A simulation made with the MARS3D model showed that PFOS inputs from the Rhône River can enter Marseille Bay at levels > EQS.

Liquid chromatographic isolation of individual carbohydrates from environmental matrices for stable carbon analysis and radiocarbon dating.

Carbohydrates are among the most abundant organic molecules in both aquatic and terrestrial ecosystems; however, very few studies have addressed their isotopic signature using compound-specific isotope analysis, which provides additional information on their origin (δ13C) and fate (Δ14C). In this study, semi-preparative liquid chromatography with refractive index detection (HPLC-RI) was employed to produce pure carbohydrate targets for subsequent offline δ13C and Δ14C isotopic analysis. δ13C analysis was performed by elemental analyzer-isotope ratio mass spectrometer (EA-IRMS) whereas Δ14C analysis was performed by an innovative measurement procedure based on the direct combustion of the isolated fractions using an elemental analyzer coupled to the gas source of a mini carbon dating system (AixMICADAS). In general, four successive purifications with Na+, Ca2+, Pb2+, and Ca2+ cation-exchange columns were sufficient to produce pure carbohydrates. These carbohydrates were subsequently identified using mass spectrometry by comparing their mass spectra with those of authentic standards. The applicability of the proposed method was tested on two different environmental samples comprising marine particulate organic matter (POM) and total suspended atmospheric particles (TSP). The obtained results revealed that for the marine POM sample, the δ13C values of the individual carbohydrates ranged from -18.5 to -16.8‰, except for levoglucosan and mannosan, which presented values of -27.2 and -26.2‰, respectively. For the TSP sample, the δ13C values ranged from -26.4 to -25.0‰. The galactose and glucose Δ14C values were 19 and 43‰, respectively, for the POM sample. On the other hand, the levoglucosan radiocarbon value was 33‰ for the TSP sample. These results suggest that these carbohydrates exhibit a modern age in both of these samples. Radiocarbon HPLC collection window blanks, measured after the addition of phthalic acid (14C free blank), ranged from -988 to -986‰ for the abovementioned compounds, indicating a very small background isotopic influence from the whole purification procedure. Overall, the proposed method does not require derivatization steps, produces extremely low blanks, and may be applied to different types of environmental samples.