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.

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.

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.

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.