Effects of gadolinium (Gd) and a Gd-based contrast agent (GBCA) on early life stages of zebrafish (Danio rerio).

Gadolinium (Gd) is one of the rare earth elements (REY) and is widely used in magnetic resonance imaging (MRI) contrast agents. Anthropogenic Gd enrichment has frequently been found in wastewater treatment plant effluents in industrialised countries, rising concerns regarding effects on aquatic biota. This study investigates the acute toxicity and sublethal effects of Gd in two forms, as inorganic salt (GdCl3) and as Gd-based contrast agent (GBCA), on early life stages of zebrafish (Danio rerio). Nominal exposure concentrations ranged from 3 to 3000 µg L-1, with an exposure duration of 96 h. None of the two tested compounds were acutely toxic to embryos and larvae. Similarly, we did not observe any effects on larval development and locomotive behaviour. However, we found significant changes in the brain activity of larvae exposed to the highest concentrations of GdCl3 and the GBCA. Our findings show that Gd can have sublethal effects on developing fish at lower concentrations than reported previously, highlighting the necessity of investigating the long-term fate and effects of GBCAs released into the aquatic environment.

Biomonitoring of rare earth elements in Southern Norway: Distribution, fractionation, and accumulation patterns in the marine bivalves Mytilus spp. and Tapes spp.

Growing extraction and usage of rare earth elements and yttrium (REY) for medical and industrial applications has resulted in increased discharges into the marine environment. Using Mytilus spp. Mussels and Tapes spp. clams as bioindicator organisms, we analyzed 15 REY in soft tissues of specimens collected at two potentially polluted sites in Southern Norway: in the vicinity of an industry producing gadolinium-based MRI contrast agents (GBCAs) (Lindesnes) and in an industrially-affected fjord (Porsgrunn). The spatial distribution of REY and shale-normalized fractionation patterns were determined to assess the potential anthropogenic contribution of REY at the sites. At both sites, the REY fractionation pattern in soft tissue was characterized by enrichment of light rare earth elements (LREE) over heavy rare earth elements (HREE), while also displaying negative cerium and small positive gadolinium (Gd) anomalies. LREEs contributed to over 80% of the total REY concentrations, with increasing relative enrichment following higher total REY. Gd anomalies remained conserved in most sites despite significant differences in total REY; however, a high Gd anomaly (Gd/Gd* = 4.4) was found downstream of the GBCA industry spillwater outlet, indicating biotic uptake of excess anthropogenic Gd at this site. Total REY concentrations in clams in Porsgrunn were one order of magnitude higher than in mussels in Lindesnes. This may be attributable to freshwater influences in Porsgrunn, where clams collected closer to the river mouth had significantly higher total REY concentrations. This study constitutes the first assessment of REY concentrations in marine bivalves in Norway and can provide useful information for future biomonitoring studies on REY contamination.

Quantifying spatial variation in the uptake of microplastic by mussels using biodeposit traps: A field-based study.

Spatial uptake patterns of microplastics (MP) by marine species are largely unexplored under field conditions. A novel "biodeposit trap" that measure uptake and egestion of MP by suspension-feeders through the analysis of their biodeposits, was designed and used to estimate the spatial variation of these processes by mussels in field conditions. Traps containing wild or farmed mussels or control empty shells were deployed at three sites characterised by different MP concentrations and water flow conditions. A different MP dimensional composition was observed between MP pools present in biodeposit and control traps, with the latter shifted towards higher dimensional range (0.05-5 mm). Conversely, mussels accumulated small MP (0.02-0.05 mm) into their biodeposits without any significant difference between wild and farmed specimens. MP uptake rates were on average 4-5 times higher at the site where MP contamination was expected to be highest and where water flow conditions were considered moderate.

An effective strategy for the monitoring of microplastics in complex aquatic matrices: Exploiting the potential of near infrared hyperspectral imaging (NIR-HSI).

Contamination by microplastics (MP) represents a critical environmental challenge with potential consequences at ecosystem, economic and societal levels. As the marine system is the final sink for MP, there is an urgent need to develop methods for the monitoring of synthetic particles in different marine compartments and sample matrices. Extensive evaluations are hindered by time and costs associated with to conventional MP spectroscopic analyses. The potential of near infrared hyperspectral imaging (NIR-HSI) has been recently evaluated. However, NIR-HSI has been poorly studied so far, limitedly to the detection of large particles (>300 µm), and its capability for direct characterization of MP in real marine matrices has not been considered yet. In the present study, a rapid near infrared hyperspectral imaging (NIR-HSI) method, coupled with a customised normalised difference image (NDI) strategy for data processing, is presented and used to detect MP down to 50 µm in environmental matrices. The proposed method is largely automated, without the need for extensive data processing, and enabled a successful identification of different polymers, both in surface water and mussel soft tissue samples, as well as on real field samples with environmentally occurring MP. NIR-HSI is applied directly on filters, without the need for particles pre-sorting or multiple sample purifications, avoiding time consuming procedures, airborne contaminations, particle degradation and loss. Thanks to the time and cost effectiveness, a large-scale implementation of this method would enable to extensively monitor the MP presence in natural environments for assessing the ecological risk related to MP contamination.

Sources, distribution and effects of rare earth elements in the marine environment: Current knowledge and research gaps.

Rare earth elements and yttrium (REY) are critical elements for a wide range of applications and consumer products. Their growing extraction and use can potentially lead to REY and anthropogenic-REY chemical complexes (ACC-REY) being released in the marine environment, causing concern regarding their potential effects on organisms and ecosystems. Here, we critically review the scientific knowledge on REY sources (geogenic and anthropogenic), factors affecting REY distribution and transfer in the marine environment, as well as accumulation in- and effects on marine biota. Further, we aim to draw the attention to research gaps that warrant further scientific attention to assess the potential risk posed by anthropogenic REY release. Geochemical processes affecting REY mobilisation from natural sources and factors affecting their distribution and transfer across marine compartments are well established, featuring a high variability dependent on local conditions. There is, however, a research gap with respect to evaluating the environmental distribution and fate of REY from anthropogenic sources, particularly regarding ACC-REY, which can have a high persistence in seawater. In addition, data on organismal uptake, accumulation, organ distribution and effects are scarce and at best fragmentary. Particularly, the effects of ACC-REY at organismal and community levels are, so far, not sufficiently studied. To assess the potential risks caused by anthropogenic REY release there is an urgent need to i) harmonise data reporting to promote comparability across studies and environmental matrices, ii) conduct research on transport, fate and behaviour of ACC-REY vs geogenic REY iii) deepen the knowledge on bioavailability, accumulation and effects of ACC-REY and REY mixtures at organismal and community level, which is essential for risk assessment of anthropogenic REY in marine ecosystems.

Atlantic cod (Gadus morhua) embryos are highly sensitive to short-term 3,4-dichloroaniline exposure.

3,4-dichloroaniline (3,4-DCA) is one of the most widely produced anilines world-wide, used in plastic packaging, fabrics, pharmaceuticals, pesticides, dyes and paints as well as being a degradation product of several pesticides. 3,4-DCA has been detected in freshwater, brackish and marine environments. Although freshwater toxicity thresholds exist, very little toxicological information is available on marine and cold-water species. In this study, we exposed Atlantic cod (Gadus morhua) embryos (3-7 days post fertilization) to 3,4-DCA concentrations ranging from 8-747 µg/L for 4 days followed by a recovery period in clean sea water until 14 days post fertilization (dpf). The cod embryos were significantly more sensitive to acute 3,4-DCA exposure compared to other species tested and reported in the literature. At the highest concentration (747 µg/L), no embryos survived until hatch, and even at the lowest concentration (8 µg/L), a small, but significant increase in mortality was observed at 14 dpf. Delayed and concentration-dependent effects on surviving yolk-sac larvae, manifested as cardiac, developmental and morphometric alterations, more than a week after exposure suggest potential long-term effects of transient embryonic exposure to low concentrations of 3,4-DCA.

Mussels facilitate the sinking of microplastics to bottom sediments and their subsequent uptake by detritus-feeders.

Microplastics (MP) are omnipresent contaminants in the oceans, however little is known about the MP transfer between marine compartments and species. Three connected laboratory experiments using the filter-feeding mussel Mytilus galloprovincialis and the omnivorous polichaete Hediste diversicolor were conducted to evaluate whether the filtering action by mussels affects the vertical transfer of MP of different sizes (MPSMALL = 41 µm; MPLARGE = 129 µm) and densities (polyamide = 1.15 g cm-3; polypropylene = 0.92 g cm-3) across compartments and species with different feeding modes. Mussels significantly removed MP from the water column by incorporating them into biodeposits. This effect was particularly evident for the MPSMALL, whose deposition from the water column to the bottom was enhanced (about 15%) by the action of mussels. The incorporation of MP into faecal pellets increased the particles' sinking velocity by about 3-4 orders of magnitude. Conversely, the MP presence significantly decreased the depositional velocities of faecal pellets, and the magnitude of this effect was greater with increasing MP size and decreasing density. The MP incorporation into mussels' biodeposits also more than doubled the amount of MP uptake by H. diversicolor. We conclude that detrital pathways could be a transfer route of MP across marine compartments and food webs, potentially affecting the distribution of MP in sediments and creating hot-spots of bioavailable MP.

Rapid and direct detection of small microplastics in aquatic samples by a new near infrared hyperspectral imaging (NIR-HSI) method.

Microplastic (MP) contamination is a critical environmental challenge with a strong impact on the ecosystems, economy and potentially for human health. The smaller the MP size, the greater is the environmental risks as well as the analytical difficulties in detecting and characterising the particles. .We propose a rapid near infrared hyperspectral imaging (NIR-HSI) method that enables the chemical identification and characterisation of small MP (down to 80 µm) in aquatic samples, directly on filters, with no pre-sorting step needed. By considerably reducing the procedural steps, the time of analysis and costs our method addresses the urgent need of cost-effective and robust tools for extensive monitoring of MP in natural systems.

Do different habits affect microplastics contents in organisms? A trait-based analysis on salt marsh species.

Salt marshes in urban watersheds are prone to microplastics (MP) pollution due to their hydrological characteristics and exposure to urban runoff, but little is known about MP distributions in species from these habitats. In the current study, MP occurrence was determined in six benthic invertebrate species from salt marshes along the North Adriatic lagoons (Italy) and the Schelde estuary (Netherlands). The species represented different feeding modes and sediment localisation. 96% of the analysed specimens (330) did not contain any MP, which was consistent across different regions and sites. Suspension and facultative deposit-feeding bivalves exhibited a lower MP occurrence (0.5-3%) relative to omnivores (95%) but contained a much more variable distribution of MP sizes, shapes and polymers. The study provides indications that MP physicochemical properties and species' ecological traits could all influence MP exposure, uptake and retention in benthic organisms inhabiting European salt marsh ecosystems.

Microplastic in wild populations of the omnivorous crab Carcinus aestuarii: A review and a regional-scale test of extraction methods, including microfibres.

Microplastic (MP) has become ubiquitous in the marine environment. Its threat to marine organisms has been demonstrated under laboratory conditions, yet studies on wild populations still face methodological difficulties. We reviewed the methods used to separate MP from soft animal tissues and highlighted a lack of standardised methodologies, particularly critical for synthetic microfibres. We further compared enzymatic and a potassium hydroxide (KOH)-based alkaline digestion protocols on wild crabs (Carcinus aestuarii) collected from three coastal lagoons in the north Adriatic Sea and on laboratory-prepared synthetic polyester (PES) of different colour and polypropylene (PP). We compared the cost-effectiveness of the two methods, together with the potential for adverse quantitative or qualitative effects on MP that could alter the capability of the polymers to be recognised via microscopic or spectroscopic techniques. Only 5.5% of the 180 examined crabs contained MP in their gastrointestinal tracts, with a notably high quantitative variability between individuals (from 1 to 117 particles per individual). All MP found was exclusively microfibres, mainly PES, with a mean length (±SE) of 0.5 ±â€¯0.03 mm. The two digestion methods provided comparable estimates on wild crabs and did not cause any visible physical or chemical alterations on laboratory-prepared microfibres treated for up to 4 days. KOH solution was faster and cheaper compared to the enzymatic extraction, involving fewer procedural steps and therefore reducing the risk of airborne contamination. With digestion times longer than 4 days, KOH caused morphological alterations of some of the PES microfibres, which did not occur with the enzymatic digestion. This suggests that KOH is effective for the digestion of small marine invertebrates or biological samples for which shorter digestion time is required, while enzymatic extraction should be considered as alternative for larger organisms or sample sizes requiring longer digestion times.