To what extent are filter feeder elasmobranchs exposed to marine pollution? A systematic review.

Filter feeding elasmobranchs may be considered as biological indicators of marine pollution, despite most of these species are under some degree of extinction risk. Among threats to this taxonomic group, marine pollution might represent an additional concern for their survival. In this review, a comprehensive systematic search of scientific literature on pollutants in filter feeding elasmobranchs was conducted to evaluate the bioaccumulation patterns, and risk for human consumers. We found that, despite an increasing trend in the number of published studies, the geographical coverage is still very limited and most of the studies focused solely on trace elements (70.8%). Among sharks, Rhincodon typus was the most represented species (66.7%), while Mobula mobular the most studied ray species (41.7%). Comparing the levels of pollutants in filter feeders between ocean basins, this review highlighted that Hg, As and Cd levels are mostly higher in those areas affected by both strong natural and anthropogenic source of emissions, such as the Indian Ocean. With regards to OCs, ΣPCB levels in muscle of C. maximus were between 4.3 and 50.5 µg kg-1 ww, highlighting a persistent contamination of PCB in the Mediterranean Sea. Some species exceeded the maximum allowable limits for foodstuff consumption for As, Cd and Pb. A total of 77.8% of the analyzed species exceeded the Environmental Quality Standards for Hg, while they were always below the EQSbiota for HCB, PBDEs, PFOS and DDT. Given their feeding mechanism that continuously samples the marine environment, further investigations are urgently needed to determine not only the extent of contaminant exposure in different hotspot locations but also the risks posed to the elasmobranch health.

Zooplankton as an indicator of the status of contamination of the Mediterranean Sea and temporal trends.

Zooplankton has been intensively used as bioindicators of water pollution at global level, however, only few comprehensive studies have been conducted from the Mediterranean Sea and manly dated back to the 1970s. To redress the urgent need for updated data, this study provides information on the presence and levels of contaminants in zooplankton from the Tyrrhenian Sea. Although banned, both PCBs (46.9 ± 37.2 ng g-1) and DDT (8.9 ± 10.7 ng g-1) are still present and widespread, but their contamination appears to be a local problem and to be declining over the past 50 years. Zooplankton accumulates high levels of certain TEs, including Zn (400 ± 388 ppm) and Pb (35.3 ± 45.5 ppm), but shows intermediate concentrations of other TEs, including Cd (1.6 ± 0.9 ppm) and Hg (0.1 ± 0.1 ppm), comparing with both strongly polluted and more pristine marine habitats, which may reflect a general improvement.

Legacy and emerging contaminants in the endangered filter feeder basking shark Cetorhinus maximus.

The status of contamination by chemical pollutants on large filter feeding sharks is still largely unknown. This study investigated for the first time the presence of legacy, emerging contaminants and trace elements in multiple tissues of basking sharks. In general, skin showed higher concentration of legacy and emerging contaminants probably due to pollutants being adsorbed onto the dermal denticles of the skin rather than accumulated in the tissue itself. Contaminants measured in both subcutaneous tissue and muscles appeared to strongly correlate with each other, indicating that the former might be a good proxy of muscle contamination in basking sharks. Considering the migratory nature of this species, longevity and feeding ecology, this species represents the perfect candidate to act as early warning bioindicator of regional contamination. In this context, non-lethal subcutaneous biopsies could allow the early detection of any temporal variation in the bioaccumulation of pollutants in the Mediterranean Sea.

Accumulation of Selected Trace Elements in Shads from Three Lakes: First Insights from Italian Pre-Alpine Area.

The investigation of trace element pollution is important for the environmental assessment and management of lacustrine ecosystems, especially when these represent critical freshwater resources in densely populated areas. In this context, this study determined the levels of 15 trace elements in muscles of shad, Alosa agone (Scopoli 1786), a commercialized zooplanktivourous fish, from three primary, but currently still poorly studied, Italian lakes, namely, Lake Como, Iseo, and Garda. Research findings show that shads present similar trace element accumulation patterns among lakes, except for arsenic, which occurs at lower levels in Lake Como. Results provide evidence also for mercury biomagnification in fish, whereas all the other selected trace elements undergo bio-dilution through the same trophic chain. Maximum allowable limits for foodstuff were exceeded for chromium and selenium in shads, whereas mercury levels exceeded the European Environmental Quality Standard biota. These results highlight the need for regular monitoring activities of trace elements in the biota of these lakes.

The extraction of microplastics from sediments: An overview of existing methods and the proposal of a new and green alternative.

Microplastics (MPs) contamination is an existing and concerning environmental issue. Plastic particles have been observed worldwide in every natural matrix, with water environments being the final sink of dispersed MPs. Microplastic distribution in water ecosystems varies as a function of multiple factors, including polymer properties (e.g., density and wettability) and environmental conditions (e.g., water currents and temperature). Because of the tendency of MPs to settle, sediment is known to be one of the most impacted environmental matrices. Despite the increasing awareness of their diffusion in sediments, a proper quantification of dispersed particles is still difficult, due to the lack of standard protocols, which avoid a proper comparison of different sites. This hampers the current knowledge on environmental implications and toxicological effects of MPs in sediments. In this work, we examined 49 studies carried out from 2004 to 2020 to describe the different extraction methods applied, and to highlight pros and cons, with the aim of evaluating the more promising protocols. Therefore, we evaluated each proposed method by considering precision, reproducibility, economic viability and greenness (in term of used reagents). Finally, we proposed a valid alternative procedure in term of reliability and costs, which can attract increasing interest for future studies.

Bioaccumulation and biomagnification in elasmobranchs: A concurrent assessment of trophic transfer of trace elements in 12 species from the Indian Ocean.

We provided the first multi-species study investigating the presence and organotropism of trace elements in three tissues of 12 elasmobranch species. Shark species showed comparable TE loads, although milk sharks and juvenile scalloped hammerhead sharks exhibited the highest Cd and Hg levels, respectively. Fins accumulated higher levels of Pb, Co, and Cr; muscles higher V, As, and Hg; livers higher Se and Cd levels. The organotropism of TEs calls for cautious when choosing a tissue to be sampled since certain tissues, like fin clips, do not provide reliable surrogate for the internal loads of some TEs. Strong correlations between essential and toxic TEs indicated detoxification mechanisms, while the TMF provided evidence for Hg, As and Se biomagnification along the food-web. Considering the difficulties in assessing elasmobranchs contamination from different areas, the proposed multi-species approach represents a valuable way to estimate the species-specific accumulation and transfer of pollutants in sharks.

First concurrent assessment of elemental- and organic-contaminant loads in skin biopsies of whale sharks from Djibouti.

The Gulf of Tadjoura (Djibouti) is an important site where the whale shark (Rhincodon typus Smith, 1828) aggregates seasonally. Because of the proximity to the port of Djibouti that is located along one of the busiest shipping areas in the world, whale sharks are potentially exposed to relatively high levels of trace elements and organochlorines. To assess their contamination status, concentrations of 15 trace elements, DDTs and PCBs were concurrently assessed for the first time in skin biopsies of 20 whale sharks. Additionally, 12 zooplankton samples were collected and analyzed for trace elements content. Concentration of As, Cu, Zn and Se were higher than in previous studies on this species. Whale shark samples exceeded the maximum allowable limits for foodstuffs for Cr, Pb Se, Cd and Zn. Results from this study suggests that Cr, Ni and Mo may biomagnify in this species. With regard to PCBs, the predominant congener were Tetra-CB, accounting for 41% of total PCBs and Penta-CB for 23%, while for DDTs, the predominant metabolite was DDE contributing for 51% of total compounds. The maximum residue limit for DDTs and for the ind-PCBs in fish set by U.S. EPA and by the EU regulation, respectively, was exceeded in 62% of whale sharks. Moreover, the p,p'DDE/ΣDDT ratios were higher than the critical value of 0.6, indicating possible recent inputs of technical DDTs in the area. This study suggests some concerns for the contamination status of whale sharks in Djibouti and, since major threats for this species include bycatch and illegal fisheries, highlights some level of risk from the exposure to elemental- and organic-contaminant via shark consumption.

Trace elements and POPs in two commercial shark species from Djibouti: Implications for human exposure.

Within Djibouti (Gulf of Aden), the scalloped hammerhead shark (Sphyrna lewini) and milk shark (Rhizoprionodon acutus) are important components of the artisanal fishery and they are caught to be exported or sold for local consumption. However, little scientific information exists on the contamination load of these species in this area of the world. With global populations of elasmobranchs in decline, understanding the extent of contaminant exposure is critical to future conservation as well as to assess the health risks for consumers of these species. The contaminants analyzed in this study comprised PCB, DDT and trace elements in livers, muscles and fins of both hammerhead sharks and milk sharks. The overall organochlorine compounds (OCs) and trace elements concentrations were similar among the two sharks' species and the pattern of PCB and DDT tissue distribution showed the highest burdens in livers compared with muscles and fins. However, the different accumulation profiles of OCs among shark species suggest species-specific accumulation of these contaminants. The p,p'DDE/∑DDT ratios were equal or slightly higher than the critic value of 0.6, suggesting possible recent inputs of technical DDT in the area. Concentration of trace elements from this study were generally comparable to those found in sharks from other areas of the world and, highlight the wide variation in metal concentrations between species, individuals and tissues. As far as Hg is concerned, scalloped hammerhead sharks showed higher accumulation in muscles compared with milk sharks. Both species showed elevated concentration of Se, which might be related to high Hg levels since Se inhibits Hg toxicity. The potential cancer risk for PCB, Cd, Ni, Cr and As fell within the range of 10-6-10-4, suggesting some concerns for the overall contamination levels in both species. Indeed, consuming of fish involves a mixture of all analyzed elements, and therefore, some potential risk might arise from regularly consuming these species.

First results on zooplankton community composition and contamination by some persistent organic pollutants in the Gulf of Tadjoura (Djibouti).

The Gulf of Tadjoura is located in the Horn of Africa and is widely recognized as an important site where the zooplanktivorous whale sharks seasonally aggregate from October to February. The surface zooplankton community (0-3m) was weekly sampled from November 2016 to February 2017 in two sites during the whale shark aggregation period. A total of 12 phyla were identified. Copepoda represented the most abundant and diverse group with 29 different genera, and contributed with an average of 82% of the mean zooplankton density of approximately 6600indm-3. During the sampling period, copepods were dominated numerically by Calanoida (3600indm-3), followed by Poicilostomatatoida (1300indm-3). Within the copepods, Paracalanidae, Calanidae, Oncaeidae and Miraciidae were the most common families. The temporal trend in zooplankton biomass at both stations revealed the highest peak in December (41.3±36.4mgm-3), and the lowest in February (6.6±3.3mgm-3). As no information is available on the occurrence of legacy contaminants use and release in this area, analysis revealed the consistent presence of both DDT and PCB residues in zooplankton samples in the Gulf of Tadjoura. Total PCB ranged from approximately 110 to 637ngg-1 d.w., while total DDT from 21 to 80ngg-1 d.w. The proportion of primary DDT in the total residue was higher than DDE and DDD, which strongly suggests that the area might actually be subjected to DDT inputs of the parent compound.

Recent DDT and PCB contamination in the sediment and biota of the Como Bay (Lake Como, Italy).

Due to its peculiar geographical and morphological characteristics, Lake Como (Northern Italy) represents an interesting study-case for investigating the sub-basin scale circulation of persistent organic pollutants (POPs) that, despite being banned since the 1970s, have reached surprisingly high concentrations in some southern alpine lakes as a consequence of their release from melting glaciers in recent years. In particular, the Como Bay, which is located in the city of Como, seems noteworthy because its waters have a longer residence time than the other areas of the lake. The analyses of the historical concentration of PCBs, pp'DDT and its metabolites in a sediment core sampled from the Como Bay covering a time-period from their ban to recent times, showed that the DDTs have never experienced a significant (p < 0.05) decrease over time, with concentrations of the most abundant homologue, pp'DDE, ranging from 27 to 75 ng g(-1) d.w. Conversely PCBs significantly (p < 0.05) decreased towards recent times, reaching concentrations around 80 ng g(-1) d.w. The contribution of high altitude and local sources was recorded also in the food web: both zooplankton and the zooplanktivorous fish agone were mainly contaminated by pp'DDE (81.4 ng g(-1) w.w. and 534.6 ng g(-1) w.w. respectively) and by the PCB metabolite hexa-CB (449.7 ng g(-1) w.w. and 1672.1 ng g(-1) w.w. respectively). The DDT concentrations in the agone (sampled during the years 2006­2009) never exceeded the limits for human consumption in Italy, while concentrations of six selected PCBs exceeded human health advisory recommendations in one of the fish samples analysed, when it was approximately two times higher than the recommended value of 125 ng g(-1) w.w.

Toxicity of 4-nonylphenol in spiked sediment to three populations of Chironomus riparius.

Nonylphenols (NPs) are the primary stable metabolites of alkylphenol polyethoxylates (APEs), a family of compounds widely used in industry and in some domestic products. As NPs accumulate in sediments in aquatic environments, the risk to benthic organisms needs to be assessed. In this study 4NP-spiked sediments were tested on larvae of the dipteran Chironomus riparius. First instar larvae obtained from populations at three different sources were used. To spike the sediments, an equilibration procedure between water and sediment was adopted to avoid the use of solvents. Lower 10-d LC50 values were determined for two populations of C. riparius from clean environments (315-465 and 315-350 microg g(-1) d.w., respectively) than those of a strain deriving from a population collected in a polluted river (600-680 microg g(-1) d.w.). Larval growth always decreased with increasing 4NP concentration but without any defined trend. The results of this study suggest that tolerance to the toxicant can be developed in populations of polluted environments and that testing procedures should be standardised.

A multispecies approach for monitoring persistent toxic substances in the Gulf of Gdansk (Baltic sea).

Bivalve mussels are usually used for biomonitoring persistent toxic substances (PTS) in coastal ecosystems. Nevertheless, these organisms, which live attached on hard substrates, can be found along the sandy coasts only on human manufactured products. In this work different species collected in the Gulf of Gdansk were compared to evaluate their suitability for monitoring PTS pollution at a local scale. The clam Mya arenaria seems to represent an excellent indicator of sediment pollution, mainly for organotin compounds which are selectively bioaccumulated. Organochlorine compounds are bioaccumulated in the different species mainly in function of their lipid body burden. Habitat conditions (salinity, substrate, pollution), however, strongly limited the occurrence of different species in the sampling sites; the most ubiquitous species, the common shrimp Crangon crangon, resulted therefore the most suitable to be used for the comparison of PTS pollution in this aquatic environment. Although the blue mussel (Mytilus trossulus) was confirmed to be a very useful sentinel species to compare pollution level inside and outside the Gulf of Gdansk, we recommend the use of other species to give a more detailed picture of the pollution situation in coastal areas.

Some chemical contaminant of surface sediments at the Baltic Sea coastal region with special emphasis on androgenic and anti-androgenic compounds.

Androgenic and anti-androgenic compounds including p,p'-DDE, Diuron, Linuron, Fenarimol, Vinclozolin, 1-(3,4-dichlorophenyl) urea (DCPU), 1-(3,4-dichlorophenyl)-3-methylurea, (DCPMU), tributyltin (TBT) and triphenyltin (TPT) and their metabolites (DBT, MBT, DPT, MPT) as well as metallic elements (Ni, Cu, Zn, As, Cd, Pb, Co, Tl, Cr, Fe, Mn, Al, K, Mg, Na, Ca, Ba, Ti, Sn), PAHs (16 indicator compounds), DDTs and PCBs have been quantified in top layer (0-10 cm) of up to 37 surface sediment samples collected from several sites in costal zone of the Gulf of Gdansk, an inland freshwater area of Brdyujscie in Poland and the tidal flats of the Norderney Island, Wadden Sea in 2002-2003. These sites differed in the degree of anthropogenic activities, including chemical pollution and related impact on biota. Especially in sediments near shipyards, ship repair facilities, harbours, other industrial activities or close to municipal sewage treatment plant outlets butyltins, PAHs and some metallic elements were found at high concentrations. Diuron, Linuron and DCPMU were detected at a few sites, Fenarimol only once, while Vinclozolin and DCPU were not detected. DDT concentrations in the sediments from the Gdansk and Gdynia region of the Gulf show a stepwise decrease following the ban for production and use, while diffusion of PCBs at some industrial sites seems to continue. Elevated PAH concentrations in sediments seem to be mainly due to pyrogenic and less to mixed pyrogenic and petrogenic sources, while for a few sites rather petrogenic sources dominated. The reference sites in the Norderney Island, Wadden Sea showed similar or slightly higher loads of DDTs, BTs, PAHs, PCBs and metallic elements when compared to sediments from the least contaminated sites in the coastal Gulf of Gdansk area, while phenyltins were not detected at both spatially distant European areas.

Toxicity of 4-nonylphenol to Tubifex tubifex and Chironomus riparius in 28-day whole-sediment tests.

Concern has been growing recently over the toxicity and the mimicking properties of 4-nonylphenol (4NP), the most persistent breakdown product of the nonionic surfactant nonylphenol ethoxylates, broadly used in industrial cleaning processes. Twenty-eight-day tests were performed to evaluate the toxicity and the effects on reproduction of 4NP spiked sediment to the benthic invertebrates Tubifex tubifex and Chironomus riparius. 4NP was directly added to the wet sediment, avoiding any solvent. The EC50 value for the emergence of chironomids was 380 microg 4NP g(-1) dry weight (dw); the EC50 values for the deposition of cocoons and the development of young worms were very similar (428 and 420 microg g(-1) dw, respectively). Regarding NP estrogenic activity and its effects on reproduction and development, no significant differences were noted in the sex ratio of the emerged chironomids when exposed to 4NP compared to the controls, but the emerged chironomids did not lay eggs at concentrations higher than the EC10 (250 microg 4NP g(-1) dw). Furthermore, at concentration of 610 microg 4NP g(-1) dw an interference in the development of the gonads of adult worms was observed, but it was impossible to determine whether this effect was due to 4NP toxicity or to its hormone mimicking properties.

Chemical analysis and sediment toxicity bioassays to assess the contamination of the River Lambro (Northern Italy).

This study consisted of a 10-day whole sediment toxicity test with the chironomid Chironomus riparius and a 28-day sediment toxicity test with the oligochaete Tubifex tubifex at seven sites to assess the quality of the River Lambro (Italy), one of the most contaminated rivers of the Po Basin. Endpoints measured were survival and growth for chironomids and cocoon deposition and development of young worms for tubificid oligochaetes. Responses were evaluated in relation to the occurence of organic micropollutants (PCBs, DDT, HCB, and HCH) representative of the industrial and agricultural contamination of the area. Though survival of the organisms remained unaffected, sublethal effects were observed at all sites. The sediment sampled at the farthest upstream site differed from the control only in the number of cocoons deposited by the worms. Both test species in the next three sediments, where concentrations of PCB and DDT were in the range 21.9-39.5 ng g(-1) DW and 0.6-1.3 ng g(-1) DW, respectively, experienced greater toxicity in terms of growth and reproduction. Contamination was particularly high in the site closest to Milan, where the river receives untreated urban and industrial discharges. Levels of total PCBs and total DDT here were up to two orders of magnitude higher than those found at the other sampling locations, and chironomid growth and the reproductive endpoints of tubificids were significantly lower than in the control and the other sites. The test results for the next two stations showed improvement relative to that of Milan, although contamination was still evident. Sublethal effects were in agreement with the measured concentrations of the principal persistent organic pollutants and should be included as part of environmental monitoring efforts as a basis for assessing the recovery of the river.

Mouthpart deformities and nucleolus activity in field-collected Chironomus riparius larvae.

Chironomid mouthpart deformities and aberrations of their polytenic chromosomes are sublethal responses to toxic stress. These endpoints have been used in several cases as bioindications for sediment pollution. In the present study we aimed to establish whether there was an association between mouthpart deformities and nucleolus activity in the polytenic chromosomes. Such information could be useful to gain insight into the mechanisms involved in the occurrence of mouthpart deformities and their consequences on the larvae. Third-instar larvae of Chironomus riparius were collected at a site downstream of a sewage treatment plant mostly contaminated by pesticides. Larvae were then raised in the laboratory in aquaria containing sediment and water from the study location. During a 16-day period, larvae ready to molt to the fourth instar were reared individually. Within a few hours of their molt, the larvae were preserved. The presence of mouthpart deformities (mentum, mandibles, and pecten epipharyngis) and the percentage of active nucleoli were assessed. Those larvae presenting mentum deformities had a significantly higher incidence of active nucleoli in their polytenic chromosomes than nondeformed larvae. Because a high number of active nucleoli generally indicates increased rRNA synthesis, deformed larvae seemed to exhibit a higher protein synthesis than normal individuals. The synthesis of additional proteins may increase deformed larva tolerance to toxicants.