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.

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.

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.

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.

Exploring bufferless iron speciation in seawater by Competitive Ligand Equilibration-Cathodic Stripping Voltammetry: Does pH control really matter?

Iron speciation in seawater is of the utmost importance as this element plays a central role in the regulation of primary productivity. Here we present the development of a CLE-CSV (Competitive Ligand Equilibration-Cathodic Stripping Voltammetry) procedure for iron speciation in seawater avoiding for the first time the use of the pH buffer (2,3-dihydroxynaphthalene is used as the added ligand, atmospheric oxygen as the catalytic enhancer and a 1 mL volume per sample aliquot). The unbuffered method was setup, validated by using known ligands and finally applied to the analysis of six seawater samples from the Ross Sea (Antarctica). The validation procedure demonstrated that ultratrace levels of ligands may be reliably determined and the application to seawater samples proved that the complex natural ligand pool can be detected with results undistinguishable from the ones obtained by the buffered procedure. The proposed method demonstrated a new principle in trace element speciation analysis by CLE-CSV, namely that the equilibration step may be performed at natural pH, whereas the pH may be set at its optimal value for sensitivity during analysis, thanks to the raise in pH at the electrode/solution interface caused by oxygen reduction. This change in paradigm paves the way to the investigation of iron speciation at natural pH in traditionally difficult samples that show circumneutral or slightly acidic pH values. The relevance of the here proposed approach to existing speciation procedures by CLE-CSV is also discussed.

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.

Fast iron speciation in seawater by catalytic Competitive Ligand Equilibration-Cathodic Stripping Voltammetry with tenfold sample size reduction.

Iron speciation analysis in seawater is a fundamental step to understand the cycling of this element in oceanic waters, in view of its central role in regulating primary productivity and its connection to global planetary cycles. At present, analytical procedures are the bottleneck for speciation analysis, in term of both time and sample size requirement. Here we present a novel instrumental configuration for the speciation analysis of iron by the Competitive Ligand Equilibration - Cathodic Stripping Voltammetry (CLE-CSV) procedure. The new system features a 1 mL microcell and a silver wire pseudoreference enabling a tenfold reduction of the sample volume. 2,3-dihydroxynaphthalene was used as the complexing ligand and atmospheric oxygen as the catalytic enhancer because they ensured the best analytical performances in terms of detection capabilities. The side reaction coefficient for the FeDHN complex αFe'DHN was calibrated against EDTA and an average value of 9.25 for logK'Fe'DHN was calculated. The method was successfully validated in UV digested seawater using diethylenetriaminepentaacetic acid (DTPA), which has known stability constant for iron. The method was lastly applied to six samples from the Ross Sea water column (Antarctica), demonstrating its fit for purpose for the detection of trace amounts of iron ligands in seawater. Thanks to the employed instrumental configuration and the high sensitivity, the proposed method achieved a tenfold reduction in sample size, a tenfold increase in sensitivity compared with other methods employing DHN and halved the analysis time with respect to the fastest method reported in the literature. Half an hour is enough to measure a 12 point titration, making the analysis of at least three titrations per day feasible. It is expected that the application of this procedure will foster the sample throughput, thanks to the reduced analysis time, and make possible the analysis of limitedly available and challenging samples, like porewater and vent fluids via the tenfold reduction in sample size.

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.

Evaluation of the Two-Dimensional Performances of Low Activity Planar Catalysts: Development and Validation of a True Scanning Reactor.

The development of a scanning reactor for planar catalysts is presented here. With respect to other existing models, this reactor is able to scan catalysts even with low turnover frequencies with a minimum sensed circular area of approximately 6 mm in diameter. The downstream gas analysis is performed with a quaprupole mass spectrometer. The apparatus performances are presented for two different reactions: the hydrogenation of butadiene over palladium films and the oxidation of CO over a gold/titania catalyst. With the final setup, true scans in both X and Y directions (or even in a previously defined complex directional pattern) are possible within a scan speed ranging from 0.1 to 5.0 mm/min. Finally, this apparatus aims at becoming a valuable tool for high throughput and combinatorial experimentation to test patterned active surfaces and catalytic libraries.

Miniaturization in voltammetry: ultratrace element analysis and speciation with twenty-fold sample size reduction.

Voltammetric techniques have emerged as powerful methods for the determination and speciation of trace and ultratrace elements without any preconcentration in several research fields. Nevertheless, large sample volumes are typically required (10 mL), which strongly limits their application and/or the precision of the results. In this work, we report a 20-fold reduction in sample size for trace and ultratrace elemental determination and speciation by conventional voltammetric instrumentation, introducing the lowest amount of sample (0.5 mL) in which ultratrace detection has been performed up to now. This goal was achieved by a careful design of a new sample holder. Reliable, validated results were obtained for the determination of trace/ultratrace elements in rainwater (Cd, Co, Cu, Ni, Pb) and seawater (Cu). Moreover, copper speciation in seawater samples was consistently determined by competitive ligand equilibration-cathodic stripping voltammetry (CLE-CSV). The proposed apparatus showed several advantages: (1) 20-fold reduction in sample volume (the sample size is lowered from 120 to 6 mL for the CLE-CSV procedure); (2) decrease in analysis time due to the reduction in purging time up to 2.5 fold; (3) 20-fold drop in reagent consumption. Moreover, the analytical performances were not affected: similar detection capabilities, precision and accuracy were obtained. Application to sample of limited availability (e.g. porewaters, snow, rainwater, open ocean water, biological samples) and to the description of high resolution temporal trends may be easily foreseen.

Optimization and validation of an automated voltammetric stripping technique for ultratrace metal analysis.

A new automated batch method for the determination of ultratrace metals (nanogram per liter level) was developed and validated. Instrumental and chemical parameters affecting the performance of the method were carefully assessed and optimized. A wide range of voltammetric methods under different chemical conditions were tested. Cadmium, lead and copper were determined by anodic stripping voltammetry (ASV), while nickel, cobalt, rhodium and uranium by adsorptive cathodic stripping voltammetry (AdCSV). The figures of merit of all of these methods were determined: very good precision and accuracy were achieved, e.g. relative percentage standard deviation in the 4-13% for ASV and 2-5% for AdCSV. The stripping methods were applied to the determination of cadmium, lead, copper, nickel, cobalt, rhodium and uranium in lake water samples and the results were found to be comparable with ICP-MS data.

On the effect of catalyst status in the quantitative determination of platinum in Pt-Sn/MgO materials.

The development of an analytical method for the determination of platinum in MgO based Pt/Sn catalysts is described. Electrothermal atomic absorption spectroscopy (ETAAS) was chosen because of its high sensitivity and robustness against spectral interferences. All the sources of chemical interferences were statistically analyzed and corrections were adopted for the presence of magnesium oxide support. The effectiveness of different mineralization procedures was critically evaluated as a function of the chemical of the solid catalyst. Microwave digestion allowed recovery of metal of 100% for all the catalysts analyzed and exhibited significant better precision values than other digestion methods, which could nevertheless be utilized under proper conditions in selected cases.