Application of SS-CS-HR-AAS measurements for the detection of Ag nanoparticles in marine invertebrates.

The present study describes the development of a fit-for-purpose analytical procedure for the detection of Ag NPs in different marine organisms by Solid Sampling Continuous Source High Resolution Atomic Absorption Spectrometry (SS-CS-HR-AAS). The detection is based on the observation of the Ag absorption peak and its atomization delay tad which is different for ionic Ag and Ag NPs. The temperature program was optimized in order to achieve the maximum difference between the t ad (Δtad ). The method was first developed using biota CRMs spiked with different Ag NPs standard solutions or Ag+ , at the same concentration. Then, laboratory exposure experiments were performed on mussels and marine sponges. The results showed that the developed methodology is suitable for the detection of Ag NPs for both groups of organisms, showing Δtad up to 3.1 s. The developed method is therefore a promising tool to assess the presence of AgNPs in marine invertebrates.

Marine sponges as coastal bioindicators of rare earth elements bioaccumulation in the French Mediterranean Sea.

In recent years, the widespread use of rare earth elements (REEs) has raised the issue of their harmful effects on the aquatic environment. REEs are now considered as contaminants of emerging concern. Despite the increasing interest of REEs in modern industry, there is still a lack of knowledge on their potential impact on the environment and especially in the marine environment. In this context, the need for monitoring tools to assess REEs pollution status in marine ecosystems is considered as the first step towards their risk assessment. Similar to mussels, filter-feeder sponges have emerged as a key bio-monitor species for marine chemical pollution. Their key position at a low level of the trophic chain makes them suitable model organisms for the study of REEs potential transfer through the aquatic food web. We therefore undertook a comparative study on seven marine sponge species, assessing their capability to bioaccumulate REEs and to potentially transfer these contaminants to higher positions in the trophic chain. A spike experiment under controlled conditions was carried out and the intra- and inter-species variability of REEs was monitored in the sponge bodies by ICP-MS. Concentrations were found to be up to 170 times higher than the corresponding control specimens. The tubular species Aplysina cavernicola showed the highest concentrations among the studied species. This study shows, for the first time, the potential of marine sponges as bio-monitor of REEs as well as their possible application in the bioremediation of polluted sites.

Scavenging of select radionuclides and trace elements by pelagic Sargassum in the Caribbean Sea.

In recent years, the North Atlantic and the Caribbean Sea have experienced unusual and unprecedented pelagic Sargassum blooms, which may adversely affect coastal ecosystems and productive ocean. Sargassum has the potential to scavenge trace elements and radionuclides from seawater, and when bioaccumulated and thus concentrated, can pose a potential threat to higher trophic organisms, including humans that consume impacted seafood. In this study, trace elements and naturally-occurring U/Th-series radionuclides were measured in Sargassum that were collected in the coastal waters of the Caribbean Sea (Antigua/Barbuda, Belize, and Barbados) to better define baseline concentrations and activities, and to assess the scavenging potential for these trace elements and radionuclides. The mean concentration of trace elements observed in Sargassum collected across these three Caribbean Sea are ranked accordingly to the following descending order: Sr > As>Fe > Mn > Zn > Ni > V > C > Cd > Se > Co > Cr > Pb > Ag > Hg. 210-Po and 210Pb activities in Sargassum were observed to be more elevated than previously reported values.

Comparative study on Hg bioaccumulation and biotransformation in Mediterranean and Atlantic sponge species.

In this work we present an assessment of mercury (Hg) and methyl mercury (MeHg) bioaccumulation in different species of marine sponges collected off the Northwestern Mediterranean and Northeastern Atlantic coasts. Overall the results showed significant accumulation of Hg in sponges, with the Mediterranean sponge Chondrilla nucula exhibiting the highest total Hg content (up to 0.5 mg kg-1) and bio-concentration factor (BCF) up to 23. A significant inter-species variability of Hg bioaccumulation was observed among species collected at the same site. The sponges, collected in marine environment contaminated with Hg show consistently higher Hg accumulation, meaning that the bioaccumulation is proportional to the Hg availability in the surrounding environment. Different extraction protocols were tested for MeHg analysis and, generally, a low MeHg ratio in Hg species (4% and 17% average for Mediterranean and Irish sponges respectively) was detected suggesting a possible demethylation process and therefore a promising role of sponges for Hg bioremediation Additionally, the Hg isotopic composition in these organisms was determined and it showed that MDF (mass dependent fractionation) is the main process in sponges, with the absence of significant MIF. This result suggests a dominant role of associated microbial population in the methylation and/or demethylation processes.

Trace elements contamination assessment in marine sediments from different regions of the Caribbean Sea.

Trace elements (TEs), rare earth elements (REEs), and methylmercury (MeHg) concentrations as well as mercury (Hg) and lead (Pb) isotope compositions in sediment samples collected from strategic locations along the Caribbean Sea were determined. The analyzed sediment samples were collected at different core depths from localities in Colombia, Cuba, Haiti, and the Dominican Republic. The evaluation of pollution assessment indices i.e. enrichment factors and geoaccumulation index revealed significant enrichment of several priority substances, such as Pb, Cd and Hg, in most of the sampling sites. Hg was found in extremely high concentrations (up to 22 ± 3 mg kg-1) in bottom samples of Colombian core, which led the authors to further investigate this area with respect to the source for Hg contamination. The analysis of Hg isotope ratios in Colombian sediments and the Pb isotope ratios in all studied cores, helped in the identification of likely pollution sources and represents a critically important record of anthropogenic influence in the region. Finally, the REEs patterns determined in all samples, also provide a needed baseline for these contaminants in the Caribbean region.

Tracing source and mobility of arsenic and trace elements in a hydrosystem impacted by past mining activities (Morelos state, Mexico).

The Sierra Huautla (Morelos State, Mexico) is a biological reserve with historical mines of Ag and Pb. In this area, waters used by inhabitants are contaminated by arsenic (As). An integrated environmental survey was realized both in waters and sediments to better constrain the source and the mobility of As and other trace elements. Two areas of interest were selected: (1) the Nexpa River ecosystem to determine the local geochemical background, and (2) the Huautla area, affected by past mining activities. This study allowed the definition of the local geochemical baseline in sediments or in waters, demonstrated uncontaminated by TE in the Nexpa area, except for As in the dissolved phase or for Cd in Suspended Particulate Matters (SPM). In the Huautla area, TE contents in water were higher than the World Health Organization (WHO) limits for Al, As and Mn in unfiltered waters, and only for As in the dissolved phase. Speciation analyses revealed arsenic to be present only as the toxic-inorganic arsenate species, As(+V). In SPM, Ag, As, Cd and Zn concentrations were higher than Sediment Quality Guidelines (SQG). The different geochemical indice (EF: 5, PLI: 3, EF: Igeo: 5-3) demonstrated that SPM were significantly contaminated and consistute an health risk for Huautla inhabitants exposed to As-contaminated waters and TE-rich SPM. The combination of mineralogy, chemistry, C and S stable isotopes with thermodynamic modeling indicate dissolutions of minerals from local geological formations, sorption-desorption phenomena from clays and oxy-hydroxides, and the weathering responsible for the transport of the TE-rich SPM (1.8 wt% for 17% of the total TE concentration). Moreover, the past mining activity would be a source of the contamination only for As in waters from flooded mines.

First assessment on trace elements in sediment cores from Namibian coast and pollution sources evaluation.

Trace elements (TEs), Rare Earth Elements (REEs) and Pb isotope ratios were determined in six small cores sampled along the Namibian coast and different indices, such as Enrichment Factor, Geo-accumulation Index and Pollution load index, were calculated to evaluate possible metal contamination in the area. Concentrations of Pb, Cu, As and Cd were strongly enhanced at the upper 7 cm of core C5, which is located at Walvis Bay, at the major harbor and urban/industrial center of Namibia, indicating the impact from the recent anthropogenic activities. Principal Component Analysis was applied to the data set indicating possible common sources of the contaminants. Pb stable isotope ratios, combined with the dating of core C5 at Walvis Bay, further confirmed the anthropogenic provenance of Pb sources in the recent sediment deposits, which occurred after 1945, when the anthropogenic activities in the area began to increase. REEs profiles were also determined, showing enrichment in REEs for some of the samples, typical for the minerals present in the area. Ce anomaly was detected in one of the cores but the REEs profile did not reveal anomalies ascribable to anthropogenic influence.

Baseline study on trace and rare earth elements in marine sediments collected along the Namibian coast.

Namibia is a fast-growing country with extensive mineral extraction activities used in diamond, fluorspar, uranium, and metals production. To assess the impact of land based human activities on the Namibian coastal marine environment, 25 elements were analyzed in 22 surface sediments samples collected along the coast. After applying a variety of pollution assessment indices (Enrichment Factor, Igeo and Pollution Load Indexes) was concluded that As, Cd and Sb were considerably enriched in the sediments from several sites, while Cu, Pb and Zn showed very high enrichment near the Walvis Bay harbor. Pearson's correlation and Principal Component Analysis were used to investigate common metal sources. Additionally, the determination of Pb isotope ratios confirmed the contribution of land based human activities at Walvis Bay and Lüderitz as sources of pollution. The analysis of REEs did not reveal any important enrichment due to anthropogenic activities, but provides a needed baseline for further investigations.

Marine sponges as a powerful tool for trace elements biomonitoring studies in coastal environment.

In this work, we performed a comparative study on six marine sponge species collected along the French Mediterranean and Irish coasts for their TEs accumulation. Intra and inter-species variabilities were examined. Among the Mediterranean species, Cymbaxinella damicornis accumulates significantly more As and Cu than others sponge species; Chondrilla nucula more Ni and Mo and Acanthella acuta more Ag. Among Irish samples, Hymeniacidon perlevis showed higher accumulation properties for most of TEs in comparison to Halichondria panicea. Bioconcentration Factors were > 1 in all species for most of TEs. This study suggests that TEs bioaccumulation is most likely associated to differences in morphological features and/or to specific bacterial communities associated to different species. The determination of Pb isotope ratios revealed mainly natural Pb sources for Mediterranean and Kilkieran Bay's samples, and rather anthropogenic influence for Belfast samples. This study confirms that sponges represent a powerful tool for biomonitoring studies.

Comparative study on the bioaccumulation and biotransformation of arsenic by some northeastern Atlantic and northwestern Mediterranean sponges.

The bioaccumulation and biotransformation of arsenic (As) were studied in six representative marine sponges from the French Mediterranean and Irish Atlantic coasts. Methodologies were carefully optimized in one of the species on Haliclona fulva sponges for two critical steps: the sample mineralization for total As analysis by ICP-MS and the extraction of As species for HPLC-ICP-MS analysis. During the optimization, extractions performed with 0.6 mol L-1 H3PO4 were shown to be the most efficient. Extraction recovery of 81% was obtained which represents the best results obtained until now in sponge samples. Total As analyses and As speciation were performed on certified reference materials and allow confirming the measurement quality both during the sample preparation and analysis. Additionally, this study represents an environmental survey demonstrating a high variability of total As concentrations among the different species, probably related to different physiological or microbial features. As speciation results showed the predominance of arsenobetaine (AsB) regardless of the sponge species, as well as the occurrence of low amounts of dimethylarsinic acid (DMA), arsenate (As(+V)), and unknown As species in some samples. The process responsible for As transformation in sponges is most likely related to sponges metabolism itself or the action of symbiont organisms. AsB is supposed to be implied in the protection against osmolytic stress. This study demonstrates the ability of sponges to accumulate and bio-transform As, proving that sponges are relevant bio-monitors for As contamination in the marine environment, and potential tools in environmental bio-remediation.

Exploratory analysis for the evaluation of lopinavir/ritonavir-versus efavirenz-based HAART regimens in antiretroviral-naive HIV-positive patients: results from the Italian MASTER Cohort.

OBJECTIVE: This retrospective longitudinal cohort study compared the virological and immunological responses to highly active antiretroviral therapy containing either efavirenz or lopinavir/ritonavir in previously antiretroviral-naive HIV-infected patients. PATIENTS AND METHODS: A total of 472 patients were selected (348 efavirenz and 124 lopinavir/ritonavir). The primary endpoint of this study was virological success (HIV RNA <50 copies/mL). The immunological response was assessed on the basis of either CD4+ T cell count variations (absolute and percentage) with respect to baseline values or categorical endpoints (defined as either a CD4+ T cell increase of > or =1;50 cells/mm(3) at week 24 or of > or =1;75 cells/mm(3) at week 48). RESULTS: At intention-to-treat (ITT) analysis, the adjusted odds ratio of virological success for patients who started lopinavir/ritonavir, compared with those who started efavirenz, was 0.54 (95% CI: 0.33-0.89, P = 0.016) at week 24 and 0.40 (95% CI: 0.33-0.89, P = 0.002) at week 48. However, patients receiving lopinavir/ritonavir had a more pronounced CD4+ T cell recovery, demonstrating both a mean absolute and percentage increase up to week 48 (MANOVA P < 0.0001). CONCLUSIONS: Although comparisons of drug efficacy in non-randomized studies should be viewed with caution, from a virological point of view efavirenz-containing regimens performed as well (on-treatment analysis) or better (ITT analysis) than those containing lopinavir/ritonavir. In contrast, immunological outcome appeared to favour lopinavir/ritonavir.