Elemental Analyzer/Isotope Ratio Mass Spectrometry (EA/IRMS) as a Tool to Characterize Plastic Polymers in a Marine Environment

In the last 60 years, plastic has become a widely used material due to its versatility and wide range of applications. This characteristic, together with its persistence, makes plastic waste a growing environmental problem, particularly in the marine ecosystems. The production of plant-derived biodegradable plastic polymers is assuming increasing importance. Here, we report the results of a first preliminary characterization of carbon stable isotopes (δ13C) of different plastic polymers (petroleum- and plant-derived) and a first experimental study aimed to determine carbon isotopic shift due to polymer degradation in an aquatic environment. The results showed that the δ13C values determined in different packaging for food uses reflect the plant origin for “BIO” materials and the petroleum-derived source for plastic materials. Considering degradation, δ13C values of both bio bags and HDPE bags showed a gradual decrease toward less negative values when kept immersed in seawater, recording a δ13C variation (Δδ13C) of 1.15 and 1.78‰, respectively. With respect to other analytical methods, the characterization of the plastic polymer composition by isotope ratio mass spectrometry is advantageous due to low cost and rapidity of analysis, small amount of sample required, high sensitivity, and the possibility of analyzing colored samples

Gold nanoparticles ingested by oyster larvae are internalized by cells through an alimentary endocytic pathway

<p>The biological fate of nanoparticles (NPs) taken up by organisms from their environment is a crucial issue for assessing ecological hazard. Despite its importance, it has scarcely been addressed due to the technical difficulties of doing so in whole organism <i>in vivo</i> studies. Here, by using transmission electron microscopy and energy dispersive X-ray spectroscopy (TEM-EDS), we describe the key aspects that characterize the interaction between an aquatic organism of global ecological and economic importance, the early larval stage of the Japanese oyster (<i>Crassostrea gigas</i>), and model gold NPs dispersed in their environment. The small size of the model organism allowed for a high-throughput visualization of the subcellular distribution of NPs, providing a comprehensive and robust picture of the route of uptake, mechanism of cellular permeation, and the pathways of clearance counterbalancing bioaccumulation. We show that NPs are ingested by larvae and penetrate cells through alimentary pinocytic/phagocytic mechanisms. They undergo intracellular digestion and storage inside residual bodies, before excretion with feces or translocation to phagocytic coelomocytes of the visceral cavity for potential extrusion or further translocation. Our mechanistically-supported findings highlight the potential of oyster larvae and other organisms which feature intracellular digestion processes to be exposed to man-made NPs and thus any risks associated with their inherent toxicity.</p

Dissolution and bandgap paradigms for predicting the toxicity of metal oxide nanoparticles in the marine environment: an <i>in vivo</i> study with oyster embryos

<p>Dissolution and bandgap paradigms have been proposed for predicting the ability of metal oxide nanoparticles (NPs) to induce oxidative stress in different <i>in vitro and in vivo</i> models. Here, we addressed the effectiveness of these paradigms <i>in vivo</i> and under conditions typical of the marine environment, a final sink for many NPs released through aquatic systems. We used ZnO and MnO₂ NPs as models for dissolution and bandgap paradigms, respectively, and CeO₂ NPs to assess reactive oxygen radical (ROS) production via Fenton-like reactions <i>in vivo</i>. Oyster embryos were exposed to 0.5–500 μM of each test NP over 24 h and oxidative stress was determined as a primary toxicity pathway across successive levels of biological complexity, with arrested development as the main pathological outcome. NPs were actively ingested by oyster larvae and entered cells. Dissolution was a viable paradigm for predicting the toxicity of NPs in the marine environment, whereas the surface reactivity based paradigms (i.e. bandgap and ROS generation via Fenton-like reaction) were not supported under seawater conditions. Bio-imaging identified potential cellular storage-disposal sites of solid particles that could ameliorate the toxicological behavior of non-dissolving NPs, whilst abiotic screening of surface reactivity suggested that the adsorption-complexation of surface active sites by seawater ions could provide a valuable hypothesis to explain the quenching of the intrinsic oxidation potential of MnO₂ NPs in seawater.</p

Organotin compounds in touristic marinas of the northern Adriatic Sea: occurrence, speciation and potential recycling at the sediment-water interface

Butyltin compound (BTC) contamination was evaluated in two north Adriatic marinas, San Rocco (Italy) and Lucija (Slovenia). BTC sedimentary concentrations (121 \ub1 46 and 352 \ub1 30 ng Sn g 121 in San Rocco and Lucija, respectively) evidenced the past use of antifouling paints, confirmed by the reduced tributyltin content (~ 46%) with respect to the sumof BTC. Elemental and organic carbon isotopic (\u3b413C) analyses of bulk sediments and its lipid and humic substances were performed in order to evaluate their role in BTC partitioning and preservation. The \u3b413C of sedimentary bulk and refractory organic matter suggested that diagenetic processes could play a role in the preservation or release of pollutants. No contamination was found in water collected from the benthic chamber and thus, fluxes at the sediment-water interface were not assessed, except for MBT efflux at Lucija (28.9 ng Sn m 122 day 121). Nevertheless, BTC concentrations in porewaters (up to 75 ng Sn l 121) and rather low sediment-porewater partitioning coefficients (Kd) with respect to the data reported in the literature would suggest a potential risk of the reintroduction of BTC into the water column at both sites: at Lucija, sedimentary contamination is high despite the greater Log Kd, whilst at San Rocco, the low BTC concentration is associated with a reduced sediment affinity

Evidence of Butyltin Biomagnification along the Northern Adriatic Food-Web (Mediterranean Sea) Elucidated by Stable Isotope Ratios

The biomagnification of tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), and total butyltins (ΣBT) was analyzed in the Northern Adriatic food-web (Mediterranean) considering trophodynamic interactions among species and carbon sources in the food-web. Although it is acknowledged that these contaminants bioaccumulate in marine organisms, it is still controversial whether they biomagnify along food-webs. A wide range of species was considered, from plankton feeders to top predators, whose trophic level (TL) was assessed measuring the biological enrichment of nitrogen stable isotopes (δ¹⁵N). Carbon isotopic signature (δ¹³C) was used to trace carbon sources in the food-web (terrestrial vs marine). At least one butyltin species was detected in the majority of samples, and TBT was the predominant contaminant. A significant positive relationship was found between TL and butyltin concentrations, implying food-web biomagnification. Coherently, the Trophic Magnification Factor resulted higher than 1, ranging between 3.88 for ΣBT and 4.62 for DBT. A negative but not significant correlation was instead found between δ¹³C and butyltin concentrations, indicating a slight decreasing gradient of contaminants concentrations in species according to the coastal influence as carbon source in their diet. However, trophodynamic mechanisms are likely more important factors in determining butyltin distribution in the Northern Adriatic food-web

New implications in the use of imposex as a suitable tool for Tributyltin contamination: experimental induction in Hexaplex trunculus (Gastropoda, Muricidae) with different stressors

Imposex, i.e. the development of additional male sex organs (penis and/or vas deferens), in females of gonochorist marine and freshwater gastropods, is known to be caused by tributyltin (TBT), and it has been widely used as a biomonitoring tool in environmental surveys for TBT pollution assessment. In this study, we experimentally tested the potential to induce imposex by another endocrine disruptor (polychlorinated biphenyls [PCBs] mixture—Aroclor 1260). Adults of Hexaplex trunculus with low imposex level, coming from an Italian Marine Protected Area, were injected separately with different doses of tributyltin chloride (TBTCl) and Aroclor 1260. The compounds were dissolved in ethanol and the organisms were narcotised by immersion in MgCl2 solution before injection. Before and after the experiment, butyltin compounds (BuTs) and PCB tissue concentrations were determined. A significant increase in imposex with respect to non-treated organisms was observed in all treatments, including artefact controls. No clear correlation was observed between BuTs and PCB tissue concentrations and indices of imposex incidence. Based on these results, no assumption can be formulated about PCB effect on imposex development. Nevertheless, they suggest that the imposex level increase, at least in H. trunculus, in laboratory conditions might not be caused by TBT only, but it would rather be a non-specific response to different stress stimuli