Philip S. Rainbow

Metal toxicity, uptake and bioaccumulation in aquatic invertebrates--modelling zinc in crustaceans.

We use published data on the different patterns of the bioaccumulation of zinc by three crustaceans, the caridean decapod Palaemon elegans, the amphipod Orchestia gammarellus and the barnacle Amphibalanus amphitrite, to construct comparative biodynamic models of the bioaccumulation of zinc into metabolically available and detoxified components of accumulated zinc in each crustacean under both field and laboratory toxicity test conditions. We then link these bioaccumulation models to the onset of toxic effects on exposure of the crustaceans to high dissolved zinc bioavailabilities, using the tenets that toxicity effects are related to the total uptake rate of the toxic metal, and that toxicity is not usually dependent on the total accumulated metal concentration but always on the concentration of accumulated metal that is metabolically available. We dismiss the general concept that there is a critical accumulated body concentration of a metal in an invertebrate at which toxicity ensues, except under specific circumstances involving a rare lack of storage detoxification of accumulated metal. We thus propose a theoretical framework that can be extended to other metals and other aquatic invertebrates (indeed other animals) to explain the variation in the relationship between bioaccumulated body concentrations and toxicity, and subsequently to predict this relationship in many other species for which we have bioaccumulation modelling data.

In vivo retention of ingested Au NPs by Daphnia magna: No evidence for trans-epithelial alimentary uptake

In vivo studies with Daphnia magna remain inconclusive as to whether engineered nanoparticles (NPs) are internalized into tissues after ingestion. Here we used a three-pronged approach to study the in vivo retention and efflux kinetics of 20 nm citrate stabilized Au NPs ingested by this key aquatic species. Daphnids were exposed to suspended particles (600 μg L(-1)) for 5 h after which they were depurated for 24 h in clean water containing algae. Light microscopy was used to follow the passage of Au NPs through the gastrointestinal tract, Au body burdens were determined by ICP-MS (inductively coupled plasma mass spectrometry), and transmission electron microscopy (TEM) was used to examine the presence and distribution of Au NPs in tissues. Results revealed that the elimination of Au NPs was bi-phasic. The fast elimination phase lasted<1h and the rate constant at which Au (of Au NPs) was eliminated was 1.12 ± 0.34 h(-1) (±SE) which accounted for ∼75% of the ingested Au. The remaining ∼25% of the ingested Au NPs was eliminated at a 100-fold slower rate. TEM analysis revealed that Au NPs in the midgut were in close proximity to the peritrophic membrane after 1 and 24h of depuration. There were no observations of Au NP uptake at the microvilli. Thus, although Au NPs were retained in the gut lumen, there was no observable internalization into the gut epithelial cells. Similar to carbon nanotubes and CuO NPs, our findings indicate that in daphnids the in vivo retention of Au NPs does not necessarily result in their internalization.

Environmental Assessment of Estuarine Ecosystems: A Case Study

Introduction, Claude Amiard-Triquet and Jean-Claude Dauvin Sedimentary Processes on Estuarine Mudflats: Examples of the Seine and Authie Estuaries, Julien Deloffre and Robert Lafite Quantification of Contaminants, Jean-Claude Amiard, Laurent Bodineau, Virginie Bragigand, Christophe Minier, and Helene Budzinski Biomarkers Based upon Biochemical Responses, Michele Romeo, Laurence Poirier, and Brigitte Berthet Biogeochemistry of Metals in Sediments: Development of Microscale Analytical Tools and Use of Indicators of Biological Activities, Baghdad Ouddane, Laurent Quillet, Olivier Clarisse, Gabriel Billon, Jean-Claude Fischer, and Fabienne Petit Organic Contaminants in Coastal and Estuarine Food Webs, Alain Abarnou Tolerance in Organisms Chronically Exposed to Estuarine Pollution, Claude Amiard-Triquet, Thierry Berthe, Anne Creach, Francoise Denis, Cyril Durou, Francois Gevaert, Catherine Mouneyrac, Jean-Baptiste Ramond, and Fabienne Petit Linking Energy Metabolism, Reproduction, Abundance, and Structure of Nereis diversicolor Populations, Catherine Mouneyrac, Cyril Durou, Patrick Gillet, Herman Hummel, and Claude Amiard-Triquet Historical Records of the Nereis diversicolor Population in the Seine Estuary, Christophe Bessineton Ecological Status and Health of the Planktonic Copepod Eurytemora affinis in the Seine Estuary, Joelle Forget-Leray, Sami Souissi, David Devreker, Kevin Cailleaud, and Helene Budzinski From Pollution to Altered Physiological Performance: The Case of Flatfish in the Seine Estuary, Christophe Minier and Rachid Amara Diatoms: Modern Diatom Distribution in the Seine and Authie Estuaries, Florence Sylvestre Foraminifera, Jean-Pierre Debenay Patterns of Abundance, Diversity, and Genus Assemblage Structure of Meiofaunal Nematodes in the Seine (Pont de Normandie) and Authie (Authie Port) Estuaries, Timothy J. Ferrero Dynamic Diagenetic Modelling and Impacts of Biota, Lionel Denis, Dominique Boust, Benedicte Thouvenin, Pierre Le Hir, Julien Deloffre, Jean-Louis Gonzalez, and Patrick Gillet Conclusions, Claude Amiard-Triquet and Philip S. Rainbow Index

Have the bioavailabilities of trace metals to a suite of biomonitors changed over three decades in SW England estuaries historically affected by mining

Many estuaries of southwest England were heavily contaminated with toxic metals associated with the mining of copper and other metals, particularly between 1850 and 1900. The question remains whether the passage of time has brought remediation to these estuaries. In 2003 and 2006 we revisited sites in 5 metal-contaminated estuaries sampled in the 1970s and 1980s - Restronguet Creek, Gannel, West Looe, East Looe and Tavy. We evaluate changes in metal contamination in sediments and in metal bioavailabilities in sediments and water to local organisms employed as biomonitors. We find that the decline in contamination in these estuaries is complex. Differences in bioavailable contamination in the water column were detectable, as were significant detectable changes in at least some estuaries in bioavailable metal contamination originating from sediments. However, in the 100 years since mining activities declined, bioavailable contamination has not declined to the regional baseline in any estuary affected by the mine wastes. The greatest decline in contamination occurred in the one instance (East Looe) where a previous industrial source of (Ag) contamination was considered. We used the macroalgae Fucus vesiculosus and Ascophyllum nodosum as biomonitors of dissolved metal bioavailabilities and the deposit feeders Nereis diversicolor and Scrobicularia plana as biomonitors of bioavailable metal in sediments. We found no systematic decrease in the atypically high Ag, Cu, Pb and Zn concentrations in the estuarine sediments over a 26 year period. Accumulated metal (Ag, As, Cu, Pb, and Zn) concentrations in the deposit feeders are similarly still atypically high in at least one estuary for each metal, and there is no consistent evidence for general decreases in sediment metal bioavailabilities over time. We conclude that the legacy of mining in sheltered estuaries of southwest England is the ongoing presence of sediments rich in metals bioavailable to deposit feeders, while dissolved metal bioavailabilities from this historical source alone are no longer atypically high.

Mayfly larvae (Baetis rhodani and B. vernus) as biomonitors of trace metal pollution in streams of a catchment draining a zinc and lead mining area of Upper Silesia, Poland

Larvae of two Baetis species were used to investigate spatial and temporal variability in the bioavailabilities of cadmium, copper, lead, zinc and iron in the river Biala Przemsza and its tributaries draining an area of lead and zinc mining in Upper Silesia, Poland. Accumulated metal concentrations were measured in April, May, August and November 2000. Both species indicated significant local geographical variability in availabilities of zinc, iron, lead and cadmium, but not copper. Accumulated concentrations of lead, zinc and cadmium confirmed the high general contamination of the Biala Przemsza system by these three trace metals. Larvae showed little seasonal variation in concentrations of cadmium, copper, lead and iron. Accumulated zinc concentrations were low in Baetis rhodani in August, perhaps as a result of insufficient time for high concentrations to accumulate since hatching of the larvae. Samples collected in August most nearly matched criteria of the greatest availability of larvae for collection and their size homogeneity, minimising the possibilities of any effect of differential larval size and/or age on accumulated metal concentrations. Mayfly larvae are members of a suite of potential stream biomonitors in Central Europe, which together can provide information on the different sources of bioavailable trace metals present in aquatic ecosystems.

Decoupling of cadmium biokinetics and metallothionein turnover in a marine polychaete after metal exposure.

This study investigated the kinetics of Cd bioaccumulation, detoxification, subcellular distribution, and efflux in the nereid polychaete Perinereis aibuhitensis after Cd pre-exposure. Cd pre-exposure increased the Cd body burden in the worms, but did not affect the overall Cd uptake and efflux rates and metallothionein-like protein (MTLP) concentrations. During short-term exposure to dissolved Cd, Cd in the cytosolic fraction increased after Cd pre-exposure, and this fraction also increased during the Cd efflux period, indicating that the insoluble fraction of Cd was presumably lost at a faster rate than the loss of cytosolic Cd. Even though the MTLP concentration remained comparable after Cd pre-exposure, both the MTLP synthesis rate and the degradation rate increased, thus leading to a high MTLP turnover in the Cd-exposed worms. However, Cd uptake and efflux into different protein size fractions did not follow the patterns of MTLP synthesis and degradation, strongly suggesting that Cd kinetics is decoupled from the MTLP kinetics in the worms. Our study adds to an increasing body of evidence on the complicated relationship between metal biokinetics and MTLP kinetics in different groups of marine invertebrates which have strong contrasts in their metal handling strategies.

Biomonitoring of trace metals along the Baltic coast of Poland using the sandhopper Talitrus saltator (Montagu) (Crustacea: Amphipoda)

Abstract In a biomonitoring survey, accumulated trace metal concentrations (Cu, Zn, Fe, Cd, Pb, Mn, Ni) have been measured in the talitrid amphipod crustacean Talitrus saltator collected from 13 sites along the Baltic coast of Poland in June Analysis of covariance has shown significant geographical differences in the local bioavailabilities of copper, zinc, iron and manganese. There have been changes in the bioavailabilities of trace metals around the Gulf of Gdansk between 1996 and 1998 reflected in changes in amphipod metal concentration, availabilities of zinc, cadmium and manganese falling, and that of lead rising.

Toxicity and accumulation of silver nanoparticles during development of the marine polychaete Platynereis dumerilii

Pollutants affecting species at the population level generate ecological instability in natural systems. The success of early life stages, such as those of aquatic invertebrates, is highly affected by adverse environmental conditions. Silver released into the environment from emerging nanotechnology represents such a threat. Sediments are sinks for numerous pollutants, which aggregate and/or associate with depositing suspended particles. Deposit feeder such as the annelid Platynereis dumerilii, which has a large associated literature on its development, is an excellent model organism for exposure studies in coastal environments. We exposed eggs, larvae, juveniles and adults of P. dumerilii to various concentrations of citrate (cit-Ag NPs) or humic acid (HA-Ag NPs) capped silver nanoparticles (Ag NPs) as well to dissolved Ag (added as AgNO3). We showed that mortality and abnormal development rate increased with younger life stages. While adults and juvenile were the most tolerant life stages, fertilized eggs were highly sensitive to AgNO3, cit-Ag NPs and HA-Ag NPs. Exposures to HA-Ag NPs triggered the highest cute toxicity responses in P. dumerilii and in most cases both Ag NPs were more toxic than AgNO3. Uptake rate of HA-Ag NPs in adult worms was also higher than from other Ag forms, consistent with toxicity to other life stages. The early stages of the life cycle of marine coastal organisms are more affected by Ag NPs than the juvenile or adult life stages, indicating that exposure experiments at the larval level contribute to realistic eco-toxicological studies in aquatic environments.

Bioaccumulation and oxidative stress responses measured in the estuarine ragworm (Nereis diversicolor) exposed to dissolved, nano- and bulk-sized silver

The impact of Ag NPs on sediment-dwelling organisms has received relatively little attention, particularly in linking bioaccumulation to oxidative injury. The polychaete Nereis diversicolor was exposed to sediments spiked with dissolved Ag (added as AgNO3), Ag NPs (63 ± 27 nm) and larger bulk Ag particles (202 ± 56 μm), for up to 11 days at sublethal concentrations (nominally 2.5, 5, 10 μg Ag g(-1) sediment (dw)). There were concentration- and time-dependent differences in the accumulation of the three Ag forms, but all three forms elicited an oxidative stress response. In the cases of Ag NPs and bulk Ag particles, changes in antioxidant markers (glutathione, SOD, CAT, GPx, SeGPx, GST and GR) occurred without significant Ag accumulation. Differences in biomarker profiles between the three Ag forms suggest that the mechanism of oxidative stress caused by particulate Ag is distinct from that of dissolved Ag.

Inhibition of potential uptake pathways for silver nanoparticles in the estuarine snail Peringia ulvae

Abstract Mechanisms involved in the uptake of Ag NPs, and NPs in general, have been long debated within nano-ecotoxicology. In vitro studies provide evidence of the different available uptake pathways, but in vivo demonstrations are lacking. In this study, pharmacological inhibitors were employed to block specific uptake pathways that have been implicated in the transport of metal NPs and aqueous metal forms; phenamil (inhibits Na+ channel), bafilomycin A1 (H+ proton pump), amantadine (clathrin-mediated endocytosis), nystatin (caveolae-mediated endocytosis) and phenylarsine oxide (PAO, macropinocytosis). Peringia ulvae (snails) were exposed to 150 µg Ag L−1 added as citrate capped Ag NPs or aqueous Ag (AgNO3) in combination with inhibitor treatment (determined by preliminary studies). Reductions in accumulated tissue burdens caused by the inhibitors were compared to control exposures (i.e. no inhibition) after 6 and 24 h. No inhibitor treatment completely eliminated the uptake of Ag in either aqueous or NP form, but all inhibitor treatments, except phenamil, significantly reduced the uptake of Ag presented as Ag NPs. Clathrin- and caveolae-mediated endocytosis appear to be mechanisms exploited by Ag NPs, with the latter pathway only active at 24 h. Inhibition of the H+ proton pump showed that a portion of Ag NP uptake is achieved as aqueous Ag and is explained by the dissolution of the particles (∼25% in 24 h). This in vivo study demonstrates that uptake of Ag from Ag NPs is achieved by multiple pathways and that these pathways are simultaneously active.