Reactivity and bioconcentration of stable cesium in a hyperturbid fluvial-estuarine continuum: A combination of field observations and geochemical modeling.

Effective, post-accidental management needs an accurate understanding of the biogeochemical behavior of radionuclides in surface environments at a regional scale. Studies on stable isotopes (element homologs) can improve this knowledge. This work focuses on the biogeochemical behavior of stable cesium (Cs) along a major European fluvial-estuarine system, the Gironde Estuary (SW France). We present results obtained from (i) a long-term monitoring (2014-2017) of dissolved (Csd) and particulate (Csp) Cs concentrations at five sites along the freshwater continuum of the Garonne watershed, (ii) Csd and Csp concentrations during four oceanographic campaigns at contrasting hydrological conditions along longitudinal profiles of the estuarine system, (iii) a 24 h cycle of Csp at the estuary mouth, and (iv) a historical trend of Cs bioconcentration in wild oysters at the estuary mouth (RNO/ROCCH, 1984-2017). In addition, we model the partitioning of Cs within the estuarine environment for clay mineral interactions via PhreeqC. At fluvial sites, we observe a geogenic dependence of the Csp and a seasonal variability of Csd, with a downstream increase of the solid-liquid partitioning (log10 Kd values from 3.64 to 6.75 L kg-1) for suspended particulate matter (SPM) < 200 mg L-1. Along the estuarine salinity gradients, Cs shows a non-conservative behavior where fresh SPM (defined as Cs-depleted particles recently put in contact with Csd) act as a Cs sink during both flood and low discharge (drought) conditions. This sorption behavior was explained by the geochemical model, highlighting the relevance of ionic strength, water and SPM residence times. However, at high salinities, the overall log10 Kd value decreases from 6.02 to 5.20 for SPM ∼300-350 mg L-1 due to the Csd oceanic endmember. Despite wild oysters showing low bioconcentration factors (∼1220 L kg-1) at the estuary mouth, they are sensitive organisms to Cs fluxes.

Seasonal and multi-decadal zinc isotope variations in blue mussels from two sites with contrasting zinc contamination levels.

Zinc (Zn) isotope compositions in soft mussel tissues help identify internal biological processes and track coastal Zn sources in coastal environments, thus aiding in managing marine metal pollution. This study investigated the seasonal and multi-decadal Zn isotope compositions of blue mussels (genus Mytilus) from two French coastal sites with contrasting Zn environmental contamination. Concurrently, we characterized the isotope ratios of sediments and plankton samples at each site to understand the associations between organisms and abiotic compartments. Our primary objective was to determine whether these isotope compositions trace long-term anthropogenic emission patterns or if they reflect short-term biological processes. The multi-decadal isotope profiles of mussels in the Loire Estuary and Toulon Bay showed no isotope variations, implying the enduring stability of the relative contributions of natural and anthropogenic Zn sources over time. At seasonal scales, Zn isotope ratios were also constant; hence, isotope effects related to spawning and body growth were not discernible. The multi-compartmental analysis between the sites revealed that Toulon Bay exhibits a remarkably lower Zn isotope ratio across all studied matrices, suggesting the upward transfer of anthropogenic Zn in the food web. In contrast, the Zn isotope variability observed for sediments and organisms from the Loire Estuary fell within the natural baseline of this element. In both sites, adsorptive geogenic material carrying significant amounts of Zn masks the biological isotope signature of plankton, making it difficult to determine whether the Zn isotope ratio in mussels solely reflects the planktonic diet or if it is further modified by biological homeostasis. In summary, Zn isotope ratios in mussels offer promising avenues for delineating source-specific isotope signatures, contingent upon a comprehensive understanding of the isotope fractionation processes associated with the trophic transfer of this element through the plankton.

The French Mussel Watch Program reveals the attenuation of coastal lead contamination over four decades.

The mid-20th century industrial peak caused severe global lead (Pb) marine contamination. Although Europe initiated Pb emission reduction regulations in the 1980s, the short- and long-term impacts remain unclear. This study investigates the evolution of Pb contamination on the French coast through elemental and isotope analysis in oysters and mussels from the French "Mussel Watch" Program. Observations at 114 monitoring stations over four decades have shown decreasing Pb levels in these bivalve mollusks. In 1988, 95 % exceeded the background reference values; this level had dropped to 39 % by 2021. The Pb isotope ratios in bivalves from eight target sites revealed a reduction in bioaccumulated anthropogenic Pb, albeit without complete elimination. The long residence time of legacy Pb combined with inputs from diffuse urban sources likely explains the persistent presence of anthropogenic Pb on the French coast. This study endorses the importance of continuous biomonitoring to evaluate environmental regulations and policies.

Bioconcentration, bioaccumulation and biomagnification of mercury in plankton of the Mediterranean Sea.

Plankton plays a prominent role in the bioaccumulation of mercury (Hg). The MERITE-HIPPOCAMPE campaign was carried out in spring 2019 along a north-south transect including coastal and offshore areas of the Mediterranean Sea. Sampling of sea water and plankton by pumping and nets was carried out in the chlorophyll maximum layer. Two size-fractions of phytoplankton (0.7-2.7 and 2.7-20 µm) and five of zooplankton (between 60 and >2000 µm) were separated, and their total mercury (THg) and monomethylmercury (MMHg) contents were measured. Bioconcentration of THg was significantly higher in the smallest phytoplankton size-fraction dominated by Synechococcus spp. The bioaccumulation and biomagnification of MMHg in zooplankton was influenced by size, food sources, biochemical composition and trophic level. MMHg was biomagnified in the plankton food web, while THg decreased toward higher trophic levels. Higher MMHg concentrations were measured in oligotrophic areas. Plankton communities in the Southern Mediterranean Sea had lower MMHg concentrations than those in the Northern Mediterranean Sea. These results highlighted the influence of environmental conditions and trophodynamics on the transfer of Hg in Mediterranean plankton food webs, with implications for higher trophic level consumers.

Contamination of planktonic food webs in the Mediterranean Sea: Setting the frame for the MERITE-HIPPOCAMPE oceanographic cruise (spring 2019).

This paper looks at experiential feedback and the technical and scientific challenges tied to the MERITE-HIPPOCAMPE cruise that took place in the Mediterranean Sea in spring 2019. This cruise proposes an innovative approach to investigate the accumulation and transfer of inorganic and organic contaminants within the planktonic food webs. We present detailed information on how the cruise worked, including 1) the cruise track and sampling stations, 2) the overall strategy, based mainly on the collection of plankton, suspended particles and water at the deep chlorophyll maximum, and the separation of these particles and planktonic organisms into various size fractions, as well as the collection of atmospheric deposition, 3) the operations performed and material used at each station, and 4) the sequence of operations and main parameters analysed. The paper also provides the main environmental conditions that were prevailing during the campaign. Lastly, we present the types of articles produced based on work completed by the cruise that are part of this special issue.

Mediterranean Mercury Assessment 2022: An Updated Budget, Health Consequences, and Research Perspectives.

Mercury (Hg) and especially its methylated species (MeHg) are toxic chemicals that contaminate humans via the consumption of seafood. The most recent UNEP Global Mercury Assessment stressed that Mediterranean populations have higher Hg levels than people elsewhere in Europe. The present Critical Review updates current knowledge on the sources, biogeochemical cycling, and mass balance of Hg in the Mediterranean and identifies perspectives for future research especially in the context of global change. Concentrations of Hg in the Western Mediterranean average 0.86 ± 0.27 pmol L-1 in the upper water layer and 1.02 ± 0.12 pmol L-1 in intermediate and deep waters. In the Eastern Mediterranean, Hg measurements are in the same range but are too few to determine any consistent oceanographical pattern. The Mediterranean waters have a high methylation capacity, with MeHg representing up to 86% of the total Hg, and constitute a source of MeHg for the adjacent North Atlantic Ocean. The highest MeHg concentrations are associated with low oxygen water masses, suggesting a microbiological control on Hg methylation, consistent with the identification of hgcA-like genes in Mediterranean waters. MeHg concentrations are twice as high in the waters of the Western Basin compared to the ultra-oligotrophic Eastern Basin waters. This difference appears to be transferred through the food webs and the Hg content in predators to be ultimately controlled by MeHg concentrations of the waters of their foraging zones. Many Mediterranean top-predatory fish still exceed European Union regulatory Hg thresholds. This emphasizes the necessity of monitoring the exposure of Mediterranean populations, to formulate adequate mitigation strategies and recommendations, without advising against seafood consumption. This review also points out other insufficiencies of knowledge of Hg cycling in the Mediterranean Sea, including temporal variations in air-sea exchange, hydrothermal and cold seep inputs, point sources, submarine groundwater discharge, and exchanges between margins and the open sea. Future assessment of global change impacts under the Minamata Convention Hg policy requires long-term observations and dedicated high-resolution Earth System Models for the Mediterranean region.

"Non-traditional" stable isotopes applied to the study of trace metal contaminants in anthropized marine environments.

The advent of Multicollector ICP-MS inaugurated the analysis of new metal isotope systems, the so-called "non-traditional" isotopes. They are now available tools to study geochemical and ecotoxicological aspects of marine metal contamination and hence, to push the frontiers of our knowledge. However, such applications are still in their infancy, and an accessible state-of-the-art describing main applications, obstacles, gaps, and directions for further development was missing from the literature. This paper fills this gap and aims to encourage the marine scientific community to explore the contributions of this newly available information for the fields of chemical risk assessment, biomonitoring, and trophic transfer of metal contaminants. In the current "Anthropocene" epoch, metal contamination will continue to threaten marine aquatic ecosystems, and "non-traditional" isotopes can be a valuable tool to detect human-induced changes across time-space involving metal contaminants, and their interaction with marine biota.

Metal stable isotopes in transplanted oysters as a new tool for monitoring anthropogenic metal bioaccumulation in marine environments: The case for copper.

Metal release into the environment from anthropogenic activities may endanger ecosystems and human health. However, identifying and quantifying anthropogenic metal bioaccumulation in organisms remain a challenging task. In this work, we assess Cu isotopes in Pacific oysters (C. gigas) as a new tool for monitoring anthropogenic Cu bioaccumulation into marine environments. Arcachon Bay was taken as a natural laboratory due to its increasing contamination by Cu, and its relevance as a prominent shellfish production area. Here, we transplanted 18-month old oysters reared in an oceanic neighbor area into two Arcachon Bay mariculture sites under different exposure levels to continental Cu inputs. At the end of their 12-month long transplantation period, the oysters' Cu body burdens had increased, and was shifted toward more positive δ65Cu values. The gradient of Cu isotope compositions observed for oysters sampling stations was consistent with relative geographic distance and exposure intensities to unknown continental Cu sources. A binary isotope mixing model based on experimental data allowed to estimate the Cu continental fraction bioaccumulated in the transplanted oysters. The positive δ65Cu values and high bioaccumulated levels of Cu in transplanted oysters support that continental emissions are dominantly anthropogenic. However, identifying specific pollutant coastal source remained unelucidated mostly due to their broader and overlapping isotope signatures and potential post-depositional Cu isotope fractionation processes. Further investigations on isotope fractionation of Cu-based compounds in an aqueous medium may improve Cu source discrimination. Thus, using Cu as an example, this work combines for the first time a well-known caged bivalve approach with metal stable isotope techniques for monitoring and quantifying the bioaccumulation of anthropogenic metal into marine environments. Also, it states the main challenges to pinpoint specific coastal anthropogenic sources utilizing this approach and provides the perspectives for further studies to overcome them.

Differences in Copper Isotope Fractionation Between Mussels (Regulators) and Oysters (Hyperaccumulators): Insights from a Ten-Year Biomonitoring Study.

Copper (Cu) isotope compositions in bivalve mollusks used in marine-monitoring networks is a promising tool to monitor anthropogenic Cu contamination in coastal and marine ecosystems. To test this new biomonitoring tool, we investigated Cu isotope variations of two bivalves-the oyster Crassostrea gigas and the mussel Mytilus edulis-over 10 years (2009-2018) in a French coastal site contaminated by diffuse Cu anthropogenic sources. Each species displayed temporal concentration profiles consistent with their bioaccumulation mechanisms, that is, the Cu-regulating mussels with almost constant Cu concentrations and the Cu-hyperaccumulating oysters with variable concentrations that track Cu bioavailability trends at the sampling site. The temporal isotope profiles were analogous for both bivalve species, and an overall shift toward positive δ65Cu values with the increase of Cu bioavailabilities was associated with anthropogenic Cu inputs. Interestingly, mussels showed wider amplitudes in the isotope variations than oysters, suggesting that each species incorporates Cu isotopes in their tissues at different rates, depending on their bioaccumulation mechanisms and physiological features. This study is the first to demonstrate the potential of Cu isotopes in bivalves to infer Cu bioavailability changes related to anthropogenic inputs of this metal into the marine environment.

Assessment of the metal contamination evolution in the Loire estuary using Cu and Zn stable isotopes and geochemical data in sediments.

In this work, a multi-elemental approach combining Cu and Zn stable isotopes is used to assess the metal contamination evolution in the Loire estuary bulk sediments. Elemental geochemical data indicate an increase of metal concentrations from the beginning of the industrial period peaking in the 1990s, followed by an attenuation of metal contamination inputs to the estuary. Zinc isotope compositions suggest a binary mixing process between Zn derived from terrigenous material and multi-urban anthropogenic sources. Copper isotope systematics indicate a single natural dominant source represented by weathered silicate particles from soils and rocks. This work demonstrates the applicability of Zn isotopes to identify anthropogenic Zn sources in coastal systems, even under a low to moderate degree of contamination. Further studies are required to constrain Cu sources and to elucidate possible effects of grain-size and mineralogy in the Cu isotope composition of sediment in the Loire estuary.

Modified 3D-printed device for mercury determination in waters.

3D printing technology is increasingly used in flow analysis, to develop low cost and tailor-made devices. The possibility of grafting specific molecules onto 3D printed parts offers new perspectives for the development of flow systems. In this study, a MPFS system including a dicarboxylate 1,5-diphenyl-3-thiocarbazone grafted 3D-printed device has been developed for mercury determination. For this purpose, the surface of 3D-printed cuboids was first modified with amine functional groups and then grafted with dicarboxylate 1,5-diphenyl-3-thiocarbazone. This new grafted device resulted in selective mercury preconcentration with extraction and elution yields higher than 90% even at high sampling flow rates. The detection can then be carried out in two ways: a direct detection of mercury extracted onto 3D-printed grafted cuboids by atomic absorption spectrophotometry after amalgam on gold or a detection of mercury in solution after elution with l-cysteine by spectrophotometry or cold vapour atomic absorption spectrometry.

Patterns of trace metal bioaccumulation and trophic transfer in a phytoplankton-zooplankton-small pelagic fish marine food web.

Trace metal contamination in the European sardine and anchovy food web was investigated in the Gulf of Lions, NW Mediterranean Sea, including seawater and size fractions of plankton. The results highlighted: i) higher and more variable concentrations in the smaller plankton size classes for all metals except cadmium; ii) higher concentrations in anchovy versus sardine for all elements except lead; iii) different patterns of metal bioaccumulation through the food web: cobalt, nickel, copper, silver, lead and zinc displayed continuously decreasing concentrations (with the exception of increased zinc in fish only), while mercury concentrations dropped considerably in larger plankton size classes and rose significantly in fish. Lastly, cadmium concentrations were found to be highest in intermediate plankton size classes, with very low levels in fish. The need to efficiently characterize the biological composition of plankton in order to fully identify its role in the mobilization and transfer of metals was highlighted.

3D-printed lab-on-valve for fluorescent determination of cadmium and lead in water.

In recent years, the development of 3D printing in flow analysis has allowed the creation of new systems with various applications. Up to now, 3D printing was mainly used for the manufacture of small units such as flow detection cells, preconcentration units or mixing systems. In the present study, a new 3D printed lab-on-valve system was developed to selectively quantify lead and cadmium in water. Different technologies were compared for lab-on-valve 3D printing. Printed test units have shown that stereolithography or digital light processing are satisfactory techniques for creating complex lab-on-valve units. The lab-on-valve system was composed of two columns, eight peripheral ports and a central port, and a coil integrating baffles to increase mixing possibilities. A selective extraction of lead was first carried out by TrisKem Pb™ Resin column. Then, cadmium not retained on the first column was extracted on a second column of Amberlite® IR 120 resin. In a following step, lead and cadmium were eluted with ammonium oxalate and potassium iodide, respectively. Finally, the two metals were sequentially detected by the same Rhod-5N™ fluorescent reagent. This 3D printed lab-on-valve flow system allowed us to quantify lead and cadmium with a linear response from 0.2 to 15 µg L-1 and detection limits of 0.17 and 0.20 µg L-1 for lead and cadmium, respectively, which seems adapted for natural water analysis.

Carbon and nitrogen elemental and isotopic ratios of filter-feeding bivalves along the French coasts: An assessment of specific, geographic, seasonal and multi-decadal variations.

Primary consumers play a key role in coastal ecosystems by transferring organic matter from primary producers to predators. Among them, suspension-feeders, like bivalve molluscs are widely used in trophic web studies. The main goal of this study was to investigate variations of C and N elemental and isotopic ratios in common bivalves (M. edulis, M. galloprovincialis, and C. gigas) at large spatial (i.e. among three coastal regions) and different temporal (i.e. from seasonal to multi-decadal) scales in France, in order to identify potential general or specific patterns and speculate on their drivers. The observed spatial variability was related to the trophic status of the coastal regions (oligotrophic Mediterranean Sea versus meso- to eutrophic English Channel and Atlantic ocean), but not to ecosystem typology (estuaries, versus lagoons versus bays versus littoral systems). Furthermore, it highlighted local specificities in terms of the origin of the POM assimilated by bivalves (e.g., mainly continental POM vs. marine phytoplankton vs. microphytobenthic algae). Likewise, seasonal variability was related both to the reproduction cycle for C/N ratios of Mytilus spp. and to changes in trophic resources for δ13C of species located close to river mouth. Multi-decadal evolution exhibited shifts and trends for part of the 30-year series with decreases in δ13C and δ15N. Specifically, shifts appeared in the early 2000's, likely linking bivalve isotopic ratios to a cascade of processes affected by local drivers.

Oligotrophy as a major driver of mercury bioaccumulation in medium-to high-trophic level consumers: A marine ecosystem-comparative study.

Mercury (Hg) is a global contaminant of environmental concern. Numerous factors influencing its bioaccumulation in marine organisms have already been described at both individual and species levels (e.g., size or age, habitat, trophic level). However, few studies have compared the trophic characteristics of ecosystems to explain underlying mechanisms of differences in Hg bioaccumulation and biomagnification among food webs and systems. The present study aimed at investigating the potential primary role of the trophic status of systems on Hg bioaccumulation and biomagnification in temperate marine food webs, as shown by their medium-to high-trophic level consumers. It used data from samples collected at the shelf-edge (i.e. offshore organisms) in two contrasted ecosystems: the Bay of Biscay in the North-East Atlantic Ocean and the Gulf of Lion in the North-West Mediterranean Sea. Seven species including crustaceans, sharks and teleost fish, previously analysed for their total mercury (T-Hg) concentrations and their stable carbon and nitrogen isotope compositions, were considered for a meta-analysis. In addition, methylated mercury forms (or methyl-mercury, Me-Hg) were analysed. Mediterranean organisms presented systematically lower sizes than Atlantic ones, and lower δ13C and δ15N values, the latter values especially highlighting the more oligotrophic character of Mediterranean waters. Mediterranean individuals also showed significantly higher T-Hg and Me-Hg concentrations. Conversely, Me-Hg/T-Hg ratios were higher than 85% for all species, and quite similar between systems. Finally, the biomagnification power of Hg was different between systems when considering T-Hg, but not when considering Me-Hg, and was not different between the Hg forms within a given system. Overall, the different parameters showed the crucial role of the low primary productivity and its effects rippling through the compared ecosystems in the higher Hg bioaccumulation seen in organisms from oligotrophic Mediterranean waters.

Chemical contaminants (trace metals, persistent organic pollutants) in albacore tuna from western Indian and south-eastern Atlantic Oceans: Trophic influence and potential as tracers of populations.

Albacore tuna (Thunnus alalunga) is a highly commercial fish species harvested in the world's Oceans. Identifying the potential links between populations is one of the key tools that can improve the current management across fisheries areas. In addition to characterising populations' contamination state, chemical compounds can help refine foraging areas, individual flows and populations' structure, especially when combined with other intrinsic biogeochemical (trophic) markers such as carbon and nitrogen stable isotopes. This study investigated the bioaccumulation of seven selected trace metals - chromium, nickel, copper (Cu), zinc (Zn), cadmium (Cd), mercury (Hg) and lead - in the muscle of 443 albacore tunas, collected over two seasons and/or years in the western Indian Ocean (WIO: Reunion Island and Seychelles) and in the south-eastern Atlantic Ocean (SEAO: South Africa). The main factor that explained metal concentration variability was the geographic origin of fish, rather than the size and the sex of individuals, or the season/year of sampling. The elements Cu, Zn, Cd and Hg indicated a segregation of the geographic groups most clearly. For similar sized-individuals, tunas from SEAO had significantly higher concentrations in Cu, Zn and Cd, but lower Hg concentrations than those from WIO. Information inferred from the analysis of trophic markers (δ13C, δ15N) and selected persistent organic pollutants, as well as information on stomach contents, corroborated the geographical differences obtained by trace metals. It also highlighted the influence of trophic ecology on metal bioaccumulation. Finally, this study evidenced the potential of metals and chemical contaminants in general as tracers, by segregating groups of individuals using different food webs or habitats, to better understand spatial connectivity at the population scale. Limited flows of individuals between the SEAO and the WIO are suggested. Albacore as predatory fish also provided some information on environmental and food web chemical contamination in the different study areas.

3D-printed flow system for determination of lead in natural waters.

The development of 3D printing in recent years opens up a vast array of possibilities in the field of flow analysis. In the present study, a new 3D-printed flow system has been developed for the selective spectrophotometric determination of lead in natural waters. This system was composed of three 3D-printed units (sample treatment, mixing coil and detection) that might have been assembled without any tubing to form a complete flow system. Lead was determined in a two-step procedure. A preconcentration of lead was first carried out on TrisKem Pb Resin located in a 3D-printed column reservoir closed by a tapped screw. This resin showed a high extraction selectivity for lead over many tested potential interfering metals. In a second step, lead was eluted by ammonium oxalate in presence of 4-(2-pyridylazo)-resorcinol (PAR), and spectrophotometrically detected at 520nm. The optimized flow system has exhibited a linear response from 3 to 120µgL-1. Detection limit, coefficient of variation and sampling rate were evaluated at 2.7µgL-1, 5.4% (n=6) and 4 sampleh-1, respectively. This flow system stands out by its fully 3D design, portability and simplicity for low cost analysis of lead in natural waters.

Atmospheric mercury concentrations observed at ground-based monitoring sites globally distributed in the framework of the GMOS network.

Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010-2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in this paper include a clear gradient of Hg concentrations between the Northern and Southern hemispheres, confirming that the gradient observed is mostly driven by local and regional sources, which can be anthropogenic, natural or a combination of both.

Effects of short-term environmental disturbances on living benthic foraminifera during the Pacific oyster summer mortality in the Marennes-Oléron Bay (France).

Sediment cores were collected from April to August 2004 on tidal mudflats of the macrotidal Marennes-Oléron Bay (SW France), famous for the cultivation of Pacific oysters (Crassostrea gigas). The response of living (stained) benthic foraminifera to short-term biogeochemical disturbances in the sediment and overlying water, which may be involved in oyster summer mortality, was monitored. Short-term hypoxia occurred in early June, in conjunction with a sudden rise in temperature. In mid-June, the ammonia content of sediment porewater increased, leading to potentially maximal flux towards overlying waters. Foraminiferal assemblages, particularly in the topmost layer, were altered. Ammonia tepida was the most tolerant to temperature increase and hypoxic conditions whereas Brizalina variabilis and Haynesina germanica were sensitive to organic degradation and hypoxia. Cribroelphidium gunteri was the most opportunistic during recolonisation. Benthic foraminifera showed that short-term biochemical changes in the sediment are toxic and may be involved in the summer mortality of Pacific oysters.