The importance of dissolved organic compounds in the accumulation of copper by the american oyster,crassostrea virginica

The influence of various dissolved organic compounds upon copper accumulation by the American oyster, Crassostrea virginica was examined. Oysters were exposed to a range of copper concentrations (^64Cu) in the presence of filtered estuarine water (FEW), UV-photooxidized FEW and FEW amended with the additions of natural dissolved organic compounds—chitin and cellular orgaanic compounds (derived from the diatom, Thalassiosira pseudonana). Copper accumulation rates were significantly greater in the UV-treated medium and decreased with the addition of dissolved organics. When normalized on a per weight DOC basis, the reductions in copper accumulation rates were greater in the presence of chitin than cellular organic compounds. The results suggest that natural dissolved organics differ markedly with respect to their influence upon copper bioavailability.     

Scales of recruitment variability in warming waters: Comparing native and introduced oysters in Hood Canal,Washington, USA

The effect of climate change on natural oyster recruitment has the potential to disrupt many of the ecosystem services oysters provide. Due to the temperature‐sensitivity of reproduction, oyster recruitment may shift as water temperatures rise. A biological imprint of climate change was revealed in a multi‐decadal time series of recruitment of non‐native Pacific oysters (Crassostrea gigas) in the main stem of Hood Canal, Washington, USA, extracted from historic fishery documents. Water in July and August warmed significantly from 1945 to 1995 (0.028 ± 0.004°C per year [±SE]) and accounted for an increase in Pacific oyster recruitment (7% per year, 0.028 ± 0.006 spat per year on log scale [±SE]); recruitment also strongly tracked inter‐annual variability in summer water temperature. Methods used to collect historical data were repeated in 2013–2015 when recruitment of both Pacific oysters and native Olympia oysters (Ostrea lurida) were recorded in main stem and lower Hood Canal. Both historic and modern data show large variation within and between years for temperature as well as recruitment. The modern data add information regarding spatial variation, in that recruitment patterns in the two regions of Hood Canal were decoupled. As temperatures continue to increase, non‐native Pacific oysters are likely to be favored over Olympia oysters, which recruit earlier at lower temperatures and presently contribute less than half of total oyster recruits. Future recruitment, however, may be limited by environmental factors other than temperature, a point indicated particularly in Hood Canal where many subtidal species already respond strongly to gradients in dissolved oxygen.     

Reductions in TBT concentrations in UK estuaries following legislation in 1986 and 1987

In 1986 the Government of the United Kingdom (UK) introduced legislation to control the sale of tribytltin (TBT)-based paints. From 1986 to 1989 monitoring was undertaken, whereby samples of water, sediment, oysters (Crassostrea gigas) and mussels (Mytilus edulis) were collected from six estuaries and water samples from five marinas/harbours, and analysed for TBT. In 1989 the concentrations of TBT in water, oysters and mussels were generally only one-third to one-quarter of those observed in 1986. The most marked decrease in concentrations of TBT in oysters and mussels occurred in 1987–1988, following the 1987 ban on the use of TBT-based paints on small boats and mariculture equipment. As the concentrations of TBT in oyster tissues had decreased there has been improvement in oyster growth in terms of both meat production and growth of thin (i.e. normally shaped) shells. Oysters with a normal shell shape can now be grown in five of the six estuaries which were monitored. In contrast to the reduction in concentrations of TBT noted in water and bivalves, changes in concentrations of TBT in sediments showed no clear trend from 1986 to 1989.     

The relationship between the copper complexing capacity of sea water and copper toxicity in shrimp zoeae

Mortality of larval coon-stripe shrimp, Pandalus danae, was related to labile copper and the copper complexing capacity of sea water, as measured by differential pulse Anodic Stripping Voltammetry (ASV). In nominal treatments of control, 5 and 10μg/litre Cu which contained less than 1·0μg/litre ASV labile Cu, zoeal development was usually complete. In treatments of 20 and 50μg/litre Cu which contained more than 7·0μg/litre ASV labile Cu, most larvae died while in the first zoeal stage. ASV labile Cu was related to the copper complexing capacity of sea water. Copper toxicity at less than 1·0 μg/litre ASV labile Cu is indicated by moulting delay and apparent Cu accumulation in zoea of the 5 and 10μg/litre Cu nominal treatments.     

Trends of trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) distributions at the oxic-anoxic interface and in sulfidic water of the Drammensfjord

Anoxic sulfidic waters provide important media for studying the effect of reducing conditions on the cycling of trace metals. In 1987–1988, dissolved and particulate trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) concentrations were determined in the water column of the anoxic Drammensfjord basins, southeastern Norway. The iminodiacetic acid type chelating resin (Chelex 100) was used for the preconcentration of trace metals. The trace metal concentrations were determined using atomic absorption spectrophotometry (AAS), differential pulse polarography (DPP), and differential pulse-anodic stripping voltammetry (DP-ASV).It was observed that the trace metals Mn and Fe were actively involved in the processes of redox cycling (oxidationreduction and precipitation-dissolution) at the O₂/H₂S interface. The dissolved concentrations of Mn, Fe and Co showed maxima just below the O₂/H₂S interface. The seasonal enhancement in the maxima of both dissolved and particulate Mn and Fe at the redox cline is mainly governed by the downward movement of water which carries oxygen. An association of Co with the Mn cycle was observed, while the total dissolved Ni was decreased by only 10–35% in the anoxic waters. The dissolved concentrations of Cu, Zn, Pb and, to a lesser extent, Cd decreased in the anoxic zone.     

Copper in the resurrection fjord, Alaska

Copper concentrations have been measured in more than 200 samples collected from an Alaskan fjord and continental shelf and slope regions in the northwestern Gulf of Alaska. Concentrations were lowest (2·1 nmol kg⁻¹) at depths of 400–1000 m in the continental slope waters of the Gulf of Alaska. Copper increased systematically with decreasing salinities shoreward to concentrations >30 nmol kg⁻¹ in fjord surface waters during summer months of high freshwater runoff. Copper concentrations increased with depth at an inner fjord station where deep basin waters have restricted circulation, and these data together with surface (<5 cm) pore water copper concentrations (mean=122 nmol kg⁻¹) about an order of magnitude higher than bottom water copper concentrations are indicative of a flux of copper across the sediment-seawater interface. This latter was estimated at 32±12 nmol cm⁻² annually, and represented less than 20% of the annual input to fjord surface water (228–411 nmol cm⁻²) added during summer months. Mass balances in bottom waters indicate a vigorous recycling of copper with a residence time estimated at 21±11 days. Most copper that is remobilized in surface sediments is returned to bottom waters and little (3%) is removed by subsequent diagenetic reaction in the buried sediments. However, an estimate of copper accumulating in anoxic fjord sediments was comparable with copper added to fjord surface waters suggesting that input-removal reactions rather than internal cycling controls copper geochemistry in this estuary.     

The Role of Suspended Oyster Culture on Nitrogen Cycle in Hiroshima Bay

The predominance of bivalves affects the cycle of materials in the coastal ecosystem. In the present study, the role of suspended oyster culture on the nitrogen cycle was demonstrated for the northern Hiroshima Bay. The nitrogen cycle was considered as two systems, (1) the primary production (PP) system and (2) the oyster culture (OC) system. The results show that about 26% of N productivity was supplied to process by cultured oysters in the OC system. This process varies seasonally due to the seasonal variations of PON, physiological activities and biomass of oysters. The N processing rates were found to be high in summer and low in winter. The biodeposition and excretion of N in the OC system are 3.0 and 2.1 ton N d^–1, while the natural sedimentation rate and N regeneration in the PP system are 8.3 and 18.0 ton N d^–1, which indicates that the PP system is a major system regenerating N in the water column. The release of total dissolved N from the bottom to the water column is about 8.3 ton N d^–1. The amount of N harvested as oyster product was about 1.3 ton N d^–1, which is about 10% of daily N loading in north Hiroshima Bay. According to the N cycle developed in the present study, the results suggest the significant role of suspended oyster culture on the nitrogen cycle in Hiroshima Bay. In addition, our results indicate that oyster production was efficiently harvested, suggesting that oyster culture could probably be used as a tool to remove N from Hiroshima Bay.     

Land inputs,behaviour and contamination levels of copper in a ria estuary (NW Spain)

Copper concentrations were measured in the sediments and dissolved phase of the water column in the Lérez Estuary (Pontevedra Ria, Galicia), NW Spain, and in the freshwater-sewage inputs to the estuary. Dissolved copper fluxes in the estuary were quantified. Results show that the freshwater end-member in the Lérez Estuary has minimal copper contamination ([Cu](Dissolved)=7+/-4 nM, Sediment Enrichment Factor=1) and the source of dissolved copper inputs is localized in the saline end-member ([Cu](Dissolved)=20-55 nM, Sediment Enrichment Factor=6-7). A non-conservative behaviour of dissolved copper showing a net addition during estuarine mixing was observed. The budgetary calculations and the copper sediment distribution suggest that the major copper input to the estuary-ria system is located at the Marín-Placeres transect, playing an important role in the net addition of copper within the estuarine mixing. The importance of upwelling in the renewal of the Galician coastal waters and dilution of continental inputs is discussed.     

Spring–summer cycling of DOC, DON and inorganic N in a highly seasonal system encompassing the Northeast Water Polynya, 1993

Dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and inorganic nutrient concentrations were determined in samples from an area encompassing the Northeast Water Polynya from June to August 1993. In June, still ice-covered polynya area surface waters (PySW) had significantly higher (p<0.05) DOC concentrations (110 μM, n=68) than surface water outside the polynya area (96 μM, n=6). Melting ice and ice algae are suggested as DOC sources. DOC concentrations found in this study are consistent with other studies showing higher DOC concentrations in the Arctic than in other ocean areas. As the productive season progressed, DOC concentrations in Polynya surface water (PySW) decreased (p<0.05) from 110 to 105 μM, while DON concentrations increased (p<0.05) from 5.6 to 6.1 μM, causing a significant decrease (p<0.05) in the C : N ratios of DOM from spring (C : N ratio 20) to summer (C : N ratio 17). We found a significant (p<0.05) decrease in the DOM C : N ratio in all water masses within the polynya area as the productive season progressed. DON was the largest fraction of total dissolved nitrogen (TDN) in PySW and surface waters outside the polynya area. TDN was calculated as the sum of DON, nitrate, nitrite and ammonium concentrations. DON increased (p<0.05) from 62% to 73% of TDN in PySW from spring to summer, a result of increasing DON concentrations and decreasing inorganic nitrogen concentrations over the productive season. The seasonal accumulation of DON and the corresponding decrease in nitrate concentrations in waters with primary production indicate that it is important to take the DON pool into account when estimating export production from nitrate concentration decreases in surface waters. PySW TDN concentrations decreased (p<0.05) from 9.1 (n=61) to 8.6 μM (n=60) from spring (May 25 through June 19) to summer (July 1 through July 27). The seasonal decrease in surface water TDN concentrations corresponded to increases in TDN concentrations in deeper water masses within the Polynya. Most of the TDN increase in deep water was in the form of DON. A possible explanation is that PON was dissolved (partially remineralized) in the water column at mid depths, causing increases in the DON concentration. Transfer of N from PySW (with a short residence time in the polynya area) to Polynya Intermediate Water and deep waters of the Norske and Westwind Trough with multi-year residence times keeps N from leaving the polynya area. In spring, nutrients from degradation of OM in PyIW could support primary production. The role of PyIW as an OM trap could be important in supporting primary production in the polynya area.     

Linkages between cellular biomarker responses and reproductive success in oysters – Crassostrea virginica

The purpose of these studies was to evaluate if there were relationships between lysosomal destabilization or glutathione concentrations and gamete viability of oysters, Crassostrea virginica. Oysters were collected from field sites during the peak spawning period (May–June) during 2001 and 2002. Lysosomal destabilization rates and glutathione concentrations of hepatopancreas tissues (e.g. digestive gland) were determined. Eggs and sperm from the same adults were also used to conduct embryo development assays with reference seawater collected from a clean site, site water, and also a range of Cd concentrations (the Cd exposures were used to determine if there were differences in susceptibility to pollutants). Baseline embryo development success (e.g. percent normal development when the assays were conducted with reference seawater or site water) was related to lysosomal destabilization, but not glutathione status. However, the susceptibility of embryos to metal toxicity was related to glutathione status, i.e., sensitivity to Cd exposures increased with decreasing glutathione levels. These studies support the hypotheses that there are linkages between embryo development success and susceptibility to pollutant stress and cellular biomarker responses. These kinds of effects on reproductive success could lead to subtle but significant long-term effects on recruitment and viability of oyster populations.     

Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary

Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 10² for zinc and 6 × 10⁶ for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.     

天津新港褶牡蛎体内Hg和As含量的季节变化

本文研究了1983年5月—1984年2月天津新港褶牡蛎(Ostrea plicatula)体内Hg和As含量的季节变化。结果表明:牡蛎体内的Hg含量在秋季与冬季略高,夏季偏低;而As含量以春末和夏季较高,冬季最低。在牡蛎体内Hg的含量范围为0.118—0.235mg╱kg(干重),年平均值为O.183mg╱kg。As的含量范围为1.20—25.98mg/kg(干重),年平均值为19.46mg╱kg。     

Seasonal survey of copper-complexing ligands and thiol compounds in a heavily utilized, urban estuary: Elizabeth River, Virginia

Concentrations of thiol compounds, copper-complexing ligands, and total dissolved copper were followed over the course of 1 year (October 2002 until September 2003) in the Elizabeth River, Virginia to evaluate seasonality. Copper-complexing ligand concentrations were determined by competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE/ACSV). Thiol detection was carried out by high performance liquid chromatography (HPLC) and calibration using a suite of nine thiol compounds (cysteine, glutathione, mercaptoacetic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, and monothioglycerol). Total dissolved copper concentrations reached a January low of 13.1 nM to a June high of 24.7 nM and were found to vary seasonally with higher concentrations occurring from June to September. With a low of 26 nM during April to a high of 56 nM in October, copper-complexing ligand (average log K′_CuL of 12.0 ± 0.2) concentrations displayed a similar seasonal pattern to that of total dissolved copper. Free cupric ion concentrations remained below 1.5 pM for a majority of the year except during March, April, and December when values reached pM levels greater than 1.5. Six of the nine thiol compounds surveyed were detected in the Elizabeth River samples and ranged in concentration from below detectable concentrations (< 5 nM) to individual highs ranging from 25.3 to168.5 nM. The thiol compound concentrations displayed a clear seasonality fluctuating at below detection limits during November to February then increasing with increasing surface water temperatures from March to July. CLE/ACSV was used to assess whether or not the suite of thiol compounds detected by HPLC could contribute to the copper-complexing ligand pool. Conditional stability constants for each one of six thiol standards (average log K′_CuL  12.1 ± 0.5) were found to be statistically equivalent to the naturally occurring copper-complexing ligands (average log K′_CuL  12.0 ± 0.2). This suggests that these thiol compounds could act as copper-complexing ligands in natural samples and could contribute to the copper-complexing ligand pool detected by CLE/ACSV. This study involving seasonality of copper-complexing ligands and thiols in an industrialized, urban estuary underscored several points that have to be substantiated in future research efforts including copper-complexing ligands sources and the role that thiol compounds as well as other unidentified organic compounds play in the copper-complexing ligand pool.     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS

In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g⁻¹), Cu (1330 μg g⁻¹) and Cd (12 μg g⁻¹) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (K_d) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.     

Modelling the influence of environmental factors on the physiological status of the Pacific oyster Crassostrea gigas in an estuarine embayment; The Baie des Veys (France)

It is well known that temporal changes in bivalve body mass are strongly correlated with temporal variations in water temperature and food supply. In order to study the influence of the year-to-year variability of environmental factors on oyster growth, we coupled a biogeochemical sub-model, which simulates trophic resources of oysters (i.e. phytoplankton biomass via chlorophyll a), and an ecophysiological sub-model, which simulates growth and reproduction (i.e. gametogenesis and spawning), using mechanistic bases. The biogeochemical sub-model successfully simulated phytoplankton dynamics using river nutrient inputs and meteorological factors as forcing functions. Adequate simulation of oyster growth dynamics requires a relevant food quantifier compatible with outputs of the biogeochemical sub-model (i.e. chlorophyll a concentration). We decided to use the phytoplankton carbon concentration as quantifier for food, as it is a better estimator of the energy really available to oysters. The transformation of chlorophyll a concentration into carbon concentration using a variable chlorophyll a to carbon ratio enabled us to improve the simulation of oyster growth especially during the starvation period (i.e. autumn and winter). Once validated, the coupled model was a suitable tool to study the influence of the year-to-year variability of phytoplankton dynamics and water temperature on the gonado-somatic growth of the Pacific oyster. Four years with highly contrasted meteorological conditions (river inputs, water temperature and light) 2000, 2001, 2002 and 2003, were simulated. The years were split into two groups, wet years (2000 and 2001) and dry years (2002 and 2003). Significant variability of the response of oysters to environmental conditions was highlighted between the four scenarios. In the wet years, an increase in loadings of river nutrients and suspended particulate matter led to a shift in the initiation and the magnitude of the phytoplanktonic spring bloom, and consequently to a shift in oyster growth patterns. In contrast, in the dry years, an increase in water temperature—especially during summer—resulted in early spawning. Thus, the gonado-somatic growth pattern of oysters was shown to be sensitive to variations in river loadings and water temperature. In this context, the physiological status of oysters is discussed using a relevant indicator of energy needs.     

Copper, lead and cadmium in coastal waters of the western North Sea

Cadmium, lead and copper have been determined in both dissolved and particulate phases for 130 surface-water samples from the coastal zone of Scotland and England in the western North Sea. The concentrations reported are, in general, lower than those published previously for the same area.The distribution of total metal concentration between the dissolved and particulate phases varies for the three elements. The lead distribution is dominated by its associations with particulate material while cadmium shows the reverse behaviour, existing almost totally in the dissolved phase. Copper is intermediate in behaviour, with the dissolved phase generally being dominant.An inverse relationship between salinity and dissolved copper concentration suggests a freshwater origin for this element. It is suggested that sedimentary and/or anthropogenic sources affect dissolved copper concentrations in coastal waters. The dissolved lead distribution reveals plumes of contaminated coastal water. The lead distribution is, however, dominated by associations with particulate material and sediments which produce a sharp concentration gradient close to the coast. The Humber estuary is identified as a significant source of cadmium to the North Sea.     

Effects of long-term exposure to silver or copper on growth, bioaccumulation and histopathology in the blue mussel Mytilus edulis

The purpose of this study was to determine the long-term accumulation of either silver or copper from low concentrations in seawater by blue mussels, Mytilus edulis. Mussels raised from eggs in the laboratory to the age of 2·5 months (approximately 4·5 mm in length) were continuously exposed to 0, 1, 5 and 10μg/liter of either silver (nitrate) or copper (chloride) and sampled at 12, 18 and 21 months for growth studies, measurements of metal accumulation and histopathological examination.Whole-body soft tissues were analyzed for the presence of both silver and copper, as background levels of copper in the incoming seawater averaged 2–4 μg/liter. Mussels exposed to silver had accumulated significant amounts of silver only at the highest test concentration (10 μg/liter Ag) after 12 months, but at 18 and 21 months significant levels were accumulated at all three test concentrations. Mussels exposed to copper accumulated significant amounts of copper at 5 and 10 μg/liter Cu after all three sampling periods, but not at 1μg/liter. Silver-exposed animals also accumulated significantly greater amounts of copper than control animals.In a comparative study, field-collected juvenile mussels (approximately 16·1 mm in shell length) and adult mussels (approximately 53·4 mm in shell length) were exposed for 12 months to 0, 5, 25 and 50 μg/liter silver only and subsequently sampled for metal-accumulation analyses and growth measurements. Juvenile mussels accumulated significant amounts of silver at all test concentrations, with the exception of mussels exposed to 5 μg/liter Ag for 6 months. Copper accumulation in the silver-exposed juveniles was significant only at 50 μg/liter Ag after 6 months, but at all test concentrations after 12 months. Adult mussels exposed to silver accumulated significant levels of both silver and copper, but at somewhat lower levels than juveniles.In the growth study, silver had no effect on laboratory reared mussels at the highest concentration of 10 μg/liter tested, whereas copper at 10 μg/liter did appear to affect growth as early as 4 months after the start of experimental exposure. Field-collected juvenile mussels did show inhibition in growth after 6 months' exposure to 25 and 50 μg/liter Ag, with some growth occurring after 12 months. Adults also showed inhibition in growth after 6 months but not at 12 months.Histopathological examination of mussels exposed to either 5 or 10 μg/liter of copper for 18 months showed changes in the digestive diverticula, gastrointestinal tract, reproductive tract and muscle tissues. These changes were more noticeable in mussels exposed to 5 μg/liter Cu than in those exposed to 10 μg/liter. Mussels exposed to silver for 21 months showed yellowish to black particulate deposition in the basement membrane and connective tissue of the various organs and tissues. Silver deposition increased with increasing test concentration.     

Molecular masses and chromophoric properties of dissolved organic ligands for copper(II) in oceanic water

The distribution of molecular masses of organic ligands for copper(II) in oceanic water was investigated. The bulk dissolved organic matter (DOM) was fractionated by ultrafiltration and organic ligands were extracted from the resultant fractions by using immobilized metal ion affinity chromatography (IMAC). Contributions of total organic ligands were 2.0–4.4% of the bulk DOM in surface waters, as determined by the UV absorbance. In the distribution of molecular masses of organic ligands, relative contribution of the fraction with low molecular masses (<1000 Da) was dominant (49–62%), while 26–33% of the total organic ligands was in the 1000–10,000 Da fraction, leaving 10–19% in the >10,000 Da fraction. The distribution of molecular masses of organic ligands shifted to higher molecular masses, as compared with that of the bulk DOM. The fluorescence intensities of organic ligands were shown to be associated with carboxyl contents, based on peak excitation/emission wavelengths and the pH-dependence of fluorescence. Two ligand classes with different conditional stability constants (log K_CuL′≈7 and 9) were determined from fluorescence quenching of ligand fractions during copper(II) titration. Organic ligands in low molecular mass fractions were relatively weak and strong ligands occurred in higher molecular mass fractions. It is suggested that the weaker ligand sites would consist of two or more carboxyl groups (log K_HL′=4), whereas carboxyl groups (log =2), which are protonated at lower pH, and primary amine may additionally contribute to the formation of more stable copper(II) complexes of the stronger ligand.     

Distribution and Seasonal Variability of Organic Matter in a Small Eutrophicated Salt Lake

Distribution and seasonal variability of dissolved organic carbon (DOC) and surface active substances (SAS) were studied along the depth profile (15 m) in a small eutrophicated and periodically anoxic sea lake (Rogoznica Lake, Eastern Adriatic coast) in 1996 and 1997. The range of DOC concentrations was characteristic for productive coastal marine ecosystems (60% of samples in the range of 1–2 mg l⁻¹and 40% between 2 and 3 mg l⁻¹). Distribution of SAS concentrations was uniform and shifted toward higher concentrations in comparison to other coastal areas in the Adriatic Sea. Eutrophication in the lake is generated by nutrient recycling under anaerobic conditions. Systematically higher concentrations of chlorophyll a, DOC and SAS were determined at the chemocline in the bottom layer (10–12 m) than in the upper water layer (0·5–2 m). Seasonal variability of organic matter was discussed regarding distributions of microphytoplankton (cells >20 μm) and photosynthetic pigments as well as oxygen and salinity changes along the depth profile. The dissolved oxygen saturation reaching up to 300% in the water layer between 8 m and 10 m depths in May and June 1996, was correlated with enhanced concentrations of phytoplankton biomass (reflected as chl a and b, fucoxanthin, peridinin, zeaxanthin) and increased concentrations of DOC and SAS.