Copper complexation by fulvic acid affects copper toxicity to the larvae of the polychaete Hydroides elegans

Copper toxicity is influenced by a variety of environmental factors including dissolved organic matter (DOM). We examined the complexation of copper by fulvic acid (FA), one of the major components of DOM, by measuring the decline in labile copper by anodic stripping voltammetrically (ASV). The data were described using a one-site ligand binding model, with a ligand concentration of 0.19micromol site mg(-1) C, and a logK' of 6.2. The model was used to predict labile copper concentration in a bioassay designed to quantify the extent to which Cu-FA complexation affected copper toxicity to the larvae of marine polychaete Hydroides elegans. The toxicity data, when expressed as labile copper concentration causing abnormal development, were independent of FA concentration and could be modeled as a logistic function, with a 48-h EC(50) of 58.9microgl(-1). However, when the data were expressed as a function of total copper concentration, the toxicity was dependent on FA concentration, with a 48-h EC(50) ranging from 55.6microgl(-1) in the no-FA control to 137.4microgl(-1) in the 20mgl(-1) FA treatment. Thus, FA was protective against copper toxicity to the larvae, and such an effect was caused by the reduction in labile copper due to Cu-FA complexation. Our results demonstrate the potential of ASV as a useful tool for predicting metal toxicity to the larvae in coastal environment where DOM plays an important role in complexing metal ions.     

Consumption of bacteria by larvae of a deep-sea polychaete

We investigated whether trochophore larvae of the polychaete Hesiocaeca methanicola, which lives on exposed ice‐like methane hydrates between 500 and 600 m, could consume near‐bottom picoplankton. In laboratory trials larvae significantly reduced the growth rates of all types of picoplankton, including heterotrophic bacteria, Prochlorococcus sp., Synechococcus‐type cyanobacteria and phototrophic eucaryotes <3 μm. Our findings suggest that these types of plankton may be important food sources for deep‐sea planktotrophic larvae.     

Adaptation of the polychaete Neanthes Arenaceodentata to copper

Neanthes arenaceodentata were exposed to 292, 146, 92 and 56 μg litre⁻¹ Cu (measured) and control seawater after a 27-day pre-exposure to a sublethal concentration of Cu (10, 16 and 28 μg litre⁻¹ and control) to determine if the worms increased their tolerance to Cu after the pre-treatment. The worms pre-exposed to 28 μg litre⁻¹ Cu were significantly more resistant to Cu toxicity than control and 10 and 16 μg litre⁻¹ Cu pre-exposed worms. For example, the time to 50 % mortality at 92 μg litre⁻¹ Cu was 18 and 11 days for worms pre-exposed to 28 μg litre⁻¹ Cu and control conditions, respectively. The net rate of Cu uptake during the toxicity test was lower for worms pre-exposed to 28 μg litre⁻¹ Cu than for the control and 10 and 16 μg litre⁻¹ Cu pre-exposed worms. For example, the net rate of Cu uptake at 292 μg litre⁻¹ Cu by worms pre-exposed to 28 μg litre⁻¹ Cu and control conditions was 42 and 102 μg g⁻¹ day ⁻¹, respectively.     

Egg masses and larvae of the polychaete Nereis falcaria (note)

Larvae from polychaete egg masses obtained from the south Wellington coast were reared to identifiable juvenile worms and were found to be Nereis falcaria (Willey, 1905). Egg masses and larvae closely correspond to those previously recorded by Kirk (1907) from an unknown polychaete.     

Copper complexation capacity in surface waters of the Venice Lagoon

Total copper (Cu(T)), copper ion activity (pCu) and the copper complexation capacity (CuCC) were determined in samples of seawater collected in July 2003 from the Venice Lagoon. Cu(T) and CuCC showed considerable spatial variability: Cu(T) ranged from 1.8 to 70.0nM, whereas the CuCC varied from 195 to 573nM. pCu values varied from 11.6 to 12.6 and are consistent with those previously reported in estuarine and coastal areas (10.9-14.1). The range of Cu(T) values compares well with those reported in the past in the lagoon and in the adjacent Adriatic Sea. The highest concentrations of Cu(T) were found in samples collected near the industrial area of Porto Marghera, whereas the lowest were measured near the Chioggia and Malamocco inlets, where an intense tidally-driven renewal of seawater takes place. Although CuCC showed a high degree of spatial variability, the values recorded in the Venice Lagoon are comparable to those reported in other estuarine systems. In addition, CuCC was positively correlated with dissolved organic carbon (DOC), suggesting that organic ligands responsible for Cu complexation are part of the bulk organic matter pool in the lagoon. The CuCC:Cu(T) molar ratio was, on average 55:1, indicating that a large excess of complexation capacity exists in the Venice Lagoon. The high levels of CuCC and the narrow range of pCu indicates the importance of the role played by organic ligands in controlling the free ion Cu concentrations in the lagoon, and as a consequence, regulating its availability and/or toxicity.     

Water temperature interacts with the insecticide imidacloprid to alter acute lethal and sublethal toxicity to mayfly larvae

ABSTRACT

Increased temperatures and exposure to agricultural insecticides are increasingly threatening freshwater ecosystems worldwide. However, their combined effects are still poorly understood. We investigated the individual and interactive effects of water temperature and imidacloprid, the most widely used neonicotinoid insecticide, on larvae of two New Zealand mayflies, Deleatidium spp. and Coloburiscus humeralis. Ninety-six-hour bioassays with imidacloprid were performed at 9, 12, 15, 18, 21 and 24°C, in a full-factorial design. Mayfly survivorship and sub-lethal responses of impairment and moulting were recorded. We documented synergistically increased mayfly mortality and immobility with exposure to imidacloprid at higher temperatures, implying temperature-enhanced toxicity of imidacloprid. Survivorship of both mayflies was synergistically reduced by the combination of imidacloprid exposure and increasing temperatures. The same interaction also affected mobility of C. humeralis and moulting frequency of Deleatidium. Our findings suggest that developing a more thorough understanding of temperature-contaminant interactions may be important to allow better protection of aquatic ecosystems.     

Metal speciation and toxicity of Tamar Estuary water to larvae of the Pacific oyster, Crassostrea gigas

As part of the PREDICT Tamar Workshop, the toxicity of estuarine waters in the Tamar Estuary (southwest England) was assessed by integration of metal speciation determination with bioassays. High temporal resolution metal speciation analysis was undertaken in situ by deployment of a Voltammetric In situ Profiling (VIP) system. The VIP detects Cd (cadmium), Pb (lead) and Cu (copper) species smaller than 4?nm in size and this fraction is termed 'dynamic' and considered biologically available. Cadmium was mainly present in the dynamic form and constituted between 56% and 100% of the total dissolved concentration, which was determined subsequently in the laboratory in filtered discrete samples. In contrast, the dynamic Pb and Cu fractions were less important, with a much larger proportion of these metals associated with organic ligands and/or colloids (45-90% Pb and 46-85% Cu), which probably reduced the toxicological impact of these elements in this system. Static toxicity tests, based on the response of Crassostrea gigas larva exposed to discrete water samples showed a high level of toxicity (up to 100% abnormal development) at two stations in the Tamar, particularly during periods of the tidal cycle when the influence of more pristine coastal water was at its lowest. Competitive ligand-exchange Cu titrations showed that natural organic ligands reduced the free cupric ion concentration to levels that were unlikely to have been the sole cause of the observed toxicity. Nonetheless, it is probable that the combined effect of the metals determined in this work contributed significantly to the bioassay response.     

Effects of salinity on sublethal toxicity of atrazine to mummichog (Fundulus heteroclitus) larvae

In coastal marshes, fish larvae may be exposed simultaneously to extreme salinities and to atrazine, a widely used herbicide. To assess the effects of salinity on the toxicity of atrazine, newly-hatched mummichog (Fundulus heteroclitus) were exposed to atrazine (0, 5, 50 and 500 microg/L) at three salinities (3, 15 and 35PSU). Whole body cortisol was measured after 24 h. Body length, condition factor, whole body proteins, lipids, residual masses and water contents were assessed after 96 h. Significants effects were found for both condition factor and water content. Condition factors were lower at salinity 3 and 35 compared to near isoosmotic salinity, 15PSU. In addition, atrazine decreased condition factor at 500 microg/L. Reduction in condition was likely due to retardation in axial growth since body length, percentages of proteins or lipids were not affected. In the absence of atrazine, salinity had no effect on the prevalence of dehydrated (81% water) or hyperhydrated (85% water) larvae. In larvae exposed to atrazine, the prevalence of hyperhydrated larvae increased at 3PSU and 5 microg/L atrazine and that of dehydrated larvae increased at 15 and 35PSU and 5 microg/L atrazine. Severity of dehydratation increased with atrazine concentration at salinity 35PSU. Thus, a short-term exposure to environmentally realistic concentrations of atrazine affects osmotic control in mummichog larvae with possible effects on buoyancy, survival and recruitment.     

Application of the fluorescence quenching titration method to the complexation of copper (II) in the Gironde Estuary (France)

Quenching of fluorescence emission by the Cu²⁺ ion is measured in five samples from the Gironde Estuary (France). Non-linear regression analysis allows us to calculate from experimental data the values of C_L (complexing capacities or total ligand concentrations), K (conditional stability constants) and I_ML (residual fluorescence at the end of the titration). The results obtained on the Gironde estuarine samples indicate that C_L values are very low (<0.1 micromolar) and K values decrease from upstream to downstream. The relatively high values of I_ML are an indication that much of the organic fluorescing matter does not bind to Cu²⁺.     

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.     

Determination of copper complexation with natural organic ligands in seawater by equilibration with MnO2 I. Theory

The theory is discussed which describes the distribution of copper ions between a weak ion exchanger, as exemplified by MnO₂, and natural organic complexing material in seawater. Application of this theory and experimental procedures are outlined in part II of this series. It is apparent from the theory that titration with Cu²⁺ of one or more organic complexing ligands can be graphically represented by straight lines; slope and y-axis intercept provide information on the conditional stability constants and the ligand concentrations. Model calculations show that measurement of metal complexation at ligand concentrations higher than normally present in seawater may produce erroneous results because of possible changes in the metal to ligand ratio in the complexes. It is therefore advisable to measure metal complexation in the original, unaltered, water sample.     

Facilitation of macroalgae by the sedimentary tube forming polychaete Diopatra cuprea

Marine foundation organisms such as seagrasses, corals, and kelps facilitate the distribution of numerous organisms by creating refuges from environmental stressors and by providing food and substrate for settlement and growth. Barren soft-sediment systems often have faunal organisms that facilitate other species by habitat modification. We investigated how an abundant (21 m⁻²) tube cap forming polychaete, Diopatra cuprea, facilitates macroalgal distribution in Hog Island Bay, a turbid shallow tidal lagoon in Virginia (USA). Seventy percent of the number of mudflat macroalgae were found incorporated into protruding D. cuprea tube caps and field experiments showed that D. cuprea facilitates algal persistence by providing a stable substrate retaining algae against hydrodynamic forces such as tidal flushing and storm surge. If tube caps were removed, simulating storm-induced erosion, they were rebuilt within days and new drift algae incorporated. Also, D. cuprea facilitated the algal assemblage by fragmenting thalli in the attachment process, thereby ensuring a constant fragment supply for vegetative re-growth if storm-induced pruning occurs. On a species-specific level, Gracilaria verrucosa and Ulva curvata benefited more from tube cap construction compared to Fucus vesiculosus, Agardhiella subulata and the alien Codium fragile ssp. tomentosoides. This was partly because G. verrucosa and U. curvata were incorporated and fragmented more readily, and partly because they probably have physiological, morphological and biomechanical traits that enable them to better co-exist with D. cuprea. These results suggest that macroalgal distribution throughout Hog Island Bay to a large extent is linked to the distribution of D. cuprea. The processes of algal attachment, retainment, recovery, re-growth and fragmentation, can have important ecosystem implications because of the sheer abundance of the Diopatra-Gracilaria/Ulva association.     

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.     

Determination of copper complexation with natural organic ligands in seawater by equilibration with MnO2 II. Experimental procedures and application to surface seawater

The MnO₂ adsorption method combined with voltammetry is proposed for the direct determination of metal complexation in seawater of various salinities as a more satisfactory alternative to direct voltammetric measurements and bioassay methods. A small quantity of MnO₂ is equilibrated with copper ions in filtered seawater. Natural organic ligands in the seawater compete for copper with the MnO₂. Total dissolved copper is measured by differential pulse anodic stripping voltammetry after filtration and acidification of the sample. Preconcentration of natural water samples is unnecessary and measurement is performed at the natural equilibrium pH of the aerated sample. The analytical limit of detection of the method depends on contamination from the filtration step, and for copper complexation a ligand concentration of 5 × 10^?8 M was obtained. The sensitivity can be increased by use of radioisotopes as tracers. The method is very versatile in that complexation of various metals may be determined by any analytical method that measures total dissolved metal concentrations. Neither organic ligands nor their complexes with copper adsorb on the MnO₂ at pH8, but at pH 1.8 MnO₂ is an efficient scavenger for electroactive organic material.Samples of surface water from the Irish Sea and the Atlantic Ocean were found to contain ligand concentrations of 1.7 × 10^?7 and 1.1 × 10^?7 M, with conditional stability constants (log values) of 9.84 ± 0.13 and 9.86 ± 0.23, respectively, at pH 8.0.     

几种常用消毒剂对杂色鲍幼鲍的急性毒性试验

在常温静水的条件下,分别用高锰酸钾、菌毒净、聚维酮碘对杂色鲍(Haliotis diversi-color Reeve)幼鲍进行急性毒性试验。试验结果表明,毒性大小依次为高锰酸钾>菌毒净>聚维酮碘。高锰酸钾对幼鲍24,48 h的LC50分别为17.1,5.18 mg/L。菌毒净对幼鲍24,48h的LC50分别为105,46.5 mg/L。聚维酮碘对幼鲍24,48 h的LC50分别为530,218 mg/L。菌毒净、聚维酮碘是较为理想的消毒药物。     

Identification of specific malformations of sea urchin larvae for toxicity assessment: Application to marine pisciculture effluents

Standard toxicity screening tests are useful tools in the management of impacted coastal ecosystems. To our knowledge, this is the first time that the sea urchin embryo development test has been used to evaluate the potential impact of effluents from land-based aquaculture farms in coastal areas. The toxicity of effluents from 8 land-based turbot farms was determined by calculating the percentage of abnormal larvae, according to two criteria: (a) standard, considering as normal pyramid-shaped larvae with differentiated components, and (b) skeletal, a new criterion that considers detailed skeletal characteristics. The skeletal criterion appeared to be more sensitive and enabled calculation of effective concentrations EC₅, EC₁₀, EC₂₀ and EC₅₀, unlike the classical criterion. Inclusion of the skeleton criterion in the sea urchin embryo development test may be useful for categorizing the relatively low toxicity of discharges from land-based marine fish farms. Further studies are encouraged to establish any causative relationships between pollutants and specific larval deformities.     

A field comparison of two methods for the determination of copper complexation: Bacterial bioassay and fixed-potential amperometry

Complexation of copper added to seawater was determined by bacterial bioassay and fixedpotential amperometry. Consistent results were obtained by these two fundamentally different methods. The results of this study support the validity of both techniques and the field applicability of fixed-potential amperometry.The intercomparison studies were performed on samples collected at the N.Y.C. sewage sludge dumpsite and in relatively unpolluted coastal waters. In this limited study, the calculated free cupric ion concentrations at ambient total copper concentrations were similar at both sites.     

Infestation of the surf clam Mesodesma donacium by the spionid polychaete Polydora bioccipitalis

The surf clam Mesodesma donacium is an economically important species for Chilean and Peruvian shellfisheries. This clam is often infested by Polydora bioccipitalis, a species belonging to the Spionidae, the most common parasitic polychaete group. To study this association, clams were sampled monthly over a one-year period in northern Chile. Collected clams covered the entire available size range and were classified into four infestation levels in order to study: (1) the relationship between prevalence of infestation (PI) and host size, (2) the temporal pattern of infestation events related to seasonal temperature changes, and (3) the relationship between infestation, body condition index (BCI) and gonado-somatic index (GSI). Additionally, growth rate and digging ability of clams with different infestation levels was studied. A logistic regression model best explained the relationship between PI and host size, with the smallest infested clam being 34 mm long and PI increasing steeply thereafter. Ontogenetic shifts in the habitat of the clam and ontogenetic changes, mainly in shell morphology, seem to explain the sigmoid pattern. Periods of increased shell blistering after infestation by P. bioccipitalis showed a similar seasonal pattern with GSI and BCI of non-infested clams, suggesting either an association between infestation ability and low condition of the clam or common environmental triggers for those factors. Heavily infested clams showed a significant lower BCI, growth rate and digging ability; however, given its low number, they are unlikely to be significant in terms of the local population survival. However, the infestation could play a key role in explaining mass mortality of northern populations during El Niño events, given the latitudinal differences in PI and the fact that infestation ability could be enhanced by increased temperature and facilitated in stressed clams.     

Chronic dietary exposure to copper affects growth, tissue lipid peroxidation, and metal composition of the grey mullet, Chelon labrosus

Juvenile grey mullet (Chelon labrosus) were fed either a basal (4.4 mg Cu/kg dry wt) or high-Cu diet (2400 mg Cu metal/kg dry wt) for 10 weeks to assess the relationship between growth and Cu-induced oxidative damage. No mortalities were observed, but growth rate and food intake were reduced by 43 and 29%, respectively, in the high-Cu group. This was not only attributed to peroxidative damage of the food which reduced food intake (palatability), but also to direct effects of hepatic lipid peroxidation. Hepatic α-tocopherol concentrations were 63% lower, while malondialdehyde (MDA) increased by 304% in mullet fed a high-Cu diet for 67d. Cu-exposure reduced apparent α-tocopherol retention by 420%. Hepatic Fe and Zn levels fell, while Cu increased (p < 0.05). The results show that oral Cu exposure induces oxidative stress in grey mullet. Quantification of lipid peroxidation (rancidity) in the food, reflecting palatability, is essential to differentiate the direct toxic effects of Cu on growth from the secondary influences of reduced food intake.