Adsorption/desorption of linear alkylbenzenesulfonate (LAS) and azoproteins by/from activated sludge flocs

Our study investigated the adsorption/desorption by/from activated sludge flocs, dispersed in river water or in diluted wastewater, of organic compounds (C(11)-LAS, azoalbumin and azocasein) at concentrations relevant to environmental conditions. Activated sludge flocs, used as a model of biological aggregates, are characterized by a very heterogeneous matrix able to sorb the three organic compounds tested at 4 degrees C. The adsorbed amount of C(11)-LAS by activated sludge flocs was higher than that of azocasein or azoalbumin, as shown by the Freundlich parameters (K(ads)=8.6+/-1.7, 1.6+/-0.3 and 0.3+/-0.1 micromol(1-1/n)g(-1)l(1/n) for C(11)-LAS, azocasein and azoalbumin, respectively; n=3 sludges). C(11)-LAS sorption from activated sludge appeared to be partially reversible in river water, while a marked hysteresis phenomenon was observed for azocasein and azoalbumin, implying a low degree of reversibility in their exchange between activated sludge and river water. It has also been displayed that the conductivity variation of bulk water (comprised between 214 and 838 microS cm(-1)) exerted no dramatic effect on the C(11)-LAS desorption from activated sludge flocs, while a little effect of it on azocasein desorption was observed. Thus, biological aggregates as activated sludge flocs can serve as an intermediate carrier for C(11)-LAS, while it represents a sink for proteins.     

Equilibrium partitioning theory to predict the sediment toxicity of the anionic surfactant C(12)-2-LAS to Corophium volutator

The study of the effect of the sorption of linear alkylbenzene sulfonates (LAS) on the bioavailability to marine benthic organisms is essential to refine the environmental risk assessment of these compounds. According to the equilibrium partitioning theory (EqP), the effect concentration in water-only exposure will be similar to the effect concentration in the sediment pore water. In this work, sorption and desorption experiments with two marine sediments were carried out using the compound C₁₂-2-LAS. The effect of the sediment sorption on the toxicity of benthic organisms was studied in water-only and in sediment bioassays with the marine mud shrimp Corophium volutator. In addition, three common spiking methods were tested for its application in the toxicity tests, as well as the stability of the surfactant during the water-only and sediment-water test duration. LC50 values obtained from water-only exposure showed a good correspondence with the pore water concentrations calculated from the sorption and desorption isotherms in the spiked sediments.     

Effect of sediment properties on the sorption of C12-2-LAS in marine and estuarine sediments

Linear alkylbenzene sulfonates (LAS) are anionic high production volume surfactants used in the manufacture of cleaning products. Here, we have studied the effect of the characteristics of marine and estuarine sediments on the sorption of LAS. Sorption experiments were performed with single sediment materials (pure clays and sea sand), with sediments treated to reduce their organic carbon content, and with field marine and estuarine sediments. C₁₂-2-LAS was used as a model compound. Sorption to the clays montmorillonite and kaolinite resulted in non-linear isotherms very similar for both clays. When reducing the organic content, sorption coefficients decreased proportionally to the fraction removed in fine grain sediments but this was not the case for the sandy sediment. The correlation of the sediment characteristics with the sorption coefficients at different surfactant concentrations showed that at concentrations below 10 μg C₁₂-2-LAS/L, the clay content correlated better with sorption, while the organic fraction became more significant at higher concentrations.     

Assessment of the individual and mixture toxicity of cadmium,copper and oxytetracycline,on the embryo-larval development of the sea urchin <Emphasis Type="Italic">Paracentrotus lividus</Emphasis>

Multiple pollutions by trace metals and pharmaceuticals have become one of the most important problems in marine coastal areas because of its excessive toxicity on organisms living in this area. This study aimed to assess the individual and mixture toxicity of Cu, Cd, and oxytetracycline frequently existing in the contaminated marine areas and the embryo-larval development of the sea urchin Paracentrotus lividus. The individual contamination of the spermatozoid for 1 h with the increasing concentrations of Cd, Cu, and OTC decreases the fertility rate and increases larvae anomalies in the order Cu > Cd > OTC. Moreover, the normal larva frequency and the length of spicules were more sensitive than the fertilization rate and normal gastrula frequency endpoints. The mixture toxicity assessed by multiple experimental designs showed clearly that concentrations of Cd, Cu, and OTC superior to 338 μg/L, 0.56 μg/L, and 0.83 mg/L, respectively, cause significant larva malformations.     

A model compound study: the ecotoxicological evaluation of five organic contaminants employing a battery of marine bioassays

This paper describes the ecotoxicological evaluation of five organic contaminants frequently detected in marine sediments (tributyltin, triphenyltin, benzo[a]pyrene, fluoranthene, and PCB 153) using three marine species (Vibrio fischeri, Tetraselmis suecica, and Tisbe battagliai). The sensitivity of each species varied for all compounds. The triorganotins were consistently the most toxic to all species. The applicability of each test system to assess the acute toxicity of environmental contaminants and their use in Toxicity Identification Evaluation (TIE) is discussed. Suitability of the Microtox and T. battagliai tests for employment in TIE studies were further assessed through spiking experiments with tributyltin. Results demonstrated that the most effective treatment to remove organotin toxicity from the sample was the C18 resin. The results of this study have important implications for risk assessment in estuarine and coastal waters in Ireland, where, at present the monitoring of sediment and water quality is predominantly reliant on chemical analysis alone.     

Effects of sample preparation on the measurement of organic carbon,hydrogen, nitrogen,sulfur, and oxygen concentrations in marine sediments

The elemental composition of marine sediment provides useful information for the study of environmental processes including biogeochemical cycling and contaminant partitioning. It is common practice to acidify marine sediment samples to remove carbonate before measuring the concentrations of organic carbon (C). To date, however the effects of acidification on the concentrations of hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) in marine sediments have not been explicitly addressed. Acidification may contaminate or alter the sediment samples and create experimental artifacts affecting the validity of resulting H/C, C/N and O/C ratios. The objective of this study was to quantify how various preparation techniques affect the measured concentrations of C, H, N, S and O in marine sediments. Effects of four different pretreatments: unacidified (whole), acidification by HCl vapor, acidification by direct addition of HCl, and combustion were evaluated using five marine sediments and a standard reference material. The magnitude of carbonate loss between the vapor and direct acidification treatments was evaluated using stable C isotope analysis. Carbonates were most effectively removed by direct addition of HCl; and our results agree with findings of other studies which found direct addition of HCl to be the most accurate method for measuring organic C. However, the acid treatments elevated the apparent concentration of H and O; and in a few cases concentrations of N and S were significantly affected by acidification. In general, combustion significantly reduced all elemental concentrations compared to the whole sample. Based on these results, we recommend analysis of the untreated whole sediment for determining N, H, O, and S.     

Relationships between pesticides and organic carbon fractions in sediments of the Danshui River estuary and adjacent coastal areas of Taiwan

In order to understand the fate of pesticides in marine environments, concentrations of pesticides and different carbonaceous fractions were determined for surface sediments in the Danshui River and nearby coastal areas of Taiwan. The major compounds detected were tetrachlorobenzene, HCHs, chlordane, aldrin, DDDs, DDEs and DDTs. Total concentrations of pesticides in the sediments ranged from not detectable to 23 ng g(-1), with the maximum value detected near the discharge point of the marine outfall from the Pali sewage treatment plant. These results confirm that pesticides persist in estuarine and nearby coastal environments of the Danshui River well after their ban. Concentrations of total pesticides significantly correlate with concentrations of total organic carbon and black carbon in these sediments, suggesting that total organic carbon and black carbon regulate the distribution of trace organic pollutants in fluvial and coastal marine sediments.     

Two new growth inhibition tests with the filamentous algae Ceramium strictum and C. tenuicorne (Rhodophyta)

Two growth inhibition tests using the red marine macroalgae Ceramium strictum and the brackish water relative C. tenuicorne have been developed. Besides using phenol as a reference substance, the toxicity of a metal, a flame retardant and a complex effluent water were assayed. The two methods are reliable and repeatable bioassays for salinities between 4 and 30 per thousandth. The coefficients of variation (CV) for toxicity of the reference substance phenol were 15% for the Stereo Microscope Analysis test and between 24 and 51% for the Computer Image Analysis test (n=5). Ceramium spp. are common and important primary producers in temperate coastal waters and are thus relevant as test organisms. Both algae grow well in laboratorial conditions and tests can be performed all year around.     

Sublethal effects of copper on some biological traits of the amphipod Gammarus aequicauda reared under laboratory conditions

The common and widespread copper contamination in marine coastal environments make toxicity data necessary to assess the aquatic hazard and risk of this metal.     

Toxicity of methyl tert-butyl ether to marine organisms: ambient water quality criteria calculation

In response to increasing concerns over the detection of methyl tert-butyl ether (MTBE) in groundwater and surface water and its potential effects in aquatic ecosystems, industry and the United States Environmental Protection Agency (USEPA) began to collaborate in 1997 to develop aquatic toxicity databases sufficient to derive ambient water quality criteria for MTBE consistent with USEPA requirements. Acute toxicity data for seven marine species, chronic toxicity data for an invertebrate, and plant toxicity data were developed to complete the saltwater database. The species tested were Cyprinodon variegatus, Gasterosteus aculeatus, Callinectes sapidus, Mytilus galloprovincialis, Palaemonetes pugio, Rhepoxynius abronius, Americamysis bahia, and Skeletonema costatum. The toxicity tests were conducted in accordance with USEPA and American Society for Testing and Materials testing procedures and Good Laboratory Practice guidelines. Data developed from this study were consistent with existing data and showed that MTBE has low acute and chronic toxicity to the marine species tested. Based upon measured MTBE concentrations, acute effects were found to range from 166 mg MTBE/l for the grass shrimp to 1950 mg MTBE/l for marine mussel. The no-observed effect concentration for the reproduction and growth of mysids was 26 mg MTBE/l during the life cycle test. The toxicity of MTBE to saltwater organisms is comparable to its toxicity to the freshwater species tested. Reported MTBE concentrations in coastal waters are several orders of magnitude lower than concentrations observed to cause effects in marine organisms.     

Comparative toxicity of acrylic acid to marine and freshwater microalgae and the significance for environmental effects assessments.

In this study, we compared the sensitivity of freshwater and marine organisms to two structurally similar substances, acrylic acid and methacrylic acid. Reported acute toxicity data (L(E)C50-values) for freshwater organisms range from 0.1 to 222 mg/l and 85 to >130 mg/l for acrylic acid and methacrylic acid, respectively. The large variation in toxicity data for acrylic acid is due to a specific toxicity to certain species of freshwater microalgae, with algae EC50-values being two to three orders of magnitude lower than L(E)C50-values reported for fish and invertebrates. To evaluate the sensitivity of marine organisms, ecotoxicity data was generated for ten species of microalgae, one invertebrate species and one fish species. For methacrylic acid, we found a marine acute toxicity that ranged from 110 to >1260 mg/l, which is comparable to reported data on freshwater organisms. In strong contrast, the resulting L(E)C50-values for acrylic acid ranged from 50 to >1000 mg/l, and there was no specific sensitivity of marine algae when compared to marine invertebrates and fish. For acrylic acid, therefore, use of the available freshwater toxicity data for an effects assessment for the marine environment is likely to overestimate the hazard and risk from this substance. Overall, the results of the study suggest that ecotoxicity data generated on freshwater species may not always be appropriate for the effects assessments of organic chemicals in the marine environment, thus emphasising the importance of using ecologically relevant data to assess environmental risk.     

Baseline concentrations of elements in the Antarctic macrolichen Umbilicaria decussata

Total concentrations of major and trace elements were determined in samples of the epilithic lichen Umbilicaria decussata from 24 ice-free areas in coastal Victoria Land (Antarctica). Overall average concentrations of trace elements except Cd were the lowest ever reported for lichens of the genus Umbilicaria. Specifically, the mean level of Pb in lichens from granitic rocks (0.46 +/- 0.18 microg g(-1) dry wt) was more than four times lower than the lowest record in Arctic lichens. No impact of local human activities was detected, but the elemental composition of U. decussata was affected by entrapment of soil or rock dust particles and probably by uptake of soluble elements from substrate. Relationships between elements and their distribution patterns in the study area indicated that the marine environment is the main source of major ions and perhaps of Cd in lichens. Accumulation of P was detected in samples from coastal sites frequented by seabirds. Although the present results can be taken as baseline levels of major and trace elements in Antarctic U. decussata from substrates with very different geochemical features, further research is necessary to evaluate the relative element contribution from each substrate with respect to those from snow, marine aerosol, salt encrustations and guano.     

Submarine wastewater discharges: dispersion modelling in the Northern Adriatic Sea

Background, aim and scope   

Opposite interests must coexist in coastal areas: the presence of significant cities and urban centres, of touristic and recreational areas, and of extensive shellfish farming. To avoid local pollution caused by treated wastewaters along the Northern Adriatic coast (Friuli Venezia-Giulia and Veneto regions), marine outfall systems have been constructed. In this study, the application of a numerical dispersion model is used to support the traditional monitoring methods in order to link information concerning the hydrodynamic circulation and the microbiological features, to evaluate possible health risks associated with recreational and coastal shellfish farming activities. The study is a preliminary analysis of the environmental impact of wastewater treatment plants (WWTPs) with submarine discharge outfalls. It also could be useful for the water profile definition according to the Directive 2006/7/EC on the quality of bathing water and for the integrated areal analysis (Ostoich et al. 2006), to define the area of influence of each submarine discharge point.     

The effects of copper ions and copper nanomaterials on the output of amino acids from marine microalgae

In this study, the marine microalgae Skeletonema costatum and Nitzschia closterium were exposed to different forms of copper, such as a metal salt (Cu²⁺), a nano-metal (nano-Cu), and nano-metal oxide (nano-CuO). During a 96-h exposure to nanoparticles (NPs) and salt, the cell number, Cu²⁺ concentration in the culture medium, morphology, and intracellular amino acids were measured to assess the toxicity of the copper materials and the toxicity mechanism of the NPs. As results, the toxicity of Cu²⁺, nano-Cu, and nano-CuO to marine phytoplankton decreased in order. The EC₅₀ values of Cu²⁺ and nano-Cu for S. costatum and N. closterium ranged from 0.356 to 0.991 mg/L and 0.663 to 2.455 mg/L, respectively. Nano-Cu inhibits the growth of marine phytoplankton by releasing Cu²⁺; however, nano-CuO is harmful to microalgae because of the effect of NPs. The secretion of extracellular polymeric substances by microalgae could also affect the toxicity of nano-Cu and nano-CuO to microalgae. S. costatum was more sensitive to copper than N. closterium. Cu²⁺, nano-Cu, and nano-CuO all reduced per-cell amino acids and the total output of algae-derived amino acids by affecting the growth of the phytoplankton. This study helps to understand the risk assessment of nano-Cu and nano-CuO to marine microalgae.

     

Ratio of the concentration of anthraquinone to anthracene in coastal marine sediments

The ratio of the concentration of the oxidation product anthraquinone to that of its parent polycyclic aromatic hydrocarbon anthracene is reported for several coastal marine sediments. The ratio ranges from 0.317 in a highly contaminated industrialized harbor to 2.81 in a remote, less contaminated site. We hypothesize that differences in this ratio result from the input source of PAHs, with input from atmospheric deposition at remote sites resulting in a predominance of anthraquinone (ratio > 1), and direct discharge to highly contaminated industrialized harbors resulting in a predominance of anthracene (ratio < 1). To support this hypothesis, the fate of anthracene in the marine environment was investigated with respect to conversion to its oxidation product, anthraquinone. Once associated with sediments, anthracene is believed to be relatively persistent; however, it can potentially be subjected to oxidation via biological (microbial degradation) and chemical (chemical oxidation and photooxidation) processes. An assessment of the extent of oxidation of anthracene associated with sediments was conducted both under conditions simulating those found in the marine environment and under rigorous conditions by exposure to UV radiation. Results of this study show that while anthracene associated with marine sediments does not readily undergo oxidation to anthraquinone under conditions normally encountered in the marine environment, under extreme conditions anthracene is photooxidized by exposure to UV radiation. The extent of oxidation is influenced by sediment characteristics such as percent organic carbon, humic acid content and sediment surface area. The relative stability of anthracene under normal conditions may help to validate the use of the anthraquinone to anthracene ratio in marine sediments as an environmental marker of contaminant source.     

Exposure assessment for trace elements from consumption of marine fish in Southeast Asia

Concentrations of 20 trace elements were determined in muscle and liver of 34 species of marine fish collected from coastal areas of Cambodia, Indonesia, Malaysia and Thailand. Large regional difference was observed in the levels of trace elements in liver of one fish family (Carangidae): the highest mean concentration was observed in fish from the Malaysian coastal waters for V, Cr, Zn, Pb and Bi and those from the Java Sea side of Indonesia for Sn and Hg. To assess the health risk to the Southeast Asian populations from consumption of fish, intake rates of trace elements were estimated. Some marine fish showed Hg levels higher than the guideline values by U.S. Environmental Protection Agency and Joint FAO/WHO Expert Committee on Food Additives (JECFA). This suggests that consumption of these fish may be hazardous to the people.     

Identification of highly brominated analogues of Q1 in marine mammals

Three novel halogenated organic compounds (HOCs) have been identified in the blubber of marine mammals from coastal New England with the molecular formulae C(9)H(3)N(2)Br(6)Cl, C(9)H(3)N(2)Br(7), and C(9)H(4)N(2)Br(5)Cl. They were identified using high and low resolution gas chromatography mass spectrometry (GCMS) and appear to be highly brominated analogues of Q1, a heptachlorinated HOC suspected to be naturally produced. These compounds were found in Atlantic white sided dolphin (Lagenorhynchus acutus), bottlenose dolphin (Tursiops truncatus), common dolphin (Delphinus delphis), Risso's dolphin (Grampus griseus), harbor porpoise (Phocoena phocoena), beluga whale (Delphinapterus leucas), fin whale (Balaenoptera physalus), grey seal (Halichoerus grypus), harp seal (Phoca groenlandica) and a potential food source (Loligo pealei) with concentrations as high as 2.7 microg/g (lipid weight). The regiospecificity of C(9)H(3)N(2)Br(6)Cl is suggestive of a biogenic origin. Debromination of C(9)H(3)N(2)Br(6)Cl may be significant in the formation of C(9)H(4)N(2)Br(5)Cl.     

Spatial variability of metallic and organic contamination of anguilliform fish in New Caledonia

New Caledonia is one of the main hot spots of biodiversity on the planet. Large amounts of contaminants are discharged into the lagoon as a result of increasing anthropogenic activities such as intense mining, urbanization, and industrialization. Concentrations of 14 trace elements and 26 persistent organic pollutants (POPs: PCBs and pesticides) were measured in the muscles of two anguilliform fish species, over a coast to barrier reef gradient in two lagoon areas differently exposed to anthropic disturbances. This study emphasizes the high trace element contamination status of anguilliform fish and also highlights slight but perceptible organic pollution. The contamination extends throughout the lagoon, from coast to barrier reef, even in areas remote from emission points. High levels of trace elements, especially those linked to mining activities (i.e., Co, Cr, Fe, Mn, and Ni), were detected in coastal sites. Furthermore, the large dispersion of most POPs throughout the entire lagoon poses the question of their potential toxicity on marine organisms from numerous habitats. Our results underline the need for long-term monitoring of various contaminants over large spatial and time scales.     

Widespread contamination by tris(4-chlorophenyl)methane and tris(4-chlorophenyl)methanol in cetaceans from the North Pacific and Asian coastal waters

For understanding global distribution, transport and behavior of tris(4-chlorophenyl)methane (TCPMe) and tris(4-chlorophenyl)methanol (TCPMOH), the two newly identified microcontaminants, the present study determined their concentrations and other persistent organochlorines (OCs) in the blubber of nine species of adult male cetaceans collected from various locations in the North Pacific Ocean and coastal waters of some Asian countries, during 1985-97. Concentrations of TCPMe and TCPMOH were found to be highest in northern right whale dolphins, which may be attributable to wide distribution of this species, including some heavily polluted areas such as coastal California. Elevated residue levels of TCPMe and TCPMOH were observed in both off-shore and coastal species, suggesting widespread contamination of these compounds in the marine environment. Higher contamination of TCPMe and TCPMOH was found in cetaceans from temperate and cold waters than those from tropical regions. The latitudinal distribution of TCPMe and TCPMOH in cetaceans from the North Pacific and Asian coastal waters was similar to that of DDTs, suggesting less transportable nature of TCPMe and TCPMOH in the marine environment. Data on the occurrence of TCPMe and TCPMOH further indicated high bioaccumulation potential of these compounds, which was comparable to DDTs. Relative concentrations of TCPMe/TCPMOH in cetaceans were apparently higher than those observed in seals, suggestive of lower metabolic capacity for these compounds in cetaceans than in pinnipeds, which is similar to classic contaminants like polychlorinated biphenyls and DDTs.     

Occurrence of butyltin compounds in the waters of selected lakes, rivers and coastal environments from China

The presence of butyltin compounds was investigated for the first time in selected lakes, rivers and coastal environments of China. Aqueous samples were pretreated by the technique of headspace solid phase micro-extraction after hydride generation with sodium tetrahydroborate (NaBH4). Quantitative measurement of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) concentrations were accomplished by capillary gas chromatography with flame photometric detector using quartz surface-induced luminescence. Experimental data demonstrated the widespread occurrence of butyltin compounds in the Chinese aquatic environment. In some locations, the concentrations of TBT were higher than the acute and chronic toxicity threshold of sensitive fresh water or marine organisms. Although DBT and MBT (which mainly come from the degradation of TBT), are less toxic, their occurrence can still affect the ecosystem over a long time frame.