Integrated biomarker response index as a useful tool for environmental assessment evaluated using transplanted mussels

Mytilus galloprovincialis mussels from a clean area were transplanted from 2003 to 2005 to several stations in the Bay of Cannes (North-Western Mediterranean Sea) including a site considered as reference, for 1 month at the end of spring (May). Several biomarkers (AChE, GST and CAT activities, TBARS and MT concentrations) were measured in the transplanted organisms. The concentrations of metals (Cd, Cu and Zn) were determined in the transplanted mussels, PAH and PCB analyses were performed in the mussels caged in 2004. The integrated biomarker response (IBR) was calculated; pollutant concentrations in mussels were displayed as star plots and compared to IBR star plots. Visualization was thus possible between sites for comparison with exposure conditions. Results demonstrated that the mussels from the Old harbour site (VP) are characterized by elevated copper and PCB concentrations, those from Canto harbour (PC) presented high PCB contents and those from the mouth of the Siagne River (ES) high PAH concentrations compared to the animals transplanted in the reference site (IL). In 2003, there was a visual correlation between the copper gradient measured in the transplanted mussels and the IBR variation. In 2004, the agreement between the copper gradient and the PCB gradient measured in the caged mussels and the IBR variation was good whereas the PAH gradient did not seem to contribute to the IBR demonstrating that the chosen biomarkers did not respond to PAHs. In 2005, IBR showed that other contaminants, not measured might be present in VP, PC and ES compared to the reference station (IL).     

A model for estimating the potential biomagnification of chemicals in a generic food web: Preliminary development

GOAL, SCOPE AND BACKGROUND: Bioaccumulation and biomagnification of organic pollutants have been increasingly assessed and modeled during the last years. Due to the complexity of these processes and the large variability of food webs, setting generic assessments for these parameters is really difficult. Equilibrium models, based on a compound's lipophylicity, are the main tool in regulatory proposals, such as for identifying Persistent, Bioaccumulative and Toxic Substances (PBTs), although a refinement has been claimed by the scientific community. Toxicokinetic studies offer an alternative for these estimations, where biomagnification is modeled as a succession of bioaccumulation processes, each one regulated by toxicokinetic parameters. METHODS: A review of kinetic models covering species belonging to different trophic levels and with different ecological behavior has been conducted. The results were employed for setting a conceptual model for estimating the biomagnification potential in a generic food web, which was mathematically implemented through system dynamic models developed under data sheet software. Crystal Ball was then employed for allowing Monte Carlo based probabilistic calculations. Bioaccumulation laboratory assays have been performed to estimate toxicokinetic parameters in mussels (Mytilus edulis) with two PAHs (chrysene and benzo[a]pyrene). The contamination was delivered via food. The exposure period lasted more than one month followed then by a depuration phase. The contaminant content was determined on an individual basis on five replicates. RESULTS AND DISCUSSION:. The reviewed information suggested the development of a tiered conceptual biomagnification model, starting with a simplified food chain which can be refined to more realistic and complex models in successive levels. CONCLUSIONS: The mathematical implementation of the conceptual model offers tools for estimating the potential for bioaccumulation and biomagnification of chemicals under very different conditions. The versatility of the model can be used for both comparative estimations and for validating the model. RECOMMENDATIONS AND PERSPECTIVES: Since bioaccumulation and biomagnification processes are crucial elements for a proper risk assessment of chemicals, their estimation by mathematical models has been widely tested. However, inregulatory assessments, too simplistic models are still being used quite often. The biomagnification model presented in this study should be amore accurate alternative to these models. In comparison to other previously published biomagnification models, the present one covers the time variation of bioaccumulation using just a few toxicokinetic parameters.     

Relationship between zooplankton distribution,geographic characteristics and hydrographic patterns off the Catalan coast (Western Mediterranean)

Astract Northern anchovy larvae, Engraulis mordax, were collected on five cruises covering the Southern California Bight, one cruise in April 1984, four cruises in January, February and May 1986. The amounts of triacylglycerol, cholesterol and polar lipid were measured in individual anchovy larvae as indicators of their nutritional condition. There was a significant difference in each of the size-specific lipid components between the stations for four of the five cruises. This indicates that all the ocean habitats within a cruise were not equal in promoting growth (and presumably survival) in the anchovy larvae. There were also differences between cruises, where the percentage of the larvae judged to be in poor condition varied from 8 to 27%. Canonical correlation analyses revealed a significant relationship in most cases between the larval fish parameters and the physical and biological data collected from each occupied station. Cholesterol and triacylglycerol were the most important larval components, and the short-term energy storage component in the copepod Calanus pacificus was the most important station component. The data, however, are not sufficient to identify and characterize stations in the field which produce anchovy larvae in good condition.     

Anatomical element localization by EDXS in Grevillea exul var. exul under nickel stress

Grevillea exul var. exul, an endemic serpentinic Proteaceae of New Caledonia, was chosen to study the spatial distribution of Ni because this species supports strong content of metals, which can allow important absorptions thus detectable by microanalysis. Fine transversal sections of axenic G. exul var. exul plants grown during 15 days on nickel sulphate medium were examined by EDXS microanalysis. It showed that in Ni treated plants, Ni was concentrated mostly in the phloem compared to the xylem and the epidermis, either in roots or in the basal part of the stems and was mostly in the epidermis in the upper part of the stems and not detectable in the leaves. This metal took the place of P and K in the treated plants whereas the localization of these macroelements was quite uniform in control sections. We assume that a mechanism of phloem loading is implicated to restrict Ni accumulation in G. exul var. exul.     

An approach to optimise nutrient management in environmental sanitation systems despite limited data

The material flow analysis method can be used to assess the impact of environmental sanitation systems on resource consumption and environmental pollution. However, given the limited access to reliable data, application of this data-intensive method in developing countries may be difficult. This paper presents an approach allowing to develop material flow models despite limited data availability. Application of an iterative procedure is of key importance: model parameter values should first be assessed on the basis of a literature review and by eliciting expert judgement. If model outputs are not plausible, sensitive input parameters should be reassessed more accurately. Moreover, model parameters can be expressed as probability distributions and variable uncertainty estimated by using Monte Carlo simulation. The impact of environmental sanitation systems on the phosphorus load discharged into surface water in Hanoi, Vietnam, is simulated by applying the proposed approach.     

Polycyclic aromatic hydrocarbon sampling in wastewaters using semipermeable membrane devices: accuracy of time-weighted average concentration estimations of truly dissolved compounds

Semipermeable membrane devices (SPMDs) previously spiked with performance reference compounds were exposed in wastewater. After 6 days of exposure, 13 polycyclic aromatic hydrocarbons (PAHs) were quantified in SPMDs. Exchange rate constants and time-weighted average (TWA) concentrations of SPMD-available PAHs in water were calculated. The bias of using SPMDs to estimate an actual TWA concentration if the concentration in water fluctuates, as can be expected in wastewater, was studied with numerical simulations. The bias increased with the exchange rate constant. However, most exchange rate constants evaluated in SPMDs exposed in wastewater were small enough for SPMDs to estimate a TWA concentration of PAHs even when the water concentration varied. TWA-SPMD-available concentrations were always below total dissolved (operationally defined as 0.7 microm) concentrations, indicating that part of the dissolved PAHs was not available for sampling. In situ partitioning coefficients K(DOC) were computed and found to be slightly higher than data from the literature. This confirms that only truly dissolved PAHs should be sampled by SPMDs in wastewater.     

Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach

Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NOx. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO(3)(-) produced a trend of high delta(18)O-low delta(15)N to low delta(18)O-high delta(15)N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.