Environmental copper: Behaviour when involved in physical adsorption at several interfaces

From a literature-based assessment of the current knowledge about both the toxic or salutary properties of copper, this study focused on the determination, at 25 °C, of the interfacial properties of CuCl_2, either alone or in mixture with carbofuran used, here, as a model of organics and/or pesticide. The interfaces under study were: i) the air/solution interface and ii) the silica/solution interface. The former is considered as a path for volatilization, whereas the latter permits a modelling of physical adsorption upon solids, which is the first and unavoidable step in any adsorption process. One should note that it can also mimic adsorption on some sandy soils. Coadsorption was clearly identified as implicated in an enhancement of the surface content of both solutes at both interfaces. However, at the two interfaces under study, the way the surface became structured led to opposite adsorption mechanisms for the organic compounds and the salt. A rough theory about ionic adsorption is also proposed.     

Biomonitoring perfluorinated compounds in Catalonia,Spain: concentrations and trends in human liver and milk samples

Background, aim and scope  

Perfluorinated compounds (PFCs) are global environmental pollutants that bioaccumulate in wildlife and humans. Laboratory experiments have revealed toxic effects such as delayed development, humoral suppression, and hepatotoxicity. Although numerous human blood levels have been reported, little is known about distribution in the human body. Knowledge about PFC distribution and accumulation in the human body is crucial to understanding uptake and subsequent effects as well as to conduct risk assessments. The present study reports PFC levels in human liver and breast milk from a general population living in Catalonia, Spain. Liver and milk levels are compared to previously reported levels in blood from the same geographic area as well as to other existing reports on human liver and milk levels in other countries.     

Characterisation of particulate exposure during fireworks displays

Little is known about the level and content of exposure to fine particles (PM_2.5) among persons who attend fireworks displays and those who live nearby. An evaluation of the levels of PM_2.5 and their elemental content was carried out during the nine launches of the 2007 Montréal International Fireworks Competition. For each event, a prediction of the location of the firework plume was obtained from the Canadian Meteorological Centre (CMC) of the Meteorological Service of Canada. PM_2.5 was measured continuously with a photometer (Sidepak?, TSI) within the predicted plume location (“predicted sites”), and integrated samples were collected using portable personal samplers. An additional sampler was located on a nearby roof (“fixed site”). The elemental composition of the collected PM_2.5 samples from the “predicted sites” was determined using both a non-destructive energy dispersive ED-XRF method and an ICP-MS method with a near-total microwave-assisted acid digestion. The elemental composition of the “fixed site” samples was determined by the ICP-MS with the near-total digestion method. The highest PM_2.5 levels reached nearly 10 000 μg m^?3, roughly 1000 times background levels. Elements such as K, Cl, Al, Mg and Ti were markedly higher in plume-exposed filters. This study shows that 1) persons in the plume and in close proximity to the launch site may be exposed to extremely high levels of PM_2.5 for the duration of the display and, 2) that the plume contains specific elements for which little is known of their acute cardio-respiratory toxicity.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

Influence of sediment composition on PAH toxicity using zebrafish (Danio rerio) and Japanese medaka (Oryzias latipes) embryo-larval assays

Due to hydrophobic and persistent properties, polycyclic aromatic hydrocarbons (PAHs) have a high capacity to accumulate in sediment. Sediment quality criteria, for the assessment of habitat quality and risk for aquatic life, include understanding the fate and effects of PAHs. In the context of European regulation (REACH and Water Framework Directive), the first objective was to assess the influence of sediment composition on the toxicity of two model PAHs, benzo[a]pyrene and fluoranthene using 10-day zebrafish embryo-larval assay. This procedure was undertaken with an artificial sediment in order to limit natural sediment variability. A suitable sediment composition might be then validated for zebrafish and proposed in a new OECD guideline for chemicals testing. Second, a comparative study of toxicity responses from this exposure protocol was then performed using another OECD species, the Japanese medaka. The potential toxicity of both PAHs was assessed through lethal (e.g., survival, hatching success) and sublethal endpoints (e.g., abnormalities, PMR, and EROD) measured at different developmental stages, adapted to the embryonic development time of both species. Regarding effects observed for both species, a suitable artificial sediment composition for PAH toxicity testing was set at 92.5 % dry weight (dw) silica of 0.2–0.5-mm grain size, 5 % dw kaolin clay without organic matter for zebrafish, and 2.5 % dw blond peat in more only for Japanese medaka. PAH bioavailability and toxicity were highly dependent on the fraction of organic matter in sediment and of the K _ow coefficients of the tested compounds. The biological responses observed were also dependent of the species under consideration. Japanese medaka embryos appeared more robust than zebrafish embryos for understanding the toxicity of PAHs following a sediment contact test, due to the longer exposure duration and lower sensitivity of sediment physical properties.     

Developmental toxicity of PAH mixtures in fish early life stages. Part II: adverse effects in Japanese medaka

In aquatic environments, polycyclic aromatic hydrocarbons (PAHs) mostly occur as complex mixtures, for which risk assessment remains problematic. To better understand the effects of PAH mixture toxicity on fish early life stages, this study compared the developmental toxicity of three PAH complex mixtures. These mixtures were extracted from a PAH-contaminated sediment (Seine estuary, France) and two oils (Arabian Light and Erika). For each fraction, artificial sediment was spiked at three different environmental concentrations roughly equivalent to 0.5, 4, and 10 μg total PAH g^?1 dw. Japanese medaka embryos were incubated on these PAH-spiked sediments throughout their development, right up until hatching. Several endpoints were recorded at different developmental stages, including acute endpoints, morphological abnormalities, larvae locomotion, and genotoxicity (comet and micronucleus assays). The three PAH fractions delayed hatching, induced developmental abnormalities, disrupted larvae swimming activity, and damaged DNA at environmental concentrations. Differences in toxicity levels, likely related to differences in PAH proportions, were highlighted between fractions. The Arabian Light and Erika petrogenic fractions, containing a high proportion of alkylated PAHs and low molecular weight PAHs, were more toxic to Japanese medaka early life stages than the pyrolytic fraction. This was not supported by the toxic equivalency approach, which appeared unsuitable for assessing the toxicity of the three PAH fractions to fish early life stages. This study highlights the potential risks posed by environmental mixtures of alkylated and low molecular weight PAHs to early stages of fish development.     

Distribution and ecological risk of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in surface sediments from the Bizerte lagoon,Tunisia

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were determined in 18 surface sediment samples collected from Bizerte lagoon, Tunisia. The total concentrations of ten PCBs (∑PCBs) and of four OCPs (∑OCPs) in the sediments from this area ranged from 0.8 to 14.6 ng g^?1 dw (average value, 3.9 ng g^?1 dw) and from 1.1 to 14.0 ng g^?1 dw (average value, 3.3 ng g^?1 dw), respectively. Among the OCPs, the range of concentrations of dichlorodiphenyltrichloroethane and its metabolites (DDTs) and hexachlorobenzene (HCB) were 0.3–11.5 ng g^?1 dw (1.9 ng g^?1 dw) and 0.6–2.5 ng g^?1 dw (1.4 ng g^?1 dw), respectively. Compositional analyses of the POPs indicated that PCB 153, 138 and 180 were the predominant congeners accounting for 60 % of the total PCBs. In addition, p,p′-DDT was found to be the dominant DDTs, demonstrating recent inputs in the environment. Compared with some other regions of the world, the Bizerte lagoon exhibited low levels of PCBs and moderate levels of HCB and DDTs. The high ratios ΣPCBs/ΣDDTs indicated predominant industrial versus agricultural activities in this area. According to the established guidelines for sediment quality, the risk of adverse biological effects from such levels of OCPs and PCBs, as recorded at most of the study sites, was insignificant. However, the higher concentrations in stations S1 and S3 could cause biological damage.     

Environmental monitoring of alcohol sulfates and alcohol ethoxysulfates in marine sediments

The study describes the environmental monitoring of anionic surfactants―alcohol sulfates (AS) and alcohol ethoxysulfates (AES)—in marine sediments. Concentration values were obtained after pressurised liquid extraction (PLE) and liquid chromatography–tandem mass spectrometry analysis (LC–MS/MS). Samples were collected from a range of wastewater discharge points along the coast of the provinces of Huelva, Málaga, Granada and Almería. Urban, agricultural and industrial wastewaters are discharged at the selected 38 sampling sites. Principal component analysis was carried out in order to evaluate the distribution and behaviour of these compounds in these coastal environments. Evaluation of the data revealed that the behaviour and sources of AS and AES in marine sediments are different, and that the distribution of AES depends on the length of the alkyl chain, while the number of ethoxylated units is not relevant. Additionally, the 38 sampling sites can be grouped into only two types of outfalls according to their AS distribution. The concentration of compounds in sediment samples ranged from 7.52 to 13.50 mg kg^?1 for AS, from 3.04 to 10.68 mg kg^?1 for AES–C₁₂E_x and from 3.83 to 11.56 mg kg^?1 for AES–C₁₄E_x.     

Spatial variability of precipitation in Spain

The spatial variability of annual and seasonal precipitation in the conterminous land of Spain has been evaluated by using correlation decay distance analysis (CDD). The CDD analysis essentially explores how the correlation between neighbouring stations varies according to distance. We analysed CDD independently for the decades 1956–1965, 1966–1975, 1976–1985, 1986–1995, and 1996–2005 using only those stations with no missing values for each decade. To this end, 972, 1,174, 1,242, 773 and 695 complete series were used for each decade, respectively. In particular, for each station and decade, we calculated the threshold distance at which the common variance between target (i) and neighbour series is higher than 50 % (r ²  = 0.5) to evaluate whether current density of the climate data set captures the spatial variability of precipitation within the study area. Results indicate that, at an annual scale, neighbouring stations with 50 % of common variance are restricted on average to about 105 km, but this distance can vary from 28 to 251 km within the study area. The lowest variability is located to the SW and in winter, while the higher spatial variability is found to the north, in the Cantabrian area, and to the east, in the Mediterranean and Pyrenees, during summer. Our results suggest that current density of climate stations (those operating in 2005) is good enough to study precipitation variability at an annual scale for winter, spring and autumn, but not enough for summer.