Distribution of PCDD/Fs and dioxin-like PCBs in sediment and plants from a contaminated salt marsh (Tejo estuary,Portugal)

Concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in sediment and plants collected from a salt marsh in the Tejo estuary, Portugal. The highest PCDD/F and dl-PCB concentrations were detected in uncolonized sediments, averaging 325.25?±?57.55 pg g^?1 dry weight (dw) and 8,146.33?±?2,142.14 pg g^?1 dw, respectively. The plants Sarcocornia perennis and Halimione portulacoides growing in PCDD/F and dl-PCB contaminated sediments accumulated contaminants in roots, stems, and leaves. It was observed that PCDD/F and dl-PCB concentrations in roots were significantly lower in comparison with stems and leaves. In general, concentration of ΣPCDD/Fs and Σdl-PCBs in H. portulacoides tissues were found to be twofold higher than those in S. perennis, indicating a difference in the accumulation capability of both species. Furthermore, congener profiles changed between sediments and plant tissues, reflecting a selective accumulation of low chlorinated PCDD/Fs and non-ortho dl-PCBs in plants.     

Degradation products of profenofos as identified by high-field FTICR mass spectrometry: Isotopic fine structure approach

This study was performed to identify the degradation products of profenofos “a phenyl organothiophosphate insecticide” in raw water (RW) collected from the entry point of Metropolitan Water Works Authority “Bangkaen, Thailand” and ultrapure water (UPW) with and without TiO₂ under simulated sunlight irradiation. Degradation of profenofos was followed with ultrahigh performance liquid chromatography (UHPLC) and follows pseudo first-order kinetic. Accordingly, high-field FTICR mass spectrometry coupled to an electrospray ionization source was used to reveal the degradation routes of profenofos and the isotopic fine structures (IFS) elucidations to approve the chemical structures of its degradation products. More degradation products were detected in UPW as compared to RW. Consequently, two main degradation pathways namely (i) interactive replacements of bromine and hydrogen by hydroxyl functional groups and (ii) rupture of PO, PS, CBr and CCl bonds were observed. None interactive replacement of chlorine by hydroxyl functional group was detected. Accordingly, mechanistical pathways of the main degradation products were established.     

Iophenoxic acid derivatives as markers of oral baits to wildlife

The bait-marker iophenoxic acid (IPA) and its derivatives are increasingly used for evaluating and optimizing the cost-effectiveness of baiting campaigns on wildlife, particularly on game species such as the wild boar. We aimed to determine whether concentrations of the three main IPA derivatives ethyl, methyl and propyl-IPA measured on thoracic liquid extracts (TLE) of hunted wild boars may be representative of two exposure doses, 40 and 200 mg, from 20 to 217 days after ingestion. Then we developed a method of detection of the three IPA derivatives by LC/ESI-MS-MS in muscle and liver to evaluate the suitability of these two other tissues for monitoring the marked bait consumption and for measuring available residues in the meat of marked animals. Three semi-captive wild boars received 40 mg of each IPA derivative, three received 200 mg, and three, as controls, did not receive IPA. Blood serum was sampled 20, 197 or 217 days after IPA exposure according to animals and to the derivative. Wild boars were shot by gun after the different times of serum sampling times, and TLE, muscle and liver were sampled. Our results suggest that TLE is not a relevant tissue for quantitatively expressing IPA exposure. Due to interference, no analytical method was validated on TLE containing digestive material. On the other hand, quantifications in the muscle and particularly in the liver could discriminate wild boars that had ingested the two IPA doses from 20 days until 7 months after exposure, especially for the two long term markers ethyl and propyl-IPA. So IPA quantifications in the liver sampled on hunted animals appear to be a reliable tool for monitoring bait consumption in the field at a large scale. Nevertheless, whatever the ingested dose, ethyl- and propyl-IPA concentrations measured in the muscle and the liver of tested animals until 217 days after exposure, remained higher than 0.01 mg/kg, the Maximal Residue Limit (MRL) is recommended for molecules for which no toxicological data are available. Based on the range of IPA residues available in these two tissues, implications for humans consuming marked animals are discussed.     

In situ stabilization of trace metals in a copper-contaminated soil using P-spiked Linz-Donawitz slag

Purpose  

A former wood exploitation revealing high Cu and As concentration of the soils served as a case study for assisted phytoextraction.     

The semiochemically mediated interactions between bacteria and insects

In natural environment, semiochemicals are involved in many interactions between the different trophic levels involving insects, plants and hosts for parasitoids or prey for predators. These volatile compounds act as messengers within or between insect species, inducing particular behaviours, such as the localisation of a source of food, the orientation to an adequate oviposition site, the selection of a suitable breeding site and the localisation of hosts or prey. In this sense, bacteria have been shown to play an important role in the production of volatile compounds which ones act as semiochemicals. This review, focusing on the semiochemically mediated interactions between bacteria and insects, highlights that bacterial semiochemicals act as important messengers for insects. Indeed, in most of the studies reported here, insects respond to specific volatiles emitted by specific bacteria hosted by the insect itself (gut, mouthparts, etc.) or present in the natural environment where the insect evolves. Particularly, bacteria from the families Enterobacteriaceae, Pseudomonaceae and Bacillaceae are involved in many interactions with insects. Because semiochemicals naturally produced by bacteria could be a very interesting option for pest management, advances in this field are discussed in the context of biological control against insect pests.     

Kinetic study of γ-hexabromocyclododecane orally given to laying hens (Gallus domesticus)

Introduction  

High concentrations of hexabromocyclododecane (HBCD) sometimes recorded in free-range hens' eggs are thought to be due to soil ingestion. Of the three stereoisomers of HBCD (α-, β-, and γ-HBCD), γ-HBCD is the main component in the commercial mixture, as well as in environmental matrices, whereas the isomer profile is α-dominated in biota. In fish and in mammals, this shift is thought to be due to a rapid elimination of γ-HBCD and to its bioisomerization to the more persistent α-HBCD. The aim of the current controlled study was to better understand the fate of ingested HBCD in laying hens. The isomer profile in soil being γ-dominated, excretion kinetics of γ-HBCD into egg yolk, and accumulation in liver and in abdominal fat were investigated.     

An investigation of the origin and mobility of phosphorus in freshwater sediments from Bort-Les-Orgues Reservoir, France

In order to assess the origin and the potential mobility of phosphorus (P) in the sediment of the Bort-Les-Orgues Reservoir, France, two sequential extraction schemes, i.e., the SMT (modified Williams method) and the Golterman schemes, were compared. Finally, the potential mobility of P in this sediment was estimated from results of sequential extraction. The SMT method appeared to be more satisfactory than the Golterman method, which is in accordance with results from a study currently carried out in the framework of the European programme Standards, Measurements and Testing. Iron-bound P and organic P were the dominant forms of P in the sediment; these forms are likely to be released at the sediment/water interface in case of anoxia and could diffuse into the water column, thus increasing the risk of eutrophication in this sensitive reservoir. The P stock (330 +/- 66 t) is not negligible and should be taken into account in any restoration project of the reservoir. The SMT procedure seems promising and will provide, in the near future, a valuable tool for water managers in the field of lake restoration.     

Review of ozone and temperature lidar validations performed within the framework of the Network for the Detection of Stratospheric Change

The use of assimilation tools for satellite validation requires true estimates of the accuracy of the reference data. Since its inception, the Network for Detection of Stratospheric Change (NDSC) has provided systematic lidar measurements of ozone and temperature at several places around the world that are well adapted for satellite validations. Regular exercises have been organised to ensure the data quality at each individual site. These exercises can be separated into three categories: large scale intercomparisons using multiple instruments, including a mobile lidar; using satellite observations as a geographic transfer standards to compare measurements at different sites; and comparative investigations of the analysis software. NDSC is a research network, so each system has its own history, design, and analysis, and has participated differently in validation campaigns. There are still some technological differences that may explain different accuracies. However, the comparison campaigns performed over the last decade have always proved to be very helpful in improving the measurements. To date, more efforts have been devoted to characterising ozone measurements than to temperature observations. The synthesis of the published works shows that the network can potentially be considered as homogeneous within +/-2% between 20-35 km for ozone and +/-1 K between 35-60 km for temperature. Outside this altitude range, larger biases are reported and more efforts are required. In the lower stratosphere, Raman channels seem to improve comparisons but such capabilities were not systematically compared. At the top of the profiles, more investigations on analysis methodologies are still probably needed. SAGE II and GOMOS appear to be excellent tools for future ozone lidar validations but need to be better coordinated and take more advantage of assimilation tools. Also, temperature validations face major difficulties caused by atmospheric tides and therefore require intercomparisons with the mobile systems, at all sites.     

Experimental exposure of juvenile savannah monitors (Varanus exanthematicus) to an environmentally relevant mixture of three contaminants: effects and accumulation in tissues

Using varanids as indicators of pollution in African continental wetlands was previously proposed. The present study aimed at understanding experimentally how monitors absorb and accumulate pollutants and how they are affected. The relevance of non-destructive sampling was also evaluated. Savannah monitors (Varanus exanthematicus) were orally exposed during 6 months to a mixture of lead, 4,4′-dichlorodiphenyltrichloroethane (4,4′-DDT) and chlorpyrifos-ethyl (CPF) or to the vehicle only. Proportionally to their mass, exposed monitors received the same dose: 20 then 10 mg lead?kg^?1, 2 then 0.5 mg CPF?kg^?1 and 4 mg 4,4′-DDT?kg^?1. Individuals surviving contamination were euthanized after 4 or 6 months of experiment. Tissues were analysed for lead by atomic absorption spectrophotometry and for DDT and CPF by gas chromatography. Exposed monitors absorbed all three pollutants but only lead (essentially in bone, tail tips and phalanxes) and 4,4′-DDT plus its main metabolites (essentially in fat and liver) accumulated. CPF killed ten individuals. Clear correlations occurred between the total quantity of lead or 4,4′-DDT administered and concentrations in tissues. Tail tips and skin samples are recommended non-destructive indicators for lead and organochlorine pesticides contamination, respectively. This work confirms that monitors can be used as relevant indicators of environmental pollution by lead and organochlorine pesticides. Although varanids withstand heavy lead and DDT contamination, our results suggest that CPF can be lethal at very low doses to the herpetofauna and emphasize the importance of considering all taxa in impact assessment studies, including reptiles.