Metal binding properties of extracellular polymeric substances extracted from anaerobic granular sludges

Extracellular polymeric substances (EPS) were extracted from four anaerobic granular sludges with different procedures to study their involvement in biosorption of metallic elements. EPS extracts are composed of closely associated organic and mineral fractions. The EPS macromolecules (proteins, polysaccharides, humic-like substances, nucleic, and uronic acids) have functional groups potentially available for the binding of metallic elements. The acidic constants of these ionizable groups are: pK _a1 (4–5) corresponding to the carboxyl groups; pK _a2 (6–7) corresponding to the phosphoric groups; pK _a3 (8–10) and pK _a4 (≈10) corresponding to the phenolic, hydroxyl, and amino groups. The polarographic study confirms the higher affinity of the EPS to bind to lead than to cadmium. Moreover, the binding of these metallic compounds with the EPS is a mix of several sorption mechanisms including surface complexation, ion exchange, and flocculation. Inorganic elements were found as ions linked to organic molecules or as solid particles. The mineral fraction affects the binding properties of the EPS, as the presence of salts decreases the EPS binding ability. Calcite and apatite particles observed on SEM images of EPS extracts can also sorb metallic elements through ion exchange or surface complexation.     

Organochlorinated pesticides, PCBs, dioxins, and PBDEs in grey mullets (Liza ramada) and allis shads (Alosa alosa) from the Vilaine estuary (France)

This study aimed to compare the contamination levels of various organohalogenated compounds in two migratory fish species in the Vilaine River in western France. Organochlorinated pesticides, polychlorinated biphenyls (PCBs), dioxins (polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/Fs)), and polybrominated diphenyl ethers (PBDEs) were analyzed in two diadromous species from the Vilaine estuary, the grey mullet (Liza ramada)—an amphihaline species, and the allis shad (Alosa alosa)—an anadromous species. Fish were collected in spring 2004 and spring 2005, upstream and downstream of the Arzal Dam. PCB contamination varied from 27 to 200 ng?g^?1 dry weight (d.w.). PCDDs/Fs, expressed in toxicity equivalent quantity (TEQ) varied from 0.4 to 2.8 pg?g^?1 d.w. Dioxins and dioxin-like PCBs expressed in total TEQ varied from 1.4 to 18.8 pg?g^?1 d.w. PBDE47 was present at around 2–10 ng?g^?1 d.w. and concentrations of the insecticide dichlorodiphenyltrichloroethane breakdown product p,p′-dichlorodiphenylchloroethylene varied from 1 to 14 ng?g^?1 d.w. For both species, specimens collected upstream were more contaminated. The grey mullet specimens were less contaminated than the allis shad when taken downstream of the dam but were more contaminated upstream. The allis shads presented intermediate contaminant concentrations with a less pronounced difference between upstream and downstream specimens. However, it is thought that shads do not feed when they spawn in the upstream parts of rivers, which should modify the contaminant concentrations. However, measurements in upstream shad samples show an unexpected increase of the contamination, which remains unexplained.     

Effect of ethylenediamine-N,N′-disuccinic acid on Fenton and photo-Fenton processes using goethite as an iron source: optimization of parameters for bisphenol A degradation

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (^?OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of ^?OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ ^?? to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.     

Synthesis of the two minor isomers, delta- and epsilon-1,2,5,6,9,10-hexabromocyclododecane, present in commercial hexabromocyclododecane

Hexabromocyclododecane (HBCD) is prepared commercially by bromination of cis,trans,trans-cyclododecatriene (ctt-CDT) and widely used as a flame retardant, particularly in polystyrene foams. Commercial HBCD consists largely of three diastereomers, alpha-, beta-, and gamma-HBCD, the structures of which have been known for many years. Recently, the presence in the mixture of small amounts of two minor diastereomers, delta- and epsilon-HBCD, has been reported. Bearing in mind the manner in which commercial HBCD is generated, it was anticipated that these components are probably formed by bromination of trans,trans,trans-cyclododecatriene (ttt-CDT), a common contaminant in commercial ctt-CDT. Indeed, when a sample of ttt-CDT was brominated it gave two products, the NMR spectra and LC/MS and GC/MS behaviour of which confirmed that they are identical to the minor components, delta- and epsilon-HBCD, present in commercial HBCD.     

Simulation and analysis of solute transport in 2D fracture/pipe networks: the SOLFRAC program

The Time Domain Random Walk (TDRW) method has been recently developed by Delay and Bodin [Delay, F. and Bodin, J., 2001. Time domain random walk method to simulate transport by advection-dispersion and matrix diffusion in fracture networks. Geophys. Res. Lett., 28(21): 4051-4054.] and Bodin et al. [Bodin, J., Porel, G. and Delay, F., 2003c. Simulation of solute transport in discrete fracture networks using the time domain random walk method. Earth Planet. Sci. Lett., 6566: 1-8.] for simulating solute transport in discrete fracture networks. It is assumed that the fracture network can reasonably be represented by a network of interconnected one-dimensional pipes (i.e. flow channels). Processes accounted for are: (1) advection and hydrodynamic dispersion in the channels, (2) matrix diffusion, (3) diffusion into stagnant zones within the fracture planes, (4) sorption reactions onto the fracture walls and in the matrix, (5) linear decay, and (6) mass sharing at fracture intersections. The TDRW method is handy and very efficient in terms of computation costs since it allows for the one-step calculation of the particle residence time in each bond of the network. This method has been programmed in C++, and efforts have been made to develop an efficient and user-friendly software, called SOLFRAC. This program is freely downloadable at the URL (labo.univ-poitiers.fr/hydrasa/intranet/telechargement.htm). It calculates solute transport into 2D pipe networks, while considering different types of injections and different concepts of local dispersion within each flow channel. Post-simulation analyses are also available, such as the mean velocity or the macroscopic dispersion at the scale of the entire network. The program may be used to evaluate how a given transport mechanism influences the macroscopic transport behaviour of fracture networks. It may also be used, as is the case, e.g., with analytical solutions, to interpret laboratory or field tracer test experiments performed in single fractures.     

The ‘Storm of the Century’ (December 1999) and the accidental escape of Siberian sturgeons (Acipenser baerii) into the Gironde estuary (Southwest France)

GOAL, SCOPE AND BACKGROUND: The Gironde estuary is considered as a reference ecosystem with a large fish assemblage (75 species) and the presence of eleven diadromous species. However, geochemical studies and biomonitoring using oysters have shown high metal pollution levels. During the December 1999 hurricane, more than 5,000 young Siberian sturgeons (Acipenser baerii) accidentally escaped from a fish farm into the estuary, where this species had not been present until then. METHODS: In 2002/2003, thirteen sturgeons were collected from the estuary and twelve were obtained from the fish farm, from the same initial batch. Analysis of five metals (cadmium, zinc, copper, lead, mercury) measured in the gills, muscle, liver and kidneys, revealed significantly higher levels of cadmium, lead and mercury in the sturgeon collected from the estuary compared with those from the fish farm. RESULTS AND DISCUSSION: Metal analysis of the stomach contents of fish collected from the estuary and artificial food used in the fish farm indicated that dietary exposure might account for the differences observed. Nevertheless, metal concentrations in sturgeons that had spent about three years in the Gironde estuary may be considered low when compared with other species (mullets, eels) or with data in the literature regarding concentrations able to induce structural and functional perturbations in fish. As the introduced Siberian sturgeons live in the same place and feed on the same prey as the juveniles of the endangered A. sturio, our results indicate in the short-term that this strictly protected species does not appear to be much affected by the polymetallic pollution in the Gironde estuary. Marked differences in the concentrations of three metals (Cd, Pb, Hg) were established in four organs (gills, liver, skeletal muscle, kidneys) of Siberian sturgeons between specimens that had accidentally escaped into the Gironde estuary (France) during the December 1999 hurricane and were collected in March/June 2003 and specimens from the same initial batch at the fish farm. RECOMMENDATIONS AND PERSPECTIVES: Based on these results, a programme will be set up, with sampling campaigns carried out in the estuary every two years, with systematic monitoring of age in order to check the origin of individuals, in conjunction with sampling of sturgeon from the fish farm. This programme will complement other studies on several biological species representative of the main trophic levels in the estuary, especially the plankton component, benthic macroinvertebrates and oysters.     

Preliminary study of ballistic impact on an industrial tank: Projectile velocity decay

Since the events of September 11, 2001, the possibility of an intentional act targeting the chemical process industry has become realistic. It is, therefore, a great concern to be able to predict the immediate consequences of such an act. This study is intended to improve our knowledge about the sequence of events that occurs when a high-speed bullet (>1000 m s⁻¹) penetrates a vessel filled with toxic liquid. We find that, prior to liquid ejection, several well-defined phases occur, including the phenomenon known as the “hydraulic ram.” This paper focuses on projectile–target interactions and explains how the decay of projectile velocity is related to the initial conditions of the target.     

Documentation of the endotoxins present in the ambient air of cotton fiber textile mills in Québec

Cotton workers are recognized as being at risk of developing occupational lung diseases. Some researchers have identified endotoxins as being a potential etiologic agent for some of the respiratory problems. This study wants to document the concentration of endotoxins found in the ambient air of textile mills where cotton fibers are handled and to identify the processing steps where the highest endotoxins concentrations in the air were found and the one where the relative limit values (RLVs) are exceeded. The 4 mills studied process cotton fibers. All the air samples were analyzed using the chromogenic Limulus Amoebocytes lysate LAL method using a kinetic detection principle based on the IRSST's standard method. In this study, a large variability in the concentrations of endotoxins in the air was observed, depending on the mill, the processing step, and the time. Despite these variations, some processes can be identified as being major generators of endotoxins in the ambient air of the mills. The highest concentrations were measured in the weaving and drawing processes and reached 10,000 EU m(-3) of air. The opening, cleaning, carding, spinning and drawing processes are the other major endotoxins generating processes with concentrations from 24 to 8,700 EU m(-3) of air. The endotoxins concentrations exceeded the RLVs for 55% of the workstations in this project. This study demonstrated that endotoxins levels in the cotton industry are high and appropriate control measures are needed.     

Soil nitrous oxide emissions following band-incorporation of fertilizer nitrogen and swine manure

Treatment of liquid swine manure (LSM) offers opportunities to improve manure nutrient management. However, N2O fluxes and cumulative emissions resulting from application of treated LSM are not well documented. Nitrous oxide emissions were monitored following band-incorporation of 100 kg N ha(-1) of either mineral fertilizer, raw LSM, or four pretreated LSMs (anaerobic digestion; anaerobic digestion + flocculation: filtration; decantation) at the four-leaf stage of corn (Zea mays L.). In a clay soil, a larger proportion of applied N was lost as N2O with the mineral fertilizer (average of 6.6%) than with LSMs (3.1-5.0%), whereas in a loam soil, the proportion of applied N lost as N2O was lower with the mineral fertilizer (average of 0.4%) than with LSMs (1.2-2.4%). Emissions were related to soil NO3 intensity in the clay soil, whereas they were related to water-extractable organic C in the loam soil. This suggests that N2O production was N limited in the clay soil and C limited in the loam soil, and would explain the interaction found between N sources and soil type. The large N2O emission coefficients measured in many treatments, and the contradicting responses among N sources depending on soil type, indicate that (i) the Intergovernmental Panel on Climate Change (IPCC) default value (1%) may seriously underestimate N2O emissions from fine-textured soils where fertilizer N and manure are band-incorporated, and (ii) site-specific factors, such as drainage conditions and soil properties (e.g., texture, organic matter content), have a differential influence on emissions depending on N source.