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.     

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.     

Precipitation of liquid swine manure phosphates using magnesium smelting by-products

Swine manure contains considerable amounts of total (P) and soluble phosphorus (PO(4)-P) which may increase the soil P content when applied in excess to crop requirements and, consequently, risk water eutrophication. The feasibility of using magnesium (Mg) from the by-product of electrolysis and foundries (BPEF) for the removal of P from liquid swine manure was studied by adding up to 3 g of Mg as BPEF per liter of nursery (NU) and grower-finisher (GF) swine manure in 25-L plastic buckets. Changes in P and other elements were monitored for up to 360 h. Small amounts of Mg as BPEF (0.5 and 1.0 g Mg L(-1) manure) reduced the total P concentration of the liquid fraction by 70 to 95% of both manure types with respect to the control treatment of mixed raw manure. A settling period of 8 h or more was necessary to significantly reduce the liquid fraction's total P concentration for both manure types. Reduction of PO(4)-P varied from 96 to 100% in the liquid fractions for both manure types, which along with natural settling, explains most of the total P reduction in that fraction. The addition of BPEF did not influence the N content of manure. The low P liquid fraction can be safely applied to saturated P soils whereas the high P solid fraction offers the opportunity of transporting manure to agricultural soils deficient in P. Since N is conserved, both liquid and solid fractions could be valuable fertilizer manure by-products.     

Evaluating the Suitability of Management Strategies of Pure Norway Spruce Forests in the Black Forest Area of Southwest Germany for Adaptation to or Mitigation of Climate Change

The study deals with the problem of evaluating management strategies for pure stands of Norway spruce (Picea abies Karst) to balance adaptation to and mitigation of climate change, taking into account multiple objectives of a forest owner. A simulation and optimization approach was used to evaluate the management of a 1000 ha model Age-Class forest, representing the age-class distribution of an area of 66,000 ha of pure Norway spruce forests in the Black Forest region of Southwest Germany. Eight silvicultural scenarios comprising five forest conversion schemes which were interpreted as “adaptation” strategies which aims at increasing the proportion of Beech, that is expected to better cope with climate change than the existing Norway spruce, and three conventional strategies including a “Do-nothing” alternative classified as “mitigation”, trying to keep rather higher levels of growing stock of spruce, were simulated using the empirical growth simulator BWINPro-S. A linear programming approach was adapted to simultaneously maximize the net present values of carbon sequestration and timber production subject to the two constraints of wood even flow and partial protection of the oldest (nature protection). The optimized plan, with the global utility of 11,687 €/ha in forty years, allocated a combination of silvicultural scenarios to the entire forest area. Overall, strategies classified as “mitigation” were favored, while strategies falling into the “adaptation”-category were limited to the youngest age-classes in the optimal solution. Carbon sequestration of the “Do-nothing” alternative was between 1.72 and 1.85 million tons higher than the other alternatives for the entire forest area while the differences between the adaptation and mitigation approaches were approximately 133,000 tons. Sensitivity analysis showed that a carbon price of 21 €/t is the threshold at which carbon sequestration is promoted, while an interest rate of above 2% would decrease the amount of carbon.     

Plant Bioavailability of “natural” and “model” Humic acid‐bound [14c] Atrazine residues

The release of bound [14C] atrazine residues and their uptake by maize plants was investigated.

“Natural”; humic acids, extracted from a brown soil, and “model”; humic acids, prepared from catechol, both containing bound [14C] atrazine residues were incubated with plants in soil. After 21 days, the maize plants contained 0.7% (plants grown in soil mixed with “natural”; humic acids) to 1.7% (plants grown in soil mixed with “model”; humic acids) of the radioactivity originally introduced.

The roots contained 55 to 70% of the [14C] residues whereas the remainder was present in the shoots. A significant amount of the total [14C] residues (29 to 53%) became again bound in plant tissues, whereas the, majority of extractable [14C] residues was present in the form of conjugates.

The behaviour of “model”; humic acid‐bound residues was comparable to that of “natural”; humic acid‐bound residues or soil‐bound residues.     

Nitrogen cycling in a hypothetical scenario of generalised organic agriculture in the Seine,Somme and Scheldt watersheds

Nitrogen contamination of ground and surface water in the Seine, Somme and Scheldt watersheds, as well as in the receiving coastal marine zones, results in severe ecological problems. Previous modelling results showed that the implementation of classical management measures involving improvement of wastewater purification and “good agricultural practices” are not sufficient to obviate these problems. A more radical scenario was therefore established, consisting of a generalised shift to organic agriculture of all agricultural areas in the three basins, with the additional constraints that livestock is fed only on local fodder production. This scenario involves an increased livestock density in the Seine and Somme and a decrease in livestock in the Scheldt basin. It leads to a significant reduction of agricultural production that finally brings the three basins closer to autotrophy/heterotrophy equilibrium. Nitrate concentrations in most of the drainage network would drop below the threshold of 2.25 mgN/l in the most optimistic hypothesis. The excess of nitrogen over silica (with respect to the requirements of marine diatoms) delivered into the coastal zones would be decreased by a factor from 2 to 5, thus strongly reducing, but not entirely eliminating the potential for marine eutrophication.     

Suspended particulate matter determines physical speciation of Fe,Mn, and trace metals in surface waters of Loire watershed

This study investigates the spatiotemporal variability of major and trace elements, dissolved organic carbon (DOC), total dissolved solids (TDS), and suspended particulate matter (SPM) in surface waters of several hydrosystems of the Loire River watershed in France. In particular, this study aims to delineate the impact of the abovementioned water physicochemical parameters on natural iron and manganese physical speciation (homoaggregation/heteroaggregation) among fine colloidal and dissolved (<?10 nm), colloidal (10–450 nm) and particulate (>?450 nm) phases in Loire River watershed. Results show that the chemistry of the Loire River watershed is controlled by two end members: magmatic and metamorphic petrographic context on the upper part of the watershed; and sedimentary rocks for the middle and low part of the Loire. The percentage of particulate Fe and Mn increased downstream concurrent with the increase in SPM and major cations concentration, whereas the percentage of colloidal Fe and Mn decreased downstream. Transmission electron microscopy analyses of the colloidal and particulate fractions (from the non-filtered water sample) revealed that heteroaggregation of Fe and Mn rich natural nanoparticles and natural organic matter to the particulate phase is the dominant mechanism. The heteroaggregation controls the partitioning of Fe and Mn in the different fractions, potentially due to the increase in the ionic strength, and divalent cations concentration downstream, and SPM concentration. These findings imply that SPM concentration plays an important role in controlling the fate and behavior of Fe and Mn in various sized fractions.

Physical speciation by heteroaggregation of (Fe-Mn) compounds: high [SPM]?→?[Fe-Mn] particulate faction; low {SPM]?→?[Fe-Mn] colloid-dissolved fraction.

     

Water and soil contaminated by arsenic: the use of microorganisms and plants in bioremediation

Environmental Science and Pollution Research - Owing to their roles in the arsenic (As)&nbsp;biogeochemical cycle, microorganisms and plants offer significant potential for developing...     

Dissolved organic matter from treated effluent of a major wastewater treatment plant: characterization and influence on copper toxicity

A combination of reverse osmosis (RO) concentration and DAX-8/XAD-4 resin adsorption techniques is used to isolate the various constituents of urban dissolved organic matter (DOM) from inorganic salts. Three fractions: hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) accounting respectively for 35%, 20% and 45% of extracted carbon, are isolated from effluents of a major French wastewater treatment plant. This atypical DOC distribution, in comparison with natural water where the HPO fraction dominates, shows the significance of HPI fraction which often gets neglected because of extraction difficulties. A number of analytical techniques (elemental, spectroscopic: UV, FTIR) allow highlighting the weak aromaticity of wastewater effluent DOM (EfOM) due to fewer degradation and condensation processes and the strong presence of proteinaceous structures indicative of intense microbial activity. Copper toxicity in the presence of DOM is estimated using an acute toxicity test on Daphnia Magna (Strauss). Results reveal the similar protective role of each EfOM fraction compared to reference Suwannee river fulvic acid despite lower EfOM aromaticity (i.e. specific UV absorbance). The environmental implications of these results are discussed with respect to the development of site-specific water quality criteria.