Synthesis of polychlorinated biphenyls (PCBs) using the Suzuki-coupling

An improved synthesis of polychlorinated biphenyls (PCBs) utilizing a palladium-catalyzed cross-coupling reaction (Suzuki-coupling) is described. The coupling of (chlorinated) aryl boronic acids 1-3 with bromochlorobenzenes 4 using the standard conditions of the Suzuki-coupling gave the desired PCB congeners 5-7 in good to excellent yields. The self-coupling product of the aryl boronic acids is the major impurity of this reaction. 3,4,5-trichlorophenyl derivatives such as 10 can be synthesized by coupling of an aryl boronic acid with the corresponding bromochloroaniline 8. The approach offers the advantage of high selectivity and good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.     

Genotoxic damage in free-living Algerian mouse (Mus spretus) after the Coto Doñana ecological disaster

The Do?ana National Park (Spain), one of the most important wildlife sites in the West of Europe, was affected (25 April 1998) by the spill of acidic waste rich in toxic metals (mainly zinc, lead, copper, etc.), arsenic and aromatic amines from the Aznalcollar mine accident. Micronuclei test with May Grunwald-Giemsa and with CREST-antikinetocore staining using DAPI as counter-staining were performed on peripheral blood erythrocytes from Algerian mice to evaluate genotoxic damage. Animals were collected in four locations each differently affected by the disaster. Higher frequencies of micronuclei and CREST-positive micronuclei were observed in the sites, which were reached by toxic sludge and contaminated water in comparison with those located within the park. The results obtained applying the two methods indicate that DAPI staining is more sensitive in detecting micronuclei. Genotoxic biomonitoring should be further carried out in the area to control the mutagenetic level in natural populations.     

Migration of colloids in discretely fractured porous media: effect of colloidal matrix diffusion

Numerical simulations of colloid transport in discretely fractured porous media were performed to investigate the importance of matrix diffusion of colloids as well as the filtration and remobilization of colloidal particles in both the fractures and porous matrix. To achieve this objective a finite element numerical code entitled COLDIFF was developed. The processes that COLDIFF takes into account include advective-dispersive transport of colloids, filtration and remobilization of colloidal particles in both fractures and porous matrix, and diffusive interactions of colloids between the fractures and porous matrix. Three sets of simulations were conducted to examine the importance of parameters and processes controlling colloid migration. First, a sensitivity analysis was performed using a porous block containing a single fracture to determine the relative importance of various phenomenological coefficients on colloid transport. The primary result of the analysis showed that the porosity of the matrix and the process of colloid filtration in fractures play important roles in controlling colloid migration. Second, simulations were performed to replicate and examine the results of a laboratory column study using a fractured shale saprolite. Results of this analysis showed that the filtration of colloidal particles in the porous matrix can greatly affect the tailing of colloid concentrations after the colloid source was removed. Finally, field-scale simulations were performed to examine the effect of matrix porosity, fracture filtration and fracture remobilization on long-term colloid concentration and migration distance. The field scale simulations indicated that matrix diffusion and fracture filtration can significantly reduce colloid migration distance. Results of all three analyses indicated that in environments where porosity is relatively high and colloidal particles are small enough to diffuse out of fractures, the characteristics of the porous matrix that affect colloid transport become more important than those of the fracture network. Because the properties of the fracture network tend to have greater uncertainty due to difficulties in their measurement relative to those of the porous matrix, prediction uncertainties associated with colloid transport in discretely fractured porous media may be reduced.     

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia,Spain

The construction in Constantí (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996–1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ng I-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ng I-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg (d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ng I-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg, respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.     

Methodology for estimating soil carbon for the forest carbon budget model of the United States, 2001

The largest carbon (C) pool in United States forests is the soil C pool. We present methodology and soil C pool estimates used in the FORCARB model, which estimates and projects forest carbon budgets for the United States. The methodology balances knowledge, uncertainties, and ease of use. The estimates are calculated using the USDA Natural Resources Conservation Service STATSGO database, with soil dynamics following assumptions based on results of site-specific studies, and area estimates from the USDA Forest Service. Forest Inventory and Analysis data and national-level land cover data sets. Harvesting is assumed to have no effect on soil C. Land use change and forest type transitions affect soil C. We apply the methodology to the southeastern region of the United States as a case study.     

Transfer of the fungicide vinclozolin from treated to untreated plants via volatilization

Head lettuce plantlets (Lactuca sativa L. var. capitata) were potted, treated with vinclozolin at the six-leaf stage according to application standards and allowed to dry for 24 h. The potted plantlets were then placed in either growth chambers with controlled temperature (20 and 25 degrees C, respectively) or in a greenhouse (approximately 12 degrees C), together with untreated spinach (Spinacia oleracea L.) and standardized grass cultures (Lolium multiflorum Lam. ssp.) While the treated lettuce pots remained in the respective growing compartments until the end of the experiments, spinach and grass were exposed to the compartment air for 24 h and their shoot material was analyzed for vinclozolin by GC-ECD and GC-high resolution mass spectrometry. Exposure and analysis of untreated spinach and grass were carried out at two- or three-day intervals during the course of the experiments. Also, air samples were taken from the compartments at intervals and analyzed for vinclozolin. Maximum vinclozolin concentration in the growth chamber air was about 330 ng m(-3) while vinclozolin contamination of the untreated plants ranged from 50 to 200 microg kg(-1) FW (fresh weight). In the greenhouse atmospheric vinclozolin concentration reached approximately 15 ngm(-3) and maximum contamination of spinach and grass were 30-40 microg kg(-1) FW. Our data clearly show that unintended contamination of plants growing in the vicinity of vinclozolin-treated plants can occur even if the fungicide layer is completely dry. Implications for safety testing and food plants are discussed.     

Transfer and effects of cadmium in an experimental food chain involving the snail Helix aspersa and the predatory carabid beetle Chrysocarabus splendens

The transfer and the toxic effects of Cd were studied in an experimental food chain involving the snail Helix aspersa as prey organism and one of its natural predators, the carabid beetle Chrysocarabus splendens. Juvenile snails were fed plant-based food enriched with 0, 10, 50 and 100 microg g(-1) of Cd, then were offered as prey to beetle larvae from egg hatching to pupation stage. Cd concentrations in snail tissues increased with increasing Cd concentration in food and with duration of exposure. Bioaccumulation factors ranged from 1.87 to 3.39, showing that H. aspersa snails, even in their early life stages, belong to macroconcentrator species for Cd. No significant reduction of snail consumption by beetles was found in exposed groups. Cd concentrations in beetle larvae remained very low (lower than 1 microg g(-1) for all groups), demonstrating a very effective regulation capacity in beetle larvae. However, Cd concentrations in highest exposed groups were higher than those found in control groups. Cd contents in adult beetles were lower than in larvae, showing a loss of Cd during metamorphosis. Despite the low Cd concentrations found in beetles, their exposure to Cd contaminated snails led to 31% of mortality, which occurred only during pupation and for the highest exposure level. No clear sublethal effects were found. These results showed that snails inhabiting heavily polluted areas may represent a risk of secondary poisoning for predatory invertebrates and provided quantitative data on the transfer of Cd between two compartments of a terrestrial food chain.     

Using polymer mats to biodegrade atrazine in groundwater: laboratory column experiments

Large-scale column experiments were undertaken to evaluate the potential of in situ polymer mats to deliver oxygen into groundwater to induce biodegradation of the pesticides atrazine, terbutryn and fenamiphos contaminating groundwater in Perth, Western Australia. The polymer mats, composed of woven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2-m-long flow-through soil columns. The polymer mats proved efficient in delivering dissolved oxygen to anaerobic groundwater. Dissolved oxygen concentrations increased from <0.2 mg l(-1) to approximately 4 mg l(-1). Degradation rates of atrazine in oxygenated groundwater were relatively high with a zero-order rate of 240-380 microg l(-1) or a first-order half-life of 0.35 days. Amendment with an additional carbon source showed no significant improvement in biodegradation rates, suggesting that organic carbon was not limiting biodegradation. Atrazine degradation rates estimated in the column experiments were similar to rates determined in laboratory culture experiments, using pure cultures of atrazine-mineralising bacteria. No significant degradation of terbutryn or fenamiphos was observed under the experimental conditions within the time frames of the study. Results from these experiments indicate that remediation of atrazine in a contaminated aquifer may be achievable by delivery of oxygen using an in situ polymer mat system.     

Spatial characteristics of fine particulate matter: identifying representative monitoring locations in Seattle, Washington

This study investigates how PM2.5 varies spatially and how these spatial characteristics can be used to identify potential monitoring sites that are most representative of the overall ambient exposures to PM2.5 among susceptible populations in the Seattle, WA, area. Data collected at outdoor sites at the homes of participants of a large exposure assessment study were used in this study. Harvard impactors (HIs) were used at 40 outdoor sites throughout the Seattle metropolitan area. Up to six sites at a time were monitored for 10 consecutive 24-hr average periods. A fixed-effect analysis of variance (ANOVA) model that included date and location effects was used to analyze the spatial variability of outdoor PM2.5 concentrations. Both date and location effects were shown to be highly significant, explaining 92% of the variability in outdoor PM2.5 measurements. The day-to-day variability was 10 times higher than the spatial variability between sites. The site mean square was more than twice the error mean square, showing that differences between sites, while modest, are potentially an important contribution to measurement error. Variances of the model residuals and site effects were examined against spatial characteristics of the monitoring sites. The spatial characteristics included elevation, distance from arterials, and distance from major PM2.5 point sources. Results showed that the most representative PM2.5 sites were located at elevations of 80-120 m above sea level, and at distances of 100-300 m from the nearest arterial road. Location relative to industrial PM2.5 sources is not a significant predictor of residential outdoor PM2.5 measurements. Additionally, for sites to be representative of the average population exposures to PM2.5 among those highly susceptible to the health effects of PM2.5, areas of high elderly population density were considered. These representative spatial characteristics were used as multiple, overlapping criteria in a Geographic Information System (GIS) analysis to determine where the most representative sites are located.     

Toxicity of methyl tert-butyl ether to marine organisms: ambient water quality criteria calculation

In response to increasing concerns over the detection of methyl tert-butyl ether (MTBE) in groundwater and surface water and its potential effects in aquatic ecosystems, industry and the United States Environmental Protection Agency (USEPA) began to collaborate in 1997 to develop aquatic toxicity databases sufficient to derive ambient water quality criteria for MTBE consistent with USEPA requirements. Acute toxicity data for seven marine species, chronic toxicity data for an invertebrate, and plant toxicity data were developed to complete the saltwater database. The species tested were Cyprinodon variegatus, Gasterosteus aculeatus, Callinectes sapidus, Mytilus galloprovincialis, Palaemonetes pugio, Rhepoxynius abronius, Americamysis bahia, and Skeletonema costatum. The toxicity tests were conducted in accordance with USEPA and American Society for Testing and Materials testing procedures and Good Laboratory Practice guidelines. Data developed from this study were consistent with existing data and showed that MTBE has low acute and chronic toxicity to the marine species tested. Based upon measured MTBE concentrations, acute effects were found to range from 166 mg MTBE/l for the grass shrimp to 1950 mg MTBE/l for marine mussel. The no-observed effect concentration for the reproduction and growth of mysids was 26 mg MTBE/l during the life cycle test. The toxicity of MTBE to saltwater organisms is comparable to its toxicity to the freshwater species tested. Reported MTBE concentrations in coastal waters are several orders of magnitude lower than concentrations observed to cause effects in marine organisms.