Formation of chlorinated hydrocarbons from the reaction of chlorine atoms and activated carbon

The reactions of chlorine atoms and activated carbon have been studied over the temperature range of 200-400 degrees C using an isothermal flow reactor in conjunction with 337 nm laser photolysis of Cl2. These studies have shown that carbon tetrachloride is the major product, with chloroform, methylene chloride, and methyl chloride being formed in progressively decreasing yields. Trace quantities of methane, ethane, and dichloroethylenes were also observed. Mechanisms of carbon fragmentation by successive addition of chlorine atoms are proposed. The formation of small chlorinated hydrocarbons by the direct reaction of chlorine with carbon may be a key link in both the de novo and precursor pathways of formation of PCDD/F.     

Mercury and organochlorine content of Dipper Cinclus cinclus eggs in south-west Ireland: trends during 1990-1999

A sample of 124 deserted/infertile dipper (Cinclus cinclus) eggs was collected in south-west Ireland during six seasons (1990-1994 and 1999) and analysed for mercury and organochlorines. Mercury was detected in three of the 6 years but no trend was observed. DDT occurred above the limit of detection in only two eggs, one each in 1993 and 1994. In contrast, two derivatives of DDT (DDE and TDE) were found much more commonly. DDE occurred in over 87% of eggs, while TDE contamination was less widespread and reached a maximum of 60% in 1993, with none detected in 1991 or 1999. There was no trend in occurrence of DDE or TDE across years. PCB contamination was present consistently over the 10-year period, with little change in the proportion of contaminated eggs collected over time. In all years, the lowest recorded occurrence of total PCBs was 69% expressed on a formulation basis as Arochlor 1254. PCB congeners 138, 153 and 180 dominated. The congener pattern was similar across years with the exception of 1990 when congener 118 dominated. A distinct trend of high values of contaminants was observed in 1990 and 1993. In 1990, PCB 118 was the dominant contaminant, while in 1993, HEOD, DDE, PCB 138 and PCB 153 were primary contributors to the observed result. Other contaminants (HCB, PCB 101, gamma-HCH, PCB 170 and PCB 180) showed little obvious patterns between years and occurred at relatively low levels. No pattern was observed in contaminants when eggs were grouped according to river or altitude. These data provide a baseline for organochlorine contamination levels in Irish freshwater ecosystems against which future trends can be assessed.     

Vanadium uptake by higher plants: Some recent developments

The occurrence of vanadium in the biosphere, and the possible roles this element may play in the metabolism of living organisms, especially higher plants, are discussed. The aqueous chemistry of the element is reviewed, and the chemical properties of the element are related to those of soils and plants. Evidence is present for a biotransformation of vanadium from vanadate (VO ₃ ^– ) to vanadyl (VO²⁺) during uptake by plants, based on tissue analysis and ESR spectra. The significance of this process on the potential impact of vanadium in the biosphere is discussed.     

UNCERTAINTY ANALYSIS OF RUNOFF ESTIMATES FROM A RUNOFF CONTOUR MAP1

ABSTRACT: The U.S. Environmental Protection Agency (EPA) in cooperation with the U.S. Geological Survey (USGS) conducted an analysis to quantify the uncertainty associated with interpolating runoff to specific sites using a runoff contour map. We interpolated runoff to 93 gaged watersheds from a runoff contour map using (1) hand interpolation to the watershed outlet, (2) a computer interpolation to the watershed outlet, and (3) hand interpolation to the watershed centroid. We compared the interpolated values to the actual gaged values and found that there was a bias in the average interpolated value for runoff estimated at basin outlets, with interpolated values being less than the actual. We found no significant difference between the hand interpolation method and the computer interpolation method except that the computer method tended to have higher variability due to factors inherent to the software used. There were no strong spatial correlations or regional patterns in the runoff interpolations, which indicates that there are no regional biases introduced in the development of the contour map. We determined that we could estimate runoff, on the average, within approximately 8.9 cm (3.5 in; 15 percent) of the measured value using the three methods. The results of this work indicate that runoff contour maps can he used in regional studies to estimate runoff to ungaged systems with quantifiable uncertainty.     

Ecotoxicological assessment of diffuse pollution using biomonitoring tool for sustainable land use in Thailand

As a developing country, Thailand has a significant issue with diffuse pollution of the soil ecosystem due to an indiscriminate use of agrichemicals and poorly regulated disposal of a wide variety of hazardous wastes. Practical risk assessment tools based on locally-occurring species are needed to assess the effects of diffuse pollutants on the soil ecosystem in Thailand because reliance on soil criteria developed for overseas conditions may provide inadequate protection. Native soil organisms in Thailand may be more or less sensitive to contaminants compared to overseas test species. This article described a biological indicator approach for ecological risk assessment of diffuse pollution in the soil ecosystem of Thailand from pesticide application with the aim of developing standardized protocols using native species and locally generated data to better evaluate the ecological risks of non-point source soil pollution. It was found that ecotoxicological assessment provided a better understanding of the ecological impacts that diffuse pollution induced on Thai environmental conditions. Thai soil biota species were more sensitive to soil contaminants than similar species overseas. Soil series also had an influence on the ecotoxicology of contaminants to soil biota. Collembolan, Cyphoderus sp., was demonstrated as a useful alternative test species to Folsomia Candida (international test species) for terrestrial ecotoxicological testing of Thai soils. In addition, the soil biota activities such as soil respiration and earthworm avoidance including soil biodiversity and the litter bag decomposition technique are also good tools to assess the effects of diffuse pollution by pesticides on the soil ecosystem of Thailand.     

Strength of evidence for density dependence in abundance time series of 1198 species

Population limitation is a fundamental tenet of ecology, but the relative roles of exogenous and endogenous mechanisms remain unquantified for most species. Here we used multi-model inference (MMI), a form of model averaging, based on information theory (Akaike's Information Criterion) to evaluate the relative strength of evidence for density-dependent and density-independent population dynamical models in long-term abundance time series of 1198 species. We also compared the MMI results to more classic methods for detecting density dependence: Neyman-Pearson hypothesis-testing and best-model selection using the Bayesian Information Criterion or cross-validation. Using MMI on our large database, we show that density dependence is a pervasive feature of population dynamics (median MMI support for density dependence = 74.7-92.2%), and that this holds across widely different taxa. The weight of evidence for density dependence varied among species but increased consistently, with the number of generations monitored. Best-model selection methods yielded similar results to MMI (a density-dependent model was favored in 66.2-93.9% of species time series), while the hypothesis-testing methods detected density dependence less frequently (32.6-49.8%). There were no obvious differences in the prevalence of density dependence across major taxonomic groups under any of the statistical methods used. These results underscore the value of using multiple modes of analysis to quantify the relative empirical support for a set of working hypotheses that encompass a range of realistic population dynamical behaviors.     

Surface-mediated formation of PBDD/Fs from the high-temperature oxidation of 2-bromophenol on a CuO/silica surface

As a model brominated hydrocarbon that may form brominated dioxins, we studied the surface-mediated, oxidative thermal degradation of 2-bromophenol on a supported copper oxide catalyst in a 1 mm i.d., fused silica flow reactor at a constant concentration of 90 ppm over a temperature range from 250 to 550 degrees C. Observed products included: dibenzo-p-dioxin (DD), 1-monobromodibenzo-p-dioxin (1-MBDD), dibromodibenzo-p-dioxin (DBDD), tribromodibenzo-p-dioxin (TrBDD), 4-monobromodibenzofuran (4-MBDF), 2,4,6-tribromophenol, 2,4- and 2,6-dibromophenol, and polybrominated benzenes. The results are compared and contrasted with previous work on surface catalyzed oxidative thermal degradation of 2-chlorophenol as well as our own work with the surface-catalyzed pyrolytic thermal degradation of 2-bromophenol. Typically 20 to 200x higher yields of PBDDs are observed for 2-bromophenol than for the analogous PCDDs for 2-chlorophenol. However the anticipated PBDF, 4,6-DBDF, was not observed and 4-MBDF was observed at very low yields. Surprisingly, the maximum yields of PBDDs were observed at higher temperatures than under pyrolytic conditions. This is attributed to regeneration of the catalytic surface due to the presence of oxygen. Higher yields of polybrominated phenols and polybrominated benzenes were also observed than for the analogous chlorinated phenols and benzenes from the oxidation of 2-chlorophenol. This can be attributed to the ease of bromination over chlorination based on the higher abundance of bromine atoms present for 2-bromophenol than chlorine atoms present for 2-chlorophenol.     

On inferring population trends of mobile waterbirds from aerial transect surveys in variable environments

Environmental and Ecological Statistics - Monitoring waterbird populations in Australia is challenging for reasons of counting logistics, and because population aggregation and dispersion can shift...