Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

PCDD/Fs, dioxin-like PCBs and marker PCBs in eggs of peregrine falcons from Germany

Thirty one egg samples of peregrine falcons were collected in different regions of Germany (South-West, North and East) and analysed for PCDD/Fs, PCBs and marker PCBs. Altogether, 37 PCB congeners were determined, allowing a more detailed discussion of different aspects of the relative importance of these individual congeners. For comparison with dioxin data from other studies, differences between toxic equivalency factors (TEF) have to be taken into consideration. The results of this study are discussed on the basis of WHO-TEFs for birds published in 1998. All samples showed high levels of PCDD/Fs (median of all samples: 368 pg WHO-PCDD/F-TEQ/g fat; range 137-1453) and even higher levels of PCBs (median 967 pg WHO-PCB-TEQ/g fat; range 243-7482). The upper range of these levels reach concentrations found at the beginning of the Belgian dioxin crisis when a significant reduction in hens' egg hatchability was observed. The relative contribution of PCBs to the total TEQ is on average 71% (range 55-92%) with a tendency to higher values in South-West Germany compared to different sites in East Germany or one site in northern Germany. Within a region, a wide range of contamination can be found. Even in the same cities (Stuttgart and Ludwigshafen), results derived from eggs collected in the same year (2003) varied by factors 5-10. These findings show the high degree of variation occurring even within the same kind of biological matrix. Therefore, to allow for comparison of regions or time trends, a considerable number of samples has to be analysed.     

Age and seasonal variability of polybrominated diphenyl ethers in free-ranging East Greenland polar bears (Ursus maritimus)

Polybrominated diphenyl ethers (PBDEs) were analysed in adipose tissue from 92 East Greenland polar bears (Ursus maritimus) sampled during 1999-2001. Mean SigmaPBDE concentrations were 70 ng/g lipid weight (lw) (range: 22-192 ng/g lw) and showed no relationship with age or sex. Of the 32 analysed PBDE congeners; BDE47, BDE153, BDE99 and BDE100 dominated, and comprised 99.6% of the SigmaPBDE concentration. The SigmaPBDE concentration had a highly significant correlation with SigmaPCB, SigmaCHL, dieldrin, HCB and SigmaHCH concentrations. We found a seasonal pattern of median SigmaPBDE concentration with 1.2 to 1.8 times higher concentrations in March to July than the rest of the year. The seasonal variation also provides a clue to the seasonal exposure, bio-availability, toxic exposure and degradation. We suggest that future geographical PBDE data comparisons may not need corrections for sex or age, but such data sets should be corrected for seasonal variability, using the presented correctional trigonometric regression.     

Minimax regret optimization analysis for a regional solid waste management system

Solid waste management (SWM) facilities are crucial for environmental management and public health in urban regions. Due to the waste management hierarchy, one of the greatest challenges that organizations face today is to figure out how to diversify the treatment options, increase the reliability of infrastructure systems, and leverage the redistribution of waste streams among incineration, compost, recycling, and other facilities to their competitive advantage region wide. Systems analysis plays an important role for regionalization assessment of integrated SWM systems, leading to provide decision makers with break-through insights and risk-informed strategies. This paper aims to apply a minimax regret optimization analysis for improving SWM strategies in the Lower Rio Grande Valley (LRGV), an economically fast growing region in the US. Based on different environmental, economic, legal, and social conditions, event-based simulation in the first stage links estimated waste streams in major cities in LRGV with possible solid waste management alternatives. The optimization analysis in the second stage emphasizes the trade-offs and associated regret evaluation with respect to predetermined scenarios. Such optimization analyses with multiple criteria have featured notable successes, either by public or private efforts, in diverting recyclables, green waste, yard waste, and biosolids from the municipal solid waste streams to upcoming waste-to-energy, composting, and recycling facilities. Model outputs may link prescribed regret scenarios in decision making with various scales of regionalization policies. The insights drawn from the system-oriented, forward-looking, and preventative study can eventually help decision-makers and stakeholders gain a scientific understanding of the consequences of short-term and long-term decisions relating to sustainable SWM in the fast-growing US-Mexico borderland.     

Integrated catalytic wet air oxidation and aerobic biological treatment in a municipal WWTP of a high-strength o-cresol wastewater

This study examines the feasibility of coupling a Catalytic Wet Air Oxidation (CWAO), with activated carbon (AC) as catalyst, and an aerobic biological treatment to treat a high-strength o-cresol wastewater. Two goals are pursued: (a) To determine the effect of the main AC/CWAO intermediates on the activated sludge of a municipal WasteWater Treatment Plant (WWTP) and (b) To demonstrate the feasibility of coupling the AC/CWAO effluent as a part of the influent of a municipal WWTP. In a previous study, a high-strength o-cresol wastewater was treated by AC/CWAO aiming to establish the distribution of intermediates and the biodegradability enhancement. In this work, the biodegradability, toxicity and inhibition of the most relevant intermediates detected in the AC/CWAO effluent were determined by respirometry. Also, the results of a pilot scale municipal WWTP study for an integrated AC/CWAO-aerobic biological treatment of this effluent are presented. The biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) of main AC/CWAO intermediates allowed the classification of the intermediates into readily biodegradable, inert or toxic/inhibitory compounds. This detailed study, allowed to understand the biodegradability enhancement exhibited by an AC/CWAO effluent and to achieve a successful strategy for coupling the AC/CWAO step with an aerobic biological treatment for a high-strength o-cresol wastewater. Using 30%, as COD, of AC/CWAO effluent in the inlet to the pilot scale WWTP, the integrated AC/CWAO-biological treatment achieved a 98% of total COD removal and, particularly, a 91% of AC/CWAO effluent COD removal without any undesirable effect on the biomass.     

A comparison of two techniques for studying sediment desorption kinetics of hydrophobic pollutants

A comparison of two techniques (gaseous purge and vial desorption) for studying the kinetics of desorption of hydrophobic pollutants from natural sediments was conducted using identical, pre-equilibrated pollutant-sediment suspensions. Desorption profiles for the two techniques [for Lindane, Aldrin, 2,2'-dichlorobiphenyl (2,2'-DCB), 4,4'-dichlorobiphenyl (4,4'-DCB), and 2,2',6,6'-tetrachlorobiphenyl (TCB)] were then compared, based on the distribution of pollutant mass between the labile (fast) and non-labile (slow) desorption phases and the release rate constants for each phase of release. The vial desorption technique shows many practical advantages over the gaseous purge technique, including its more realistic mixing conditions, the use of an independent sample for each data point (as opposed to a calculation of a cumulative mass purged at each time point), the fact that the vials constitute a closed system and are therefore less subject to ambient contamination, and the relatively low demands of time and money for the vial technique. No consistent trends in labile rate constants or in pollutant distribution between the labile and non-labile phase were observed between the two techniques. A comparison of kinetic parameters shows much faster non-labile rate constants for the gaseous purge technique, attributed to the violent, continuous agitation employed, which likely disrupted sediment aggregates and oxidized the natural organic matter associated with the sediment. Non-labile rate constants have implications for the long-term fate of compounds adsorbed to repetitively disturbed sediments. This study suggests that the traditionally less popular vial desorption technique may yield more realistic non-labile desorption rate constants.     

‘A powerful alternative to Williams’ test with application to toxicological dose-response relationships of normally distributed data

The comparison of increasing doses of a treatment to a negative control is frequently part of toxicological studies. For normally distributed data Williams (1971, 1972) introduced a maximum likelihood test under total order restriction. But until now there seems to have been no solution for the arbitrary unbalanced case. According to the idea proposed by Robertson et al. (1988) we will apply in this article the basic concept of Williams on the class of multiple contrast tests for the general unbalanced parametric set-up. Simulation results for size and power and two examples for estimating the minimal toxic dose (MTD) are given.     

Ökotoxikologische und humantoxikologische Risikobewertung PAK-belasteter Böden vor und nach biologischer Behandlung

The goal of the present work is to assess the adverse effects of soil bound polycyclic aromatic hydrocarbons (PAH) which remain in soils after biological remediation. We focus on risk assessment for mammalian species with respect to the oral uptake of contaminated soil particles and compare the results of a biomarker test with those of an ecotoxicological assay, the bioluminescence inhibition test withVibrio fischeri. As a biomarker effect in mammals, we determined the liver microsomal cytochrome P450 enzyme CYP1A1 which is induced by PAH in exposed rats. After biological soil treatment, different amounts of PAH remain in the soil depending on the soil properties and initial pollutant composition. Particularly, higher condensated PAH resists biological treatment due to its hydrophobicity. In addition, high amounts of organic carbon in the soils affect remediation efficiency. In the bioluminescence inhibition test, eluates of all biologically treated soils studied do not reveal any or only low inhibitory effects. In contrast, the oral uptake of biologically treated contaminated soils leads to induction levels for CYP1A1 similar to those in the untreated samples. A good correlation is obtained between CYP1A1 levels and the amount of 5 and 6-ring PAH in the soil samples. The main result is that the remediation efficiency determined by the luminescence test is not reflected by the biomarker test, a finding which indicates the high bioavailability of residual PAH in soils. Consequently, new criteria for human risk assessment can be delineated.     

Environmental degradation by mud in tropical estuaries

In wet tropical countries, the intense rainfall and the lack of effective restrictions on human activities in the river catchment leads to increased rates of soil erosion. This has increased the sediment loads many times over from the natural level. As a result, estuarine and coastal waters are becoming increasingly muddy with associated losses for society in terms of increased flooding and a degradation of the environment, the fisheries and the economic use of these waters. It is suggested that science-based models be used to predict the fate of mud in estuaries and coastal waters when planning development in river catchments, particularly in wet tropical countries. This would help integrate land and water management. Modelling technology is demonstrated by a combination of field and model studies in four turbid tropical estuaries, namely the Fly River in Papua New Guinea, the Mekong River in Vietnam, the Cimanuk River in Indonesia, and Hinchinbrook Channel in Australia. The final model is adapted to local conditions and extensively uses data assimilation especially for open boundary conditions. There can be a feedback between the hydrodynamics and the mud dynamics when the system silts; in wet tropical countries this can occur rapidly, sometimes in only 30 years. Electronic Publication     

Characterization of coffee residues pellets and their performance in a residential combustor

Spent coffee grounds (SCG) and coffee husks (CH) were evaluated as biofuels, after densification, for energy production. CH represent a specific problem for the coffee industry due to a low calorific value, high ash content, and a very low bulk density. Hence, the energetic potential of SCG (95 wt%)/CH (5 wt%) blend and pure SCG (100%) were examined. The blend of SCG and CH was limited to 5 wt% of CH because of the low bulk density of CH. Therefore, physicochemical and energetic characterizations of the produced pellets were performed. Thermogravimetric analyses were performed under nitrogen and air atmospheres to evaluate the CH behavior in the blend. Characterization study shows that both produced pellets could reach the French Agropellets standard (AQI). Thermal degradation showed that the mean reactivity of the SCG/HC pellets was higher than pure SCG. Then, combustion experiments were performed in a domestic combustor, after modification of the boiler power in order to improve its energetic performances. The presence of CH led to a rise of CO, NOx, VOC’s, and particle emissions. Nevertheless, the performances of the biofuels are almost in agreement the NF EN 12809 standard.