Oxidative properties of ambient PM2.5 and elemental composition: Heterogeneous associations in 19 European cities

We assessed the extent to which constituents of PM_2.5 (transition metals, sodium, chloride) contribute to the ability to generate hydroxyl radicals (OH) in vitro in PM_2.5 sampled at 20 locations in 19 European centres participating in the European Community Respiratory Health Survey. PM_2.5 samples (n = 716) were collected on filters over one year and the oxidative activity of particle suspensions obtained from these filters was then assessed by measuring their ability to generate OH in the presence of hydrogen peroxide. Associations between OH formation and the studied PM constituents were heterogeneous. The total explained variance ranged from 85% in Norwich to only 6% in Albacete. Among the 20 centres, 15 showed positive correlations between one or more of the measured transition metals (copper, iron, manganese, lead, vanadium and titanium) and OH formation. In 9 of 20 centres OH formation was negatively associated with chloride, and in 3 centres with sodium. Across 19 European cities, elements which explained the largest variations in OH formation were chloride, iron and sodium.     

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.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

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.     

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.     

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.     

Synthesis of polyhydroxyalkanoates in municipal wastewater treatment.

Biologically derived polyesters known as polyhydroxyalkanoates (PHAs) represent a potentially "sustainable" replacement to fossil-fuel-based thermoplastics. However, current commercial practices that produce PHA with pure microbial cultures grown on renewable, but refined, feedstocks (i.e., glucose) under sterile conditions do not represent a sustainable commodity. Here, we report on PHA production with a mixed microbial consortium indigenous to an activated sludge process on carbon present in municipal wastewaters. Reactors operated under anaerobic/aerobic and aerobic-only mode and fed primary solids fermenter liquor maintained a mixed microbial consortium capable of synthesizing PHA at 10 to 25% (w/w), while reducing soluble COD by approximately 62 to 71%. More critically, an aerobic batch reactor seeded from the anaerobic/aerobic reactor and fed fermenter liquor achieved approximately 53% PHA (w/w). Results presented suggest that environmentally benign production of biodegradable polymers is feasible. We further used PHA-rich biomass to produce a natural fiber-reinforced thermoplastic composite that can be used to offset advanced wastewater treatment costs.     

Assessment of oxidative and UV-C treatments for inactivating bacterial biofilms from groundwater wells

Microorganisms are ubiquitous in natural environments and in water supply infrastructure including groundwater wells. Sessile-state microorganisms may build up on well surfaces as biofilms and, if excessive, cause biofouling that reduces well productivity and water quality. Conditions can be improved using biocides and other traditional well rehabilitation measures; however, biofilm regrowth is inevitable given the continuous introduction of microorganisms from the surrounding environment. Alternative and less invasive well maintenance approaches are desirable for reducing biofilm densities while also minimizing harmful disinfection-by-products. The primary objective of this research was to evaluate effectiveness of alternative treatments for inactivating microorganisms comprising biofilms. A novel approach was designed for in situ growth of biofilms on steel coupons suspended from ‘chandeliers’. After more than 100 days of in situ growth, biofilms were harvested, sampled, and baseline biofilm densities quantified through cultivation. Ultraviolet-C (UV-C) and oxidative treatments including hydrogen peroxide (H₂O₂), ozone (O₃) and mixed oxidants were then applied to the biofilms in laboratory-scale treatments. Microbial inactivation was assessed by comparing treated versus baseline biofilm densities. H₂O₂ was the most effective treatment, and decreased density below baseline by as much as 3.1 orders of magnitude. Mixed oxidants were effective for the well having a lower density biofilm, decreasing density below baseline by as much as 1.4 orders of magnitude. Disparity in the response to treatment was apparent in the wells despite their spatial proximity and common aquifer source, which suggests that microbiological communities are more heterogeneous than the natural media from which they originate.     

Generalists and specialists along a latitudinal transect: patterns of thermal adaptation in six species of damselflies

Tropical organisms colonizing temperate environments face reduced average temperatures and dramatic thermal fluctuations. Theoretical models postulate that thermal specialization should be favored either when little environmental variation is experienced within generations or when among-generation variation is small relative to within-generation variation. To test these predictions, we studied six temperate species of damselflies differing in latitudinal distribution. We developed a computer model simulating how organisms experience environmental variation (accounting for diapause and voltinism) and performed a laboratory experiment assaying thermal sensitivities of growth rates. The computer model showed opposing latitudinal trends in among- and within-generation thermal variability: within-generation thermal variability decreased toward higher latitudes, whereas relative levels of among-generation thermal variability peaked at midlatitudes (where a shift in voltinism occurred). The growth experiment showed that low-latitude species were more thermally generalized than mid- and high-latitude species, supporting the prediction that generalists are favored under high levels of within-generation variation. Northern species had steeper, near-exponential reaction norms suggestive of thermal specialization. However, they had strikingly high thermal optima and grew very slowly over most of the thermal range they are expected to experience in the field. This observation is at present difficult to explain. These results highlight the importance of considering interactions between life history and environmental variation when deriving expectations of thermal adaptation.