A comparison of measured and simulated ozone concentrations in the rural areas of the eastern United States during summer 1995

The recent regulatory actions toward a longer-term (i.e., 8-hr) average ozone standard have brought forth the potential for many rural areas in the eastern United States to be in noncompliance. However, since a majority of these rural areas have generally few sources of anthropogenic emissions, the measured ozone levels primarily reflect the effects of the transport of ozone and its precursor pollutants and natural emissions. While photochemical grid models have been applied to urban areas to develop ozone mitigation measures, these efforts have been limited to high ozone episode events only and do not adequately cover rural regions. In this study, we applied a photochemical modeling system, RAMS/UAM-V, to the eastern United States from June 1-August 31, 1995. The purpose of the study is to examine the predictive ability of the modeling system at rural monitoring stations that are part of the Clean Air Status Trends Network (CASTNet) and the Gaseous Pollutant Monitoring Program (GPMP). The results show that the measured daily 1-hr ozone maxima and the seasonal average of the daily 1-hr ozone maxima are in better agreement with the predictions of the modeling system than those for the daily 8-hr ozone maxima. Also, the response of the modeling system in reproducing the measured range of ozone levels over the diurnal cycle is poor, suggesting the need for improvement in the treatment of the physical and chemical processes of the modeling system during the nighttime and morning hours if it is to be used to address the 8-hr ozone standard.     

Degradation mechanism of azo dye C. I. reactive red 2 by iron powder reduction and photooxidation in aqueous solutions

We have made a comparison of the UV-VIS spectra of three azo dyes, C. I. reactive red 2, orange II and C. I. reactive black 8, in aqueous solutions during treatment with iron powder reduction and photooxidation. From this, we propose their mechanisms for reduction photooxidation. GC/MS analyses of the degradation products of the dye C. I. reactive red 2 demonstrated some important steps producing hydrogenated azo structure, substituted benzene and substituted naphthalene.     

Reconstruction of centuries-old Daphnia communities in a lake recovering from acidification and metal contamination

Paleolimnological and molecular genetic techniques were combined to reconstruct the long-term patterns in Daphnia community composition in Hannah Lake--a lake recovering from industrial acidification, metal contamination and faunal extirpation. Like many zooplankters, Daphnia produce diapausing eggs that can remain viable for decades and even over a century. Yet, the appearance of D. mendotae in Hannah Lake during the last two decades is likely the outcome of dispersal from other nearby lakes, not by colonization from the sediment egg-bank. Our genetic tests using PCR, SSCP and sequencing indicate that D. mendotae diapausing eggs are absent within the sediment record of the previous 250 years and that, prior to metal smelting operations in the region, the community was dominated by D. pulicaria. This species shift following the lake's chemical restoration is consistent with earlier historical changes in lake acidity. Environmental fluctuations may have governed community composition throughout Hannah Lake's more ancient past. Extending this molecular-paleolimnological approach to other lakes should help develop more accurate formulations of the biological recovery process.     

Bioremediation of chlorobenzene-contaminated ground water in an in situ reactor mediated by hydrogen peroxide

New in situ reactive barrier technologies were tested nearby a local aquifer in Bitterfeld, Saxonia-Anhalt, Germany, which is polluted mainly by chlorobenzene (CB), in concentrations up to 450 microM. A reactor filled with original aquifer sediment was designed for the microbiological remediation of the ground water by indigenous bacterial communities. Two remediation variants were examined: (a) the degradation of CB under anoxic conditions in the presence of nitrate; (b) the degradation of CB under mixed electron acceptor conditions (oxygen+nitrate) using hydrogen peroxide as the oxygen-releasing compound. Under anoxic conditions, no definite degradation of CB was observed. Adding hydrogen peroxide (2.94 mM) and nitrate (2 mM) led to the disappearance of CB (ca. 150 microM) in the lower part of the reactor, accompanied by a strong increase of the number of cultivable aerobic CB degrading bacteria in reactor water and sediment samples, indicating that CB was degraded mainly by productive bacterial metabolism. Several aerobic CB degrading bacteria, mostly belonging to the genera Pseudomonas and Rhodococcus, were isolated from reactor water and sediments. In laboratory experiments with reactor water, oxygen was rapidly released by hydrogen peroxide, whereas biotic-induced decomposition reactions of hydrogen peroxide were almost four times faster than abiotic-induced decomposition reactions. A clear chemical degradation of CB mediated by hydrogen peroxide was not observed. CB was also completely degraded in the reactor after reducing the hydrogen peroxide concentration to 880 microM. The CB degradation completely collapsed after reducing the hydrogen peroxide concentration to 440 microM. In the following, the hydrogen peroxide concentrations were increased again (to 880 microM, 2.94 mM, and 880 microM, respectively), but the oxygen demand for CB degradation was higher than observed before, indicating a shift in the bacterial population. During the whole experiment, nitrate was uniformly reduced during the flow path in the reactor.     

Production of reactive oxygen species and 8-hydroxy-2'deoxyguanosine in KB cells co-exposed to benzo[a]pyrene and UV-A radiation

Previous studies have shown that ultraviolet (UV) A light and the polycyclic aromatic hydrocarbon benzo[a]pyrene (BaP) can synergistically enhance the formation of 8-hydroxy-2'deoxyguanosine (8-OHdG) in living cells. It has been postulated that the underlying mechanism is production of reactive oxygen species (ROS) via photosensitization, but direct evidence supporting this hypothesis has been lacking. This study examined intracellular ROS production in living cells co-exposed to UV-A and BaP as well as the relationship between intracellular production of ROS and formation of 8-OHdG. KB cells were exposed to BaP for 24 h, followed by exposure to UV-A (365 nm) or UV-B (312 nm). The levels of intracellular ROS were directly measured by use of the fluorescent probe dihydrorhodamine 123 (DHR-123) in flow cytometry. Levels of 8-OHdG were measured by high performance liquid chromatography coupled with electrochemical detection (HPLC-ECD). The results demonstrated that UV-B itself induced a much greater level of intracellular ROS than did UV-A alone under the same dose of energy (0.10 mW/cm(2), 20 min). The presence of BaP (13.3 microM) substantially increased ROS production in UV-A-treated cells (2.9-fold), but only slightly enhanced ROS production in UV-B-treated cells (1.3-fold). These results show that BaP acts mainly as a photosensitizer of UV-A, but not UV-B. Furthermore, greater intracellular ROS production was proportional to both BaP concentration and UV-A dosage. There was a linear relationship between ROS production and 8-OHdG formation in cells co-exposed to BaP and UV-A. Results of this study suggest that UV-A and BaP act synergistically to enhance ROS production and formation of 8-OHdG, resulting in increased DNA damage.     

Adsorption capacity of powdered activated carbon for 3,5-dichlorophenol in activated sludge

The objectives of this study were to evaluate the performance of powdered activated carbon treatment (PACT) process based on the adsorption capacity of powdered activated carbon (PAC) in activated sludge and the effect of dissolved organic substances in activated sludge on the adsorption capacity of PAC. The DCP adsorption capacity of three PACs originated from different raw materials (coal, soft coal and sawdust) in activated sludge were 29%, 34% and 17% of that of new PAC, respectively. The performance of PACT process for shock loading of 3,5-dichlorophenol (3,5-DCP) was different among PACs in spite of the same adsorption capacity in new PAC. The performance of PACT process for removal of DCP is dependent not on the adsorption capacity of new PAC but on the adsorption capacity of PAC in the aeration tank. Dissolved organic matter (DOM) with molecular weight smaller than 50kDa did not affect the adsorption capacity of PAC for 3,5-DCP in the activated sludge reactor. DOM with molecular weight larger than 50kDa and biofilm developed on the surface of PAC seemed to be responsible for the decreased adsorption capacity of PAC for the DCP.     

Uptake and accumulation behaviour of angiosperms irrigated with solutions of different arsenic species

Uptake and metabolisation of arsenic as a function of both the plant type and the chemical form of arsenic were examined. For this purpose two different plant species (Silene vulgaris and Plantago major) were selected that differed in their vitality and accumulation behaviour on arsenic-loaded substrates. The plants were cultivated on soil and irrigated with aqueous solutions of an inorganic arsenic compound (arsenious acid) and an organic compound (dimethylarsinate). The arsenic species accumulated in the parts of the plants above ground were extracted by PLE and determined using IC-ICP-MS. The concentrations and metabolisation products of arsenic found in the extracts indicate different mechanisms of arsenic uptake and transformation in both angiosperms. The arsenic species pattern showed that S. vulgaris was more arsenic--tolerable than P. major which is attributed to a low arsenate to arsenite concentration ratio in the plant compartments. S. vulgaris was also able to demethylate and reduce dimethylarsinate to form arsenite in a high extent. P. major accumulated only eight times lower concentration of arsenic, and the arsenate to arsenite concentration ratio shifted to higher values. Metabolisation products of dimethylarsinate did not occur under the present experimental conditions. The vitality of the angiosperms seems to be very dependent on the ability of the plant to reduce arsenate to arsenite.     

PAH-pools in soils along a PAH-deposition gradient

The objectives of this study are to characterize different PAH-pools (soil horizons, microsites influenced by stem flow, aggregate core and surface fractions, particle size fractions) in soils affected by depositions. Three forest soils affected by the emissions of an aluminium plant near Ziar/Central Slovakia were sampled to analyze 20 PAHs. The organic layers have high concentrations of PAHs (40-200 mg kg(-1)), decreasing as soil depth and distance from the aluminium plant increases. At the two sites nearest to the plant PAH-concentrations are higher in microsites affected by stem flow than in microsites not influenced by stem flow. They are also higher in aggregate surface fractions than in aggregate core fractions and in bulk soil samples than in aggregates. Sand- and siltsize particles contain decreasing percentages of the sum PAH-concentrations as distance from the plant increases. This microscale heterogeneity affects PAH-availability and has to be considered when assessing environmental risks.     

Regional distribution of organochlorinated pesticides in pine needles and its indication for socioeconomic development

The regional distribution of 10 potentially harmful organochlorinated pesticides (OCPs) was investigated in pine needles from 18 sites in six Chinese regions. The OCPs concentrations in six regions were as follows: sigmaHCH (sigmaHCH=alpha-+beta-+gamma-+delta-HCH), 4.7-51.5 ng/g; sigmaDDT (p,p'-DDT+p,p'-DDE+p,p'-DDD), 0.9-30.9 ng/g; hexachlorobenzene (HCB), 1.1-5.3 ng/g; sigmachlordane (cis-chlordane+trans-chlordane), no detected-4.3 ng/g, on dry weight basis. Samples from southeast Chinese area contained the highest concentrations of sigmaHCH, sigmaDDT and sigmachlordane, while the contamination levels of most OCPs in southwest Chinese area were the lowest. The ratios of alpha/gamma-HCH (ranged from 1.7 to 5) were observed to be noticeable increase from north to south China, and the ratio of 1.7 revealed the presence of the recent use of lindane in north Chinese area. The significant decrease of the sum concentrations of alpha-+gamma-HCH from mid-1980s to the present and the strong correlation between alpha-, beta-, gamma-, delta-HCH (r=0.87-0.98, n=18, p<0.05) indicated the main usage of the technical HCH in history in China. The p,p'-DDE/p,p'-DDT ratios of <1 revealed the new input of p,p'-DDT in south, southeast and southwest Chinese areas, which could be partly contributed to the new use of impure dicofol. Economic development will leave its mark in the environment, however, its impact on the input and distribution of OCPs on a regional scale is unknown. We attempted to use the socioeconomic index (gross domestic product (GDP) per capita) to explain the distribution and input of OCPs and found that HCB and sigmaDDT seemed to be linked to the economic development, while no relationship of HCH was observed. DDE% of sigmaDDT also showed a negative correlation with the GDP per capita.     

(M)VOC and composting facilities. Part 1: (M)VOC emissions from municipal biowaste and plant refuse

GOAL, SCOPE AND BACKGROUND: Malodorous volatiles derived from the decomposition of biowaste within the process of composting might pose a risk to human health. Different techniques of process engineering have been developed to minimise the burden of malodorous compounds in air possibly affecting compost workers and residents in the vicinity. METHODS: In the present study, three different composting facilities were examined for the emission of volatiles to estimate the impact of process engineering on the dispersal of odorous compounds and to discuss its relevance for human health. RESULTS AND DISCUSSION: Concentrations of single compounds belonging to alcohols, ketones, furanes, sulfur-containing compounds and especially terpenes ranged from 10(2) up to nearly 10(6) ng/m3 depending on the sampling sites and the process engineering. The ratio of MVOC and total VOC measured changed throughout the process of biodegradation. A certain combination of volatile compounds coincided with the occurrence of typical compost odour. CONCLUSION: The type of process engineering seemed to have a major impact on the emission of volatiles, as amounts of (microbial) volatiles emitted were characteristic for the different techniques used. Thus, the MVOC emission basically depends on the degree of biodegradation. It is likely that the concentrations workers are exposed to can have an impact on human health. RECOMMENDATIONS AND OUTLOOK: It is obvious that less sophisticated types of process engineering give rise to greater amounts of bioaerosols and volatiles and, therefore, technical devices have to be improved and controlled regularly to minimise adverse health effects on workers.