Decolorization of synthetic dyes by the Fenton reagent and the Cu/pyridine/H2O2 system

Representative azo, triphenylmethane, heterocyclic and polymeric synthetic dyes have been decolorized by two biological non-ezymatic systems, copper/pyridine/H2O2 and the Fenton reagent. With the former system, intensive decolorization measured after 1 h was obtained with phenol red (89%), tropaeolin 00 (58%), Evans blue (95%), eosin yellowish (84%), and Poly B-411 (92%). The rate of decolorization was not affected by pH in the range of 3-9 and increased with increasing temperature. The use of the radical scavengers thiourea and superoxide dismutase showed that hydroxyl radicals rather than superoxide anions are involved in the reaction. Omission of pyridine led to a substantial decrease in the extent of decolorization (20-50% decolorization). The use of organic peroxide instead of H2O2 resulted in slightly slower decolorization, similar values of decolorization being obtained only after a 2-h incubation. Decolorization of the dyes by the Fenton reagent was also very effective but slower than that obtained with the first system. Except for phenol red and eosin yellowish, (decolorization 8% and 52%, respectively) the dyes were decolorized up to 99% after 1-day incubation.     

Effects of land use data on dry deposition in a regional photochemical model for eastern Texas

Land use data are among the inputs used to determine dry deposition velocities for photochemical grid models such as the Comprehensive Air Quality Model with extensions (CAMx) that is currently used for attainment demonstrations and air quality planning by the state of Texas. The sensitivity of dry deposition and O3 mixing ratios to land use classification was investigated by comparing predictions based on default U.S. Geological Survey (USGS) land use data to predictions based on recently compiled land use data that were collected to improve biogenic emissions estimates. Dry deposition of O3 decreased throughout much of eastern Texas, especially in urban areas, with the new land use data. Predicted 1-hr averaged O3 mixing ratios with the new land use data were as much as 11 ppbv greater and 6 ppbv less than predictions based on USGS land use data during the late afternoon. In addition, the area with peak O3 mixing ratios in excess of 100 ppbv increased significantly in urban areas when deposition velocities were calculated based on the new land use data. Finally, more detailed data on land use within urban areas resulted in peak changes in O3 mixing ratios of approximately 2 ppbv. These results indicate the importance of establishing accurate, internally consistent land use data for photochemical modeling in urban areas in Texas. They also indicate the need for field validation of deposition rates in areas experiencing changing land use patterns, such as during urban reforestation programs or residential and commercial development.     

Developing a multimedia model of chemical dynamics in an urban area.

A multimedia model has been developed to account for the movement of semi-volatile organic compounds (SOCs) in an urban environment. The model, based on a Level III fugacity model of D. Mackay (Multimedia Environmental Models: The Fugacity Approach, Lewis Publishers, Boca Raton, FL, 1991), consists of six compartments: air, surface water, sediment, soil, vegetation, and an organic film that coats impervious surfaces. The latter is a newly identified compartment into which gas-phase SOCs partition and particle-phase SOCs are believed to be efficiently captured (M.L. Diamond, S.E. Gingrich, K. Fertuck, B.E. McCarry, G.A. Stern, B. Billeck, B. Grift, D. Brooker, T.D. Yager, Environ. Sci. Technol., 34 (2000a), 2900-2908). The model, parameterized for downtown Toronto, Ontario, Canada, and run with an illustrative emission rate for selected polycyclic aromatic hydrocarbons and homologues of polychlorinated dibenzodioxins, indicates that the film achieves the highest concentrations among media but that soils are the greatest sink for all but the least hydrophobic chemicals. The film "reflects" the more volatile chemicals into air, facilitates removal to surface waters by wash-off, and provides a surface on which photolytic degradation can occur. As such, the film is a transient sink that increases chemical mobility in urban areas by increasing air concentrations and the cycling of these compounds between air and urban surfaces and increasing water concentrations. Vegetation also accumulates SOCs, a portion of which is transferred to soil that reduces chemical mobility.     

Isotopic modelling of the significance of bacterial sulphate reduction for phenol attenuation in a contaminated aquifer

A Triassic sandstone aquifer polluted with a mixture of phenolic hydrocarbons has been investigated by means of high-resolution groundwater sampling. Samples taken at depth intervals of 1 m have revealed the presence of a diving pollutant plume with a sharply defined upper margin. Concentrations of pollutant phenols exceed 4 g/l in the plume core, rendering it sterile but towards the diluted upper margin evidence for bacterial sulphate reduction (BSR) has been obtained. Groundwaters have been analysed for both delta34S-SO4 and delta18O-SO4. Two reservoirs have been identified with distinct sulphate oxygen isotope ratios. Groundwater sulphate (delta18O-SO4 = 3-5/1000) outside the plume shows a simple linear mixing trend with an isotopically uniform pollutant sulphate reservoir (delta18O-SO4 = 10-12/1000) across the plume margin. The sulphur isotope ratios do not always obey a simple mixing relation, however, at one multilevel borehole, enrichment in 34SO4 at the plume margin is inversely correlated with sulphate concentration. This and the presence of 34S-depleted dissolved sulphide indicate that enrichment in 34SO4 is the result of bacterial sulphate reduction. Delta34S analysis of trace hydrogen sulphide within the plume yielded an isotope enrichment factor (epsilon) of -9.4/1000 for present-day bacterial sulphate reduction. This value agrees with a long-term estimate (-9.9/1000) obtained from a Rayleigh model of the sulphate reduction process. The model was also used to obtain an estimate of the pre-reduction sulphate concentration profile with depth. The difference between this and the present-day profiles then gave a mass balance for sulphate consumption. The organic carbon mineralisation that would account for this sulphate loss is shown to represent only 0.1/1000 of the phenol concentration in this region of the plume. Hence, the contribution of bacterial sulphate reduction to biodegradation has thus far been small. The highest total phenolic concentration (TPC) at which there is sulphur isotope evidence of bacterial sulphate reduction is 2000 mg/l. We suggest that above this concentration, the bactericidal properties of phenol render sulphate-reducing bacteria inactive. Dissolved sulphate trapped in the concentrated plume core will only be utilised by sulphate reducers when toxic phenols in the plume are diluted by dispersion during migration.     

Real-world vehicle emissions: a summary of the Ninth Coordinating Research Council On-Road Vehicle Emissions Workshop

In April 1999, the Coordinating Research Council sponsored a workshop focusing on our understanding of real-world emissions from motor vehicles. This summary presents the latest information on in-use light- and heavy-duty vehicle tailpipe and evaporative emissions, the effects of fuels on emissions, field programs designed to understand the contribution of mobile sources to emission inventories, efforts to evaluate and improve mobile source emission models, progress of vehicle inspection/maintenance programs, and topics for future research. While significant progress has been made in understanding in-use vehicle emissions, further improvements are necessary. Moreover, the impact of current and future changes in emission control technologies and control programs will have to be monitored for effectiveness and incorporated into the emission factor models.     

Toxaphene in standard solutions and cleaned biota extracts--results of the first QUASIMEME interlaboratory studies. Quality Assurance of Information for Marine Environmental Monitoring in Europe

Two interlaboratory studies on individual toxaphene congeners have been organised by the project Quality Assurance of Information for Marine Environmental Monitoring in Europe (QUASIMEME). Fifteen laboratories analysed two standard solutions in the first study and 13 laboratories analysed a standard solution and two cleaned biota extracts in the second study. The coefficients of variation obtained for the standard solutions were 6-21% and for the cleaned extracts 16-39%. Although the results were comparable to those of other studies, further improvement in the level of agreement between the participating laboratories was considered possible.     

Second generation chemical mass balance source apportionment of sulfur oxides and sulfate at the Grand Canyon during the Project MOHAVE summer intensive

Receptor-based chemical mass balance (CMB) analysis techniques are designed to apportion species that are conserved during pollutant transport using conserved source profiles. The techniques will fail if non-conservative species (or profiles) are not properly accounted for in the CMB model. The straightforward application of the CMB model developed for Project MOHAVE using regional profiles resulted in a significant under-prediction of total sulfate oxides (SOx, SO2 plus fine particulate sulfate) for many samples at Meadview, AZ. In addition, for these samples the concentration of the inert tracer emitted from the MOHAVE Power Project (MPP), ocPDCH, was also under-predicted. A second-generation model has been developed which assumes that separation of particles and SO2 can occur in the MPP plume during nighttime stable plume conditions. This second-generation CMB model accounts for all SOx present at the various receptor sites. In addition, the concentrations of ocPDCH and the presence of other inert tracers of emission from regional sources are accurately predicted. The major source of SOx at Meadview was the MPP, but the major source of sulfate at this site was the Las Vegas urban area. At Hopi Point in the Grand Canyon, the Baja California region (Imperial Valley and northwestern Mexico) was the major source of both SOx and sulfate.     

Windblown dust contributes to high PM2.5 concentrations

The revised National Ambient Air Quality Standards for PM include fine particulate standards based upon mass measurements of PM2.5. It is possible in arid and semi-arid regions to observe significant coarse mode intrusion in the PM2.5 measurement. In this work, continuous PM10, PM2.5, and PM1.0 were measured during several windblown dust events in Spokane, WA. PM2.5 constituted approximately 30% of the PM10 during the dust event days, compared with approximately 48% on the non-dusty days preceding the dust events. Both PM10 and PM2.5 were enhanced during the dust events. However, PM1.0 was not enhanced during dust storms that originated within the state of Washington. During a dust storm that originated in Asia and impacted Spokane, PM1.0 was also enhanced, although the Asian dust reached Washington during a period of stagnation and poor dispersion, so that local sources were also contributing to high particulate levels. The "intermodal" region of PM, defined as particles ranging in aerodynamic size from 1.0 to 2.5 microns, was found to represent a significant fraction of PM2.5 (approximately 51%) during windblown dust events, compared with 28% during the non-dusty days before the dust events.     

Genetic engineering in the improvement of plants for phytoremediation of metal polluted soils

Metal concentrations in soils are locally quite high, and are still increasing due to many human activities, leading to elevated risk for health and the environment. Phytoremediation may offer a viable solution to this problem, and the approach is gaining increasing interest. Improvement of plants by genetic engineering, i.e. by modifying characteristics like metal uptake, transport and accumulation as well as metal tolerance, opens up new possibilities for phytoremediation. So far, only a few cases have been reported where one or more of these characteristics have been successfully altered; e.g. mercuric ion reduction causing improved resistance and phytoextraction, and metallothionein causing enhanced cadmium tolerance. These, together with other approaches and potentially promising genes for transformation of target plants are discussed.     

Pesticides in rainfall in Europe

Papers and published reports investigating the presence of pesticides in rainfall in Europe were reviewed. Approximately half of the compounds that were analysed for were detected. For those detected, most concentrations were below about 100 ng/l, but larger concentrations, up to a few thousand nanograms per litre, were detected occasionally at most monitoring sites. The most frequently detected compounds were lindane (gamma-HCH) and its isomer (alpha-HCH), which were detected on 90-100% of sampling occasions at most of the sites where they were monitored. For compounds developed more recently, detection was usually limited to the spraying season. A classification of pesticides according to their deposition pattern is proposed.