Trace metals in interstitial waters from sandstones: acidic inputs to shallow groundwaters

There is some evidence from southern Britain that shallow groundwaters in non-carbonate lithologies may be affected by acidic deposition. To investigate this, interstitial water profiles down to 12 m have been obtained from unsaturated sands or semi-consolidated sandstones from the Folkestone Beds (Lower Greensand) of Surrey and the Sherwood Sandstone of the West Midlands. The pH of the interstitial waters generally increased with depth and reflected an increase in the base saturation of the exchange complex. Beneath the highly acidic surface soil horizons (pH 3.0-3.5), interstitial waters with a pH of 4.0-4.5 were found down to depths of several metres. The pH progressively increased to around pH 5.5 because of base cation desorption and the weathering of silicate minerals. High concentrations of aluminium (10-20 mg litre(-1)) and other metals (Fe, Mn, Cu, Ni, Co, Zn, Be) were found in the interstitial water in the upper unsaturated zone. Most metal concentrations were strongly pH-dependent but also reflected the geochemical characteristics of the parent sands or sandstones. H+ and trace element concentrations were slightly higher beneath areas of afforestation than beneath heathland. The downward fluxes of solutes have been estimated using rainfall-derived chloride as a non-reactive solute. The profiles retain a record of 10-20 years input allowing the past inputs from SO4 and other species to be estimated using solute/chloride ratios. Cation exchange sites are probably depleted over a period of decades and there can be a significant decrease in the unsaturated zone pH as a result of increased or sustained acidic deposition. The shallow groundwater environment (0-15 m) in non-carbonate terrains is therefore a sensitive environment where high metal concentrations may be generated and may ultimately lead to water quality problems in shallow water supplies.     

Effects of atmospheric ammonia and ammonium sulphate on Douglas fir (Pseudotsuga menziesii)

Three-year-old Douglas firs (Pseudotsuga menziesii) were fumigated with 180 microg m(-3) NH3 or clean (charcoal-filtered) air. During these fumigations the plants received 15 mm artificial rain weekly, supplemented with 20, 500 or 2500 micromol litre(-1) (NH4)2SO4. Exposure to NH3 and NH4+ for 14 weeks resulted in a change of the nutrient status of the needles. The most remarkable effect was the increase in the N/K ratio, due to both uptake of N and leaching of K. The action of NH3 was stronger than that of NH4+. Both NH3 and (NH4)2SO4 affected the epicuticular wax layer and decreased mycorhiza frequency. Following fumigation and artificial rain treatments, needles were incubated for 8 h in a medium containing 0, 50, 250, 500 and 2500 micromol litre(-1) (NH4)2SO4. Almost no exchange of Ca, Mg and K for NH4+ was found. Therefore this ion exchange probably explains only a minor part of the changes in nutrient status of the whole trees.     

Real-world vehicle emissions: a summary of the tenth coordinating research council on-road vehicle emissions workshop

The Coordinating Research Council (CRC) held its tenth workshop in March 2000, focusing on results from the most recent real-world vehicle emissions research. In this paper, we summarize the presentations from researchers who are engaged in improving our understanding of the contribution of mobile sources to emission inventories. Participants in the workshop discussed efforts to improve mobile source emission models and emission inventories, results from gas- and particle-phase emissions studies from spark-ignition and diesel-powered vehicles, new methods for measuring mobile source emissions, improvements in vehicle emission control systems (ECSs), and evaluation of motor vehicle inspection/maintenance (I/M) programs, as well as topics for future research.     

Effects of thiobencarb herbicide to an alga (Nannochloris oculata) and the cladoceran (Daphnia magna)

Chronic toxicity studies were conducted with an algae (Nannochloris oculata) and the cladoceran (Daphnia magna) to determine their relative sensitivities to the thiocarbamate herbicide thiobencarb (S-4-chlorobenzyl diethylthiocarbamate). Most of the algal populations were initially affected by exposure to the herbicide. Thiobencarb concentrations higher than 0.5 mg/L significantly reduced algal densities after 24-h exposure. The 24-h static EC50 in D. magna was 3.01 mg/L. The sublethal effects of 0.3, 0.37, 0.5, 0.75, and 1.5 mg/L of thiobencarb concentrations on the survival, reproduction, and growth of D. magna were monitored for 21 days. The parameters used to determined the effect of the herbicide on D. magna were mean total young per female; mean brood size; days to first brood; intrinsic rate of natural increase (r); growth; and survival. Reproduction was significantly reduced at thiobencarb concentrations of 0.30 mg/L and higher while survival was affected after exposure to 0.75 and 1.5 mg/L of the pesticide. The r value decreased with increasing concentrations of thiobencarb. Growth, as measured by body length, was depressed significantly after exposure to all herbicide concentrations tested.     

Adsorption of methabenzthiazuron on six allophanic and nonallophanic soils: effect of organic matter amendment

This article reports on methabenzthiazuron [1-(1,3-benzothiazol-2-yl)-1,3-dimethylurea] (MBT) adsorption process on six agricultural allophanic and nonallophanic soils. The effect of amendment with exogenous organic matter was also studied. Adsorption kinetic fits an hyperbolic model. MBT adsorption reached an apparent equilibrium within 2 h and followed a second-order reaction. The maximum adsorbed amounts for natural soils ranged from 32 to 145 microg g(-1). Rate constants were considered relatively low (0.27-1.5 x 10(-4) [microg g(-1)](1-n) s-1); the slow process was attributed to a combined effect of difussion and adsorption. MBT adsorption fits the Freundlich model with r values > or =0.998 at P < or = 0.001 significance levels. Kf and Freundlich exponents (l/n) ranged from 5.3 to 82.1 cm3 g(-1) and from 0.66 to 0.73, respectively. Kf values for soils with a low organic matter content were lower than that obtained from the only typical allophanic soil derived from volcanic ash under study. Lineal regression analysis between Kf and organic matter content of nonallophanic soils gave a correlation coefficient of 0.980 (P = 0.02). Dispersion of Kd values together with close values of K(OM) indicate that organic matter (OM) was the principal component responsible for MBT adsorption in unamended soils. Addition of peat decreased soil pH and increased adsorption capacity for allophanic and nonallophanic soils. Kinetic experiments showed enhancements of Xmax values and lower rate constants.     

Surfactant enhanced recovery of tetrachloroethylene from a porous medium containing low permeability lenses. 1. Experimental studies

A matrix of batch, column and two-dimensional (2-D) box experiments was conducted to investigate the coupled effects of rate-limited solubilization and layering on the entrapment and subsequent recovery of a representative dense NAPL, tetrachloroethylene (PCE), during surfactant flushing. Batch experiments were performed to determine the equilibrium solubilization capacity of the surfactant, polyoxyethylene (20) sorbitan monooleate (Tween 80), and to measure fluid viscosity, density and interfacial tension. Results of one-dimensional column studies indicated that micellar solubilization of residual PCE was rate-limited at Darcy velocities ranging from 0.8 to 8.2 cm/h and during periods of flow interruption. Effluent concentration data were used to develop effective mass transfer coefficient (Ke) expressions that were dependent upon the Darcy velocity and duration of flow interruption. To simulate subsurface heterogeneity, 2-D boxes were packed with layers of F-70 Ottawa sand and Wurtsmith aquifer material within 20-30 mesh Ottawa sand. A 4% Tween 80 solution was then flushed through PCE-contaminated boxes at several flow velocities, with periods of flow interruption. Effluent concentration data and visual observations indicated that both rate-limited solubilization and pooling of PCE above the fine layers reduced PCE recovery to levels below those anticipated from batch and column measurements. These experimental results demonstrate the potential impact of both mass transfer limitations and subsurface layering on the recovery of PCE during surfactant enhanced aquifer remediation.     

The effects of crude oil and the effectiveness of cleaner application following oiling on US Gulf of Mexico coastal marsh plants

Field studies were conducted in two different marsh habitats in Louisiana coastal wetlands to evaluate the effects of oiling (using South Louisiana Crude oil, SLC) and the effectiveness of a shoreline cleaner (COREXIT 9580) in removing oil from plant canopies. The study sites represented two major marsh habitats; the brackish marsh site was covered by Spartina patens and the freshwater marsh was covered by Sagittaria lancifolia. Field studies were conducted in each habitat using replicated 5.8 m2 plots that were subjected to three treatments; oiled only, oiled + cleaner (cleaner was used 2 days after oiling), and a control. Plant gas exchange responses, survival, growth, and biomass accumulation were measured. Results indicated that oiling led to rapid reductions in leaf gas exchange rates in both species. However, both species in 'oiled + cleaned' plots displayed improved leaf conductance and CO2 fixation rates. Twelve weeks after treatment initiation, photosynthetic carbon fixation in both species had recovered to normal levels. Over the short-term, S. patens showed more sensitivity to oiling with SLC than S. lancifolia as was evident from the data of the number of live shoots and above-ground biomass. Above-ground biomass remained significantly lower than control in S. patens under 'oiled' and 'oiled + cleaned' treatments while it was comparable to controls in S. lancifolia. These studies indicated that the cleaner removed oil from marsh grasses and alleviated the short-term impact of oil on gas exchange function of the study plants. However, use of cleaner had no detectable effects on above-ground biomass production or regeneration at the end of the first growing season in S. patens. Similarly, no beneficial effects of cleaner on carbon fixation and number of live shoots were apparent beyond 12 weeks in S. lancifolia.     

Determination of source contributions to ambient PM2.5 in Kaohsiung, Taiwan, using a receptor model

Ambient particulates of PM2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM2.5. The mean concentration of ambient PM2.5 was 42.69-53.68 micrograms/m3 for the sampling period. The abundant species in ambient PM2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO4(2-) (12.8-15.1%), NO3- (8.1-10.3%), NH4+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO4(2-) and NO3-), and outdoor burning of agriculture wastes (13-17%).     

Performance evaluation of laser-induced breakdown spectrometry as a multimetal continuous emission monitor

Laser-induced breakdown spectroscopy (LIBS) has been evaluated as a multimetal continuous emissions monitor (CEM) at the U.S. Environmental Protection Agency (EPA) rotary kiln incinerator simulator (RKIS) facility in Raleigh, NC. Two detection systems with a bifurcated optical fiber bundle were used for simultaneously monitoring the concentrations of Be, Cd, Cr, and Hg in the test. Two calibration techniques were evaluated in the laboratory for the field measurements. On-line calibration of relative metal concentration was also performed in the simulated incinerator gas stream. Toxic metal concentrations measured with LIBS have been compared with the EPA reference method (RM) results.     

Changes in concentration of five PCDD/F congeners after cooking beef from treated cattle

A large piece of meat taken from a single animal, which had been dosed with five selected PCDD/Fs, was prepared and cooked by a selection of different methods; burgers (fried, grilled, barbecued), roasts (cooked using conventional and microwave ovens) and stews (open pan and pressure cooked). For some of the cooking methods, concentration changes, on a whole product basis, were observed between raw and cooked product. However, in all cases these could be explained simply through changes arising from loss of water and elimination of PCDD/Fs with released fat. The total amounts of PCDD/Fs present in the system (including in released fat) remained unchanged. Dietary intake of PCDD/Fs could therefore be reduced by the removal of visible fat from meat before cooking and by discarding any fat released from foods during the cooking process.