Comparison of episodic acidification in Canada, Europe and the United States

Episodic acidification is practically a ubiquitous process in streams and drainage lakes in Canada, Europe and the United States. Depressions of pH are often smaller in systems with low pre-episode pH levels. Studies on European surface waters have reported episodes most frequently with minimum pH levels below 4.5. In Canada and the United States, studies have also reported a number of systems that have had minimum pH levels below 4.5. In all areas, change in water flowpath during hydrological events is a major determinant of episode characteristics. Episodic acidification is also controlled by a combination of other natural and anthropogenic factors. Base cation decreases are an important contributor to episodes in circumneutral streams and lakes. Sulphate pulses are generally important contributors to episodic acidification in Europe and Canada. Nitrate pulses are generally more important to episodic acidification in the Northeast United States. Increases in organic acids contribute to episodes in some streams in all areas. The sea-salt effect is important in near-coastal streams and lakes. In Canada, Europe and the United States, acidic deposition has increased the severity (minimum pH reached) of episodes in some streams and lakes.     

Contribution of canopy leaching to sulphate deposition in a Scots pine forest

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.     

Effect of nickel on some aspects of protein metabolism in the gill and kidney of the freshwater fish, Cyprinus carpio L

Nickel has an adverse effect on some aspects of protein metabolism of the freshwater fish, Cyprinus carpio. The main changes observed were: (a) Decrease in soluble, structural and total proteins, AlAT and AAT activities with an increase in the levels of free amino acids, protease and GDH activities and ammonia in the gill and kidney at 1, 2, 3, and 4 days of exposure to a lethal concentration, 40 mg litre(-1) of nickel; (b) Increase in soluble, structural and total proteins, free amino acids and the activities of protease, AlAT, AAT and GDH with a decrease in ammonia and urea in these organs at 1, 5, 10 and 15 days of exposure to sublethal concentration, 8 mg litre(-1); (c) The magnitude in these changes increased over time with both concentrations of the metal, and was more marked in gill than in kidney.     

Response of the Plastic Lake catchment, Ontario, to reduced sulphur deposition

As a consequence of decreases in the emission rate of sulphur in eastern North America in the late 1970s and early 1980s, sulphate deposition in central Ontario declined by about 40%, but has remained constant for about six years. Plastic Lake, a small, dilute lake on the Precambrian shield that the authors have studied since 1979, acidified between the start of the study and about 1986, but since then has not changed. The authors also monitored the chemistry of streamwater draining the Plastic Lake catchment. Water quality of runoff from an upland site improved rapidly (pH and alkalinity increased, SO4(2-) and Al decreased), but two factors offset these improvements. A small wetland area downstream reversed most of these changes, resulting in a constant output of strong acid from the catchment. In addition, in extremely dry years (1983, 1987, 1989) there were very high concentrations of SO4(2-) in the streamwater, suggesting substantial re-oxidation of reduced S in the catchment.     

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.     

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.     

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.     

Seveso Women's Health Study: does zone of residence predict individual TCDD exposure?

The compound, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), is produced as an unwanted by-product of various chemical reactions and combustion processes, including the manufacture of chlorinated phenols and derivatives. In animals, TCDD exposure is associated with toxic, carcinogenic, developmental, and reproductive effects. In 1976, a chemical plant explosion in Seveso, Italy, exposed the residents in the surrounding community to the highest exposure to TCDD known in humans. Materials from an aerosol cloud of sodium hydroxide, sodium trichlorophenate and TCDD were deposited over an 18.1 km2 area. As evidence of the significant level of TCDD exposure, numerous animals died and 193 cases of chloracne were reported among residents of the area. Initially, the contaminated area was divided into three major exposure Zones (A, B, R) based on the concentration of TCDD in surface soils. To date, the majority of epidemiologic studies conducted in Seveso have used Zone of residence as a proxy measure of exposure. The purpose of the present study is to validate the use of Zone of residence in Seveso as a proxy measure of exposure against individual serum TCDD measurement, and to determine whether questionnaire information can improve the accuracy of the exposure classification. Using data collected from the Seveso Women's Health Study (SWHS), the first comprehensive epidemiologic study of the reproductive health of women in Seveso, we determined that Zone of residence is a good predictor of individual serum TCDD level, explaining 24% of the variance. Using questionnaire information could have improved prediction of individual exposure levels in Seveso, increasing the percent of the variation in serum TCDD levels explained to 42%.     

Time to death response in carabid beetles exposed to multiple stressors along a gradient of heavy metal pollution

We investigated the responses of invertebrates inhabiting polluted environments to multiple stressors. Carabid beetles (Pterostichus oblongopunctatus F.) were subjected to food deprivation and insecticide treatment (dimethoate) to resolve trends associated with a gradient of heavy metal pollution. Metal concentrations along the gradient of five sites ranged from approximately 150 to 10,500 mg/kg Zn, 136 to 2600 mg/kg Pb, and 0.84 to 81.9 mg/kg Cd. There was no difference in body mass along the pollution gradient. However, the beetles originating from the most contaminated sites were significantly less tolerant to food deprivation than beetles from the reference site. Median survival time was 120 h for the two most polluted sites, compared with 168 h at the reference site. Beetles from the two most polluted sites were also significantly more susceptible to dimethoate at 0.1 microgram active ingredient/beetle. Median survival times were 12 and 123 h for beetles from the two most polluted sites and 359 h for the reference site. Carabid beetles exposed to chronic pollution, therefore, exhibit elevated susceptibility to additional stressors.