Partitioning of dioxin and dibenzofuran congeners between plasma and cell fractions of blood from 10 adult male patients

We previously characterized levels of dioxin and dibenzofuran congeners in adipose tissue and plasma fraction of blood collected from 20 adult males, using paired speciments. It has been found that the 2,3,7,8-TCDD level reported on a lipid basis was similar, although not identical, in plasma lipid and in adipose tissue lipid from the same patients, however, higher levels of the more chlorinated dioxins and dibenzofurans existed in plasma lipid as compared to adipose tissue lipid. This study reports measurements from ten individuals' blood cell fraction and compares this to the plasms fraction and to adipose tissue lipid. In all cases where readily detectable amounts of PCDD/Fs were found, a minimum of 85% was in the plasma fraction and less than 15% in the cellular component. Congeners varied in percentage for each component.     

Effects of clearfelling on stream and soil water aluminium chemistry in three UK forests

Data are presented demonstrating how clearfelling has changed soil and stream water aluminium chemistry. For soil waters, a strong empirical relationship was observed between inorganic aluminium (Al(inorg)) and total inorganic anion (TIA) concentrations. Before felling, chloride and sulphate accounted for the largest proportion of the TIA concentration. After felling, in soils where nitrification was active, nitrate became increasingly important. Where this led to an increase in TIA, Al(inorg) concentrations increased. Over five years, nitrate concentrations have fallen, along with TIA, resulting in a sympathetic decline in Al(inorg). Streams draining clearfelled areas initially became more acid, although chloride and sulphate concentrations decreased. Stream water nitrate concentrations increased soon after felling and remained higher than controls for up to four years. While nitrate concentrations were high, Al(inorg) remained unchanged. Subsequently, as nitrate and TIA decreased, Al(inorg) also declined to concentrations below those in the control stream. Clearfelling upland forests will not necessarily result in immediate improvements in water quality, although long-term benefits may be seen before canopy-closure of the next crop.     

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.     

Critical loads for Finnish lakes: comparison of three steady-state models

Three simple steady-state water-chemistry models are used to calculate critical loads of sulfur for lakes in Finland. Because of the high concentrations of organic matter in Finnish lakes, the influence of organic anions on the calculation of critical loads has been given special attention. The first two methods are well known ion-balance methods which have been used in many previous lake-acidification studies. The third method, developed for this study, includes the numerical solution of equilibrium equations for organic anions, inorganic carbon species and inorganic monomeric aluminum. The original pH and aluminum concentration of the lakes are estimated with this model, and a method to estimate the original acid neutralizing capacity (ANC) by simulating a Gran-titration is also tested on the lake data. Uncertainty in the predictions is estimated by varying the most critical model parameters.     

Deposition of atmospheric ammonia to moorlands

Micrometeorological methods were applied to measure fluxes of atmospheric ammonia (NH3) to moorlands. Measurements were made in a wide variety of surface conditions and included both Calluna vulgaris (L.) Hull and Eriophorum vaginatum L. dominated sites. NH3 was found to deposit rapidly to all the sites investigated, providing large deposition velocities (Vd, typically 10-40 mm s(-1)) and usually minimal surface resistances (rc). A small number of measurements were made in frozen conditions and suggest a possible exception to this pattern with mean rc of 50-200 s m(-1). The effect of vegetation drying was also investigated and a possible increase in rc observed, though this was small (< 10 s m(-1)). The results are interpreted in terms of the processes controlling exchange; it is shown that NH3 deposition is predominantly to the leaf surfaces and that the net NH3 compensation point approaches zero. Annual estimates show that dry deposition of NH3 is a major source of atmospheric nitrogen to moorland ecosystems. For two typical UK sites subject to background air concentrations, NH3 dry deposition is of similar magnitude to equivalent NH4+ inputs in wet deposition. In the vicinity of emission sources, NH3 dry deposition is expected to dominate inputs of atmospheric nitrogen.     

Comparative impacts of forest harvest and acid precipitation on soil and streamwater acidity

Annual H+ budgets were calculated for a catchment with a 65-year-old spruce-fir forest, and for an adjacent catchment at three years after a whole-tree harvest. In the harvested catchment sinks for H+ due to weathering and mineralization reactions were 85% greater, and sources of H+ due to biomass uptake were 60% greater than in the undisturbed catchment. There was an overall net consumption of 550 eq H+ ha(-1) year(-1) at year 3 after harvest compared to a net generation of 520 eq H+ ha(-1) year(-1) for the 65-year-old forest. Soil pH increased by 0.2-0.4 units soon after harvest, but there was little change in pH of streamwater from the harvested watershed. The whole-tree harvest resulted in a total production of about 30,000 eq H+ ha(-1) due to biomass removal. In contrast, wet and dry deposition at rates measured in this study could add more than 50,000 eq H+ ha(-1) in the 65-year period before the next harvest. Reducing the intensity of harvest may lessen long-term impacts of these sources of H+ on acidification of soils and streams.     

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.     

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.     

On the behavior of approaches to simulate reactive transport

Two families of approaches exist to simulate reactive transport in groundwater: The Direct Substitution Approach (DSA), based on Newton-Raphson and the Picard or Sequential Iteration Approach (SIA). We applied basic versions of both methods to several test cases and compared both computational demands and quality of the solution for varying grid size. Results showed that the behavior of the two approaches is sensitive to both grid size and chemistry. As a general rule, the DSA is more robust than the SIA, in the sense that its convergence is less sensitive to time step size (any approach will converge given a sufficiently small time step). Moreover, the DSA leads to a better simulation of sharp fronts, which can only be reproduced with fine grids after many iterations when the SIA is used. As a consequence, the DSA runs faster than SIA in chemically difficult cases (i.e., highly non-linear and/or very retarded), because the SIA may require very small time steps to converge. On the other hand, the size of the system of equations is much larger for the DSA than for the SIA, so that its CPU time and memory requirements tend to be less favorable with increasing grid size. As a result, the SIA may become faster than the DSA for very large, chemically simple problems. The use of an iterative linear solver for the DSA makes its CPU time less sensitive to grid size.