Former mining activities lasting 140 years in the Ducktown Mining District, Tennessee, USA, has contaminated the streams draining the district with acid-mine drainage (AMD). North Potato Creek and its major tributary, Burra Burra Creek, are two of the most heavily AMD-impacted streams in the district. The removal of dissolved metals from the water in these creeks is largely attributable to the sorption of Cu, Zn, Co, Al, and Mn on suspended hydroxide precipitates of Fe. The fraction of trace metals remaining in solution decreases with increasing pH in the sequence Pb < Cu < Zn < Co. The concentration of Fe in solution also decreases with increasing pH due to the formation of ferric hydroxide precipitates which accounted for up to 81.4% by weight of the total suspended sediment. The concentration of suspended sediment substantially decreases as the water of North Potato Creek flows through a large settling basin, where 1.3 (±0.3) x 10⁶ kg/year of trace-metal-laden suspended sediment would be annually deposited. In spite of this attempt to purify it, the water discharged into the river is acidic (pH 3.6) and still contains high concentrations of dissolved trace metals, which would resorb on to suspended sediment and be ultimately transported to a downstream reservoir, Ocoee No. 3 Lake.

The representativeness of soil pore water extracted by suction lysimeters in ground-water monitoring studies is a problem that often confounds interpretation of measured data. Current soil water sampling techniques cannot delineate from which soil volume a pore water sample is extracted, neither macroscopic, microscopic, or preferential flowpath. This research was undertaken to compare δ¹⁸O and Br- values of extracted suction lysimeters samples from intact soil cores with samples obtained by the direct extraction methods of centrifugation and azeotropic distillation. Also, the study was concerned with determining what portion of soil pore water is sampled by each method and explaining differences in concentrations of the extracted water from each method to allow a determination of the accuracy and viability of the three methods of extraction. Intact soil cores (30 cm diameter by 40 cm height) were extracted from two different sites. Site 1 was rapid infiltration basin number 50, near Altamonte Springs in Seminole County, Florida. Site 2 was the Missouri Management System Evaluation Area (MSEA) near Centralia in Boone County, Missouri. Isotopically (¹⁸Oδ) labeled water and bromide concentrations within water samples taken by suction lysimeters was compared with samples obtained by methods of centrifugation and azeotropic distillation. The ¹⁸Oδ water was analyzed by mass spectrometry while bromide concentration, applied in the form of KBr was measured using standard IC procedures. Water collected by centrifugation and azeotropic distillation data were about 0.25[per thousand] more negative than that collected by suction lysimeter values from a sandy soil and about 2-7[per thousand] more negative from a well structured soil. Results indicate that the majority of soil water in well-structured soil is strongly bound to soil grain surfaces and is not easily sampled by suction lysimeters. In cases where a sufficient volume of water has passed through the soil profile and displaced previous pore water, suction lysimeters will collect a representative sample of soil pore water from the sampled depth interval. It is suggested that for stable isotope studies monitoring precipitation and soil water, suction lysimeter be installed at shallow depths (10 cm). Samples should also be coordinated with precipitation events. The data also suggest that each extraction method samples a separate component of soil-pore water. Centrifugation can be used with success, particularly for efficient sampling of large areas. Azeotropic distillation is more appropriate when strict qualitative and quantitative data on sorption desorption, and various types of kinetic studies may be needed.

The bursting of the mining dam of Aznalcollar (Seville, Spain) triggered an increase in the concentration of heavy metals in the soils of the river Guadiamar valley as a result of the leaching of the pyritic sludge deposited on them. After the cleaning operations which included, as well as mechanical clearing, the addition of different amendments, some areas with residual sludge remained, from which some heavy metals are being mobilized by the cyclical recharge and discharge processes of water in the profiles. This paper analyzes the effect of the soil recovery operations and the climatology on the concentration of metals and their distribution in the soil profile in an area affected by the toxic spill. Fourteen points have been selected in a plot in which acidity persists, there is no vegetation, and residual sludge stains can be seen at a glance. The temporal and spatial evolution of the extractable metals: Fe, Cu, Mn and Zn, the pH and the oxidable fraction has been measured in-depth. The results obtained up to now indicate a leaching of the pollutant towards deeper horizons, finding, at a depth of 757 cm, pH values of 3.5 and very high Fe and Mn concentrations available, especially in the profiles with large sized pores, with a big fraction of sand. On the surface, seasonally, there are low pH values of around 2.5 and extractable Fe contents of over 4000 ppm, which might have an influence on the quality of surface runoff or underground water.

Two identical experimental subsurface-flow constructed wetlands were operated at relatively high organic loading rates (23 g COD m-² day-¹) for 4 months to evaluate their relative ability to remove either dissolved organic carbon (glucose, considered to be a readily biodegradable substrate) or particulate organic carbon (starch, considered to be a slowly biodegradable substrate). The systems were built using plastic containers (0.93 m long, 0.59 m wide and 0.52 m high) that were filled with an 0.35 m layer of wetted gravel (D₆₀ = 3.5 mm, uniformity coefficient Cu = D₆₀/D₁₀ = 1.7) and the water level was maintained at 0.05 m under the gravel surface to give a water depth of 0.30 m. The results indicated that there was no significant difference in COD removal between the two systems. Both systems generally had COD removal rates of over 90%, which is quite high if the heavy load applied is taken into account. The removal of ammonium was greater in the glucose-fed system (57%) in comparison with the starch-fed system (43%). Based on mass balance calculations and stoichiometric relationships, it was estimated that denitrification and sulphate reduction were minor pathways for the removal of organic matter. Indirect observations allowed to assume that methanogenesis made a highly significant contribution to the removal of organic matter.

Using within-weather-group air pollution prediction models developed in Part I of this research, this study estimates future air pollution levels for a variety of pollutants (specifically, carbon monoxide – CO, nitrogen dioxide – NO₂, ozone – O₃, sulphur dioxide – SO₂, and suspended particles – SP) under future climate scenarios for four cities in south-central Canada. A statistical downscaling method was used to downscale five general circulation model (GCM) scenarios to selected weather stations. Downscaled GCM scenarios were used to compare respective characteristics of the weather groups developed in Part I; discriminant function analysis was used to allocate future days from two windows of time (2040–2059 and 2070–2089) into one of four weather groups. In Part I, the four weather groups were characterised as hot, cold, air pollution-related, and other (defined as relatively good air quality and comfortable weather conditions). In estimating future daily air pollution concentrations, three future pollutant emission scenarios were considered: Scenario I – emissions decreasing 20% by 2050, Scenario II – future emissions remaining at the same level as at the end of the twentieth century, and Scenario III – emissions increasing 20% by 2050. The results showed that, due to increased temperatures, the average annual number of days with high O₃ levels in the four selected cities could increase by more than 40–100% by the 2050s and 70–200% by the 2080s (from the current areal average of 8 days) under the three pollutant emission scenarios. The corresponding number of low O₃ days could decrease by 4–10% and 5–15% (from the current areal average of 312 days). For the rest of the pollutants, future air pollution levels will depend on future pollutant emission levels. Under emission Scenarios II and III, the average annual number of high pollution days could increase 20–40% and 80–180%, respectively, by the middle and late part of this century. In contrast, under Scenario I, the average annual number of high pollution days could decrease by 10–65%.

We intensively surveyed the concentrations of chemical species in aerosols and gases using a four-stage filter-pack method at a site in Japan facing the Sea of Japan in winter with 6-h sample intervals. A few chloride species emitted anthropogenically were detected, and the HCl (g) concentration was quite low. The number of chloride species artifacts was also low. The HNO₃ (g) concentration was significantly higher when the monitored air mass passed over the Korean Peninsula compared to when it did not pass over the Korean Peninsula. In addition, the HNO₃ (g) concentration was significantly higher when the air mass arrived at the monitoring site by passing the route at lower latitude than the latitude of the monitoring site. On the other hand, the SO₂ (g) concentration showed no change between various trajectories of the air mass. The [Formula: see text] (p)/non-seasalt- (nss-) [Formula: see text] (p) ratio was intermediate between the compositions of (NH₄)₂SO₄ and NH₄HSO₄ when the air mass passed over the Korean Peninsula, whereas it was intermediate between NH₄HSO₄ and H₂SO₄ when the air mass did not pass over the Korean Peninsula. We detected the transboundary transport of sulfur dioxide with high time-resolution monitoring at two separate monitoring points: the current monitoring site and Oki Island.

Analytical procedure for the determination of exchangeable Cr(VI) was developed. In order to optimise the extraction procedure, the efficiency of extraction of exchangeable Cr(VI) in soil samples was investigated in KH₂PO₄-K₂HPO₄ buffer solutions (0.015 up to 0.2 mol l-¹), adjusted to the pH of the soil. Phosphate buffer was used to efficiently desorb Cr(VI) from soil particles. The extraction time (mechanical shaking) ranged from 1 up to 72 h. Cr(VI) in soil extracts was determined by anion-exchange fast protein liquid chromatography with electrothermal atomic absorption detection (FPLC-ETAAS). The study was performed on soil samples from the field treated with the tannery waste for seventeen years. Samples were analysed in the 16 year after the last waste application. It was experimentally proven that the optimal phosphate buffer concentration was 0.1 mol l-¹ and extraction time 16 h. An additional experiment was done to confirm that during the extraction, soluble Cr(III) was not oxidised to Cr(VI) by Mn(IV) oxides present in soil samples. For this purpose soil with the same characteristics, but not treated with tannery waste, was spiked with Cr(III) and the analytical procedure performed. No measurable Cr(VI) concentrations were detected. The repeatability of measurement was 2.5%, while the reproducibility of measurement was 6.9%. The accuracy of the analytical procedure was tested by spiking of soil samples with Cr(VI). The recoveries were better than 95%. The analytical procedure with limit of detection (LOD) 15 ng g-¹ of Cr(VI) was sensitive enough for the determination of exchangeable Cr(VI) in soils. In field soil samples analysed the concentrations of exchangeable Cr(VI) were found to be about 200 ng g-¹.

We attempted to elucidate seasonal variations in fossil-fuel-derived carbon (FC) and biomass-derived carbon (BC) in urban atmospheric aerosols. We undertook continuous measurements of the composition of fine particle (PM₂.₁) in central Tokyo, including the ¹⁴C/¹²C ratio. The percent modern carbon (pMC) contained in all samples averaged 43, and the highest was 54 in late December and the lowest was 31 in early August. From the observed carbonaceous component concentrations and the pMC we could calculate the content ratio of FC and BC in PM₂.₁ and investigate their seasonal variations. Although there was almost no seasonal variation in the ratio of FC, the ratio of BC was observed to rise in early winter. This indicates that FC is influenced by the emission sources without seasonal variations (such as automobiles driven in urban areas). Furthermore, there is significant correlation between BC and organic carbon (OC), and even for urban areas, it is considered that the contribution of biomass carbon to OC in PM₂.₁ is high.

This study deals with Particle Matter (PM) levels in the metropolitan area of Lisbon and shows that EU directive is exceeded in a systematic way, mainly due to the inner city traffic. Results show that it is important to develop an epidemiological study in Lisbon to find a possible association between PM levels, sources and morbidity. Some important issues related with a monitor's representation of regional, sub-regional, and local air pollution exposures to the population in the metropolitan area are highlighted. PM₂.₅ and PM₁₀ total mass concentration measured in several places located in both centre of Lisbon and the outskirts are quite well correlated, mainly considering that two measuring methodologies (automatic and gravimetric) were used and areas with different classifications (urban and suburban) were analysed. However, the results imply that a source-oriented evaluation of PM health effects needs to take into account the uncertainty associated with spatial representativity of the species measured at a single sampling station. Temporal correlation across sampling stations, within relatively short separation distances, varied considerably for some important elements (Zn, Sb, Cu, As and Br), indicating that the precision of population exposure estimates for specific elements can vary depending on the species.

Former gold mining at Rodalquilar in southeastern Spain exploited a high sulphidation epithermal silicified ore deposit that contained significant enrichments in several metals/metalloids such as As, Sb, Bi, and Te. Treatment of this ore took place adjacent to the village and involved physical crushing then chemical extraction of gold using cyanide and zinc. The waste materials from this processing system, contaminated with a range of trace elements, were deposited immediately below the mine, and have been left exposed to erosion. Over the last 40 years these oxidised ferruginous tailings have not only polluted the local drainage system but also provided a point source for contaminated aeolian dust under the prevailing dry, windy climate. Chemical analyses of particulate matter mechanically resuspended from the tailings materials show enrichments in metals and metalloids due to the preferential incorporation of these elements into the inhalable size fraction (PM₁₀). Of particular concern is the fact that these PM₁₀ can contain >1,500 ppm As and >40 ppm Sb. Given that both As and Sb are clastogenic metalloids with proven negative health effects, and that their oxidised forms are especially toxic, such contamination levels in windblown dusts around old mine sites are highly undesirable.