Source and persistence of pesticides in a semi-confined chalk aquifer of southeast England

Pesticide contamination in groundwater is an increasing problem that poses a significant long-term threat to water quality. Following the detection of elevated concentrations of diuron in boreholes in a semi-confined chalk aquifer from southeast England, a sampling programme was undertaken. Between 2003 and 2004 diuron was observed in 90% of groundwaters analysed. In 60% of groundwater samples metabolites of diuron were more prevalent than the parent compound. Longer-term (1989-2005) monitoring shows that pollution of the aquifer by atrazine, simazine, and more recently diuron, shows a positive correlation with periods of high groundwater levels. Results from groundwater residence time indicators suggest that the highest diuron concentrations are associated with waters containing the greatest proportion of recent recharge. There is some evidence to indicate that diuron occurrence can be spatially related to areas of urban and industrial development and is probably correlated with amenity usage.     

PAH and soot emissions from burning components of medical waste: examination/surgical gloves and cotton pads

This is a laboratory investigation on the emissions from batch combustion of representative infectious ("red bag") medical waste components, such as medical examination latex gloves and sterile cotton pads. Plastics and cloth account for the majority of the red bag wastes by mass and, certainly, by volume. An electrically heated, horizontal muffle furnace was used for batch combustion of small quantities of shredded fuels (0.5-1.5 g) at a gas temperature of approximately 1000 degrees C. The residence time of the post-combustion gases in the furnace was approximately 1 s. At the exit of the furnace, the following emissions were measured: CO, CO2, NOx, particulates and polynuclear aromatic compounds (PACs). The first three gaseous emissions were measured with continuous gas analyzers. Soot and PAC emissions were simultaneously measured by passing the furnace effluent through a filter (to collect condensed-phase PACs) and a bed of XAD-4 adsorbent (to capture gaseous-phase PACs). Analysis involved soxhlet extraction, followed by gas chromatography-mass spectrometry (GC-MS). Results were contrasted with previously measured emissions from batch combustion of pulverized coal and tire-derived fuel (TDF) under similar conditions. Results showed that the particulate soot) and cumulative PAC emissions from batch combustion of latex gloves were more than an order of magnitude higher than those from cotton pads. The following values are indicative of the relative trends (but not necessarily absolute values) in emission yields: 26% of the mass of the latex was converted to soot, 11% of which was condensed PAC. Only 2% of the mass of cotton pads was converted to soot, and only 3% of the weight of that soot was condensed PAC. The PAC yields from latex were comparable to those from TDF. The PAC yields from cotton were higher than those from coal. A notable exception to this trend was that the three-ring gas-phase PAC yields from cotton were more significant than those from latex. Emission yields of CO and CO2 from batch combustion of cotton were, respectively, comparable and higher than those from latex, despite the fact that the carbon content of cotton was half that of latex. This is indicative of the more effective combustion of cotton. Nearly all of the mass of carbon of cotton gasified to CO and CO2 while only small fractions of the carbon in latex were converted to CO2 and CO (20% and 10%, respectively). Yields of NOx from batch combustions of latex and cotton accounted for 15% and 12%, respectively, of the mass of fuel nitrogen indicating that more fuel nitrogen was converted to NOx in the former case, possibly due to higher flame temperatures. No SO2 emissions were detected, indicating that during the fuel-rich combustion of latex, its sulfur content was converted to other compounds (such as H2S) or remained in the soot.     

Dissolved organic matter fractions formed during composting of winery and distillery residues: evaluation of the process by fluorescence excitation-emission matrix

The aim of the present paper is to assess the maturity degree reached by different samples of several mixtures from winery and distillery residues composted using the Rutgers composting system, by means of excitation-emission matrix (EEM) fluorescence spectroscopy. The composts were sampled once a week for about 200d. EEM spectra indicate the presence of different fluorophores. The fluorescence intensities of these peaks show trends related to the maturity of the composting samples selected. The "contour density" of EEM maps is strongly modified through time. We have used the quantitative method of fluorescence regional integration (FRI). The EEMs were delineated into five excitation-emission regions. The degree of compost maturity could be correlated with the percentage of the volumetric integration under the EEM within each region. Further refinement of these techniques should provide a relatively rapid method for assessing the suitability of the compost to soil application.     

Tracing sources of atmospheric sulphur using epiphytic lichens

The overall objective of this work was to measure the spatial variation of sulphur isotopic composition of lichens across the island of Newfoundland in order to assess the degree to which the atmosphere is being affected by long-range transport of anthropogenic sulphur from eastern North America, and/or local pollution sources. A contour map (based on over 80 composite samples of the lichen Alectoria sarmentosa) illustrates the spatial distribution of sulphur isotopic composition of the Newfoundland atmosphere. It shows a gradient of delta(34)S of sulphur in lichen, decreasing from the coast to the interior of the island. It also shows local anomalies corresponding to the city of St. John's, the Come-By-Chance Oil Refinery, mining areas and fossil-fuel powered pulp and paper mills in central and western Newfoundland. The study strongly suggests that the isotopic composition of sulphur in the Newfoundland atmosphere is influenced more by the ocean (sea salt sulphate) and local anthropogenic activities in the province, than by long-range transport of continental North American sulphate.     

Formaldehyde Dose-Response in Healthy Nonsmokers

Industrial, commercial, and domestic levels of formaldehyde exposure range from <0.1 to >5.0 ppm. Irritation of the eyes and upper respiratory tract predominate, and bronchoconstriction is described in case reports. However, pulmonary function and irritant symptoms together have not been assessed over a range of HCHO concentrations in a controlled environment. We investigated dose response in both symptoms and pulmonary function associated with 3-h exposures to 0.0-3.0 ppm HCHO in a controlled environmental chamber. Ten subjects were randomly exposed to 0.0, 0.5, 1.0, and 2.0 ppm HCHO at rest plus 2.0 ppm HCHO with exercise and nine additional subjects were randomly exposed to 0.0,1.0,2.0, and 3.0 ppm HCHO at rest plus 2.0 ppm HCHO with exercise. Significant dose-response relationships in odor and eye irritation were observed (p < 0.05). Nasal flow resistance was increased at 3.0 ppm (p < 0.01), but not at 2.0 ppm HCHO. There were no significant decrements in pulmonary function (FVC, FEV₁, FEF_25-75%, SGaw) or increases in bronchial reactivity to methacholine (log PD_35SGaw) with exposure to 0.5-3.0 ppm HCHO at rest or to 2.0 ppm HCHO with exercise.     

Nutrient accumulation in trees and soil following irrigation with municipal effluent in Australia

Irrigation of tree crops is being evaluated as a method of land disposal of municipal effluent in Australia. A study was carried out from 1980-84 in which seven tree species were sprinkler-irrigated with effluent at an annual rate of 1191-1752 mm. Effective weed control and frequent irrigation resulted in good survival of all species (range 83-100%) at 12 months. Total productivity was estimated at age 4 years by measuring biomass of each species inclusive of litter and roots to a soil depth of 80 cm. Biomass production of the high-yielding species, flooded gum (Eucalyptus grandis) and Sydney blue gum (E. saligna), was around 10 kg m(-2). Percentage leaf mass of these species was small (8-9%) compared with 25% and 29% for the relatively slow-growing river she-oak (Casuarina cunninghamiana) and radiata pine (Pinus radiata). Accumulation of nutrients in the total biomass differed significantly between species and ranged from 34-54 g m(-2) for nitrogen, 4.0-10.4 g m(-2) for phosphorus, 2.1-12.2 g m(-2) for sodium, 22-34 g m(-2) for potassium, 12-61 g m(-2) for calcium and 4.7-9.3 g m(-2) for magnesium. River she-oak and river red gum (E. camaldulensis), because of their relatively large crown and litter masses, accumulated more nitrogen, phosphorus, potassium and calcium than flooded gum or Sydney blue gum. Chemical properties of soils (0-150 cm) were measured in 1980 and again in 1984. Irrigation significantly increased pH (by around 1 unit), throughout the profile. Concentrations of total phosphorus, and exchangeable sodium, calcium and magnesium were increased in the upper profile. Overall, soil chemical properties were not adversely affected by effluent irrigation over the 4-year period, though there was a trend towards more sodic conditions in the soil profile. Nutrient accumulation in soil occurred mainly in the 0-35 cm depth, coinciding with the main root zone of the trees. Renovation of the effluent was therefore estimated as the amount of each nutrient accumulated in the biomass (averaged over the seven species) plus soil (0-35 cm), expressed as a percentage of amount applied in irrigation over the 4 years; that is, nitrogen, 29%; phosphorus, 78%; sodium, 15%; potassium, 26%; calcium, 98% and magnesium, 54%.     

The influence of gill and liver metabolism on the predicted bioconcentration of three pharmaceuticals in fish

The potential for xenobiotic compounds to bioconcentrate is typically expressed through the bioconcentration factor (BCF), which has gained increased regulatory significance over the past decade. Due to the expense of in vivo bioconcentration studies and the growing regulatory need to assess bioconcentration potential, BCF is often calculated via single-compartment models, using K(OW) as the primary input. Recent efforts to refine BCF models have focused on physiological factors, including the ability of the organism to eliminate the compound through metabolic transformation. This study looks at the ability of in vitro biotransformation assays using S9 fractions to provide an indication of metabolic potential. Given the importance of the fish gill and liver in metabolic transformation, the metabolic loss of ibuprofen, norethindrone and propranolol was measured using rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) gill and liver S9 fractions. Metabolic transformation rates (k(M)) were calculated and integrated into a refined BCF model. A significant difference was noted between BCF solely based on K(OW) and BCF including k(M). These studies indicate that the inclusion of k(M) in BCF models can bring predicted bioconcentration estimates closer to in vivo values.     

The solid-phase controls on the mobility of heavy metals at the Copper Cliff tailings area, Sudbury, Ontario, Canada

The Copper Cliff Tailings Disposal Area, located near Sudbury, Ontario, covers an area of approximately 2200 ha and constitutes more than 10% of the total area of all mine tailings in Canada. The area has been utilized since 1936, receiving sulphide-containing tailings from the Inco Sudbury operations. Field measurements of pore-gas oxygen and carbon dioxide in the vadose zone indicate that sulphide oxidation has progressed to depths of 1.6 m to 1.7 m within the tailings. The oxidation of sulphide minerals within the vadose zone, and the accompanying dissolution of carbonate and aluminosilicate minerals within these tailings releases SO₄, Fe(II) and other metals to the pore water. In the vadose and saturated zones, concentrations of Fe and Ni exceed 10100 mg/l and 2210 mg/l, respectively. These high concentrations of dissolved metals are attenuated by a series of precipitation, coprecipitation and adsorption reactions. The precipitation of secondary sulphate and hydroxide phases also create hardpan layers at or near the oxidation front. Geochemical modelling of the pore-water chemistry suggests that pH-buffering reactions are occurring within the shallow oxidized zones, and that secondary-phase precipitation is occurring at or near the underlying hardpan and transition zones. Mineralogical study of the tailings confirmed the presence of jarosite, gypsum and goethite within the shallow tailings, suggesting that these phases are controlling the dissolved concentrations of Fe, SO₄ and Ca. Extraction experiments conducted on the tailings solids indicate that the constituents contained in the water-soluble fraction of the shallow, weathered tailings are derived from the original pore water and the dissolution of highly soluble phases such as gypsum. The acid-leachable fraction of the weathered tailings accounts for up to 25% of the heavy metals, and the reducible fraction may contain up to 100% of the heavy metals within the shallow, weathered tailings. Based on the pore water profiles and the geochemistry of the tailings solids, a relative mobility scale of Fe=Mn=Ni=Co>Cd Zn>Cr=Pb>Cu can be determined.     

Antimony distribution and environmental mobility at an historic antimony smelter site, New Zealand

A historic antimony smelter site at Endeavour Inlet, New Zealand has smelter residues with up to 17 wt.% antimony. Residues include coarse tailings (cm scale particles, poorly sorted), sand tailings (well sorted) and smelter slag (blocks up to 30 cm across). All of this material has oxidised to some degree over the ca. 100 years since the site was abandoned. Oxidation has resulted in acidification of the residues down to pH 2-5. Smelter slag contains pyrrhotite (FeS) and metallic antimony, and oxidation is restricted to surfaces only. The coarse tailings are the most oxidised, and few sulfide grains persist. Unoxidised sand tailings contain 10-20 vol.% stibnite (Sb2S3) containing up to 5% As, with subordinate arsenopyrite (FeAsS), and minor pyrite (FeS2). The sand tailings are variably oxidised on a scale of 2-10 cm, but original depositional layering is preserved during oxidation and formation of senarmontite (Sb2O3). Oxidation of sand tailings has resulted in localised mobility of both Sb and As on the cm scale, resulting in redistribution of these metalloids with iron oxyhydroxide around sand grain boundaries. Experiments demonstrate that Sb mobility decreases with time on a scale of days. Attenuation of both As and Sb occurs due to adsorption on to iron oxyhydroxides which are formed during oxidation of the smelter residues. There is no detectable loss of Sb or As from the smelter site into the adjacent river, <50 m away, which has elevated Sb (ca. 20 microg/l) and As (ca. 7 microg/l) from mineralised rocks upstream. Despite the high concentrations of Sb and As in the smelter residues, these metalloids are not being released into the environment.