The effect of the presence of trace metals on the oxidation of Sb(III) by hydrogen peroxide in aqueous solution

Despite its importance for understanding the behaviour of antimony in the environment, the oxidation kinetics of Sb(III) with natural oxidants is still not well understood. We have studied the oxidation of Sb(III) by hydrogen peroxide on a time scale of hours in the presence of some trace metals, Cu(II), Mn(II), Zn(II) and Pb(II), under pH and concentration conditions close to natural ones. The effects that these trace metals have on Sb(iii) oxidation by hydrogen peroxide vary. Zn(II) had no catalytic effect at all, but Cu(II), Mn(II) and Pb(II) did, though their effects were not uniform. Cu(II) significantly accelerated the reaction, which remained first-order with respect to Sb(III) at any Cu(II) concentration tested. Pb(II) and Mn(II) also enhanced the reaction rates, but the apparent order of the reaction with respect to Sb(III) changed to two. The trace metal effect observed was concentration dependent for Pb(II). The addition of the hydroxyl radical scavenger 2-propanol suggests that the trace metal catalytic effect observed involves the action of hydroxyl radicals, but that they are not responsible for the oxidation of Sb(III) by H2O2 in the absence of trace metals. The fact that Sb(III) can be oxidized by hydroxyl radicals present in water, even if it is not capable of producing them, has important environmental implications because hydroxyl radicals are known to be abundant in many natural waters such as seawater, humic-rich surface waters or rainwater.     

Managing brown bears and wilderness recreation on the Kenai Peninsula,Alaska, USA

The Russian River-Cooper Lake-Resurrection River trail system, on the Kenai Peninsula, Alaska, traverses essential brown bear habitat. To set management guidelines for this area, the trail system was monitored using questionnaire cards and electronic trail counters from 1984 through 1987. This helped to determine the extent and type of human use and human-bear encounters in the area. Management recommendations were intended to reduce the potential displacement of brown bears by hikers and to inform wilderness users of the proper camping techniques to avoid attracting bears to the campsite. An average of 5800 visitors hiked or camped along the trail system each year. Encounters between hikers and brown bears averaged 7/yr while encounters with black bears averaged 35/yr. Minor problems occurred with both the electronic trail counters and the questionnaire. Modilications to these methods are discussed. A Limits of Acceptable Change format should be considered for the trail system to determine the character and future direction of recreational activities and monitoring of the trail system should continue in the future.     

A mechanistic model for mercury capture with in situ-generated titania particles: role of water vapor

A mechanistic model to predict the capture of gas-phase mercury (Hg) species using in situ-generated titania nanosize particles activated by UV irradiation is developed. The model is an extension of a recently reported model for photochemical reactions by Almquist and Biswas that accounts for the rates of electron-hole pair generation, the adsorption of the compound to be oxidized, and the adsorption of water vapor. The role of water vapor in the removal efficiency of Hg was investigated to evaluate the rates of Hg oxidation at different water vapor concentrations. As the water vapor concentration is increased, more hydroxy radical species are generated on the surface of the titania particle, increasing the number of active sites for the photooxidation and capture of Hg. At very high water vapor concentrations, competitive adsorption is expected to be important and reduce the number of sites available for photooxidation of Hg. The predictions of the developed phenomenological model agreed well with the measured Hg oxidation rates in this study and with the data on oxidation of organic compounds reported in the literature.     

Experimental design methodology for the preparation of carbonaceous sorbents from sewage sludge by chemical activation--application to air and water treatments

The objective of this study is to optimize experimental conditions of sorbent preparation from sewage sludge using experimental design methodology. Series of carbonaceous sorbents have been prepared by chemical activation with sulfuric acid. The sorbents produced were characterized, and their properties (surface chemistry, porous and adsorptive properties) were analyzed as a function of the experimental conditions (impregnation ratio, activation temperature and time). Carbonaceous sorbents developed from sludge allow copper ion, phenol and dyes (Acid Red 18 and Basic Violet 4) to be removed from aqueous solution as well as VOC from gas phase. Indeed, according to experimental conditions, copper adsorption capacity varies from 77 to 83 mg g(-1), phenol adsorption capacity varies between 41 and 53 mg g(-1) and VOC adsorption capacities (acetone and toluene) range from 12 to 54 mg g(-1). Each response has been described by a second-order model that was found to be appropriate to predict most of the responses in every experimental region. The most influential factors on each experimental design response have been identified. Regions in which optimum values of each factor were achieved for preparation of activated carbons suitable for use in wastewater and gas treatments have been determined using response surfaces methodology. In order to have a high mass yield and to minimize the energetic cost of the process, the following optimal conditions, 1.5 g of H2SO4 g(-1) of sludge, 700 degrees C and 145 min are more appropriate for use of activated carbon from sludge in water and gas treatments.     

Heavy metal contamination in the Tanat Valley,North Wales

The Tanat Valley area of North Powys, Wales, has a long history of metalliferous mining, the most active period of extraction being during the 18th century, while the largest mine, Llangynog, was in production until 1899. Ore minerals found in the area include galena (PbS), sphalerite (ZnS) and chalcopyrite (CuFeS2). Below the Llangynog mine the valley is heavily contaminated with elevated levels of Pb, Zn, Cu and Cd in soils and river sediments. On the valley floor subsoil metal levels frequently greatly exceed those of topsoils which probably reflects contamination of the floodplain during the peak period of mining. High levels of base metals in the stream sediments some 2 km downstream of the mine area are thought to be due to river erosion of the contaminated bank material. Contamination derived from the old mine tips results in extremely high levels of heavy metals in soils and stream sediments in the immediate vicinty of the old workings. Some metal contamination is also thought to derive from previously undetected mineralisation.     

Addressing analytical uncertainties in the determination of trichloroacetic acid in soil

Soil is an important compartment in the environmental cycling of trichloroacetic acid (TCA), but soil TCA concentration is a methodologically defined quantity; analytical methods either quantify TCA in an aqueous extract of the soil, or thermally decarboxylate TCA to chloroform in the whole soil sample. The former may underestimate the total soil TCA, whereas the latter may overestimate TCA if other soil components (e.g. humic material) liberate chloroform under the decarboxylation conditions. The aim of this work was to show that extraction and decarboxylation methods yield different TCA concentrations because the decarboxylation method can also determine "bound" TCA. Experiments with commercial humic acid solutions showed there was no additional chloroform formation under decarboxylation conditions, and that all TCA in a TCA-humic acid mixture could be quantitatively determined (108 +/- 13%). Anion exchange resin was used as a provider of solid-phase TCA binding; only 5 +/- 1% of a TCA solution mixed with the resin was present in the aqueous extract subsequently separated from the resin, yet the decarboxylation method yielded mass balance (123 +/- 22%) with TCA remaining in the resin. In aqueous extraction of a range of soil samples (with or without added TCA spike), the decarboxylation method was able to satisfactorily account for TCA in the extractant + residue post-extraction, compared with whole-soil TCA (+ spike) pre-extraction: e.g. mass balances for unspiked soil from Sikta spruce and larch forest were 99 +/- 8% and 93 +/- 6%, respectively, and for TCA-spiked forest and agricultural soils were 114 +/- 13% and 102 +/- 2%. In each case recovery of TCA in the extractant was substantially less than 100%(<20% for unspiked soils, <55% for spiked soils). Extraction efficiencies were generally lower in more organic soils. The results suggest that analytical methods which utilise aqueous extraction may underestimate whole-soil TCA concentrations. Application of both methodologies together may enhance insight into TCA behaviour in soil.     

Bioremediation of metal contamination

A study was initiated to evaluate the use of the fungus Aspergillus niger for bioleaching and then todetermine the effect of process steps, the tailingsconcentration and type of substrate. An oxidized miningtailing containing mainly copper (7240 mg kg^-1 tailings) was studied. A sucrose and mineral salts medium was initially used to produce citric and gluconic acids by A. niger atvarious concentrations of tailings (1, 5, 7, 10 and 15% w/v).Maximal removal of up to 60% of the copper was obtained forthe 5% tailings when the organic acid supernatant was addedto the tailings. In a single step process, A. niger wasthen grown in the presence of mining tailings at variousconcentrations. Maximum copper solubilization (63%) occurredwith 10% mining tailings using sucrose as the substrate.Other substrates were then evaluated including molasses, corncobs and brewery waste (10% mining tailings). Sucrose gavethe best results for copper removal, followed by molasses,corn cobs and brewery waste. Other experiments usingultrasound as a pretreatment showed that 80% removal of thecopper could be obtained for a 5% tailings concentration. Inconclusion, leaching of copper from mining tailings istechnically feasible using A. niger but furtherresearch will be required to increase the economic feasibilityof the process.     

HIA and pollution prevention control: What they can learn from each other

Following the implementation of the Pollution Prevention and Control (England and Wales) Regulations on 1st August 2000, health authorities (now Primary Care Trusts) became statutory consultees for permits issued to industry by the environmental regulators (the Environmental Agency, Local Authorities). The aims of this paper are to review the process of providing public health input in the light of its similarities to and differences from HIA and to identify the opportunities for both HIA and PPC to learn from each other's practice. We emphasise the challenges that are encountered by public health professionals who provide the public health input in the PPC. We use both our own experience of providing this input on behalf of health authorities and our expertise in HIA, environmental epidemiology and contaminated land.