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.     

EDTA and HEDTA effects on Cd, Cr, and Ni uptake by Helianthus annuus

Phytoremediation has shown great potential as an alternative treatment for the remediation of heavy-metal-contaminated soils and groundwater. However, the lack of a clear understanding pertaining to metal uptake/translocation mechanisms, enhancement amendments, and external effects on phytoremediation has hindered its full-scale application. The objective of this research was to investigate the ability of synthetic chelators for enhancing the phytoremediation of cadmium-, chromium- and nickel-contaminated soil. Ethylenediaminetriacetic acid (EDTA) and N-(2-hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA) were applied to the soil at various dosages to elevate metal mobility. Uptake into and translocation within Helianthus annuus was determined. It was found that EDTA at a rate of 0.5 g/kg significantly increased the shoot concentrations of Cd and Ni from 34 and 15 to 115 and 117 mg/kg, respectively. The total removal efficiency for EDTA was 59 microg/plant. HEDTA at the same application rate resulted in a total metal uptake of 42 microg/plant. These research demonstrated that chelator enhancement is plant- and metal-specific and is subjective to inhibition when multiple heavy metals are present. Results also showed that chelator toxicity reduced the plant's biomass, thereby decreasing the amount of metal accumulation.     

Application of a constructed wetland for industrial wastewater treatment: a pilot-scale study

The main objective of this study was to examine the efficacy and capacity of using constructed wetlands on industrial pollutant removal. Four parallel pilot-scale modified free water surface (FWS) constructed wetland systems [dimension for each system: 4-m (L)x1-m (W)x1-m (D)] were installed inside an industrial park for conducting the proposed treatability study. The averaged influent contains approximately 170 mg l(-1) chemical oxygen demand (COD), 80 mg l(-1) biochemical oxygen demand (BOD), 90 mg l(-1) suspend solid (SS), and 32 mg l(-1) NH(3)-N. In the plant-selection study, four different wetland plant species including floating plants [Pistia stratiotes L. (P. stratiotes) and Ipomoea aquatica (I. aquatica)] and emergent plants [Phragmites communis L. (P. communis) and Typha orientalis Presl. (T. orientalis)] were evaluated. Results show that only the emergent plant (P. communis) could survive and reproduce with a continuous feed of 0.4m(3)d(-1) of the raw wastewater. Thus, P. communis was used in the subsequent treatment study. Two different control parameters including hydraulic retention time (HRT) (3, 5, and 7d) and media [vesicles ceramic bioballs and small gravels, 1cm in diameter] were examined in the treatment study. Results indicate that the system with a 5-d HRT (feed rate of 0.4m(3)d(-1)) and vesicles ceramic bioballs as the media had the acceptable and optimal pollutant removal efficiency. If operated under conditions of the above parameters, the pilot-plant wetland system can achieve removal of 61% COD, 89% BOD, 81% SS, 35% TP, and 56% NH(3)-N. The treated wastewater meets the current industrial wastewater discharge standards in Taiwan.     

Modelling episodic acidification of surface waters: the state of science

Field studies of chemical changes in surface waters associated with rainfall and snowmelt events have provided evidence of episodic acidification of lakes and streams in Europe and North America. Modelling these chemical changes is particularly challenging because of the variability associated with hydrological transport and chemical transformation processes in catchments. This paper provides a review of mathematical models that have been applied to the problem of episodic acidification. Several empirical approaches, including regression models, mixing models and time series models, support a strong hydrological interpretation of episodic acidification. Regional application of several models has suggested that acidic episodes (in which the acid neutralizing capacity becomes negative) are relatively common in surface waters in several regions of the US that receive acid deposition. Results from physically based models have suggested a lack of understanding of hydrological flowpaths, hydraulic residence times and biogeochemical reactions, particularly those involving aluminum. The ability to better predict episodic chemical responses of surface waters is thus dependent upon elucidation of these and other physical and chemical processes.     

Chlorinated hydrocarbon contaminants in Hong Kong surficial sediments.

Twenty surficial sediments were sampled from nearshore Hong Kong waters during 1997-1998, and analyzed for a range of chlorinated pesticides and polychlorinated biphenyls (PCBs). Results showed that concentrations (on a dry weight basis) of total HCHs were in the range 0.1-16.7 ng g-1, and total DDTs 0.3-14.8 ng g-1. PCBs, measured as an Aroclor 1242, 1248, 1254, 1260 (1:1:1:1) mixture, were found to be in a range of 0.5-97.9 ng g-1, and were at highest concentrations in Victoria Harbour. Results indicated that chlorinated pesticides and PCBs in Hong Kong nearshore sediments were most likely derived from waste discharge from a variety of sources, including agricultural, sewage, industrial waste disposal and shipping-related activities. In addition, as the north and west sides of Hong Kong are subject to influence from the Pearl River (due mainly to agricultural activities in the Pearl River Delta, and to a lesser extent developments around the Shenzhen Special Economic Zone), these inputs are also thought to be likely sources of contamination.     

Bioavailability of persistent organic pollutants in soils and sediments--a perspective on mechanisms, consequences and assessment

It has been observed that as soil-pollutant contact time increases, pollutant bioavailability and extractability decreases. This phenomenon has been termed 'ageing'. Decreased chemical extractability with increased soil-chemical contact time is evident where both 'harsh' techniques, e.g. dichloromethane Soxhlet extraction, and 'non-exhaustive' techniques, e.g. butanol shake extraction, have been used. It has also been observed that the amount of chemical extracted by these techniques varies considerably over time. Similarly, decreases in bioavailability with increased soil-pollutant contact time have been described in bacterial, earthworm and other organism studies. From these investigations, it has been shown that the fraction of pollutant determined to be bioavailable can vary between organisms. Thus, there is an immediate definition problem, what is bioavailability? Additionally, if bioavailability is to be assessed by a chemical means, which organisms should (or can) be mimicked by the extraction procedure? This review provides a background to the processes inherent to ageing, a discussion of its consequences on bioavailability and ends with some reflections on the appropriateness of chemical extraction techniques to mimic bioavailability     

An assessment of endocrine disrupting activity changes during wastewater treatment through the use of bioassays and chemical measurements.

The objective of this study was to assess the removal efficiencies of secondary wastewater treatment processes for compounds causing endocrine disrupting activity. The study used bioassays and chemical measurements, such as gas chromatography with mass spectrometry and enzyme immunosorbent assays. A total of seven full-scale water reclamation facilities using different unit operations and two pilot-scale membrane bioreactors were examined. Findings of this study imply that estrogenic disrupting activity in primary effluent is mainly caused by two steroidal hormones (17beta-estradiol and estriol) and, to a lesser extent, by synthetic chemicals, such as bisphenol A, 4-nonylphenol, and 4-tert-octylphenol. During secondary treatment, steroidal hormones were removed to a higher degree than nonylphenol and bisphenol A. The total estrogenic activity was removed by an average of 96%. The remaining concentrations of targeted steroids in secondary effluents, except for estriol, still had the potential to elicit a positive response in the human breast cell cancer assay. For the majority of facilities, the remaining activity was likely attributed to residual concentrations of two steroidal hormones (17beta-estradiol and estriol).     

The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.