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.     

The effects of crude oil and the effectiveness of cleaner application following oiling on US Gulf of Mexico coastal marsh plants

Field studies were conducted in two different marsh habitats in Louisiana coastal wetlands to evaluate the effects of oiling (using South Louisiana Crude oil, SLC) and the effectiveness of a shoreline cleaner (COREXIT 9580) in removing oil from plant canopies. The study sites represented two major marsh habitats; the brackish marsh site was covered by Spartina patens and the freshwater marsh was covered by Sagittaria lancifolia. Field studies were conducted in each habitat using replicated 5.8 m2 plots that were subjected to three treatments; oiled only, oiled + cleaner (cleaner was used 2 days after oiling), and a control. Plant gas exchange responses, survival, growth, and biomass accumulation were measured. Results indicated that oiling led to rapid reductions in leaf gas exchange rates in both species. However, both species in 'oiled + cleaned' plots displayed improved leaf conductance and CO2 fixation rates. Twelve weeks after treatment initiation, photosynthetic carbon fixation in both species had recovered to normal levels. Over the short-term, S. patens showed more sensitivity to oiling with SLC than S. lancifolia as was evident from the data of the number of live shoots and above-ground biomass. Above-ground biomass remained significantly lower than control in S. patens under 'oiled' and 'oiled + cleaned' treatments while it was comparable to controls in S. lancifolia. These studies indicated that the cleaner removed oil from marsh grasses and alleviated the short-term impact of oil on gas exchange function of the study plants. However, use of cleaner had no detectable effects on above-ground biomass production or regeneration at the end of the first growing season in S. patens. Similarly, no beneficial effects of cleaner on carbon fixation and number of live shoots were apparent beyond 12 weeks in S. lancifolia.     

Means to improve the effect of in situ bioremediation of contaminated soil: an overview of novel approaches

Different aspects of bacterial degradation of organic contaminants in soil, and how to improve the efficiency and reproducibility is discussed in this review. Although bioremediation in principle includes the use of any type of organism in improving the condition of a contaminated site, most commonly bacteria are the degraders and other organisms, such as soil animals or plant roots, play a role in dissemination of bacteria and, indirectly, plasmids between bacteria, and in providing nutrients and co-substrates for the bacteria active in the degradation process. There are a number of different procedures that have been tested more-or-less successfully in attempts to improve reliability, cost efficiency and speed of bioremediation. The methods range from minimal intervention, such as mere monitoring of intrinsic bioremediation, through in situ introduction of nutrients and/or bacterial inocula or improvement of physico-chemical conditions, all the way to excavation followed by on site or ex situ composting in its different varieties. In the past the rule has been that more intervention (leading to higher costs) has been more reliable, but novel ideas are continuously tried out, both as a means to come up with new truly functional applications and also as a line of studies in basic soil microbial ecology. Both approaches generate valuable information needed when predicting outcome of remediation activities, evaluating environmental risks, deciding on cleaning-up approaches, etc. The emphasis of this review is to discuss some of the novel methods for which the value has not been clearly shown, but that in our view merit continued studies and efforts to make them work, separately or in combination.     

Acute toxicity of aromatic and non-aromatic fractions of naphthenic acids extracted from oil sands process-affected water to larval zebrafish

The toxicity of oil sands process-affected water (OSPW) has regularly been attributed to naphthenic acids, which exist in complex mixtures. If on remediation treatment (e.g., ozonation) or on entering the environment, the mixtures of these acids all behave in the same way, then they can be studied as a whole. If, however, some acids are resistant to change, whilst others are not, or are less resistant, it is important to establish which sub-classes of acids are the most toxic.     

Long-term increases in surface water dissolved organic carbon: observations, possible causes and environmental impacts

Dissolved organic carbon (DOC) concentrations in 22 UK upland waters have increased by an average of 91% during the last 15 years. Increases have also occurred elsewhere in the UK, northern Europe and North America. A range of potential drivers of these trends are considered, including temperature, rainfall, acid deposition, land-use, nitrogen and CO2 enrichment. From examination of recent environmental changes, spatial patterns in observed trends, and analysis of time series, it is suggested that DOC may be increasing in response to a combination of declining acid deposition and rising temperatures; however it is difficult to isolate mechanisms based on monitoring data alone. Long-term DOC increases may have wide-ranging impacts on freshwater biota, drinking water quality, coastal marine ecosystems and upland carbon balances. Full understanding of the significance of these increases requires further knowledge of the extent of natural long-term variability, and of the natural "reference" state of these systems.     

Photocatalytic oxidation of triclosan

In the spring of 2003, there was an outbreak of the severe respiratory syndrome (SARS) in Hong Kong. Health concerns have thus triggered an increased and predominant use of various types of household cleansing agents such as triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol). However, it has been reported recently that triclosan could be photochemically converted to toxic 2,8-dichlorodibenzo-p-dioxin (2,8-Cl(2)DD) in the environment. It is therefore necessary to develop environmentally friendly methods for the treatment of triclosan. To this end, photocatalytic degradation of triclosan in aqueous solution was conducted using TiO(2) (Degussa P25) under irradiation of UV light (lambda < 365 nm). It was found that triclosan could be degraded by this approach. Hydrogen peroxide was added to enhance the degradation process, and the optimal initial hydrogen peroxide concentration for triclosan degradation was 0.005% (w/v). Product identification indicated that triclosan oxidation occurred at its phenol moiety and yielded quinone and hydroquinone intermediates. The formation of a dichlorophenol intermediate in triclosan degradation suggested bond-breaking of the ether linkage occurred during the process. Moreover, no chlorinated dibenzo-p-dioxin congener was detected. These findings confirm that the photocatalytic degradation of triclosan is an environmentally friendly process.     

Factors influencing arsenic accumulation by Pteris vittata: a comparative field study at two sites

This study compared the factors influencing arsenic (As) accumulation by Pteris vittata at two sites, one containing As along with Au mineralization and the other containing Hg/Tl mineralization. The soils above these two sites contained high As concentrations (26.8-2955 mg kg(-1)). Although the As concentration, pH, soil cation exchange capacity and plant biomass differed significantly between the two sites, no differences were observed in the As concentrations in the fronds and roots, or the translocation factors, of P. vittata, suggesting that this species has consistent As hyperaccumulation properties in the field. The As concentration in the fronds was positively related to phosphorus (P) and potassium (K), but negatively related to calcium (Ca), at one site. This suggested that P, K and Ca influenced As accumulation by P. vittata in the field.     

Mechanisms of lead, copper, and zinc retention by phosphate rock

The solid-liquid interface reaction between phosphate rock (PR) and metals (Pb, Cu, and Zn) was studied. Phosphate rock has the highest affinity for Pb, followed by Cu and Zn, with sorption capacities of 138, 114, and 83.2 mmol/kg PR, respectively. In the Pb-Cu-Zn ternary system, competitive metal sorption occurred with sorption capacity reduction of 15.2%, 48.3%, and 75.6% for Pb, Cu, and Zn, respectively compared to the mono-metal systems. A fractional factorial design showed the interfering effect in the order of Pb>Cu>Zn. Desorption of Cu and Zn was sensitive to pH change, increasing with pH decline, whereas Pb desorption was decreased with a strongly acidic TCLP extracting solution (pH = 2.93). The greatest stability of Pb retention by PR can be attributed to the formation of insoluble fluoropyromorphite [Pb(10)(PO(4))(6)F(2)], which was primarily responsible for Pb immobilization (up to 78.3%), with less contribution from the surface adsorption or complexation (21.7%), compared to 74.5% for Cu and 95.7% for Zn. Solution pH reduction during metal retention and flow calorimetry analysis both supported the hypothesis of retention of Pb, Cu, and Zn by surface adsorption or complexation. Flow calorimetry indicated that Pb and Cu adsorption onto PR was exothermic, while Zn sorption was endothermic. Our research demonstrated that PR can effectively remove Pb from solutions, even in the presence of other heavy metals (e.g. Cu, Zn).     

Status of trace elements in paddy soil and sediment in Taihu Lake region

Thirteen paddy soil profiles and river sediments which are sources of irrigation water were collected around the Taihu Lake, and the trace elements were estimated. The content of La and Ce in paddy soil and sediment were 39.3 and 68.6 mg/kg soil and 36.9 and 65.1 mg/kg soil, being within the range of background values. The values for Pb, Cu, Ni, Cr, Co, Mn, Zn, Se in paddy soil were 23.3, 27.8, 25.5, 63.5, 10.2, 386, 68.7 and 0.25 mg/kg soil respectively, all below the national permission level. There was a decline of Zn in paddy soil. Some of the river sediments were seriously polluted. The river in Yangjin site was most contaminated with 5.47 g Cu/kg and 7.4 g Zn/kg. The high concentration of Pb and Ni also was observed in this sediment. River in Weitang, Huashi, Xinzhuang and Meiyan were contaminated with Pb, Cu and Ni to some extent. Zn, Cu and Pb were the main pollutants in present experiment sites. The fast development of village/township industries have caused severe environmental pollution in the Taihu Lake region, especially irrigation river sediments. Se content in plant and seed was 0.04 and 0.03 mg/kg respectively, showed Se-deficiency in paddy soil in the Taihu Lake region.