Provenancing anthropogenic Pb within the fluvial environment: developments and challenges in the use of Pb isotopes

The potentially deleterious presence of ore-derived Pb within riverine environments has been a long-term impact of industrial and anthropogenic activity in general. The surface drainage network has been widely established as a key transport mechanism and storage environment for anthropogenically-derived Pb and other potentially harmful trace metals. Lead isotopes ((204)Pb, (206)Pb, (207)Pb, (208)Pb) have been utilized as a geochemical tracer of Pb origin in a variety of environmental media, notably in atmospheric aerosols. However, given the relative complexity of dispersal processes within riverine environments, the use of Pb isotopes as geochemical tracers has been relatively limited and it is only relatively recently that a growing body of research has applied Pb isotopes to provenancing fluvially-dispersed Pb. This paper seeks to synthesize the developments in the use of Pb isotopes within riverine environments. In doing so it outlines the Pb-isotope fingerprinting technique and associated analytical developments, and assesses the application of Pb isotopes in establishing the origin and dispersal mechanisms of anthropogenically- and geogenically-derived Pb at a range of temporal and spatial scales. Of particular importance are the approaches quantifying source inputs using Pb isotopic signatures and the challenges faced, and options available in quantifying source inputs at the catchment scale; where Pb may be sourced from a variety (n=>2) of sources. The Pb isotopic signature of contemporary riverine Pb loads is shown to reflect a spatially complex influence of mineralization chemistry, anthropogenic activity as well as the hydro-morphological controls exerted upon Pb release, dispersal and storage. In relation to this, the long-term environmental legacy, and its influence upon Pb fingerprinting studies, of tetra-ethyl Pb, sourced from the combustion of leaded-petrol is also discussed. Finally, this paper places the use of Pb isotopes in the context of recently developed Cu and Zn isotopic fingerprinting techniques and assesses the role of Pb, Cu and Zn isotopes in a multi-proxy approach to geochemical tracing.     

Comprehensive two-dimensional gas chromatography time of flight mass spectrometry (GC×GC-TOFMS) for environmental forensic investigations in developing countries

The disposal and dumping of toxic waste is a matter of growing concern in developing countries, including South Africa. Frequently these countries do not possess access to gas chromatography-high resolution mass spectrometry (GC-HRMS) for the determination of persistent organic pollutants (POPs). This publication describes an alternative approach to the investigation of toxic waste using comprehensive gas chromatography coupled to time of flight mass spectrometry (GC × GC-TOFMS). The technology permits both comprehensive screening of toxic samples for numerous classes of organic pollutants and also quantitative analysis for the individual compounds. This paper describes the use of this technique by analysing samples obtained from a hazardous waste treatment facility in South Africa. After sampling and extraction the samples were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and four dioxin-like non-ortho substituted polychlorinated biphenyls (PCBs). The quantitative values, as well as detection limits, obtained using the GC × GC-TOFMS methodology compares well with those obtained using GC-HRMS; the accepted benchmark technology for this analysis. Although GC × GC-TOFMS is not a target compound analytical technique (as is GC-HRMS), it is possible to obtain information on numerous other classes of organic pollutants present in the samples in one analytical run. This is not possible with GC-HRMS. Several different column combinations have been investigated for handling very complex waste samples and suggestions are presented for the most suitable combination.     

The role of hydrostatic pressure on developmental stages of Pomatoceros lamarcki (Polychaeta: Serpulidae) exposed to water accommodated fractions of crude oil and positive genotoxins at simulated depths of 1000-3000 m

The effect of high hydrostatic pressures on the ecotoxicological profile of pollutants is an unexplored research area. Using Pomatoceros lamarcki as a surrogate organism for this eco-barotoxicological study, it was found that in a 48 h larval bioassay with water accommodated fractions (WAF) of crude oil of up to 15.1 mg L⁻¹ (total hydrocarbon content) and hydrostatic pressures up to 300 bar (3000 m), an additive response was found (p < 0.001) rather than any synergism (p = 0.881). Comprehensive cytogenetic analysis of 6-h (15 °C) embryos exposed to WAF (0.19 mg L⁻¹) at 100 bar showed no effects on mitotic fidelity or cell division rate over the 1 bar treatment. However, embryo's treated with the clastogen mitomycin-c at 100 bar exhibited a significant increase in mitotic aberrations over 1 bar treated as was the case with hypo/hypersaline treatments (p < 0.05). Conversely, an increase in hydrostatic pressure actually reduced the effects of spindle inhibition by the aneugen colchicine (p < 0.05).     

The demography of feral alfalfa (<Emphasis Type="BoldItalic">Medicago sativa</Emphasis> L.) populations occurring in roadside habitats in Southern Manitoba,Canada: implications for novel trait confinement

Purpose  

Feral populations of cultivated crops can act as reservoirs for novel genetically engineered (GE) traits and aid in trait movement at the landscape level. However, little information is available on the potential of cultivated crops to become feral. In this study, we investigated the ferality of alfalfa populations (non-GE version) occurring in roadside habitats. Knowledge on the nature of roadside alfalfa populations would be useful for designing efficient trait confinement protocols and coexistence strategies in alfalfa.     

Neighbourhood-based waste management: a solution for solid waste problems in Jakarta, Indonesia

Municipal solid waste management in the capital city of Indonesia, Jakarta, is examined from a point of view of researchers and waste management practitioners. Major impediments to waste management in Jakarta include non-involvement of stakeholders in planning and decision-making, unskilled staff undertaking the duty, the absence of long-term waste management strategies, and weak coordination between authorities and neighbourhood association workers who undertake primary collection. It was revealed that lack of resources is seen as the least important of all impediments. The success of managing solid waste in Jakarta cannot be separated from the presence and the role of a neighbourhood association, which performs waste collection on a daily basis as well as keeping their respective areas clean by employing their own waste service workers. A neighbourhood-based waste management strategy is a promising solution for Jakarta, because it is more applicable and suitable for Jakarta's context compared to community-based waste management. The performance of this approach is examined and the improvement for wider adoption is discussed for a long-term solution.     

Biomonitoring with Gammarus pulex at the Meuse (NL), Aller (GER) and Rhine (F) rivers with the online Multispecies Freshwater Biomonitor

Biological early warning systems represent a set of tools that may be able to respond to certain chemical monitoring requirements of recent European legislation, the Water Framework Directive (WFD2000/60/EC), that aims to improve and protect water quality across Europe. In situ biomonitoring was performed along the rivers Meuse (NL), Aller (GER) and Rhine (F) within the frame of the European Union-funded Project SWIFT-WFD. Gammarus pulex was used as a test organism during the evaluation of the Multispecies Freshwater Biomonitor(R) (MFB), an online biomonitor to quantitatively record different behaviour patterns of animals. At the river Meuse G. pulex reacted to pulse exposure of either a mixture of trace metals or of several organic xenobiotics, by showing up to 20% decreased locomotory activity (already at the 1st pulse) and increased mortality (at 2nd or 3rd pulse only). G. pulex deployed within the MFB system were observed to survive well at the monitoring station on the Aller (100%) and monitoring did not result in the measurement of chemical irregularities. In contrast, deployment at the monitoring station on the Rhine river demonstrated that the test organism was able to detect chemical irregularities by up to 20% decreased locomotory activity in the animals. The MFB proved to be an alert system for water quality monitoring at sensitive sites and sites with accidental pollution.     

Degradation of octylphenol and nonylphenol by ozone - part II: indirect reaction

The indirect reaction of octylphenol (OP) and nonylphenol (NP) with hydroxyl radicals (*OH) during ozonation was investigated at pH values ranging from 6 to 9. A parameter Rct, representing the ratio of the *OH-exposure to the ozone-exposure, was measured using a method involving a low concentration of p-chlorobenzoic acid as a *OH-probe compound during the ozonation. By assuming that Rct is a constant value at a given pH, the second order rate constants of the alkylphenol reaction with hydroxyl radicals were determined as 1.4(+/-0.2) x 10(10) and 1.1(+/-0.2) x 10(10) M(-1) s(-1) for OP and NP, respectively. The proportions of each alkylphenol degraded by direct molecular ozone reaction and indirect hydroxyl radical reaction were predicted at different pH values. The contribution of indirect *OH reactions with each AP was found to represent over 50% of the total degradation for pH approximately 7, and the contribution increases substantially with pH>7.     

Chemcatcher and DGT passive sampling devices for regulatory monitoring of trace metals in surface water

This work aimed to evaluate whether the performance of passive sampling devices in measuring time-weighted average (TWA) concentrations supports their application in regulatory monitoring of trace metals in surface waters, such as for the European Union's Water Framework Directive (WFD). The ability of the Chemcatcher and the diffusive gradient in thin film (DGT) device sampler to provide comparable TWA concentrations of Cd, Cu, Ni, Pb and Zn was tested through consecutive and overlapping deployments (7-28 days) in the River Meuse (The Netherlands). In order to evaluate the consistency of these TWA labile metal concentrations, these were assessed against total and filtered concentrations measured at relatively high frequencies by two teams using standard monitoring procedures, and metal species predicted by equilibrium speciation modeling using Visual MINTEQ. For Cd and Zn, the concentrations obtained with filtered water samples and the passive sampling devices were generally similar. The samplers consistently underestimated filtered concentrations of Cu and Ni, in agreement with their respective predicted speciation. For Pb, a small labile fraction was mainly responsible for low sampler accumulation and hence high measurement uncertainty. While only the high frequency of spot sampling procedures enabled the observation of higher Cd concentrations during the first 14 days, consecutive DGT deployments were able to detect it and provide a reasonable estimate of ambient concentrations. The range of concentrations measured by spot and passive sampling, for exposures up to 28 days, demonstrated that both modes of monitoring were equally reliable. Passive sampling provides information that cannot be obtained by a realistic spot sampling frequency and this may impact on the ability to detect trends and assess monitoring data against environmental quality standards when concentrations fluctuate.     

Assessing multiple novel tracers to improve the understanding of the contribution of agricultural farm waste to diffuse water pollution

A study was undertaken on drained and undrained 1 ha grassland lysimeters to assess the effectiveness of multiple novel tracing techniques in understanding how agricultural slurry waste moves from land to water. Artificial fluorescent particles designed to mimic the size and density of organic slurry particles were found to move off the grassland via inter-flow (surface + lateral through-flow) and drain-flow. Where both pathways were present the drains carried the greater number of particles. The results of the natural fluorescence and δ13C of water samples were inconclusive. Natural fluorescence was higher from slurry-amended lysimeters than from zero-slurry lysimeters, however, a fluorescence decay experiment suggested that no slurry signal should be present given the time between slurry application and the onset of drainage. The δ13C values of >0.7 microm and <0.7 microm material in drainage were varied and unrelated to discharge. The mean value of >0.7 microm δ13C in water from the drain-flow pathways was higher from the lysimeter which had received naturally enriched maize slurry compared to the lysimeter which received grass slurry indicating a contribution of slurry-derived material. Values of <0.7 microm δ13C from the same pathway, however, produced counter intuitive trends and may indicate that different fractions of the slurry have different δ13C values.     

Distribution and partitioning of depleted uranium (DU) in soils at weapons test ranges - investigations combining the BCR extraction scheme and isotopic analysis

Depleted uranium (DU) has become a soil contaminant of considerable concern in many combat zones and weapons-testing sites around the world, including locations in Europe, the Middle East and the USA, arising from its dispersion via the application of DU-bearing munitions. Once DU is released into the environment its mobility and bioavailability will, like that of other contaminants, largely depend on the type of associations it forms in soil and on the nature of the soil components to which it binds. In this study we used the BCR sequential extraction scheme to determine the partitioning of DU amongst soil fractions of texturally varying soils from locations affected by weapons-testing activities. Isotopic analyses (MC-ICP-MS and alpha-spectrometry) were performed to verify the presence of DU in whole soils and soil fractions and to determine any preferential partitioning of the contaminant. Results identified soil organic matter as being consistently the most important component in terms of DU retention, accounting for 30-100% of DU observed in the soils examined. However, at greater distances from known contamination points, DU was also found to be largely associated with the exchangeable fraction, suggesting that DU can be mobilised and transported by surface and near-surface water and does remain in an exchangeable (and thus potentially bioavailable) form in soils.