Diffuse sources of heavy metals entering an urban wastewater catchment

New legislation such as the Water Framework Directive (WFD) will require Member States to better understand the concentrations and loads of contaminants entering surface waters. This will include inputs from wastewater treatment plants (WWTP) as well as from other urban, industrial and agricultural sources. A review of available literature revealed a shortage of data on the levels and sources of heavy metals entering WWTP from urban sources. As a consequence, the concentrations of heavy metals (cadmium, chromium, copper, mercury, nickel, lead and zinc) were determined in the wastewater from an urban catchment located in the UK, as part of a project undertaken for UK Water Industry Research (UKWIR). Both foul and surface water samples were taken. Metal concentrations varied considerably in the foul water samples, both between sources and over the course of the week. Concentrations of most metals were higher in the Monday town centre samples, attributed to leaching from stagnant water remaining in the pipework of office buildings over the weekend. Runoff concentrations were higher in the light industrial estate samples than in the domestic samples for all the metals, and exhibited highest levels in the 'first flush' samples, coincident with the initial flow of runoff containing the highest concentrations of suspended solids.     

Assessing the natural attenuation of organic contaminants in aquifers using plume-scale electron and carbon balances: model development with analysis of uncertainty and parameter sensitivity

A quantitative methodology is described for the field-scale performance assessment of natural attenuation using plume-scale electron and carbon balances. This provides a practical framework for the calculation of global mass balances for contaminant plumes, using mass inputs from the plume source, background groundwater and plume residuals in a simplified box model. Biodegradation processes and reactions included in the analysis are identified from electron acceptors, electron donors and degradation products present in these inputs. Parameter values used in the model are obtained from data acquired during typical site investigation and groundwater monitoring studies for natural attenuation schemes. The approach is evaluated for a UK Permo-Triassic Sandstone aquifer contaminated with a plume of phenolic compounds. Uncertainty in the model predictions and sensitivity to parameter values was assessed by probabilistic modelling using Monte Carlo methods. Sensitivity analyses were compared for different input parameter probability distributions and a base case using fixed parameter values, using an identical conceptual model and data set. Results show that consumption of oxidants by biodegradation is approximately balanced by the production of CH4 and total dissolved inorganic carbon (TDIC) which is conserved in the plume. Under this condition, either the plume electron or carbon balance can be used to determine contaminant mass loss, which is equivalent to only 4% of the estimated source term. This corresponds to a first order, plume-averaged, half-life of > 800 years. The electron balance is particularly sensitive to uncertainty in the source term and dispersive inputs. Reliable historical information on contaminant spillages and detailed site investigation are necessary to accurately characterise the source term. The dispersive influx is sensitive to variability in the plume mixing zone width. Consumption of aqueous oxidants greatly exceeds that of mineral oxidants in the plume, but electron acceptor supply is insufficient to meet the electron donor demand and the plume will grow. The aquifer potential for degradation of these contaminants is limited by high contaminant concentrations and the supply of bioavailable electron acceptors. Natural attenuation will increase only after increased transport and dilution.     

Lead contamination of UK dusts and soils and implications for childhood exposure: An overview of the work of the Environmental Geochemistry Research Group,Imperial College,London, England 1981–1992

Over the course of the last decade, research conducted by the Imperial College Environmental Geochemistry Research Group has focused on the nature and effects of lead in UK dusts and soils. An initial nationwide reconnaissance survey demonstrated that approximately 10% of the population is exposed to lead levels in excess of 2,000 g g^–1 in house-hold dust. Subsequent exposure studies revealed that for 2 year old children in the UK urban environment, approximately 50% of lead intake was from dust ingested as a result of hand-to-mouth activity. Follow-up computer controlled scanning electron microscopy (CCSEM) analysis of urban household dust and particulate material wiped from children's hands showed that important sources of dust lead include lead-based paint, road dust and soils. CCSEM identification of specific soil lead tracer particles (from minewaste contaminated soils) in dusts and on children's hands further documented the important role of soil as a source of exposure. Speciation studies of soil lead of this origin indicated that the form of the lead, which is largely influenced by the soil environment, is the primary control on bioavailability. It appears that although lead of minewaste origin may be present at elevated levels in dusts and soils, it does not necessarily contribute to elevated blood lead levels when the lead is present in relatively insoluble form.     

Arsenic,antimony and bismuth in soil and pasture herbage in some old metalliferous mining areas in England

Soil and pasture herbage samples from some historical metalliferous mining and smelting areas in England were analysed for As, Sb and Bi by ICP-AES using a hydride generation method after ashing with Mg(NO₃)₂. The results showed that As, Sb and Bi concentrations in soils were elevated because of their associations with the Pb-Zn mineralisation in Derbyshire and Somerset, and Sn-Cu mineralisation in Cornwall. The distribution of As, Sb and Bi in soils reflected the chemical nature of different mine waste materials, and on a regional basis clearly reflected the geochemistry of the three mineral provinces. Historical smelting and calcination have caused intensive contamination in soils in the immediate vicinity of these activities. Antimony was highly elevated in soils at an old Pb smelter site in Derbyshire. Although the concentrations of As, Sb and Bi were generally low in the pasture herbage samples examined, the concentrations of As and Sb in herbage often reflected those of the corresponding soils. Soil pH had a large effect on the plant uptake of Bi from soils. The pasture herbage contaminated by soil can be an important exposure pathway of these elements to livestock grazing on contaminated land.     

Effect of light and turbulent mixing on the growth of<Emphasis Type="Italic"> Skeletonema costatum</Emphasis> (Bacillariophyceae)

Skeletonema costatum was grown in an outdoor mesocosm to test the hypothesis that fluctuations in irradiance brought about by changes in mixing time and depth can reduce diatom growth and biomass in the turbulent mixed layer. The light environment and mixing regime within the mesocosm were comparable to those in shallow lakes and coastal waters. Experiments showed no significant differences for 24-h mean and 7-day mean chlorophyll a and carbon-specific growth for mixed depths of 1 m and 3 m, and mixing times between 4 min and 65 min. Fluctuations in irradiance brought about by turbulent mixing had no significant effect on specific growth. The relationship between mixed depths and critical depths for S. costatum was therefore independent of fluctuations in irradiance in the turbulent mixed layer. The results indicated that to control growth of S. costatum mixed depths would have to exceed photic depths by a factor of 15, instead of the conventionally accepted factor of 5. Thus, it is likely that artificial mixing of shallow (<10 m) eutrophic waters will be more effective in controlling slow-growing summer biomass than fast-growing spring blooms dominated by diatoms.Communicated by P.W. Sammarco, Chauvin     

Effect of zinc on growth and development of larvae of the Pacific oyster Crassostrea gigas

Following the observation of periodic high concentrations of zinc in estuarine waters used in the White Fish Authority's oyster hatchery at Conway, North Wales, two beaker trials were conducted to study the effect of zinc, over the range recorded, on the young stages of larvae of Crassostrea gigas. Zinc, added to sea water both as zinc sulphate and as a natural mine-adit water, was applied for a period of 5 days, after which larvae were maintained for a further 5 days in sea water alone. Increasing concentrations over the range 125 to 500 g/l Zn resulted in decreasing growth, and increasing incidence of abnormality and larval mortality. A second trial with zinc sulphate showed 50 g/l Zn to have little effect on larval development, a progressive decrease in growth at 100 and 150 g/l, and no growth at 200 g/l. It is suggested that the deleterious effect of short-term exposure to zinc may well have contributed to the intermittent failure of larvae and irregular productivity previously recorded at the hatchery. It is also possible that zinc contamination in estuaries may affect natural oyster breeding, and may have to be considered in the future siting of hatcheries for seed production.     

Influence of uraniferous black shales on cadmium,molybdenum and selenium in soils and crop plants in the Deog-Pyoun-g area of Korea

The influence of naturally occurring uraniferous black shales on cadmium, molybdenum and selenium concentrations in soils and plants is examined. The possible implications of element concentrations to animal and human health are considered for the Deog-Pyoung area. Geochemical surveys have been undertaken within 13 river tributary valleys in the area underlain by uraniferous black shales and black slates or grey chlorite schists. Sampling of rocks, soils and plants has been carried out along transect lines within each valley. Samples were analysed for trace elements by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) and for uranium by Neutron Activation Analysis (NAA). Soil pH, cation exchange capacity, loss on ignition and particle size distribution have been measured for selected samples. Average trace element concentrations of the Okchon uraniferous black shales were 6.3 μg g⁻¹ Cd, 136 μg g⁻¹ Mo and 8.6 μg g⁻¹ Se. Soils derived from these rocks tend to reflect their extreme geochemical composition. Trace element concentrations in alluvial soils derived in part from these black shales averaged 1.2 μg g⁻¹ Cd, 20 μg g⁻¹ Mo and 1.5 μg g⁻¹ Se. Trace element concentrations in plants were found to be influenced by those of soils. Cadmium accumulated in tobacco leaves up to 46 μg g⁻¹ (D.M.) and leafy plants such as lettuce contain up to 0.5 μg g⁻¹ Se (D.M.). In addition to total concentrations in soils, soil pH is a major factor influencing uptake of Mo into crop plants and soil texture for Se. Concentrations of trace elements in plants also varied between plant species. The relative concentrations of Cd were found to vary in the order tobacco > lettuce > red pepper > rice grain. Elevated concentrations of Cd in crop plants and in tobacco may possibly have deleterious effects on human health in this area. The low Cu:Mo ratio in rice stalk of 2.65:1 may be associated with disturbed Cu metabolism in ruminant animals which regularly consume this material.     

Biogeochemical characterisation of a coal tar distillate plume

The distillation of acidified coal tars for up to 50 years has given rise to a phenol plume approximately 500 m long, 50 m deep and containing up to 15 g l(-1) dissolved organic carbon (DOC) in the Triassic Sandstones aquifer. A conceptual biogeochemical model based on chemical and microbiological analysis of groundwater samples has been developed as a preliminary to more detailed studies of the controls on natural attenuation. While the development of redox zones and the production of methane and carbon dioxide provide evidence of natural attenuation, it appears that degradation is slow. The existence of sulphate in the plume indicates that this electron acceptor has not been depleted and that consequently methanogenesis is probably limited. Based on a simple estimate of sulphate input concentration, a half-life of about 15 years has been estimated for sulphate reduction. Geochemical modelling predicts that increased alkalinity within the plume has not led to carbonate precipitation, and thus within the limits of accuracy of the measurement, alkalinity may reflect the degree of biodegradation. This implies a loss of around 18% of the DOC over a 30-year period. Despite limited degradation, microbial studies show that there are diverse microbial communities in the aquifer with the potential for both anaerobic and aerobic biodegradation. Microbial activity was found to be greatest at the leading edge of the plume where DOC concentrations are 60 mg l(-1) or less, but activity could still be observed in more contaminated samples even though cells could not be cultured. The study suggests that degradation may be limited by the high phenol concentrations within the core of the plume, but that once diluted by dispersion, natural attenuation may proceed. More detailed studies to confirm these initial findings are identified and form the basis of associated papers.     

Sensitivity to change for low-ANC eastern US lakes and streams and brook trout populations under alternative sulfate deposition scenarios

A weight-of-evidence approach was used by the US National Acid Precipitation Assessment Program (NAPAP) to assess the sensitivity of chemistry and biology of lakes and streams to hypothesized changes in sulfate deposition over the next 50 years. The analyses focused on projected effects in response to differences in the magnitude and the timing of changes in sulfate deposition in the north-eastern United States, the Mid-Appalachian Highlands, and the Southern Blue Ridge Province. A number of tools was used to provide the weight of evidence that is required to have confidence in an assessment that has many uncertainties because of the complexity of the systems for which the projections of future conditions were made and because of limited historical data. The MAGIC model provided the projections of chemical changes in response to alternative deposition scenarios. Projected chemical conditions were input into biological models that evaluate effects on fish populations. The sensitivity of water chemistry and brook trout resources to the hypothesized changes in deposition was found to be greatest in the Adirondacks and Mid-Atlantic Highlands. Under the hypothesized sulfur deposition reduction scenarios, chemical conditions suitable for fish were projected to improve 20-30 years sooner than with the scenario that assumed no new legislated controls. Other lines of evidence, e.g. other models, field observations, and paleolimnological findings, were used to evaluate uncertainty in the projections. Model parameter/calibration uncertainty for the chemical models and population sampling uncertainty were explicitly quantified. Model structural uncertainties were bracketed using model comparisons, recent measured changes, and paleolimnological reconstructions of historical changes in lake chemistry.