Developing understanding of the fate and behaviour of silver in fresh waters and waste waters.

The Windermere Humic Aqueous Model (WHAM) is often used for risk assessment of metals; WHAM can be used to estimate the potential bioavailability of dissolved metals, where metals complexed to dissolved organic matter (DOM) are expected to be less toxic than ionic forms. Silver is a potential metal of concern but WHAM has not been rigorously tested against experimental measurements. This study compares WHAM predictions to measured ionic silver during fixed pH (4, 8 or 10) argentometric titrations of DOM from diverse origins. There were almost two orders of magnitude variation in free silver between sources but, within model uncertainty, WHAM captured this variability. This agreement, between measurements and models, suggests that WHAM is an appropriate tool for silver risk assessment in surface receiving waters when DOM is predominantly in the form of humic/fulvic acids. In sewage samples WHAM dramatically underestimated silver binding by approximately 3 orders of magnitude. Simulations with additional specific strong silver binding sulphide-like binding sites could explain Ag binding at low loadings, but not at higher loadings. This suggests the presence of additional intermediate strength binding sites. These additional ligands would represent components of the raw sewage largely absent in natural waters unimpacted by sewage effluents. A revised empirical model was proposed to account for these sewage-specific binding sites. Further, it is suspected that as sewage organic matter is degraded, either by natural attenuation or by engineered treatment, that sewage organic matter will degrade to a form more readily modelled by WHAM; i.e., humic-like substances. These ageing experiments were performed starting from raw sewage, and the material did in fact become more humic-like, but even after 30 days of aerobic incubation still showed greater Ag+ binding than WHAM predictions. In these incubation experiments it was found that silver (up to 1000 µg/L) had minimal impact on ammonia oxidation kinetics.

Deriving environmental quality standards in European surface waters: when are there too few data?

Recent technical guidance has been published by the European Commission that outlines methodologies for the derivation of Environmental Quality Standards (EQS) in European surface waters under the Water Framework Directive (WFD). The guidance allows the derivation of a long-term EQS from a small dataset. Specifically an EQS can be derived from just three acute data points, although the safety factors built into such an EQS are large (e.g. up to a factor of 1,000). Large safety factors make such EQS uncertain, and often difficult to achieve in practice. We examine dataset requirements for the derivation of EQS and specifically the minimum number of tests needed for setting EQS for long-term chemical exposures that result in reduced relative uncertainty, as assessed simply through the reduction in standard deviation of the means of the values derived. Using ecotoxicity datasets for four example chemicals, for which EQS have been derived in many jurisdictions, we show that variation in the EQS is greatest when using the minimum dataset allowable under the WFD guidance, but decreases rapidly when seven or more datapoints are available. Increasing the minimum number of ecotoxicity data in deriving an EQS results in a greater understanding of ecotoxicological effects. With this knowledge, the mitigating effects of water chemistry can be accounted for in deriving an EQS, even with relatively limited datasets. The new guidance suggests "simplistic" approaches to account for chemical availability, but does not detail how this might be undertaken. We provide examples of ways by which water chemistry effects can be included in deriving implementable EQS for metals with relatively few reliable and relevant data.

The effect of advanced treatment of sewage effluents on metal speciation and (bio)availability.

The bioavailability of metals can be strongly influenced by dissolved organic carbon (DOC). Wastewater treatment effluents add considerable quantities of DOC and metals to receiving waters, and as effluent controls become more stringent advanced effluent treatments may be needed. We assessed the effects of two types of advanced treatment processes on metal availability in wastewater effluents. Trace metal availability was assessed using diffuse gradients in thin films and predicted through speciation modelling. The results show little difference in metal availability post-advanced treatment. EDTA-like compounds are important metal complexants in the effluents.

Occurrence and concentration of dissolved silver in rivers in England and Wales.

There is a paucity of monitoring data for silver in freshwater environments in Europe. There are several reasons for this, including the relatively low levels of silver in the aquatic environment and the requirement for commensurately low levels of detection (<100 ng l⁻¹), which are generally not routinely achieved in analytical laboratories. In this study 425 separate analytical determinations for dissolved (<0.45 µm) silver from 84 Environment Agency monitoring stations were carried out. Sampling was carried out on a monthly basis over a period of 6 months. Of the 425 samples, 346 were reported as having dissolved silver concentrations below the limit of quantification (6.6 ng l⁻¹) and, of these, 280 samples were reported as below the reporting limit of detection (3 ng l⁻¹). The mean of the maximum dissolved silver concentrations reported at each station was calculated as 6.1 ng l⁻¹ using a statistical extrapolation technique to allow for the high level of censorship in the dataset. The maximum mean dissolved silver concentration recorded at a station was 19.8 ng l⁻¹. A freshwater Predicted No Effect Concentration (PNEC) of 40 ng l⁻¹ was used in this study.

Copper and zinc water quality standards under the EU Water Framework Directive: the use of a tiered approach to estimate the levels of failure.

Environmental quality standards are an important tool for assessing the chemical quality of water bodies under the Water Framework Directive. However, there must be confidence in assessments of any failure to avoid disproportionate investment in unnecessary risk reduction. Metals present a number of unique challenges for environmental regulators in that they are naturally occurring and their ecotoxicology is driven, in part, by the physico-chemical conditions of the water body in which they are present. This paper describes the use of a tiered approach that could be adopted to assess compliance with any future environmental quality standards for metals under the Water Framework Directive. Through this approach, the use of background concentrations is considered and also bioavailability via the use of biotic ligand models. This assessment is based on an analysis of routine Environment Agency chemical monitoring data combined with biological indices to support results of the approach. Using copper and zinc as examples, it is shown that it is important to take account of background concentrations and the bioavailability of metals, otherwise the risk of impact from metals may be significantly overestimated. The approach presented here provides a methodology by which regulators and the regulated community may implement surface water standards for metals under the Water Framework Directive.

Estimates of ambient background concentrations of trace metals in soils for risk assessment.

Site-specific or soil type-specific ambient background concentrations (ABCs) of trace metals in soils are needed for risk assessment. We investigated three different methods for estimating ABCs in soils using a dataset of 5691 soil samples from England and Wales. The concentrations of Co, Cr and Ni were strongly associated with Al and Fe, and multiple regressions explained 62-85% of their variation, and Al and Fe can therefore be used to predict ABCs for these metals. Soil texture had a major influence on the concentrations of Cd, Co, Cr, Cu, Ni and Zn, and the medians were 3-5 fold higher in clayey than in sandy soils. This was used to predict texture-specific ABCs. Lead concentration was higher in acidic peaty soils than in other soils. A probability graph method was used to estimate ABC for Pb in a population of relatively uncontaminated soils. Potential applications of ABCs are discussed.

Copper availability in seven Israeli soils incubated with and without biosolids.

Land application is becoming a preferred option for disposal of sewage sludge (biosolids) from wastewater treatment plants. However, it creates potential risks due to the heavy metal contents of these materials, with copper (Cu) being of chief concern. The long-term fate of biosolid metals applied to agricultural soils is not well understood, particularly in the soils of the Middle East. This investigation was conducted to determine whether the availability of Cu changes with time in biosolid-amended and nonamended soils from Israel. Seven soils, typifying the span of properties and formation environments encountered in Israel, were incubated with and without biosolids for 7 yr, and changes in organic carbon (OC) content and labile Cu concentration were determined. Isotopic exchange techniques, using 64Cu, and ion activity measurements, using a Cu2+ ion selective electrode, revealed that the available Cu concentration remained relatively low and stable over the 7-yr incubation. This was despite substantial reductions in OC. This study shows that, with regard to Cu, application of such biosolids to these soils at rates of up to 250 Mg ha(-1) does not pose a threat to the environment in the short to medium term.

Temporal trends of total and potentially available element concentrations in sewage biosolids: a comparison of biosolid surveys conducted 18 years apart.

The application of biosolids to agricultural land is becoming increasingly popular because of the many benefits they can offer in terms of improved soil fertility and productivity, and also because land application offers an economically viable disposal option. However, the heavy metal and nutrient content of biosolids are potential causes for concern due to the possibility of their accumulation in soils to levels that may adversely affect the environment. Therefore, total concentrations of elements in biosolids and the fraction potentially available to organisms must be known in order to accurately gauge the risks and to classify the biosolids. In 1983, deVries conducted a survey to determine the total and available contents of elements in biosolids collected from various treatment plants around Australia. We conducted a similar survey on biosolids collected in 2001, and thus were able to identify temporal trends in biosolid characteristics. The 2001 survey included biosolids from several treatment plants sampled in 1983, thus some direct comparisons were possible, and in four cases, it was possible to examine temporal trends in biosolid characteristics within individual treatment plants. Total element concentrations were determined by aqua regia digestion, and available element concentrations were determined by 0.01 M CaCl(2) extraction. Results showed total concentrations of Cu, Mn, Ni, Na, and Ca changed little over the period examined, however the 2001 median values of Cd, Mg, Pb, and Zn were all reduced by 60% or greater. Median total concentration of K was more than 50% higher, and P 120% higher, in the 2001 survey. Changes in the availability of elements surveyed in 1983 and 2001 were varied for different elements and for different biosolids. Extractable element concentrations (viewed as percentages of total concentrations) of Cu, Cd, and Ni all fell by 50-72% between 1983 and 2001, while K extractability fell by 35%.

Cadmium sorption in biosolids amended soils: results from a field trial.

The effect of biosolids amendment on cadmium sorption coefficient (K(d)) was determined for soils in a biosolids field trial. The sorptive properties of biosolids are thought to have a significant controlling effect upon the availability/uptake and mobility of potentially toxic metals. K(d) values for the three biosolids were 10-30 times greater than those for unamended soil. Elevated K(d) values were still apparent 1 and 2 years after biosolids amendment (100 t ha(-1)) for two of the three biosolids. Chemical extractants (sodium hypochlorite and hydrofluoric acid, respectively) were used in an attempt to determine K(d) values of isolated inorganic and organic fractions. For both biosolids amended soils and unamended controls, Cd sorption appeared to be dominated by the inorganic fraction, potentially indicating the overriding importance of this fraction in controlling metal mobility. However, for the biosolids themselves, the sum of inorganic and organic fraction contributions to K(d) accounted for less than half the K(d) of the whole biosolids. This discrepancy was attributed to the loss of highly sorptive water soluble species in both chemical extractions.

Determination of metal--EDTA complexes in soil solution and plant xylem by ion chromatography-electrospray mass spectrometry.

An ion chromatography-electrospray mass spectrometry (IC-MS) method was developed to quantify the metal complexes of ethylenediaminetetraacetic acid (EDTA) in soil solution and plant xylem exudate. Suitable separation of the metal-EDTA complexes was achieved on a Dionex AS5 column using 2 mM Na2CO3 as the eluant. However, satisfactory detection by eluant suppressed IC-MS, in either the positive or negative ion detection mode, could not be attained. A new eluant that still attained suitable separation and produced ionic species that could be detected by MS in the negative ion mode was developed. The eluant consisted of 2.5 mM (NH4)2CO3, 9.7 mM NH4OH, and 4% (v/v) methanol and had a pH 9.9. Even though eluant suppressed IC-MS degraded detection limits by a factor of 4 over the nonsuppressed system, using the retention time and not the m/z (mass-to-charge ratio) of the intact chelate for identification, the latter allowed the metal complexes to be detected intact and was optimized for the analysis of environmental samples. The number of metal-EDTA species that could be detected was limited by the eluant used for ion chromatography (i.e. only those complexes that were stable at high pH), with metal-EDTA complexes of Al, Cd, Cu, Co, Mn, Ni, Pb, and Zn being adequately resolved. Iron(III), Ca, MgEDTA, and EDTA itself were not detected. Detection limits for the various complexes ranged from 0.1 to 1 microM.

Trophic barriers to fertilizer Cd bioaccumulation through the food chain: a case study using a plant--insect predator pathway.

The objective of this study was to assess the uptake and subsequent transfer of Cd and Zn from a soil amended with a single application (150 kg P ha(-1)) of triple super phosphate fertilizer to wheat plants, aphids, and a predator and biocontrol agent of aphids, lacewings. The fertilizer amended soil and wheat plants grown on this soil had elevated concentrations of Cd compared to the controls, but similar concentrations of Zn. Aphids feeding on wheat plants on the fertilized soil had between three and seven times the concentrations of Cd and Zn observed in aphids feeding on the control plants. However, the lacewings showed no significant accumulation of Cd or Zn, and no differences in larval performance were recorded. Changes in the availability of Cd and Zn in the soils and the transfer through the plant-insect pathway were monitored using isotope dilution, by labeling the soils with carrier-free (109)Cd and (65)Zn. Decreases in the specific activities for Cd in the plants and aphids were observed for the fertilized soils compared to the controls, suggesting an increase in bioavailable Cd. On the fertilized soils the Cd:Zn ratio of the phloem-feeding aphids (0.008) was significantly less than the host plants (0.025), indicating a reduced relative uptake of Cd and a possible barrier for Cd along the soil--plant--herbivorous insect pathway--reducing uptake by phloem feeders and subsequently their predators.

The uptake of cadmium and zinc by the bird-cherry oat aphid Rhopalosiphum padi (Homoptera:Aphididae) feeding on wheat grown on sewage sludge amended agricultural soil.

A greenhouse trial investigated the uptake of cadmium and zinc by the bird-cherry oat aphid (Rhopalosiphum padi) feeding on wheat grown on sewage sludge amended soil. The trial was conducted at application rates of 0, 5, 7.5, 10, 15 and 20 tonnes ha(-1) dry solids. Concentrations of Cd and Zn were within current UK limits for potentially toxic elements in soils amended with sewage sludge. Cd and Zn in wheat plants were significantly greater than controls. Batches of aphids feeding on the wheat also showed a significant increase in the uptake of Cd and Zn. This study demonstrates a potential route of exposure to Cd and Zn for the predators of cereal aphids.