The influence of sewage sludge properties on sludge-borne metal availability

With the advent of more stringent controls on wastewater treatment, sewage sludge production in Europe and many parts of the world is increasing. With this increase comes the problem of sludge disposal, and recycling to land arguably offers an economically and environmentally sustainable option. However, a major limitation of sewage sludge reuse is the potential release of heavy metals from the sludge and heavy metal accumulation to toxic levels in topsoils. The properties of the sludge play a crucial role in determining the initial release and subsequent availability of heavy metals in amended soils. Bioavailable forms of heavy metals in recently amended soils are most likely to be those that are bioavailable in the sewage sludge. In this paper, published research on the importance of sewage sludge characteristics on metal release and bioavailability will be reviewed and contrasted with original research. A selection of sludges from around Australia has been collected for this purpose. Through the use of incubation studies, isotope dilution techniques, ion-selective electrode measurements and ¹³C-NMR spectroscopy, the importance of a range of sludge properties on heavy metal behaviour in sludges and sludge-amended soils is addressed.     

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.     

Assessment of the effects of nickel on benthic macroinvertebrates in the field

A field-based evaluation of the biological effects of potential nickel (Ni) exposures was conducted using monitoring data for benthic macroinvertebrates and water chemistry parameters for streams in England and Wales. Observed benthic community metrics were compared to expected community metrics under reference conditions using RIVPACS III+?software. In order to evaluate relationships between Ni concentrations and benthic community metrics, bioavailable Ni concentrations were also calculated for each site. A limiting effect from Ni on the 90th percentile of the maximum achievable ecological quality was derived at “bioavailable Ni” exposures of 10.3 μg l^?1. As snails have been identified as particularly sensitive to nickel exposure, snail abundance in the field in response to nickel exposure, relative to reference conditions, was also analysed. A “low effects” threshold for snail abundance based on an average of spring and autumn data was derived as 3.9 μg l^?1 bioavailable Ni. There was no apparent effect of Ni exposure on the abundance of Ephemeroptera (mayflies), Plecoptera (stoneflies) or Tricoptera (caddisflies) when expressed relative to a reference condition within the range of “bioavailable Ni” exposures observed within the dataset. Nickel exposure concentrations co-vary with the concentrations of other stressors in the dataset, and high concentrations of Ni are also associated with elevated concentrations of other contaminants.     

Changes in sewage sludge carbon forms along a treatment stream

The behaviour and fate of macronutrients and pollutants in sewage sludge applied to the land are affected by the chemical composition of the sludge organic matter, which in turn is influenced by both sewage source and by sewage treatment processes. In this study, (13)C nuclear magnetic resonance (NMR) spectroscopy was used to characterise the organic matter of sludges collected at three different points along the treatment stream of a municipal sewage works with a domestic catchment. Sludge at the first point, an undigested liquid (UL) sludge, had a substantially different composition to the anaerobically digested (AD) and dewatered sludge cake (DC) materials, which were similar to each other. In particular, the UL sludge contained more alkyl C than the AD or DC sludges. All three sludges were found to contain mobile alkyl C that is poorly observed using the cross polarisation (CP) technique, necessitating the use of the less sensitive, but more quantitatively reliable direct polarisation (DP) technique to obtain accurate distributions of C types.     

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.     

Advanced solid-state carbon-13 nuclear magnetic resonance spectroscopic studies of sewage sludge organic matter: detection of organic "domains"

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.     

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.     

Characterization of sewage sludge organic matter using solid-state carbon-13 nuclear magnetic resonance spectroscopy

Six sewage sludges from five sewage treatment plants in Australia were characterized using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Spectra were acquired both before and after removal of mineral components through treatment with hydrofluoric acid (HF). Carbon mass balance indicated that little organic matter was lost on HF treatment, which significantly improved NMR sensitivity and spectral resolution, and decreased acquisition time and hence cost of NMR analysis. Two NMR techniques were used, the standard cross polarization (CP) technique and Bloch decay (BD). The BD technique had not been applied previously to the analysis of sewage sludge. For each sludge sample, both before and after HF treatment, the BD spectrum contained significantly more alkyl carbon. Spin counting, another technique applied to sewage sludge here for the first time, showed that the BD spectra of the HF-treated sludges were quantitative, while approximately 30% of the CP NMR signal went undetected. The discrepancy between CP and BD spectra was attributed to the presence of alkyl carbon with such high molecular mobility that the efficiency of cross polarization is affected. This study shows that sewage sludge organic matter is significantly different in chemistry to soil organic matter and has implications for the application of sewage sludge to agricultural land.     

Water quality guidelines for chemicals: learning lessons to deliver meaningful environmental metrics

Many jurisdictions around the globe have well-developed regulatory frameworks for the derivation and implementation of water quality guidelines (WQGs) or their equivalent (e.g. environmental quality standards, criteria, objectives or limits). However, a great many more still do not have such frameworks and are looking to introduce practical methods to manage chemical exposures in aquatic ecosystems. There is a potential opportunity for learning and sharing of data and information between experts from different jurisdictions in order to deliver efficient and effective methods to manage potential aquatic risks, including the considerable reduction in the need for aquatic toxicity testing and the rapid identification of common challenges. This paper reports the outputs of an international workshop with representatives from 14 countries held in Hong Kong in December 2011. The aim of the workshop and this paper was to identify ‘good practice’ in the development of WQGs to deliver to a range of environmental management goals. However, it is important to broaden this consideration to cover often overlooked facets of implementable WQGs, such as demonstrable field validation (i.e. does the WQG protect what it is supposed to?), fit for purpose of monitoring frameworks (often an on-going cost) and finally how are these monitoring data used to support management decisions in a manner that is transparent and understandable to stakeholders. It is clear that regulators and the regulated community have numerous pressures and constraints on their resources. Therefore, the final section of this paper addresses potential areas of collaboration and harmonisation. Such approaches could deliver a consistent foundation from which to assess potential chemical aquatic risks, including, for example, the adoption of bioavailability-based approaches for metals, whilst reducing administrative and technical burdens in jurisdictions.