An evaluation of biotic ligand models predicting acute copper toxicity to Daphnia magna in wastewater effluent

This is the author's accepted manuscript. The final published article is available from the link below. Copyright @ 2010 SETAC.The toxicity of Cu to Daphnia magna was investigated in a series of 48-h immobilization assays in effluents from four wastewater treatment works. The assay results were compared with median effective concentration (EC50) forecasts produced by the HydroQual biotic ligand model (BLM), the refined D. magna BLM, and a modified BLM that was constructed by integrating the refined D. magna biotic ligand characterization with the Windermere humic aqueous model (WHAM) VI geochemical speciation model, which also accommodated additional effluent characteristics as model inputs. The results demonstrated that all the BLMs were capable of predicting toxicity by within a factor of two, and that the modified BLM produced the most accurate toxicity forecasts. The refined D. magna BLM offered the most robust assessment of toxicity in that it was not reliant on the inclusion of effluent characteristics or optimization of the dissolved organic carbon active fraction to produce forecasts that were accurate by within a factor of two. The results also suggested that the biotic ligand stability constant for Na may be a poor approximation of the mechanisms governing the influence of Na where concentrations exceed the range within which the biotic ligand stability constant value had been determined. These findings support the use of BLMs for the establishment of site-specific water quality standards in waters that contain a substantial amount of wastewater effluent, but reinforces the need for regulators to scrutinize the composition of models, their thermodynamic and biotic ligand parameters, and the limitations of those parameters.EPSRC and Severn Trent Water

The effect of wastewater effluent derived ligands on copper and zinc complexation.

The shift toward bioavailability-based standards for metals such as copper and zinc not only improves the ecological relevance of the standard but also introduces significant complexity into assessing compliance. This study examined differences in the copper and zinc complexation characteristics of effluents from a range of different sewage treatment works and in relation to so-called 'natural' samples. This information is essential to determine whether the inclusion of effluent-specific complexation characteristics within the regulatory framework could enhance the environmental relevance of compliance criteria. The data show that for copper, binding affinity was not greater than that measured for materials derived from the receiving water environment, with a mean log K of between 4.4 and 5.15 and mean complexation capacity ranging from 38 to 120 μg/mg dissolved organic carbon (DOC) for effluents compared with a log K of 5.6 and complexation capacity of 37 μg/mg DOC for the Suwannee River fulvic acid. For zinc, however, effluents exhibited a much higher complexation capacity, with effluent means ranging from 3 to 23 μg/mg DOC compared with the Suwannee River fulvic acid, for which the complexation capacity could not be determined. Synthetic ligands in sewage effluent, such as ethylenediaminetetraacetic acid (EDTA), are implicated as contributing to these observed differences. This suggests that the current biotic ligand models for zinc might overstate the risk of harm in effluent-impacted waters. The data also show that the copper and zinc complexation characteristics of effluent samples obtained from the same sewage treatment works were less different from one another than those of effluents from other treatment works and therefore that sewage source has an important influence on complexation characteristics. The findings from this study support the case that the contribution to complexation from effluent-derived ligands could enhance the environmental relevance of bioavailability-based compliance criteria, in particular for zinc, owing to the additional complexation capacity afforded by effluent-derived ligands

Predicting copper speciation in estuarine waters – Is dissolved organic carbon a good proxy for the presence of organic ligands?

A new generation of speciation-based aquatic environmental quality standards (EQS) for metals have been developed using models to predict the free metal ion concentration, the most ecologically relevant form, to set site-specific values. Some countries such as the U.K. have moved toward this approach by setting a new estuarine and marine water EQS for copper, based on an empirical relationship between copper toxicity to mussels (<i>Mytilus</i> sp.) and ambient dissolved organic carbon (DOC) concentrations. This assumes an inverse relationship between DOC and free copper ion concentration owing to complexation by predominantly organic ligands. At low DOC concentrations, the new EQS is more stringent, but above 162 μM DOC it is higher than the previous value. However, the relationship between DOC and copper speciation is poorly defined in estuarine waters. This research discusses the influence of DOC from different sources on copper speciation in estuaries and concludes that DOC is not necessarily an accurate predictor of copper speciation. Nevertheless, the determination of ligand strength and concentrations by Competitive Ligand Exchange Adsorptive Cathodic Stripping Voltammetry enabled the prediction of the free metal ion concentration within an order of magnitude for estuarine waters by using a readily available metal speciation model (Visual MINTEQ)

Absence of Gradients and Nernstian Equilibrium Stripping (AGNES) for the determination of [Zn2+] in estuarine waters

Zinc (Zn) has been classified as a 'Specific Pollutant' under Annex VIII of the EU Water Framework Directive by two thirds of the EU member states. As a result, the UK Environmental Quality Standard (EQS) for Transitional and Coastal (TrAC) Waters has been reduced from 612 nM to 121 nM total dissolved Zn. It is widely accepted that the free metal ion ([Zn2+]) is the most bioavailable fraction, but there are few techniques available to determine its concentration in these waters. In this work, Absence of Gradients and Nernstian Equilibrium Stripping (AGNES) has been applied, for the first time, to determine [Zn2+] in estuarine waters. The AGNES method had a mean RSD of +/- 18%, a (deposition time dependent) limit of detection of 0.73 nM and a [Zn2+] recovery of 112 +/- 19% from a certified reference material (BCR-505; Estuarine Water). AGNES results for 13 estuarine samples (salinity 0.1-31.9) compared well (P = 0.02) with Competitive Ligand Exchange Cathodic Stripping Voltammetry (CLE-AdCSV) except for one sample. AGNES requires minimal sample manipulation, is unaffected by adsorption of interfering species at the electrode surface and allows direct determination of free zinc ion concentrations. Therefore AGNES results can be used in conjunction with ecotoxicological studies and speciation modelling to set and test compliance with water quality standards.This PhD research is co-funded by the International Zinc Association, the International Copper Association, and Plymouth University. Warm thanks to Dr. Chris Cooper for his helpful comments, and to Marjan Heidarkhan Tehrani and Mireia Lao Martinez for their invaluable help and advice in the laboratory

Accurate attribute mapping from volunteered geographic information: issues of volunteer quantity and quality

Crowdsourcing is a popular means of acquiring data, but the use of such data is limited by concerns with its quality. This is evident within cartography and geographical sciences more generally, with the quality of volunteered geographic information (VGI) recognized as a major challenge to address if the full potential of citizen sensing in mapping applications is to be realized. Here, a means to characterize the quality of volunteers, based only on the data they contribute, was used to explore issues connected with the quantity and quality of volunteers for attribute mapping. The focus was on data in the form of annotations or class labels provided by volunteers who visually interpreted an attribute, land cover, from a series of satellite sensor images. A latent class model was found to be able to provide accurate characterisations of the quality of volunteers in terms of the accuracy of their labelling, irrespective of the number of cases that they labelled. The accuracy with which a volunteer could be characterized tended to increase with the number of volunteers contributing but was typically good at all but small numbers of volunteers. Moreover, the ability to characterize volunteers in terms of the quality of their labelling could be used constructively. For example, volunteers could be ranked in terms of quality which could then be used to select a sub-set as input to a subsequent mapping task. This was particularly important as an identified subset of volunteers could undertake a task more accurately than when part of a larger group of volunteers. The results highlight that both the quantity and quality of volunteers need consideration and that the use of VGI may be enhanced through information on the quality of the volunteers derived entirely from the data provided without any additional information

Development of a chemical source apportionment decision support framework for catchment management.

EU legislation, including the Water Framework Directive, has led to the application of increasingly stringent quality standards for a wide range of chemical contaminants in surface waters. This has raised the question of how to determine and to quantify the sources of such substances so that measures can be taken to address breaches of these quality standards using the polluter pays principle. Contaminants enter surface waters via a number of diffuse and point sources. Decision support tools are required to assess the relative magnitudes of these sources and to estimate the impacts of any programmes of measures. This work describes the development and testing of a modeling framework, the Source Apportionment Geographical Information System (SAGIS). The model uses readily available national data sets to estimate contributions of a number of nutrients (nitrogen and phosphorus), metals (copper, zinc, cadmium, lead, mercury, and nickel) and organic chemicals (a phthalate and a number of polynuclear aromatic hydrocarbons) from multiple sector sources. Such a tool has not previously been available on a national scale for such a wide range of chemicals. It is intended to provide a common platform to assist stakeholders in future catchment management

Comparing the quality of crowdsourced data contributed by expert and non-experts

There is currently a lack of in-situ environmental data for the calibration and validation of remotely sensed products and for the development and verification of models. Crowdsourcing is increasingly being seen as one potentially powerful way of increasing the supply of in-situ data but here are a number of concerns over the subsequent use of the data, in particular over data quality. This paper examined crowdsourced data from the Geo-Wiki crowdsourcing tool for land cover validation to determine whether there were significant differences in quality between the answers provided by experts and non-experts in the domain of remote sensing and therefore the extent to which crowdsourced data describing human impact and land cover can be used in further scientific research. The results showed that there was little difference between experts and non-experts in identifying human impact although results varied by land cover while experts were better than non-experts in identifying the land cover type. This suggests the need to create training materials with more examples in those areas where difficulties in identification were encountered, and to offer some method for contributors to reflect on the information they contribute, perhaps by feeding back the evaluations of their contributed data or by making additional training materials available. Accuracies were also found to be higher when the volunteers were more consistent in their responses at a given location and when they indicated higher confidence, which suggests that these additional pieces of information could be used in the development of robust measures of quality in the future

Modelling impacts of seasonal wastewater treatment plant effluent permits and biosolid substitution for phosphorus management in catchments and river systems

The issues of diffuse and point source phosphorus (P) pollution in river systems are presented using a catchment model to assess nutrient behaviour, seasonal effluent standards and biosolid substitution. A process-based, dynamic water quality model (INCA-P) has been applied to four UK catchments, namely, the Rivers Tywi, Wensum, Lunan and Hampshire Avon, to simulate water fluxes, sediments, total phosphorus and soluble reactive phosphorus (SRP) concentrations. The model has been used to assess impacts of both agricultural runoff and point P sources from wastewater treatment plants (WWTPs) on water quality. With increasing costs for P fertilizer and P reduction at WWTPs, a strategy of recycling P from WWTPs as biosolids to substitute for fertilizers in vulnerable catchments has been investigated. Significant reductions in P concentrations are achieved if this substitution were implemented on a large scale. Reductions in SRP of between 6% and 41% can be achieved using this strategy. The effects of implementing new WWTP standards are shown to reduce SRP by 30%. Seasonal consent standards applied in only summer months could reduce SRP by 53% and achieve a substantial reduction in treatment costs year round

Engineering Comes Home: Co-designing nexus infrastructure from the bottom-up

The ‘nexus’ between water, food and energy systems is well established. It is conventionally analysed as a supply-side problem of infrastructure interdependencies, overlooking demand-side interactions and opportunities. The home is one of the most significant sites of nexus interactions and opportunities for redesigning technologies and infrastructure. New developments in ‘smart city’ technologies have the potential to support a bottom-up approach to designing and managing nexus infrastructure. The Engineering Comes Home was a research project that turned infrastructure design on its head. The objectives of the project were to: Demonstrate a new paradigm for engineering design starting from the viewpoint of the home, looking out towards systems of provision to meet household demands. Integrate thinking about water, energy, food, waste and data at the domestic scale to support userled innovation and co-design of technologies and infrastructure. Test new design methods that connect homes to communities, technologies and infrastructure, enhancing positive interactions between data, water, energy, food and waste systems. Develop a robust Lifecycle Assessment (LCA) Calculator tool to support environmental decisionmaking in co-design. Working with residents of the Meakin Estate in South London, the project followed a co-design method to identify requirements, analyse options and develop and test a detailed design for a preferred option. The outputs were: 1) Ethnographic study of how residents use water, energy and food resources in their homes and key opportunities for engineering design to improve wellbeing and reduce resource consumption. 2) Co-design of decentralised infrastructural systems in three workshops in 2016-2017. The first workshop identified key priorities for development from the community using a novel token-based system design method, to enable participants to build up alternative designs for local provision of water, energy, food and waste services. The second workshop provided participants with factsheets and photographs of the candidate technologies, which were then analysed using a LCA Calculator tool. 47 Rainwater harvesting was selected as the technology for further co-design in the third workshop, which focussed on scaling up a pilot installation. 3) Pilot-scale smart rainwater system was installed in partnership with the Over The Air Analytics (OTA). OTA’s system enables remote control of the rainwater storage tanks to optimise their performance as stormwater attenuation as well as non-potable water supply. 4) Lifecycle Assessment (LCA) Calculator to enable quick estimation of the impacts of new systems and technology to deliver water, energy and food, and manage waste at the household and neighbourhood scale. 5) Stakeholders, including utilities, design consultancies and community based organisations, were engaged in three workshops to inform the wider relevance and development of the co-design methods and tools. 6) Toolbox and method statements to standardise and disseminate the methods used in the project for wider application and development

Participation in Transition(s):Reconceiving Public Engagements in Energy Transitions as Co-Produced, Emergent and Diverse

This paper brings the transitions literature into conversation with constructivist Science and Technology Studies (STS) perspectives on participation for the first time. In doing so we put forward a conception of public and civil society engagement in sustainability transitions as co-produced, relational, and emergent. Through paying close attention to the ways in which the subjects, objects, and procedural formats of public engagement are constructed through the performance of participatory collectives, our approach offers a framework to open up to and symmetrically compare diverse and interconnected forms of participation that make up wider socio-technical systems. We apply this framework in a comparative analysis of four diverse cases of civil society involvement in UK low carbon energy transitions. This highlights similarities and differences in how these distinct participatory collectives are orchestrated, mediated, and subject to exclusions, as well as their effects in producing particular visions of the issue at stake and implicit models of participation and ‘the public’. In conclusion we reflect on the value of this approach for opening up the politics of societal engagement in transitions, building systemic perspectives of interconnected ‘ecologies of participation’, and better accounting for the emergence, inherent uncertainties, and indeterminacies of all forms of participation in transitions