Linking bioavailability and toxicity changes of complex chemicals mixture to support decision making for remediation endpoint of contaminated soils.

A six-month laboratory scale study was carried out to investigate the effect of biochar and compost amendments on complex chemical mixtures of tar, heavy metals and metalloids in two genuine contaminated soils. An integrated approach, where organic and inorganic contaminants bioavailability and distribution changes, along with a range of microbiological indicators and ecotoxicological bioassays, was used to provide multiple lines of evidence to support the risk characterisation and assess the remediation end-point. Both compost and biochar amendment (p = 0.005) as well as incubation time (p = 0.001) significantly affected the total and bioavailable concentrations of the total petroleum hydrocarbons (TPH) in the two soils. Specifically, TPH concentration decreased by 46% and 30% in Soil 1 and Soil 2 amended with compost. These decreases were accompanied by a reduction of 78% (Soil 1) and 6% (Soil 2) of the bioavailable hydrocarbons and the most significant decrease was observed for the medium to long chain aliphatic compounds (EC16-35) and medium molecular weight aromatic compounds (EC16-21). Compost amendment enhanced the degradation of both the aliphatic and aromatic fractions in the two soils, while biochar contributed to lock the hydrocarbons in the contaminated soils. Neither compost nor biochar affected the distribution and behaviour of the heavy metals (HM) and metalloids in the different soil phases, suggesting that the co-presence of heavy metals and metalloids posed a low risk. Strong negative correlations were observed between the bioavailable hydrocarbon fractions and the ecotoxicological assays suggesting that when bioavailable concentrations decreased, the toxicity also decreased. This study showed that adopting a combined diagnostic approach can significantly help to identify optimal remediation strategies and contribute to change the over-conservative nature of the current risk assessments thus reducing the costs associated with remediation endpoint.

Prediction of bioavailability and toxicity of complex chemical mixtures through machine learning models.

Empirical data from a 6-month mesocosms experiment were used to assess the ability and performance of two machine learning (ML) models, including artificial neural network (NN) and random forest (RF), to predict temporal bioavailability changes of complex chemical mixtures in contaminated soils amended with compost or biochar. From the predicted bioavailability data, toxicity response for relevant ecological receptors was then forecasted to establish environmental risk implications and determine acceptable end-point remediation. The dataset corresponds to replicate samples collected over 180 days and analysed for total and bioavailable petroleum hydrocarbons and heavy metals/metalloids content. Further to this, a range of biological indicators including bacteria count, soil respiration, microbial community fingerprint, seeds germination, earthworm's lethality, and bioluminescent bacteria were evaluated to inform the environmental risk assessment. Parameters such as soil type, amendment (biochar and compost), initial concentration of individual compounds, and incubation time were used as inputs of the ML models. The relative importance of the input variables was also analysed to better understand the drivers of temporal changes in bioavailability and toxicity. It showed that toxicity changes can be driven by multiple factors (combined effects), which may not be accounted for in classical linear regression analysis (correlation). The use of ML models could improve our understanding of rate-limiting processes affecting the freely available fraction (bioavailable) of contaminants in soil, therefore contributing to mitigate potential risks and to inform appropriate response and recovery methods.

Insights into mixed contaminants interactions and its implication for heavy metals and metalloids mobility, bioavailability and risk assessment.

Mobility of heavy metals at contaminated sites is mainly influenced by the soil physicochemical properties and environmental conditions, therefore assessing heavy metals (HMs) and metalloids fractionation can provide insights into their potential risk and the mechanisms that regulate bioavailability. A 12-months mesocosms experiment was setup to investigate the effect of physicochemical factors (pH, moisture, and temperature) and weathering (time) on HMs and metalloids fractionation in three different multi-contaminated soil matrices (low, medium, and high contamination) collected from a soil treatment facility located in the United Kingdom, and two rural contaminated soil samples. The study demonstrates that even though Pb and Zn were found associated with the exchangeable fraction in the soil with the highest contamination (total average Pb 3400 mg/kg, and total average Zn 2100 mg/kg in Soil C), neither the condition applied nor the weathering caused an increase in their mobility. Although it was expected that lower pH (4.5) would favours the dissociation of HMs and metalloids, no significant differences were observed, potentially due to the initial alkaline pH of the genuine-contaminated soil samples. The results show that even though total concentration of Pb, Cu, and Zn exceed the soil standards and guideline values, HMs were predominantly associated with the non-exchangeable fraction, while only 5% were dissolved in the pore water fraction (potentially bioavailable). In addition, the mobility and bioavailability of HMs remained constant over the 12 months monitoring, suggesting that these soils pose negligible risk to the environment.

Assessing bioavailability of complex chemical mixtures in contaminated soils: Progress made and research needs.

Understanding the distribution, behaviour and interactions of complex chemical mixtures is key for providing the evidence necessary to make informed decisions and implement robust remediation strategies. Much of the current risk assessment frameworks applied to manage land contamination are based on total contaminant concentrations and the exposure assessments embedded within them do not explicitly address the partitioning and bioavailability of chemical mixtures. These oversights may contribute to an overestimation of both the eco-toxicological effects of the fractions and the mobility of contaminants. In turn, this may limit the efficacy of risk frameworks to inform targeted and proportionate remediation strategies. In this review we analyse the science surrounding bioavailability, its regulatory inclusion and the challenges of incorporating bioavailability in decision making process. While a number of physical and chemical techniques have proven to be valuable tools for estimating bioavailability of organic and inorganic contaminants in soils, doubts have been cast on its implementation into risk management soil frameworks mainly due to a general disagreement on the interchangeable use of bioavailability and bioaccessibility, and the associated methods which are still not standardised. This review focuses on the role of biotic and abiotic factors affecting bioavailability along with soil physicochemical properties and contaminant composition. We also included advantages and disadvantages of different extraction techniques and their implications for bioavailability quantitative estimation. In order to move forward the integration of bioavailability into site-specific risk assessments we should (1) account for soil and contaminant physicochemical characteristics and their effect on bioavailability; (2) evaluate receptor's potential exposure and uptake based on mild-extraction; (3) adopt a combined approach where chemical-techniques are used along with biological methods; (4) consider a simplified and cost-effective methodology to apply at regulatory and industry setting; (5) use single-contaminant exposure assessments to inform and predict complex chemical mixture behaviour and bioavailability.

Integrating horizon scanning and strategic risk prioritisation using a weight of evidence framework to inform policy decisions.

Poor connection between data on emerging issues and credible policy decisions continues to challenge governments, and is only likely to grow as demands on time and resources increase. Here we summarise recent efforts to integrate horizon scanning and risk prioritisation approaches to better connect emerging issues to the political discourse on environmental and food-related issues. Our categorisation of insights including potential future risks and opportunities to inform policy discussions has emerged from a structured three-year programme of horizon scanning for a UK pan-governmental futures partnership led by the Department for Environment, Food and Rural Affairs (Defra). Our efforts to integrate horizon scanning and risk prioritisation, utilising a qualitative weight of evidence framework, has created a systematic process for identifying all signals of potential future change with significant impact for the strategic mission and underlying values of policy actors. Our approach encourages an exploration of factors out of the control of organisations, recognising that resilience depends on the flexibility of management strategies and the preparedness to deal with a variety of unexpected outcomes. We discuss how this approach addresses key cultural and evaluative challenges that policy actors have had in embedding horizon scanning in evidence-based policy processes, and suggest further developments to build confidence in the use of horizon scanning for strategic planning.

Scientific commentary: Strategic analysis of environmental policy risks--heat maps, risk futures and the character of environmental harm.

We summarise our recent efforts on the policy-level risk appraisal of environmental risks. These have necessitated working closely with policy teams and a requirement to maintain crisp and accessible messages for policy audiences. Our comparative analysis uses heat maps, supplemented with risk narratives, and employs the multidimensional character of risks to inform debates on the management of current residual risk and future threats. The policy research and ensuing analysis raises core issues about how comparative risk analyses are used by policy audiences, their validation and future developments that are discussed in the commentary below.

Two-phase reactors applied to the removal of substituted phenols: comparison between liquid-liquid and liquid-solid systems.

In this paper, a comparison is provided between liquid-liquid and liquid-solid partitioning systems applied to the removal of high concentrations of 4-nitrophenol. The target compound is a typical representative of substituted phenols found in many industrial effluents while the biomass was a mixed culture operating as a conventional Sequencing Batch Reactor and acclimatized to 4-nitrophenol as the sole carbon source. Both two-phase systems showed enhanced performance relative to the conventional single phase bioreactor and may be suitable for industrial application. The best results were obtained with the polymer Hytrel which is characterized by higher partition capability in comparison to the immiscible liquid solvent (2-undecanone) and to the polymer Tone™. A model of the two systems was formulated and applied to evaluate the relative magnitudes of the reaction, mass transfer and diffusion characteristic times. Kinetic parameters for the Haldane equation, diffusivity and mass transfer coefficients have been evaluated by data fitting of batch tests for liquid-liquid and liquid-solid two phase systems. Finally, preliminary results showed the feasibility of polymer regeneration to facilitate polymer reuse by an extended contact time with the biomass.