Metal concentrations in transitional and coastal waters measured by passive (Diffusive Gradients in Thin-films) and spot sampling: MONITOOL Project Dataset.

The MONITOOL project (2017-2023) was carried out to describe the relationships between total dissolved and labile metal concentrations measured in spot water samples and in concurrently deployed Diffusive Gradients in Thin-films (DGTs) passive samplers, respectively. The ultimate aim was to adapt existing marine metal Environmental Quality Standards (EQS marine water) for DGTs, enabling their use in the context of the European Directives (the Water Framework Directive (WFD) and the Marine Strategy Framework Directive (MSFD)). Time-integrated metal concentrations provided by DGTs, representing several days, are an advantage compared to conventional spot sampling, especially in highly dynamic systems, such as transitional waters. Hence, the MONITOOL project aimed to provide a robust database of dissolved and labile metal concentrations in transitional and coastal waters, based upon co-deployments of DGTs and collection of spot water samples at several sampling sites (England, France, Ireland, Italy, Northern Ireland, Portugal, Scotland and Spain), followed subsequently by DGT and water metal analysis. Samplings were carried out in 2018 and 2022, following agreed protocols developed in the framework of the project. The MONITOOL dataset includes metal concentrations from DGTs, measured with Inductively Coupled Plasma Mass Spectrometry (ICP-MS: Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) and in concurrently collected spot water samples by ICP-MS (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and Anodic/Cathodic Stripping Voltammetry (ASV/CSV: Cd, Pb, Ni). Moreover, data on seawater physical-chemical parameters (salinity, temperature, dissolved oxygen, pH, turbidity, total suspended solids, dissolved organic carbon, and total organic carbon) is provided. This database presents the results obtained using, concurrently, different forms of sampling and analytical techniques, enabling the comparison of the results obtained by these strategies and allowing the adaptation of EQS in marine water (EQS marine water) to DGTs (EQS DGT), in the context of the WFD. Moreover, due to the large number of sampling sites, it could also be used for other types of research, such as those dealing with metal speciation or the determination of baseline levels.

A river basin spatial model to quantitively advance understanding of riverine tree response dynamics to water availability and hydrological management.

Ecological condition continues to decline in arid and semi-arid river basins globally due to hydrological over-abstraction combined with changing climatic conditions. Whilst provision of water for the environment has been a primary approach to alleviate ecological decline, how to accurately monitor changes in riverine trees at fine spatial and temporal scales, remains a substantial challenge. This is further complicated by constantly changing water availability across expansive river basins with varying climatic zones. Within, we combine rare, fine-scale, high frequency temporal in-situ field collected data with machine learning and remote sensing, to provide a robust model that enables broadscale monitoring of physiological tree water stress response to environmental changes via actual evapotranspiration (ET). Physiological variation of Eucalyptus camaldulensis (River Red Gum) and E. largiflorens (Black Box) trees across 10 study locations in the southern Murray-Darling Basin, Australia, was captured instantaneously using sap flow sensors, substantially reducing tree response lags encountered by monitoring visual canopy changes. Actual ET measurement of both species was used to bias correct a national spatial ET product where a Random Forest model was trained using continuous timeseries of in-situ data of up to four years. Precise monthly AMLETT (Australia-wide Machine Learning ET for Trees) ET outputs in 30 m pixel resolution from 2012 to 2021, were derived by incorporating additional remote sensing layers such as soil moisture, land surface temperature, radiation and EVI and NDVI in the Random Forest model. Landsat and Sentinal-2 correlation results between in-situ ET and AMLETT ET returned R2 of 0.94 (RMSE 6.63 mm period-1) and 0.92 (RMSE 6.89 mm period-1), respectively. In comparison, correlation between in-situ ET and a national ET product returned R2 of 0.44 (RMSE 34.08 mm period-1) highlighting the need for bias correction to generate accurate absolute ET values. The AMLETT method presented here, enhances environmental management in river basins worldwide. Such robust broadscale monitoring can inform water accounting and importantly, assist decisions on where to prioritize water for the environment to restore and protect key ecological assets and preserve floodplain and riparian ecological function.

Metals concentrations in transitional and coastal waters by ICPMS and voltammetry analysis of spot samples and passive samplers (DGT).

This study investigates the relationships among Ni, Cd and Pb's different chemical forms determined by different methodologies in coastal and transitional waters across a broad geographical scale. Concentrations were measured in spot samples and through passive sampling (DGT). High variability of metal concentrations was found among sampling sites and methodologies due to natural water fluctuations rather than to a given metal or method. Total dissolved metal concentrations in spot samples were lower than the EQS-WFD values. The labile fractions of Cd and Pb, measured in spot samples by Anodic Stripping Voltammetry and by DGT-ICPMS, were highly correlated. Similar labilities were found for Cd, while for Pb, the ASV labile fraction was ≈50% lower. These results reflect the pool of mobile and labile species available towards each technique kinetic window, and they seem not to be affected by discrete sampling flaws.

Concurrent sampling of transitional and coastal waters by Diffusive Gradient in Thin-films (DGT) and spot sampling for trace metals analysis.

This protocol was developed based on the knowledge acquired in the framework of the Interreg MONITOOL project (EAPA_565/2016) where extensive sampling campaigns were performed in transitional and coastal waters covering eight European countries. It provides detailed procedures and guidelines for the sampling of these waterbodies by concurrent collection of discrete water samples and the deployment of Diffusive Gradient in Thin-films (DGT) passive samplers for the measurement of trace metal concentrations. In order to facilitate the application of this protocol by end-users, it presents steps to follow in the laboratory prior to sampling campaigns, explains the procedures for field campaigns (including in situ measurement of supporting parameters) and subsequent sample processing in the laboratory in preparation for trace metal analyze by inductively coupled plasma-mass spectrometry (ICP-MS) and voltammetry. The protocol provides a systematic, coherent field sampling and sample preparation strategy that was developed in order to ensure comparability and reproducibility of the data obtained from each project Partner in different regions. • Standardization of the concurrent sampling of transitional and coastal waters by DGT passive samplers and spot sampling. • Robust procedures and tips based on existing international standards and comprehensive practical experience. • Links to demonstration videos produced within the MONITOOL project.

Assessing variability in the ratio of metal concentrations measured by DGT-type passive samplers and spot sampling in European seawaters.

The current study evaluates the effect of seawater physico-chemical characteristics on the relationship between the concentration of metals measured by Diffusive Gradients in Thin films (DGT) passive samplers (i.e., DGT-labile concentration) and the concentrations measured in discrete water samples. Accordingly, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to measure the total dissolved metal concentrations in the discrete water samples and the labile metal concentrations obtained by DGT samplers; additionally, lead and cadmium conditional labile fractions were determined by Anodic Stripping Voltammetry (ASV) and total dissolved nickel was measured by Cathodic Stripping Voltammetry (CSV). It can be concluded that, in general, the median ratios of DGT/ICP and DGT/ASV(CSV) were lower than 1, except for Ni (median ratio close to 1) and Zn (higher than 1). This indicates the importance of speciation and time-integrated concentrations measured using passive sampling techniques, which is in line with the WFD suggestions for improving the chemical assessment of waterbodies. It is the variability in metal content in waters rather than environmental conditions to which the variability of the ratios can be attributed. The ratios were not significantly affected by the temperature, salinity, pH, oxygen, DOC or SPM, giving a great confidence for all the techniques used. Within a regulatory context such as the EU Water Framework Directive this is a great advantage, since the simplicity of not needing to use corrections to minimize the effects of environmental variables could help in implementing DGTs within monitoring networks.

From Water-Use to Water-Scarcity Footprinting in Environmentally Extended Input-Output Analysis.

Environmentally extended input-output analysis (EEIOA) supports environmental policy by quantifying how demand for goods and services leads to resource use and emissions across the economy. However, some types of resource use and emissions require spatially explicit impact assessment for meaningful interpretation, which is not possible in conventional EEIOA. For example, water use in locations of scarcity and of abundance are not environmentally equivalent. Opportunities for spatially explicit impact assessment in conventional EEIOA are limited because official input-output tables tend to be produced at the scale of political units, which are not usually well-aligned with environmentally relevant spatial units. In this study, spatially explicit water-scarcity factors and a spatially disaggregated Australian water-use account were used to develop water-scarcity extensions that were coupled with a multiregional input-output model (MRIO). The results link demand for agricultural commodities to the problem of water scarcity in Australia and globally. Important differences were observed between the water-use and water-scarcity footprint results as well as the relative importance of direct and indirect water use, with significant implications for sustainable production and consumption-related policies. The approach presented here is suggested as a feasible general approach for incorporating spatially explicit impact assessments in EEIOA.

Australia is 'free to choose' economic growth and falling environmental pressures.

Over two centuries of economic growth have put undeniable pressure on the ecological systems that underpin human well-being. While it is agreed that these pressures are increasing, views divide on how they may be alleviated. Some suggest technological advances will automatically keep us from transgressing key environmental thresholds; others that policy reform can reconcile economic and ecological goals; while a third school argues that only a fundamental shift in societal values can keep human demands within the Earth's ecological limits. Here we use novel integrated analysis of the energy-water-food nexus, rural land use (including biodiversity), material flows and climate change to explore whether mounting ecological pressures in Australia can be reversed, while the population grows and living standards improve. We show that, in the right circumstances, economic and environmental outcomes can be decoupled. Although economic growth is strong across all scenarios, environmental performance varies widely: pressures are projected to more than double, stabilize or fall markedly by 2050. However, we find no evidence that decoupling will occur automatically. Nor do we find that a shift in societal values is required. Rather, extensions of current policies that mobilize technology and incentivize reduced pressure account for the majority of differences in environmental performance. Our results show that Australia can make great progress towards sustainable prosperity, if it chooses to do so.

Land use efficiency: anticipating future demand for land-sector greenhouse gas emissions abatement and managing trade-offs with agriculture, water, and biodiversity.

Competition for land is increasing, and policy needs to ensure the efficient supply of multiple ecosystem services from land systems. We modelled the spatially explicit potential future supply of ecosystem services in Australia's intensive agricultural land in response to carbon markets under four global outlooks from 2013 to 2050. We assessed the productive efficiency of greenhouse gas emissions abatement, agricultural production, water resources, and biodiversity services and compared these to production possibility frontiers (PPFs). While interacting commodity markets and carbon markets produced efficient outcomes for agricultural production and emissions abatement, more efficient outcomes were possible for water resources and biodiversity services due to weak price signals. However, when only two objectives were considered as per typical efficiency assessments, efficiency improvements involved significant unintended trade-offs for the other objectives and incurred substantial opportunity costs. Considering multiple objectives simultaneously enabled the identification of land use arrangements that were efficient over multiple ecosystem services. Efficient land use arrangements could be selected that meet society's preferences for ecosystem service provision from land by adjusting the metric used to combine multiple services. To effectively manage competition for land via land use efficiency, market incentives are needed that effectively price multiple ecosystem services.

Bringing ecosystem services into integrated water resources management.

In this paper we propose an ecosystem service framework to support integrated water resource management and apply it to the Murray-Darling Basin in Australia. Water resources in the Murray-Darling Basin have been over-allocated for irrigation use with the consequent degradation of freshwater ecosystems. In line with integrated water resource management principles, Australian Government reforms are reducing the amount of water diverted for irrigation to improve ecosystem health. However, limited understanding of the broader benefits and trade-offs associated with reducing irrigation diversions has hampered the planning process supporting this reform. Ecosystem services offer an integrative framework to identify the broader benefits associated with integrated water resource management in the Murray-Darling Basin, thereby providing support for the Government to reform decision-making. We conducted a multi-criteria decision analysis for ranking regional potentials to provide ecosystem services at river basin scale. We surveyed the wider public about their understanding of, and priorities for, managing ecosystem services and then integrated the results with spatially explicit indicators of ecosystem service provision. The preliminary results of this work identified the sub-catchments with the greatest potential synergies and trade-offs of ecosystem service provision under the integrated water resources management reform process. With future development, our framework could be used as a decision support tool by those grappling with the challenge of the sustainable allocation of water between irrigation and the environment.

Investigation of design space for freeze-drying: use of modeling for primary drying segment of a freeze-drying cycle.

In this work, we explore the idea of using mathematical models to build design space for the primary drying portion of freeze-drying process. We start by defining design space for freeze-drying, followed by defining critical quality attributes and critical process parameters. Then using mathematical model, we build an insilico design space. Input parameters to the model (heat transfer coefficient and mass transfer resistance) were obtained from separate experimental runs. Two lyophilization runs are conducted to verify the model predictions. This confirmation of the model predictions with experimental results added to the confidence in the insilico design space. This simple step-by-step approach allowed us to minimize the number of experimental runs (preliminary runs to calculate heat transfer coefficient and mass transfer resistance plus two additional experimental runs to verify model predictions) required to define the design space. The established design space can then be used to understand the influence of critical process parameters on the critical quality attributes for all future cycles.