Benchmarking the Persistence of Active Pharmaceutical Ingredients in River Systems.

Assessing the persistence of organic micropollutants from field data has been notoriously laborious, requiring extensive data including emissions and chemical properties, and the application of detailed mass-balance models, which often contain parameters that are impossible to measure. To overcome some of these obstacles, we developed the concept of persistence benchmarking for large rivers that receive numerous emissions and provide enough residence time to observe the dissipation of compounds. We estimated the dissipation rate constants of 41 compounds (mostly active pharmaceutical ingredients) from five measurement campaigns in the Rhine and Danube rivers using concentration rate profiles with respect to carbamazepine. Dissipation rates clearly distinguished between known fast- and slow-degrading compounds, and campaign-specific boundary conditions had an influence on a minor subset of compounds only. Benchmarking provided reasonable estimates on summer total system half-lives in the Rhine compared to previous laboratory experiments and a mass-balance modeling study. Consequently, benchmarking can be a straightforward persistence assessment method of continuously emitted organic micropollutants in large river systems, especially when it is supported by field monitoring campaigns of proper analytical quality and spatial resolution.

From market to environment - consumption-normalised pharmaceutical emissions in the Rhine catchment.

Direct and indirect threats by organic micropollutants can only be reliably assessed and prevented if the exposure to these chemicals is known, which in turn requires a confident estimate of their emitted amounts into the environment. APIs (Active Pharmaceutical Ingredients) enter surface waters mostly through the sewer system and wastewater treatment plants (WWTPs). However, their effluent fluxes are highly variable and influenced by several different factors that challenge robust emission estimates. Here, we defined a dimensionless, theoretically consumption-independent 'escape factor' (kesc) for estimating the amount of APIs (expected to be) present in WWTP effluents. The factor is determined as the proportion of marketed and actually emitted amounts of APIs. A large collection of German and Swiss monitoring datasets were analyzed to calculate stochastic kesc values for 31 APIs, reflecting both the magnitude and uncertainty of consumption-normalised emissions. Escape factors provide an easy-to-use tool for the estimation of average API emissions and expected variability from numerous WWTPs given that consumption data are provided, thereby supporting simulation modeling of the fate of APIs in stream networks or exposure assessments.

Do biotransformation data from laboratory experiments reflect micropollutant degradation in a large river basin?

Identifying a chemical's potential for biotransformation in the aquatic environment is crucial to predict its fate and manage its potential hazards. Due to the complexity of natural water bodies, especially river networks, biotransformation is often studied in laboratory experiments, assuming that study outcomes can be extrapolated to compound behavior in the field. Here, we investigated to what extent outcomes of laboratory simulation studies indeed reflect biotransformation kinetics observed in riverine systems. To determine in-field biotransformation, we measured loads of 27 wastewater treatment plant effluent-borne compounds along the Rhine and its major tributaries during two seasons. Up to 21 compounds were detected at each sampling location. Measured compound loads were used in an inverse model framework of the Rhine river basin to derive k'bio,field values - a compound-specific parameter describing the compounds' average biotransformation potential during the field studies. To support model calibration, we performed phototransformation and sorption experiments with all the study compounds, identifying 5 compounds that are susceptible towards direct phototransformation and determining Koc values covering four orders of magnitude. On the laboratory side, we used a similar inverse model framework to derive k'bio,lab values from water-sediment experiments run according to a modified OECD 308-type protocol. The comparison of k'bio,lab and k'bio,field revealed that their absolute values differed, pointing towards faster transformation in the Rhine river basin. Yet, we could demonstrate that relative rankings of biotransformation potential and groups of compounds with low, moderate and high persistence agree reasonably well between laboratory and field outcomes. Overall, our results provide evidence that laboratory-based biotransformation studies using the modified OECD 308 protocol and k'bio values derived thereof bear considerable potential to reflect biotransformation of micropollutants in one of the largest European river basins.

Stochastic simulation of phytoplankton biomass using eighteen years of daily data - predictability of phytoplankton growth in a large, shallow lake.

During the past decades, on-line monitoring of freshwater lakes has developed rapidly. To use high frequency time-series in lake management, novel models are needed that are simple and provide insight into the complexity of phytoplankton dynamics. Chlorophyll a (Chl), a proxy for phytoplankton biomass and environmental drivers were monitored on-line in large, shallow Lake Balaton during the vegetation periods between 2001 and 2018. Growth and non-growth (G and non-G) states of algae were deduced from daily change in Chl. Random forests (RF) were used to find stochastic response rules of phytoplankton to growth-supporting environmental habitat templates. The stochastic G/non-G state was translated into long-term daily biomass dynamics by a deterministic biomass model to assess uncertainty and to distinguish between inevitable and unpredictable blooms. A biomass peak was qualified as inevitable or unpredictable if the lower 95% confidence limit of simulations exceeded or remained at the baseline Chl level, respectively. Compared to a stochastic null model based on monthly Markovian transition probabilities, RF-based models captured wax and wane of biomass realistically. Timing of peaks could be better simulated than their magnitude, likely because habitat templates were primarily determined by light whereas peak sizes might depend on unmeasured processes, such as phosphorus availability. In general, algal growth was favored by wind-induced sediment resuspension that decreased light availability but simultaneously enhanced the P supply. Seasonal temperature and an integral of departures from the "normal" seasonal temperature over 2 to 3 generations were important drivers of phytoplankton growth, whereas short-term (diel and day to day) changes in water temperature appeared to be irrelevant. Four types of years could be distinguished during the study period with respect to algal growth conditions. The present modeling approach can reasonably be used even in highly variable aquatic environments when 3 to 4 years of daily data are available.

Biotransformation of Chemicals at the Water-Sediment Interface-Toward a Robust Simulation Study Setup.

Studying aquatic biotransformation of chemicals in laboratory experiments, i.e., OECD 308 and OECD 309 studies, is required by international regulatory frameworks to prevent the release of persistent chemicals into natural water bodies. Here, we aimed to address several previously described shortcomings of OECD 308/309 studies regarding their variable outcomes and questionable environmental relevance by broadly testing and characterizing a modified biotransformation test system in which an aerated water column covers a thin sediment layer. Compared to standard OECD 308/309 studies, the modified system showed little inter-replicate variability, improved observability of biotransformation, and consistency with first-order biotransformation kinetics for the majority of 43 test compounds, including pharmaceuticals, pesticides, and artificial sweeteners. To elucidate the factors underlying the decreased inter-replicate variability compared to OECD 309 outcomes, we used multidimensional flow cytometry data and a machine learning-based cell type assignment pipeline to study cell densities and cell type diversities in the sediment and water compartments. Our here presented data on cell type composition in both water and sediment allows, for the first time, to study the behavior of microbial test communities throughout different biotransformation simulation studies. We found that sediment-associated microbial communities were generally more stable throughout the experiments and exhibited higher cell type diversity than the water column-associated communities. Consistently, our data indicate that aquatic biotransformation of chemicals can be most robustly studied in test systems providing a sufficient amount of sediment-borne biomass. While these findings favor OECD 308-type systems over OECD 309-type systems to study biotransformation at the water-sediment interface, our results suggest that the former should be modified toward lower sediment-water ratios to improve observability and interpretability of biotransformation.

Multi-criteria decision analysis for integrated water quality assessment and management support.

In densely populated areas, surface waters are affected by many sources of pollution. Besides classical pollutants like nutrients and organic matter that lead to eutrophication, micropollutants from various point- and non-point sources are getting more attention by water quality managers. For cost-effective management an integrated assessment is needed that takes into account all relevant pollutants and all sources of pollution within a catchment. Due to the difficulty of identifying and quantifying sources of pollution and the need for considering long-term changes in boundary conditions, typically substantial uncertainty exists about the consequences of potential management alternatives to improve surface water quality. We therefore need integrated assessment methods that are able to deal with multiple objectives and account for various sources of uncertainty. This paper aims to contribute to integrated, prospective water management by combining a) multi-criteria decision support methods to structure the decision process and quantify preferences, b) integrated water quality modelling to predict consequences of management alternatives accounting for uncertainty, and c) scenario planning to consider uncertainty from potential future climate and socio-economic developments, to evaluate the future cost-effectiveness of water quality management alternatives at the catchment scale. It aims to demonstrate the usefulness of multi-attribute value functions for water quality assessment to i) propagate uncertainties throughout the entire assessment procedure, ii) facilitate the aggregation of multiple objectives while avoiding discretization errors when using categories for sub-objectives, iii) transparently communicate the results. We show how to use such multi-attribute value functions for model-based decision support in water quality management. We showcase the procedure for the Mönchaltorfer Aa catchment on the Swiss Plateau. We evaluate ten different water quality management alternatives, including current practice, that tackle macro- and micropollutants from a wide spectrum of agricultural and urban sources. We evaluate costs and water quality effects of the alternatives under four different socio-economic scenarios for the horizon 2050 under present and future climate projections and visualize their uncertainty. While the performance of alternatives is catchment specific, the methods can be transferred to other places and other management situations. Results confirm the need for cross-sectoral coordination of different management actions and interdisciplinary collaboration to support the development of prospective strategies to improve water quality.

Simulation Studies to Explore Biodegradation in Water-Sediment Systems: From OECD 308 to OECD 309.

Studies according to OECD 308 and OECD 309 are performed to simulate the biodegradation of chemicals in water-sediment systems in support of persistence assessment and exposure modeling. However, several shortcomings of OECD 308 have been identified that hamper data evaluation and interpretation, and its relation to OECD 309 is still unclear. The present study systematically compares OECD 308 and OECD 309 and two variants thereof to derive recommendations on how to experimentally address any shortcomings and improve data for persistence and risk assessment. To this end, four (14)C-labeled compounds with different biodegradation and sorption behavior were tested across standard OECD 308 and 309 test systems and two modified versions thereof. The well-degradable compounds showed slow equilibration and the least mineralization in OECD 308, whereas the modified systems provided the highest degree of mineralization. Different lines of evidence suggest that this was due to increased oxygenation of the sediment in the modified systems. Particularly for rapidly degrading compounds, non-extractable residue formation was in line with degradation and did not follow the sediment-water ratio. For the two more slowly degrading compounds, sorption in OECD 309 (standard and modified) increased with time beyond levels proposed by equilibrium partitioning, which could be attributed to the grinding of the sediment through the stirring of the sediment suspension. Overall, the large differences in degradation observed across the four test systems suggest that refined specifications in test guidelines are required to reduce variability in test outcomes. At the same time, the amount of sediment and its degree of oxygenation emerged as drivers across all test systems. This suggests that a unified description of the systems was possible and would pave the way toward a more consistent consideration of degradation in the water-sediment systems across different exposure situations and regulatory frameworks.

Bridging across OECD 308 and 309 Data in Search of a Robust Biotransformation Indicator.

The OECD guidelines 308 and 309 define simulation tests aimed at assessing biotransformation of chemicals in water-sediment systems. They should serve the estimation of persistence indicators for hazard assessment and half-lives for exposure modeling. Although dissipation half-lives of the parent compound are directly extractable from OECD 308 data, they are system-specific and mix up phase transfer with biotransformation. In contrast, aerobic biotransformation half-lives should be easier to extract from OECD 309 experiments with suspended sediments. Therefore, there is scope for OECD 309 tests with suspended sediment to serve as a proxy for degradation in the aerobic phase of the more complicated OECD 308 test, but that correspondence has remained untested so far. Our aim was to find a way to extract biotransformation rate constants that are universally valid across variants of water-sediment systems and, hence, provide a more general description of the compound's behavior in the environment. We developed a unified model that was able to simulate four experimental types (two variants of OECD 308 and two variants of OECD 309) for three compounds by using a biomass-corrected, generalized aerobic biotransformation parameter (k'bio). We used Bayesian calibration and uncertainty assessment to calibrate the models for individual experimental types separately and for combinations of experimental types. The results suggested that k'bio was a generally valid parameter for quantifying biotransformation across systems. However, its uncertainty remained significant when calibrated on individual systems alone. Using at least two different experimental types for the calibration of k'bio increased its robustness by clearly separating degradation from the phase-transfer processes taking place in the individual systems. Overall, k'bio has the potential to serve as a system-independent descriptor of aerobic biotransformation at the water-sediment interface that is equally and consistently applicable for both persistence and exposure assessment purposes.

Deriving persistence indicators from regulatory water-sediment studies ­ opportunities and limitations in OECD 308 data.

The OECD guideline 308 describes a laboratory test method to assess aerobic and anaerobic transformation of organic chemicals in aquatic sediment systems and is an integral part of tiered testing strategies in different legislative frameworks for the environmental risk assessment of chemicals. The results from experiments carried out according to OECD 308 are generally used to derive persistence indicators for hazard assessment or half-lives for exposure assessment. We used Bayesian parameter estimation and system representations of various complexities to systematically assess opportunities and limitations for estimating these indicators from existing data generated according to OECD 308 for 23 pesticides and pharmaceuticals. We found that there is a disparity between the uncertainty and the conceptual robustness of persistence indicators. Disappearance half-lives are directly extractable with limited uncertainty, but they lump degradation and phase transfer information and are not robust against changes in system geometry. Transformation half-lives are less system-specific but require inverse modeling to extract, resulting in considerable uncertainty. Available data were thus insufficient to derive indicators that had both acceptable robustness and uncertainty, which further supports previously voiced concerns about the usability and efficiency of these costly experiments. Despite the limitations of existing data, we suggest the time until 50% of the parent compound has been transformed in the entire system (DegT(50,system)) could still be a useful indicator of persistence in the upper, partially aerobic sediment layer in the context of PBT assessment. This should, however, be accompanied by a mandatory reporting or full standardization of the geometry of the experimental system. We recommend transformation half-lives determined by inverse modeling to be used as input parameters into fate models for exposure assessment, if due consideration is given to their uncertainty.

Micropollutant biotransformation kinetics associate with WWTP process parameters and microbial community characteristics.

The objective of this work was to identify relevant wastewater treatment plant (WWTP) parameters and underlying microbial processes that influence the biotransformation of a diverse set of micropollutants. To do this, we determined biotransformation rate constants for ten organic micropollutants in batch reactors seeded with activated sludge from ten diverse WWTPs. The estimated biotransformation rate constants for each compound ranged between one and four orders of magnitude among the ten WWTPs. The biotransformation rate constants were tested for statistical associations with various WWTP process parameters, amoA transcript abundance, and acetylene-inhibited monooxygenase activity. We determined that (i) ammonia removal associates with oxidative micropollutant biotransformation reaction rates; (ii) archaeal but not bacterial amoA transcripts associate with both ammonia removal and oxidative micropollutant biotransformation reaction rates; and (iii) the activity of acetylene-inhibited monooxygenases (including ammonia monooxygenase) associates with ammonia removal and the biotransformation rate of isoproturon, but does not associate with all oxidative micropollutant biotransformations. In combination, these results lead to the conclusion that ammonia removal and amoA transcript abundance can potentially be predictors of oxidative micropollutant biotransformation reactions, but that the biochemical mechanism is not necessarily linked to ammonia monooxygenase activity.

Identification of phosphorus emission hotspots in agricultural catchments.

An enhanced transport-based management approach is presented, which is able to support cost-effective water quality management with respect to diffuse phosphorus pollution. Suspended solids and particulate phosphorus emissions and their transport were modeled in two hilly agricultural watersheds (Wulka River in Austria and Zala River in Hungary) with an improved version of the catchment-scale PhosFate model. Source and transmission areas were ranked by an optimization method in order to provide a priority list of the areas of economically efficient (optimal) management alternatives. The model was calibrated and validated at different gauges and for various years. The spatial distribution of the emissions shows that approximately one third of the catchment area is responsible for the majority of the emissions. However, only a few percent of the source areas can transport fluxes to the catchment outlet. These effective source areas, together with the main transmission areas are potential candidates for improved management practices. In accordance with the critical area concept, it was shown that intervention with better management practices on a properly selected small proportion of the total area (1-3%) is sufficient to reach a remarkable improvement in water quality. If soil nutrient management is also considered in addition to water quality, intervention on 4-12% of the catchment areas can fulfill both aspects.

Balancing between retention and flushing in river networks--optimizing nutrient management to improve trophic state.

River basin management can frequently involve decisive situations, when conflicting interests must be resolved. In the Zala River catchment (Western Hungary) local efforts to improve water quality by reducing algal biomass are not always harmonized with the requirement of sustaining the same objective in its recipient, Lake Balaton. The PhosFate catchment model is a GIS tool designed to estimate the spatial variability and fate of diffuse phosphorus emission during transport. Besides diffuse pollution, a simplified annual hydrologic balance is also calculated. A new module was added to PhosFate that tracked the development of entrained algae during their travel downstream. The extended model was used to simulate the current average algal concentrations in the river network. The numerous small reservoirs and impoundments on the tributaries of the Zala River were identified as the key elements in determining algal biomass, since they fundamentally increase the water residence time (WRT) in the system. Without reservoirs, the short WRT in the drainage network would successfully prevent the development of suspended algal biomass despite the fairly high SRP concentrations. However, the removal of such standing waters is impossible for socio-economic reasons and reducing the overall P load to Lake Balaton would also require increasing WRT in the system. As a resolution to these conflicting interests, a hybrid management strategy was designed to simultaneously reach both goals: (i) switching from WRT to P limitation in reservoirs responsible for most of algal growth, and (ii) optimized deployment of buffer zones and the introduction of best agricultural practices on the remaining majority of the catchment to reduce the overall P load. The suggested management approach could be applied in other river catchments too, due to the extensive presence of reservoirs and impoundments in many stream networks.