Unpredicted ecosystem response to compound human impacts in a European river.

Climate change elevates the threat of compound heat and drought events, with their ecological and socioeconomic impacts exacerbated by human ecosystem alterations such as eutrophication, salinization, and river engineering. Here, we study how multiple stressors produced an environmental disaster in a large European river, the Oder River, where a toxic bloom of the brackish-water planktonic haptophyte Prymnesium parvum (the "golden algae") killed approximately 1000 metric tons of fish and most mussels and snails. We uncovered the complexity of this event using hydroclimatic data, remote sensing, cell counts, hydrochemical and toxin analyses, and genetics. After incubation in impounded upstream channels with drastically elevated concentrations of salts and nutrients, only a critical combination of chronic salt and nutrient pollution, acute high water temperatures, and low river discharge during a heatwave enabled the riverine mass proliferation of B-type P. parvum along a 500 km river section. The dramatic losses of large filter feeders and the spreading of vegetative cells and resting stages make the system more susceptible to new harmful algal blooms. Our findings show that global warming, water use intensification, and chronic ecosystem pollution could increase likelihood and severity of such compound ecoclimatic events, necessitating consideration in future impact models.

Flow rate and kinetics of trace organic contaminants removal in black carbon-amended engineered media filters for improved stormwater runoff treatment.

Urban stormwater runoff is considered a key component of future water supply portfolios for water-stressed cities. Beneficial use of runoff, such as capture for recharge of drinking water aquifers, relies on improved stormwater treatment. Many dissolved constituents, including metals and trace organic contaminants (TrOCs) such as hydrophilic pesticides and poly- and perfluoroalkyl substances (PFASs), are of concern due to their toxicity, persistence, prevalence in stormwater runoff, and poor removal in conventional stormwater control measures. This study explores the operational flow rate limitations of black carbon (BC)-amended engineered media filters for removal of a wide suite of dissolved metals and TrOCs and provides validation for a previously developed predictive TrOC transport model. Column experiments were conducted with face velocities of 40 and 60 cm h-1 to assess Douglas Fir-based biochar and regenerated activated carbon (RAC) filter performance in light of media-contaminant removal kinetic limitations. This study found that increasing the face velocity in BC-amended filters to 40 and 60 cm h-1, which are representative of field conditions, decreased the removal of total suspended solids, turbidity, dissolved hydrophilic TrOCs, and PFASs when expressed as volume treated relative to previous studies conducted at 20 cm h-1. Dissolved metals and hydrophobic TrOCs removal were not substantially affected by the increased flow rates. A predictive 1-d intraparticle pore diffusion-limited sorption model with sorption and effective tortuosity parameters determined previously from experiments conducted at 20 cm h-1 was validated for these higher flow rates. This work provides insights to the kinetic limitations of contaminant removal within biochar and RAC filters and implications for stormwater filter design and operation.

Advanced oxidation processes for water and wastewater treatment - Guidance for systematic future research.

Advanced oxidation processes (AOPs) are a growing research field with a large variety of different process variants and materials being tested at laboratory scale. However, despite extensive research in recent years and decades, many variants have not been transitioned to pilot- and full-scale operation. One major concern are the inconsistent experimental approaches applied across different studies that impede identification, comparison, and upscaling of the most promising AOPs. The aim of this tutorial review is to streamline future studies on the development of new solutions and materials for advanced oxidation by providing guidance for comparable and scalable oxidation experiments. We discuss recent developments in catalytic, ozone-based, radiation-driven, and other AOPs, and outline future perspectives and research needs. Since standardized experimental procedures are not available for most AOPs, we propose basic rules and key parameters for lab-scale evaluation of new AOPs including selection of suitable probe compounds and scavengers for the measurement of (major) reactive species. A two-phase approach to assess new AOP concepts is proposed, consisting of (i) basic research and proof-of-concept (technology readiness levels (TRL) 1-3), followed by (ii) process development in the intended water matrix including a cost comparison with an established process, applying comparable and scalable parameters such as UV fluence or ozone consumption (TRL 3-5). Subsequent demonstration of the new process (TRL 6-7) is briefly discussed, too. Finally, we highlight important research tools for a thorough mechanistic process evaluation and risk assessment including screening for transformation products that should be based on chemical logic and combined with complementary tools (mass balance, chemical calculations).

Handling of problematic ion chromatograms with the Automated Target Screening (ATS) workflow for unsupervised analysis of high-resolution mass spectrometry data.

Liquid chromatography (LC) or gas chromatography (GC) coupled to high-resolution mass spectrometry (HRMS) is a versatile analytical method for the analysis of thousands of chemical pollutants that can be found in environmental and biological samples. While the tools for handling such complex datasets have improved, there are still no fully automated workflows for targeted screening analysis. Here we present an R-based workflow that is able to cope with challenging data like noisy ion chromatograms, retention time shifts, and multiple peak patterns. The workflow can be applied to batches of HRMS data recorded after GC with electron ionization (GC-EI) and LC coupled to electrospray ionization in both negative and positive mode (LC-ESIneg/LC-ESIpos) to perform peak annotation and quantitation fully unsupervised. We used Orbitrap HRMS data of surface water extracts to compare the Automated Target Screening (ATS) workflow with data evaluations performed with the vendor software TraceFinder and the established semi-automated analysis workflow in the MZmine software. The ATS approach increased the overall evaluation performance of the peak annotation compared to the established MZmine module without the need for any post-hoc corrections. The overall accuracy increased from 0.80 to 0.86 (LC-ESIpos), from 0.77 to 0.83 (LC-ESIneg), and from 0.67 to 0.76 (GC-EI). The mean average percentage errors for quantification of ATS were around 30% compared to the manual quantification with TraceFinder. The ATS workflow enables time-efficient analysis of GC- and LC-HRMS data and accelerates and improves the applicability of target screening in studies with a large number of analytes and sample sizes without the need for manual intervention.

Widely used herbicide metolachlor can promote harmful bloom formation by stimulating cyanobacterial growth and driving detrimental effects on their chytrid parasites.

Metolachlor (MET) is a widely used herbicide that can adversely affect phytoplanktonic non-target organisms, such as cyanobacteria. Chytrids are zoosporic fungi ubiquitous in aquatic environments that parasitize cyanobacteria and can keep their proliferation in check. However, the influence of organic pollutants on the interaction between species, including parasitism, and the associated ecological processes remain poorly understood. Using the host-parasite system consisting of the toxigenic cyanobacterium Planktothrix agardhii and its chytrid parasite Rhizophydium megarrhizum, we investigated the effects of environmentally relevant concentrations of MET on host-parasite interactions under i) continuous exposure of chytrids and cyanobacteria, and ii) pre-exposure of chytrids. During a continuous exposure, the infection prevalence and intensity were not affected, but chytrid reproductive structures were smaller at the highest tested MET concentration. In the parasite's absence, MET promoted cyanobacteria growth possibly due to a hormesis effect. In the pre-exposure assay, MET caused multi- and transgenerational detrimental effects on parasite fitness. Chytrids pre-exposed to MET showed reduced infectivity, intensity, and prevalence of the infection, and their sporangia size was reduced. Thus, pre-exposure of the parasite to MET resulted in a delayed decline of the cyanobacterial cultures upon infection. After several parasite generations without MET exposure, the parasite recovered its initial fitness, indicating that detrimental effects are transient. This study demonstrates that widely used herbicides, such as MET, could favor cyanobacterial bloom formation both directly, by promoting cyanobacteria growth, and indirectly, by inhibiting their chytrid parasites, which are known to play a key role as top-down regulators of cyanobacteria. In addition, we evidence the relevance of addressing multi-organism systems, such as host-parasite interactions, in toxicity assays. This approach offers a more comprehensive understanding of the effects of pollutants on aquatic ecosystems.

Predicting PFAS and Hydrophilic Trace Organic Contaminant Transport in Black Carbon-Amended Engineered Media Filters for Improved Stormwater Runoff Treatment.

Improved stormwater treatment is needed to prevent toxic and mobile contaminant transport into receiving waters and allow beneficial use of stormwater runoff. In particular, safe capture of stormwater runoff to augment drinking water supplies is contingent upon removing dissolved trace organic contaminants (TrOCs) not captured by conventional stormwater control measures. This study builds upon a prior laboratory-based column study investigating biochar and regenerated activated carbon (RAC) amendment for removing hydrophilic trace organic contaminants (HiTrOCs) and poly- and perfluoroalkyl substances (PFASs) from stormwater runoff. A robust contaminant transport model framework incorporating time-dependent flow and influent concentration is developed and validated to predict HiTrOC and PFAS transport in biochar- and RAC-amended stormwater filters. Specifically, parameters fit using a sorption-retarded intraparticle pore diffusion transport model were validated using data further along the depth of the column and compared to equilibrium batch isotherms. The transport model and fitted parameters were then used to estimate the lifetime of a hypothetical stormwater filter in Seal Beach, CA, to be 35 ± 6 years for biochar- and 51 ± 17 years for RAC-amended filters, under ideal conditions with no filter clogging. This work offers insights on the kinetics of HiTrOC and PFAS transport within biochar and RAC filters and on the impact of filter design on contaminant removal performance and longevity.

Black Carbon-Amended Engineered Media Filters for Improved Treatment of Stormwater Runoff.

Urban stormwater runoff is a significant driver of surface water quality impairment. Recently, attention has been drawn to potential beneficial use of urban stormwater runoff, including augmenting drinking water supply in water-stressed areas. However, beneficial use relies on improved treatment of stormwater runoff to remove mobile dissolved metals and trace organic contaminants (TrOCs). This study assesses six engineered media mixtures consisting of sand, zeolite, high-temperature gasification biochar, and regenerated activated carbon (RAC) for removing a suite of co-contaminants comprising five metals, three herbicides, four pesticides, a corrosion inhibitor, six per- and polyfluoroalkyl substances (PFASs), five polychlorinated biphenyls (PCBs), and six polycyclic aromatic hydrocarbons (PAHs). This long-term laboratory-scale column study uses a novel approach to generate reproducible synthetic stormwater that incorporates catch basin material and straw-derived dissolved organic carbon. Higher flow conditions (20 cm hr-1), larger sized media (0.42-1.68 mm), and downflow configuration with outlet control increase the relevance of this study to better enable implementation in the field. Biochar- and RAC-amended engineered media filters removed nearly all of the TrOCs in the effluent over the course of three months of continuous flow (480 empty bed volumes), while sample ports spaced at 25% and 50% along the column depth provide windows to observe contaminant transport. Biochar provided greater benefit to TrOC removal than RAC on a mass basis. This study used relatively high concentrations of contaminants and low biochar and RAC content to observe contaminant transport. Performance in the field is likely to be significantly better with higher biochar- and RAC-content filters and lower ambient stormwater contaminant concentrations. This study provides proof-of-concept for biochar- and RAC-amended engineered media filters operated at a flow rate of 20 cm hr-1 for removing dissolved TrOCs and metals and offers insights on the performance of biochar and RAC for improved stormwater treatment and field trials.

Evaluation of pilot-scale biochar-amended woodchip bioreactors to remove nitrate, metals, and trace organic contaminants from urban stormwater runoff.

Stormwater is increasingly being valued as a freshwater resource in arid regions and can provide opportunities for beneficial reuse via aquifer recharge if adequate pollutant removal can be achieved. We envision a multi-unit operation approach to capture, treat, and recharge (CTR) stormwater using low energy, cost-effective technologies appropriate for larger magnitude, less frequent events. Herein, we tested nutrient, metal, and trace organic contaminant removal of a pilot-scale CTR system in the laboratory using biochar-amended woodchip bioreactors following eight months of aging under field conditions with exposure to real stormwater. Replicate columns with woodchips and biochar (33% by weight), woodchips and straw, or woodchips only were operated with continuous, saturated flow for eight months using water from a watershed that drained an urban area consisting of residential housing and parks in Sonoma, California. After aging, columns were challenged for five months by continuous exposure to synthetic stormwater amended with 50 µg L-1 of six trace organic contaminants (i.e., fipronil, diuron, 1H-benzotriazole, atrazine, 2,4-D, and TCEP) and five metals (Cd, Cu, Ni, Pb, Zn) frequently detected in stormwater in order to replicate the treatment unit operation of a CTR system. Throughout the eight-month aging and five-month challenge experiment, nitrate concentrations were below the detection limit after treatment (i.e., <0.05 mg N L-1). The removal efficiencies for metals in all treatments were >80% for Ni, Cu, Cd, and Pb. For Zn, about 50% removal occurred in the woodchip-biochar systems while the other systems achieved about 20% removal. No breakthrough of the trace organic compounds was observed in any biochar-containing columns. Woodchip columns without biochar removed approximately 99% of influent atrazine and 90% of influent fipronil, but exhibited relatively rapid breakthrough of TCEP, 2,4-D, 1H-benzotriazole, and diuron. The addition of straw to the woodchip columns provided no significant benefit compared to woodchips alone. Due to the lack of breakthrough of trace organics in the biochar-woodchip columns, we estimated column breakthrough with a diffusion-limited sorption model. Results of the model indicate breakthrough for the trace organics would occur between 10,000 and 32,000 pore volumes. Under ideal conditions this could be equivalent to decades of service, assuming failure by other processes (e.g., clogging, biofouling) does not occur. These results indicate that multiple contaminants can be removed in woodchip-biochar reactors employed in stormwater treatment systems with suitable flow control and that the removal of trace organic contaminants is enhanced significantly by addition of biochar.

Carbon, Hydrogen, and Nitrogen Isotope Fractionation Trends in N-Nitrosodimethylamine Reflect the Formation Pathway during Chloramination of Tertiary Amines.

Assessing the precursors and reactions leading to the carcinogenic N-nitrosodimethylamine (NDMA) during drinking water disinfection is a major challenge. Here, we investigate whether changes of 13C/12C, 2H/1H, and 15N/14N ratios of NDMA give rise to isotope fractionation trends that can be used to infer NDMA formation pathways. We carried out compound-specific isotope analysis (CSIA) of NDMA during chloramination of four tertiary amines that produce NDMA at high yields, namely ranitidine, 5-(dimethylaminomethyl)furfuryl alcohol, N,N-dimethylthiophene-2-methylamine, and N,N-dimethylbenzylamine. Carbon and hydrogen isotope ratios of NDMA function as fingerprints of the N(CH3)2 moiety and exhibit only minor isotope fractionation during the disinfection process. Nitrogen isotope ratios showed that NH2Cl is the source of the N atom of the nitroso group. The large enrichment of 15N in NDMA was indicative of the isotope effects pertinent to bond-cleavage and bond-formation reactions during chloramination of the tertiary amines. Correlation of δ15N versus δ13C values of NDMA resulted in trend lines that were not affected by the type of tertiary amine and treatment conditions, suggesting that the observed C and N isotope fractionation in NDMA may be diagnostic for NDMA precursors and formation pathways during chloramination.

Formation of N-Nitrosodimethylamine during Chloramination of Secondary and Tertiary Amines: Role of Molecular Oxygen and Radical Intermediates.

N-Nitrosodimethylamine (NDMA) is a carcinogenic disinfection byproduct from water chloramination. Despite the identification of numerous NDMA precursors, essential parts of the reaction mechanism such as the incorporation of molecular O2 are poorly understood. In laboratory model systems for the chloramination of secondary and tertiary amines, we investigated the kinetics of precursor disappearance and NDMA formation, quantified the stoichiometries of monochloramine (NH2Cl) and aqueous O2 consumption, derived 18O-kinetic isotope effects (18O-KIE) for the reactions of aqueous O2, and studied the impact of radical scavengers on NDMA formation. Although the molar NDMA yields from five N,N-dimethylamine-containing precursors varied between 1.4% and 90%, we observed the stoichiometric removal of one O2 per N,N-dimethylamine group of the precursor indicating that the oxygenation of N atoms did not determine the molar NDMA yield. Small 18O-KIEs between 1.0026 ± 0.0003 and 1.0092 ± 0.0009 found for all precursors as well as completely inhibited NDMA formation in the presence of radical scavengers (ABTS and trolox) imply that O2 reacted with radical species. Our study suggests that aminyl radicals from the oxidation of organic amines by NH2Cl and N-peroxyl radicals from the reaction of aminyl radicals with aqueous O2 are part of the NDMA formation mechanism.

Compound-specific carbon, nitrogen, and hydrogen isotope analysis of N-nitrosodimethylamine in aqueous solutions.

Mitigation of N-nitrosodimethylamine (NDMA) and other hazardous water disinfection byproducts (DBP) is currently hampered by a limited understanding of DBP formation mechanisms. Because variations of the stable isotope composition of NDMA can potentially reveal reaction pathways and precursor compounds, we developed a method for the compound-specific isotope analysis (CSIA) of (13)C/(12)C, (15)N/(14)N, and (2)H/(1)H ratios of NDMA by gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS). Method quantification limits for the accurate isotope analysis of NDMA, N-nitrosodiethyl-, -dipropyl-, and -dibutylamine as well as N-nitrosopyrrolidine were between 0.18 to 0.60 nmol C, 0.40 to 0.80 nmol N, and 2.2 to 5.8 nmol H injected on column. Coupling solid phase extraction (SPE) to GC/IRMS enabled the precise quantification of C, N, and H isotope ratios of NDMA in aqueous samples at concentrations of 0.6 µM (45 µg L(-1)). We validated the proposed method with a laboratory experiment, in which NDMA was formed with stoichiometric yield (97 ± 4%) through chloramination of the pharmaceutical ranitidine (3 µM). δ(13)C and δ(2)H values of NDMA remained constant during NDMA formation while its δ(15)N increased due to a reaction at a N atom in the rate-limiting step of NDMA formation. The δ(2)H value of NDMA determined by SPE-GC/IRMS also corresponded well to the δ(2)H value of the N(CH3)2-group of ranitidine measured by quantitative deuterium nuclear magnetic resonance spectroscopy. This observation implies that the N(CH3)2-moiety of ranitidine is transferred to NDMA without being chemically altered and illustrates the accuracy of the proposed method.

Biotransformation of benzotriazoles: insights from transformation product identification and compound-specific isotope analysis.

Benzotriazoles are widely used domestic and industrial corrosion inhibitors and have become omnipresent organic micropollutants in the aquatic environment. Here, the range of aerobic biological degradation mechanisms of benzotriazoles in activated sludge was investigated. Degradation pathways were elucidated by identifying transient and persistent transformation products in batch experiments using liquid chromatography-high-resolution tandem mass spectrometry (LC-HR-MS/MS). In addition, initial reactions were studied using compound-specific isotope analysis (CSIA). Biodegradation half-lives of 1.0 days for 1H-benzotriazole, 8.5 days for 4-methyl-1H-benzotriazole, and 0.9 days for 5-methyl-1H-benzotriazole with activated sludge confirmed their known partial persistence in conventional wastewater treatment. Major transformation products were identified as 4- and 5-hydroxy-1H-benzotriazole for the degradation of 1H-benzotriazole, and 1H-benzotriazole-5-carboxylic acid for the degradation of 5-methyl-1H-benzotriazole. These transformation products were found in wastewater effluents, showing their environmental relevance. Many other candidate transformation products, tentatively identified by interpretation of HR-MS/MS spectra, showed the broad range of possible reaction pathways including oxidation, alkylation, hydroxylation and indicate the significance of cometabolic processes for micropollutant degradation in biological wastewater treatment in general. The combination of evidence from product analysis with the significant carbon and nitrogen isotope fractionation suggests that aromatic monohydroxylation is the predominant step during the biotransformation of 1H-benzotriazole.

Isotope Effects as New Proxies for Organic Pollutant Transformation.

Assessing the pathways and rates of organic pollutant transformation in the environment is a major challenge due to co-occurring transport and degradation processes. Measuring changes of stable isotope ratios (e.g. (13)C/(12)C, (2)H/(1)H, (15)N/(14)N) in individual organic compounds by compound-specific isotope analysis (CSIA) makes it possible to identify degradation pathways without the explicit need to quantify pollutant concentration dynamics. The so-called isotope fractionation observed in an organic pollutant is related to isotope effects of (bio)chemical reactions and enables one to characterize pollutant degradation even if multiple processes take place simultaneously. Here, we illustrate some principles of CSIA using benzotriazole, a frequently observed aquatic micropollutant, as example. We show subsequently how the combined C and N isotope fractionation analysis of nitroaromatic compounds reveals kinetics and mechanisms of reductive and oxidative reactions as well as their (bio)degradation pathways in the environment.

Compound-specific isotope analysis of benzotriazole and its derivatives.

Compound-specific isotope analysis (CSIA) is an important tool for the identification of contaminant sources and transformation pathways, but it is rarely applied to emerging aquatic micropollutants owing to a series of instrumental challenges. Using four different benzotriazole corrosion inhibitors and its derivatives as examples, we obtained evidence that formation of organometallic complexes of benzotriazoles with parts of the instrumentation impedes isotope analysis. Therefore, we propose two strategies for accurate [Formula: see text]C and [Formula: see text]N measurements of polar organic micropollutants by gas chromatography isotope ratio mass spectrometry (GC/IRMS). Our first approach avoids metallic components and uses a Ni/Pt reactor for benzotriazole combustion while the second is based on the coupling of online methylation to the established GC/IRMS setup. Method detection limits for on-column injection of benzotriazole, as well as its 1-CH[Formula: see text]-, 4-CH[Formula: see text]-, and 5-CH[Formula: see text]-substituted species were 0.1-0.3 mM and 0.1-1.0 mM for δ(13)C and δ(15)N analysis respectively, corresponding to injected masses of 0.7-1.8 nmol C and 0.4-3.0 nmol N, respectively. The Ni/Pt reactor showed good precision and was very long-lived ([Formula: see text]1000 successful measurements). Coupling isotopic analysis to offline solid-phase extraction enabled benzotriazole-CSIA in tap water, wastewater treatment effluent, activated sludge, and in commercial dishwashing products. A comparison of [Formula: see text]C and [Formula: see text]N values from different benzotriazoles and benzotriazole derivatives, both from commercial standards and in dishwashing detergents, reveals the potential application of the proposed method for source apportionment.

Two GacA-dependent small RNAs modulate the quorum-sensing response in Pseudomonas aeruginosa.

In Pseudomonas aeruginosa, the GacS/GacA two-component system positively controls the quorum-sensing machinery and the expression of extracellular products via two small regulatory RNAs, RsmY and RsmZ. An rsmY rsmZ double mutant and a gacA mutant were similarly impaired in the synthesis of the quorum-sensing signal N-butanoyl-homoserine lactone, the disulfide bond-forming enzyme DsbA, and the exoproducts hydrogen cyanide, pyocyanin, elastase, chitinase (ChiC), and chitin-binding protein (CbpD). Both mutants showed increased swarming ability, azurin release, and early biofilm development.