Antimicrobial, Preservative, and Hazard Assessments from Eight Chemical Classes.

Preservatives, such as isothiazolinones and formaldehyde-releasing compounds, provide safety and stability in consumer products by preventing microbial contamination. Yet these ingredients present human and environmental hazards, including allergic contact dermatitis and aquatic toxicity. The development of safer alternatives has been stymied by trade-offs between safety and efficacy. To enable the identification of safer preservatives, substances from eight functional classes were assessed for antimicrobial efficacy and human and environmental hazards. First, 130 substances were evaluated for microbial inhibitory activity against two relevant model microorganisms, Aspergillus brasiliensis (filamentous fungi) and Pseudomonas aeruginosa (Gram-negative bacteria). High-performing compounds within each class were assessed for hazards across a broad suite of human and environmental health end points. Four promising compounds were selected for further testing based on microbial inhibition, hazard profiles, and commercial availability. These ingredients were tested for biocidal activity in model home care formulations using methods adapted from industrial preservative challenge guidelines (USP-51). Two substances were identified, caprylhydroxamic acid and caprylyl glycol, that provided adequate preservation and improved toxicity profiles compared to isothiazolinone and formaldehyde-releasing preservatives. This study highlights trade-offs between antimicrobial activity and hazards across a broad spectrum of chemical classes relevant to safer preservative development.

Bioretention Design Modifications Increase the Simulated Capture of Hydrophobic and Hydrophilic Trace Organic Compounds.

Stormwater rapidly moves trace organic contaminants (TrOCs) from the built environment to the aquatic environment. Bioretention cells reduce loadings of some TrOCs, but they struggle with hydrophilic compounds. Herein, we assessed the potential to enhance TrOC removal via changes in bioretention system design by simulating the fate of seven high-priority stormwater TrOCs (e.g., PFOA, 6PPD-quinone, PAHs) with log KOC values between -1.5 and 6.74 in a bioretention cell. We evaluated eight design and management interventions for three illustrative use cases representing a highway, a residential area, and an airport. We suggest two metrics of performance: mass advected to the sewer network, which poses an acute risk to aquatic ecosystems, and total mass advected from the system, which poses a longer-term risk for persistent compounds. The optimized designs for each use case reduced effluent loadings of all but the most polar compound (PFOA) to <5% of influent mass. Our results suggest that having the largest possible system area allowed bioretention systems to provide benefits during larger events, which improved performance for all compounds. To improve performance for the most hydrophilic TrOCs, an amendment like biochar was necessary; field-scale research is needed to confirm this result. Our results showed that changing the design of bioretention systems can allow them to effectively capture TrOCs with a wide range of physicochemical properties, protecting human health and aquatic species from chemical impacts.

Persistent Trace Organic Contaminants Are Transformed Rapidly under Sulfate- and Fe(III)-Reducing Conditions in a Nature-Based Subsurface Water Treatment System.

Subsurface treatment systems, such as constructed wetlands, riverbank filtration systems, and managed aquifer recharge systems, offer a low-cost means of removing trace organic contaminants from treated municipal wastewater. To assess the processes through which trace organic contaminants are removed in subsurface treatment systems, pharmaceuticals and several major metabolites were measured in porewater, sediment, and plants within a horizontal levee (i.e., a subsurface flow wetland that receives treated municipal wastewater). Concentrations of trace organic contaminants in each wetland compartment rapidly declined along the flow path. Mass balance calculations, analysis of transformation products, microcosm experiments, and one-dimensional transport modeling demonstrated that more than 60% of the contaminant removal could be attributed to transformation. Monitoring of the system with and without nitrate in the wetland inflow indicated that relatively biodegradable trace organic contaminants, such as acyclovir and metoprolol, were rapidly transformed under both operating conditions. Trace organic contaminants that are normally persistent in biological treatment systems (e.g., sulfamethoxazole and carbamazepine) were removed only when Fe(III)- and sulfate-reducing conditions were observed. Minor structural modifications to trace organic contaminants (e.g., hydroxylation) altered the pathways and extents of trace organic contaminant transformation under different redox conditions. These findings indicate that subsurface treatment systems can be designed to remove both labile and persistent trace organic contaminants via transformation if they are designed and operated in a manner that results in sulfate-and Fe(III)-reducing conditions.

Bioretention Cells Provide a 10-Fold Reduction in 6PPD-Quinone Mass Loadings to Receiving Waters: Evidence from a Field Experiment and Modeling.

Road runoff to streams and rivers exposes aquatic organisms to complex mixtures of chemical contaminants. In particular, the tire-derived chemical 6PPD-quinone (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone) is acutely toxic to several species of salmonids, which are critical to fisheries, ecosystems, and Indigenous cultures. We therefore urgently require interventions that can reduce loadings of 6PPD-quinone to salmonid habitats. Herein, we conducted a spike and recovery experiment on a full-scale, mature bioretention cell to assess the efficacy of stormwater green infrastructure technologies in reducing 6PPD-quinone loadings to receiving waters. We then interpreted and extended the results of our experiment using an improved version of the "Bioretention Blues" contaminant transport and fate model. Overall, our results showed that stormwater bioretention systems can effectively mitigate >∼90% of 6PPD-quinone loadings to streams under most "typical" storm conditions (i.e., < 2-year return period). We therefore recommend that stormwater managers and other environmental stewards redirect stormwater away from receiving waters and into engineered green infrastructure systems such as bioretention cells.

Methane-Oxidizing Activity Enhances Sulfamethoxazole Biotransformation in a Benthic Constructed Wetland Biomat.

Ammonia monooxygenase and analogous oxygenase enzymes contribute to pharmaceutical biotransformation in activated sludge. In this study, we hypothesized that methane monooxygenase can enhance pharmaceutical biotransformation within the benthic, diffuse periphytic sediments (i.e., "biomat") of a shallow, open-water constructed wetland. To test this hypothesis, we combined field-scale metatranscriptomics, porewater geochemistry, and methane gas fluxes to inform microcosms targeting methane monooxygenase activity and its potential role in pharmaceutical biotransformation. In the field, sulfamethoxazole concentrations decreased within surficial biomat layers where genes encoding for the particulate methane monooxygenase (pMMO) were transcribed by a novel methanotroph classified as Methylotetracoccus. Inhibition microcosms provided independent confirmation that methane oxidation was mediated by the pMMO. In these same incubations, sulfamethoxazole biotransformation was stimulated proportional to aerobic methane-oxidizing activity and exhibited negligible removal in the absence of methane, in the presence of methane and pMMO inhibitors, and under anoxia. Nitrate reduction was similarly enhanced under aerobic methane-oxidizing conditions with rates several times faster than for canonical denitrification. Collectively, our results provide convergent in situ and laboratory evidence that methane-oxidizing activity can enhance sulfamethoxazole biotransformation, with possible implications for the combined removal of nitrogen and trace organic contaminants in wetland sediments.

Pharmaceutical Biotransformation is Influenced by Photosynthesis and Microbial Nitrogen Cycling in a Benthic Wetland Biomat.

In shallow, open-water engineered wetlands, design parameters select for a photosynthetic microbial biomat capable of robust pharmaceutical biotransformation, yet the contributions of specific microbial processes remain unclear. Here, we combined genome-resolved metatranscriptomics and oxygen profiling of a field-scale biomat to inform laboratory inhibition microcosms amended with a suite of pharmaceuticals. Our analyses revealed a dynamic surficial layer harboring oxic-anoxic cycling and simultaneous photosynthetic, nitrifying, and denitrifying microbial transcription spanning nine bacterial phyla, with unbinned eukaryotic scaffolds suggesting a dominance of diatoms. In the laboratory, photosynthesis, nitrification, and denitrification were broadly decoupled by incubating oxic and anoxic microcosms in the presence and absence of light and nitrogen cycling enzyme inhibitors. Through combining microcosm inhibition data with field-scale metagenomics, we inferred microbial clades responsible for biotransformation associated with membrane-bound nitrate reductase activity (emtricitabine, trimethoprim, and atenolol), nitrous oxide reduction (trimethoprim), ammonium oxidation (trimethoprim and emtricitabine), and photosynthesis (metoprolol). Monitoring of transformation products of atenolol and emtricitabine confirmed that inhibition was specific to biotransformation and highlighted the value of oscillating redox environments for the further transformation of atenolol acid. Our findings shed light on microbial processes contributing to pharmaceutical biotransformation in open-water wetlands with implications for similar nature-based treatment systems.

Emerging investigator series: contributions of reactive nitrogen species to transformations of organic compounds in water: a critical review.

Reactive nitrogen species (RNS) pose a potential risk to drinking water quality because they react with organic compounds to form toxic byproducts. Since the discovery of RNS formation in sunlit surface waters, these reactive intermediates have been detected in numerous sunlit natural waters and engineered water treatment systems. This critical review summarizes what is known regarding RNS, including their formation, contributions to contaminant transformation, and products resulting from RNS reactions. Reaction mechanisms and rate constants have been described for nitrogen dioxide (˙NO2) reacting with phenolic compounds. However, significant knowledge gaps remain regarding reactions of RNS with other types of organic compounds. Promising methods to quantify RNS concentrations and reaction rates include the use of selective quenchers and probe compounds as well as electron paramagnetic resonance spectroscopy. Additionally, high resolution mass spectrometry methods have enabled the identification of nitr(os)ated byproducts that form via RNS reactions in sunlit surface waters, UV-based treatment systems, treatment systems that employ chemical oxidants such as chlorine and ozone, and certain types of biological treatment processes. Recommendations are provided for future research to increase understanding of RNS reactions and products, and the implications for drinking water toxicity.

Enabling Water Reuse by Treatment of Reverse Osmosis Concentrate: The Promise of Constructed Wetlands.

As more cities experience water stress, the use of reverse osmosis (RO) membranes for wastewater treatment and reuse will expand. The concentrated waste stream resulting from RO treatment can pose chronic ecotoxicity risks if discharged to surface waters or shallow coastal ecosystems. Most existing RO concentrate treatment technologies are cost prohibitive, but constructed wetlands hold promise as a viable multibenefit solution because they have the potential to provide simultaneous treatment of nutrients, metals, and trace organic contaminants at a relatively low cost. They also are popular with the public. A handful of water-stressed cities have already begun experimenting with constructed wetlands for RO concentrate treatment. However, further research is needed to reduce the land area needed for treatment and increase the reliability of constructed wetland systems.

Transformation of Trace Organic Contaminants from Reverse Osmosis Concentrate by Open-Water Unit-Process Wetlands with and without Ozone Pretreatment.

Reverse osmosis (RO) treatment of municipal wastewater effluent is becoming more common as water reuse is implemented in water-stressed regions. Where RO concentrate is discharged with limited dilution, concentrations of trace organic contaminants could pose risks to aquatic ecosystems. To provide a low-cost option for removing trace organic compounds from RO concentrate, a pilot-scale treatment system comprising open-water unit-process wetlands with and without ozone pretreatment was studied over a 2-year period. A suite of ecotoxicologically relevant organic contaminants was partially removed via photo- and bio-transformations, including ß-adrenergic blockers, antivirals, antibiotics, and pesticides. Biotransformation rates were as fast as or up to approximately 50% faster than model predictions based upon data from open-water wetlands that treated municipal wastewater effluent. Phototransformation rates were comparable to or as much as 60% slower than those predicted by models that accounted for light penetration and scavenging of reactive oxygen species. Several compounds were transformed during ozone pretreatment that were poorly removed in the open-water wetland. The combined treatment system resulted in a decrease in the risk quotients of trace organic contaminants in the RO concentrate, but still dilution may be required to protect sensitive species from urban-use pesticides with low environmental effect concentrations.

The Role of Reactive Nitrogen Species in Sensitized Photolysis of Wastewater-Derived Trace Organic Contaminants.

Under conditions typically encountered in the aquatic environment, the absorption of sunlight by nitrite and nitrate leads to the transformation of trace organic contaminants. In addition to the well understood mechanism through which hydroxyl radical (·OH) produced by nitrate and nitrite photolysis oxidizes contaminants, absorption of light also results in the formation of reactive nitrogen species that transform organic contaminants. To assess the importance of this process on the fate of trace organic contaminants, radical quenchers and transformation product analysis were used to discriminate among potential reaction pathways. For sulfamethoxazole, an antibiotic that is frequently detected in municipal wastewater effluent, nitrate and nitrite-sensitized photolysis pathways resulted in production of transformation products that were not detected during direct photolysis or reaction with ·OH. The reactivity of sulfamethoxazole with the reactive species produced when nitrite absorbed sunlight was affected by the presence of hydroxyl radical scavengers, indicating the likely involvement of nitrogen dioxide, which forms when nitrite reacts with hydroxyl radical. Reactive nitrogen species also reacted with emtricitabine, propranolol, and other trace organic contaminants commonly detected in wastewater effluent, indicating the potential importance of this process to the fate of other trace organic contaminants. A kinetic model indicated that reactive nitrogen species could be important to the phototransformation of trace organic contaminants when relatively high concentrations of nitrite are present (e.g., in surface waters receiving reverse osmosis concentrate from potable water reuse projects or in agricultural runoff).

Predictors of pesticide concentrations in freshwater trout - The role of life history.

Concentrations of halogenated pesticides in freshwater fish can be affected by age, size, trophic position, and exposure history. Exposure history may vary for individual fish caught at a single location due to different life histories, e.g. they may have hatched in different tributaries before migrating to a specific lake. We evaluated correlations of pesticide concentrations in freshwater brown trout (Salmo trutta) from the Clutha River, New Zealand, with potential predictors including capture site, age, length, trophic level, and life history. Life history was determined from otolith (fish ear bone) strontium isotope signatures, which vary among tributaries in the region of our study. Variability in pesticide concentrations between individual fish was not well explained by capture site, age, length, or trophic level. However, hexachlorobenzene (HCB) and chlorpyrifos concentrations were distinct in lake-based trout with different life histories. Additionally, one of the riverine life histories was associated with relatively high concentrations of total endosulfans. Linear models that included all potential predictor variables were evaluated and the resulting best models for HCB, chlorpyrifos, and total endosulfans included life history. These findings show that in cases where otolith isotope signatures vary geographically, they can be used to help explain contaminant concentration variations in fish caught from a single location.

Recovery of dilute aqueous acetone, butanol, and ethanol with immobilized calixarene cavities.

Macrocyclic calixarene molecules were modified with functional groups of different polarities at the upper rim and subsequently grafted to mesoporous silica supports through a single Si atom linker. The resulting materials were characterized by thermogravimetric analysis, UV-visible spectroscopy, nitrogen physisorption, and solid-state NMR spectroscopy. Materials were then used to separate acetone, n-butanol, and ethanol from dilute aqueous solution, as may be useful in the recovery of fermentation-based biofuels. For the purpose of modeling batch adsorption isotherms, the materials were considered to have one strong adsorption site per calixarene molecule and a larger number of weak adsorption sites on the silica surface and external to the calixarene cavity. The magnitude of the net free energy change of adsorption varied from approximately 15 to 20 kJ/mol and was found to decrease as upper-rim calixarene functional groups became more electron-withdrawing. Adsorption appears to be driven by weak van der Waals interactions with the calixarene cavity and, particularly for butanol, minimizing contacts with solvent water. In addition to demonstrating potentially useful new sorbents, these materials provide some of the first experimental estimates of the energy of interaction between aqueous solutes and hydrophobic calixarenes, which have previously been inaccessible because of the insolubility of most nonionic calixarene species in water.