Defining the Chemical Additives Driving In Vitro Toxicities of Plastics.

Increases in the global use of plastics have caused concerns regarding potential adverse effects on human health. Plastic products contain hundreds of potentially toxic chemical additives, yet the exact chemicals which drive toxicity currently remain unknown. In this study, we employed nontargeted analysis and in vitro bioassays to identify the toxicity drivers in plastics. A total of 56 chemical additives were tentatively identified in five commonly used plastic polymer pellets (i.e., PP, LDPE, HDPE, PET, and PVC) by employing suspect screening and nontargeted analysis. Phthalates and organophosphates were found to be dominant in PVC pellets. Triphenyl phosphate and 2-ethylhexyl diphenyl phosphate accounted for a high amount (53.6%) of the inhibition effect of PVC pellet extract on human carboxylesterase 1 (hCES1) activity. Inspired by the high abundances of chemical additives in PVC pellets, six different end-user PVC-based products including three widely used PVC water pipes were further examined. Among them, extracts of PVC pipe exerted the strongest PPARγ activity and cell viability suppression. Organotins were identified as the primary drivers to these in vitro toxicities induced by the PVC pipe extracts. This study clearly delineates specific chemical additives responsible for hCES1 inhibition, PPARγ activity, and cell viability suppression associated with plastic.

Oxidation of Microcystis aeruginosa and Microcystins with Peracetic Acid.

Peracetic acid (PAA) shows potential for use in drinking water treatment as an alternative to prechlorination, such as for mussel control and disinfection by-product precursor destruction, though its impact as a preoxidant during cyanobacterial blooms remains underexplored. Here, Microcystis aeruginosa inactivation and microcystin-LR and -RR release and degradation using PAA were explored. The toxin degradation rates were found to be higher in alkaline conditions than in neutral and acidic conditions. However, all rates were significantly smaller than comparable rates when using free chlorine. The inactivation of M. aeruginosa cells using PAA was faster at acidic pH, showing immediate cell damage and subsequent cell death after 15-60 min of exposure to 10 mg/L PAA. In neutral and alkaline conditions, cell death occurred after a longer lag phase (3-6 h). During cell inactivation, microcystin-LR was released slowly, with <35% of the initial intracellular toxins measured in solution after 12 h of exposure to 10 mg/L PAA. Overall, PAA appears impractically slow for M. aeruginosa cell inactivation or microcystin-LR and -RR destruction in drinking water treatment, but this slow reactivity may also allow it to continue to be applied as a preoxidant for other purposes during cyanobacterial blooms without the risk of toxin release.

Using total adenosine triphosphate (tATP) measurements for cyanobacterial bloom monitoring and response assessment during algaecide treatments.

Total adenosine triphosphate (tATP) was investigated for its potential as a rapid indicator of cyanobacterial growth and algaecide effectiveness. tATP and other common bloom monitoring parameters were measured over the growth cycles of cyanobacteria and green algae in laboratory cultures and examined at a drinking water source during an active bloom. Strong correlations (R2>0.78) were observed between tATP and chlorophyll-a in cyanobacteria cultures. tATP offered greater sensitivity by increasing two orders of magnitude approximately 7 d before changes in chlorophyll-a or optical density were observed in Lyngbya sp. and Dolichospermum sp. cultures. Increases in tATP per cell coincided with the onset of exponential growth phases in lab cultures and increase in cell abundance in field samples, suggesting that ATP/cell is a sensitive indicator that may be used to identify the development of blooms. Bench-scale trials using samples harvested during a bloom showed that tATP exhibited a clear dose-response during copper sulfate (CuSO4) and hydrogen peroxide (H2O2) treatment compared to chlorophyll-a and cell counts, indicating that cellular production and storage of ATP decreases even when live and dead cells cannot be distinguished. During Copper (Cu) algaecide application at a reservoir used as a drinking water source, tATP and cell counts decreased following initial algaecide application; however, the bloom rebounded within 10 d showing that the Cu algaecide only has limited effectiveness. In this case, tATP was a sensitive indicator to bloom rebounding after algaecide treatments and correlated positively with cell counts (R2=0.7). These results support the use of tATP as a valuable complementary bloom monitoring tool for drinking water utilities to implement during the monitoring and treatment of cyanobacterial blooms.

Comparison of pipe loop and pipe section reactor methods for estimating chloramine decay in harvested distribution system pipes.

To assess chloramine decay, this study compared the use of pipe loops, which incorporate continuously flowing water, to static pipe section reactors (PSRs). Unlined cast iron (UCI) and cement-lined ductile iron (CLDI) were harvested from distribution systems. These were directly compared to virgin polyvinyl chloride (PVC) pipe at low (0.03 m/s) and high (0.09 m/s) water velocities as well as hydraulic residence times (HRT) of 6 and 24 h. Pipe material was observed to exert the greatest impact on chloramine decay, followed by flow velocity. First-order decay coefficients obtained using pipe loops were statistically similar to those for PSR trials when considering UCI and CLDI pipe, irrespective of pipe velocity or water age. Overall results suggest that the use of PSRs may serve as a viable and cost-effective alternative to pipe loops for assessing the impact of operational variables on disinfectant decay.

Adsorption of Per- and Polyfluoroalkyl Substances (PFAS) and Microcystins by Virgin and Weathered Microplastics in Freshwater Matrices.

Microplastics and per- and polyfluoroalkyl substances (PFAS) both represent persistent groups of environmental contaminants that have been associated with human health risks. Microcystin toxins are produced and stored in the cells of cyanobacteria and may be released into sources of drinking water. Recent concerns have emerged regarding the ability of microplastics to adsorb a range of organic contaminants, including PFAS and microcystins. This study examined the adsorption of two long-chain and two short-chain PFAS, as well as two common microcystins, by both virgin and weathered microplastics in freshwater. Natural weathering of microplastic surfaces may decrease adsorption by introducing hydrophilic oxygen-containing functional groups. Up to 50% adsorption of perfluorooctanesulfonic acid (PFOS) was observed for virgin PVC compared to 38% for weathered PVC. In contrast, adsorption capacities for microcystins by virgin LDPE were approximately 5.0 µg/g whereas no adsorption was observed following weathering. These results suggest that adsorption is driven by specific polymer types and dominated by hydrophobic interactions. This is the first known study to quantify PFAS and microcystins adsorption when considering environmentally relevant concentrations as well as weathered microplastics.

Assessment of Biofilm Growth on Microplastics in Freshwaters Using a Passive Flow-Through System.

Biofilms that colonize on the surface of microplastics (MPs) in freshwaters may pose a potential health risk. This study examined factors that influence MP-associated biofilm growth, including polymer type, degree of weathering, and source water quality. Weathered MPs produced in-lab were employed in biofilm trials conducted on site using a passive flow-through system with raw water at drinking water treatment facility intakes. Adenosine triphosphate (ATP) was used to quantify biofilm abundance; biofilm composition was assessed via metagenomic sequencing. Biofilm growth was observed on all polymer types examined and most prevalent on polyvinyl chloride (PVC), where ATP levels were 6 to 12 times higher when compared to other polymers. Pathogen-containing species including Salmonella enterica and Escherichia coli were present on all polymers with relative abundance up to 13.7%. S. enterica was selectively enriched on weathered MPs in specific water matrices. These findings support the need to research the potential accumulation of pathogenic organisms on microplastic surfaces.

Microplastic Removal from Drinking Water Using Point-of-Use Devices.

The occurrence of microplastics in drinking water has drawn increasing attention due to their ubiquity and unresolved implications regarding human health. Despite achieving high reduction efficiencies (70 to >90%) at conventional drinking water treatment plants (DWTPs), microplastics remain. Since human consumption represents a small portion of typical household water use, point-of-use (POU) water treatment devices may provide the additional removal of microplastics (MPs) prior to consumption. The primary objective of this study was to evaluate the performance of commonly used pour-through POU devices, including those that utilize combinations of granular activated carbon (GAC), ion exchange (IX), and microfiltration (MF), with respect to MP removal. Treated drinking water was spiked with polyethylene terephthalate (PET) and polyvinyl chloride (PVC) fragments, along with nylon fibers representing a range of particle sizes (30-1000 µm) at concentrations of 36-64 particles/L. Samples were collected from each POU device following 25, 50, 75, 100 and 125% increases in the manufacturer's rated treatment capacity, and subsequently analyzed via microscopy to determine their removal efficiency. Two POU devices that incorporate MF technologies exhibited 78-86% and 94-100% removal values for PVC and PET fragments, respectively, whereas one device that only incorporates GAC and IX resulted in a greater number of particles in its effluent when compared to the influent. When comparing the two devices that incorporate membranes, the device with the smaller nominal pore size (0.2 µm vs. ≥1 µm) exhibited the best performance. These findings suggest that POU devices that incorporate physical treatment barriers, including membrane filtration, may be optimal for MP removal (if desired) from drinking water.

Evaluation of ultraviolet/peracetic acid to degrade M. aeruginosa and microcystins -LR and -RR.

The reactivity of peracetic acid (PAA) alone, and PAA exposed to ultraviolet radiation (UV), was investigated on Microcystis aeruginosa cells, and on microcystin-LR and -RR. Reaction rates between PAA and MC-LR (k = 3.46 M-1 s-1) and MC-RR (k = 2.67 M-1 s-1) were determined in an unbuffered acidic solution, and they are approximately 35-45 times lower than a previously reported reaction rate between MC-LR and chlorine at pH 6. Peracetic acid reacted with M. aeruginosa cells as a function of PAA and cell concentrations, with 10 mg/L PAA resulting in 1-log reduction of total MC-LR within 15 min. Advanced oxidation by UV/PAA readily degraded MC-LR and MC-RR, outperforming UV/H2O2 at pH 7.7 by > 50% on an equimolar basis. Indirect photolysis at this pH is due to •OH and organic radicals, as determined by trials in the presence of excess tert-butanol to scavenge •OH. The process is less effective when the pH departs from neutral conditions (5.9 or 10.6) due to the decreased effects of both radicals. These findings suggest that PAA alone might be a viable option for cyanobacteria and microcystins control in preoxidation applications and that UV/PAA is an effective process for degrading MC-LR and MC-RR at neutral pH.

Assessment of microplastic sampling and extraction methods for drinking waters.

To date, no standardized methods have been proposed for conducting microplastic analyses in treated drinking waters, resulting in challenges associated with direct comparisons among studies. This study compares known methods for collecting and extracting microplastics from drinking waters: an in-laboratory (in-lab) filtration method and an in-line filtration method (i.e., water filtered on-site without an intermediate storage and/or transportation step). In-lab methods have been the predominant method for sample collection in drinking water matrices, and in-line methods are emerging due to the potential to sample large volumes of water on site and minimize contamination from airborne particles, but the two methods have yet to be directly compared using real samples. In response, this study evaluates both methods in terms of recovering spiked reference microplastics, collecting microplastics from tap water samples using the same water volume, and quantifying the removal of microplastics through a full-scale ultrafiltration system. In-line filtration was shown to have higher recoveries for all the reference microplastics examined (+37 % for PVC fragments, +23 % for PET fragments, +22 % for nylon fibers and +7 % for PET fibers) and a greater potential to reduce microplastic contamination. It also resulted in lower standard deviations for total microplastic counts in the tap water and UF influent and effluent samples. The filtration capacity of the proposed in-line filtration method could exceed 350 L of treated water, but this is highly dependent on the water quality. This study therefore supports the use of in-line filtration methods towards the standardization of microplastic collection procedures in drinking water.

Benthic cyanobacteria: A utility-centred field study.

Although there is growing evidence that benthic cyanobacteria represent a significant source of toxins and taste and odour (T&O) compounds in water bodies globally, water utilities rarely monitor for them. Benthic cyanobacteria grow in an array of matrices such as sediments, biofilms, and floating mats, and they can detach and colonize treatment plants. The occurrence of compounds produced by benthic species across matrix and climate types has not been systematically investigated. Consequently, there is a lack of guidance available to utilities to monitor for and mitigate the risk associated with benthic cyanobacteria. To assess toxin and T&O risk across climatic zones and provide guidance to water utilities for the monitoring of benthic mats, two field surveys were conducted across three continents. The surveys examined the occurrence of six secondary metabolites and associated genes, namely, geosmin, 2-methylisoborneol (MIB), anatoxin-a, saxitoxin, microcystin, and cylindrospermopsin, in benthic environmental samples collected across three climates (i.e., temperate, sub-tropical, and tropical) and a range of matrix types. Existing enzyme-linked immunosorbent assays (ELISAs) and qPCR assays and were used to measure compound concentrations and their associated genes in samples. A novel qPCR assay was designed to differentiate the production of MIB by actinobacteria from that of cyanobacteria. MIB occurrence was higher in warmer climates than temperate climates. Cyanobacteria in benthic mats were the major producers of taste and odour compounds. Floating mats contained significantly higher concentrations of geosmin and saxitoxins compared to other matrix types. Samples collected in warmer areas contained significantly more saxitoxin and cylindrospermopsin than samples collected in temperate climates. While these trends were mainly indicative, they can be used to establish monitoring practices. These surveys demonstrate that benthic mats are significant contributors of secondary metabolites in source water and should be monitored accordingly. Benthic cyanobacteria were the sole producers of T&O in up to 17% of the collected samples compared to actinobacteria, which were sole producers in only 1% of the samples. The surveys also provided a platform of choice for the transfer of methodologies and specific knowledge to participating utilities to assist with the establishment of monitoring practices for benthic cyanobacteria and associated secondary metabolites.

Adsorption of fluoranthene and phenanthrene by virgin and weathered polyethylene microplastics in freshwaters.

Concern exists regarding potential health impacts associated with contaminants of emerging concern (CECs) that adsorb to microplastics (MPs). Previous studies have examined MPs as potential contaminant vectors in marine environments as opposed to freshwaters that represent drinking water sources. This study examined adsorption of two polycyclic aromatic hydrocarbons (PAHs), phenanthrene and fluoranthene, by virgin and weathered polyethylene (PE) in both artificial and natural freshwater matrices. Adsorption kinetics and isotherms conducted in artificial freshwater (AFW) consistently showed higher adsorption onto smaller (200 µm) PE when compared to 1090 µm PE. Adsorption mechanisms were primarily associated with hydrophobic interactions and monolayer chemisorption. As well, environmental factors including dissolved organic matter (DOC), pH, and polymer weathering also impacted adsorption. This work provides new insights regarding the adsorption of organic pollutants to better understand the risk of MPs in drinking water sources.

Conventional and biological treatment for the removal of microplastics from drinking water.

This study examines the removal of microplastics and other anthropogenic particles (>10 µm) from surface water by a full-scale conventional drinking water treatment plant. The treatment process is composed of coagulation with aluminum hydroxide, flocculation, anthracite-sand filtration, and chlorination. Samples were also collected from pilot-scale biological filters consisting of anthracite-sand or granular activated carbon (GAC) media operated with or without pre-ozonation and at a range of different empty-bed contact times (EBCTs). Particles in 10 L water samples collected in duplicate using a fully enclosed sampling apparatus were separated using sieves with 500 µm, 300 µm, 125 µm, and 45 µm openings followed by filtration through 10 µm polycarbonate filters. Particles were counted using stereomicroscopy and characterized using µ-Raman spectroscopy. Full-scale conventional treatment removed 52 % of anthropogenic particles when comparing raw (42 ± 18 particles/L) and finished water (20 ± 8 particles/L). Coagulation, flocculation, and sedimentation accounted for the highest removal (70 %) of any individual unit process. Overall removal was reduced to 52 %, the difference being attributed to airborne particle deposition that occurred while water was detained in a clearwell (exposed to atmosphere via ventilation) that was used to achieve the required contact time for disinfection. The majority of the particles (>80 %) were identified as fibers 10-45 µm; microplastics were predominantly composed of polyester while the non-plastic anthropogenic particles were primarily cellulose. None of the pilot filter configurations examined resulted in significantly fewer microplastics when compared to full-scale conventional filtration. This study illustrates that the removal efficiency of conventional treatment may be limited when considering microfibers <45 µm in size.

Machine learning for anomaly detection in cyanobacterial fluorescence signals.

Many drinking water utilities drawing from waters susceptible to harmful algal blooms (HABs) are implementing monitoring tools that can alert them to the onset of blooms. Some have invested in fluorescence-based online monitoring probes to measure phycocyanin, a pigment found in cyanobacteria, but it is not clear how to best use the data generated. Previous studies have focused on correlating phycocyanin fluorescence and cyanobacteria cell counts. However, not all utilities collect cell count data, making this method impossible to apply in some cases. Instead, this paper proposes a novel approach to determine when a utility needs to respond to a HAB based on machine learning by identifying anomalies in phycocyanin fluorescence data without the need for corresponding cell counts or biovolume. Four widespread and open source algorithms are evaluated on data collected at four buoys in Lake Erie from 2014 to 2019: local outlier factor (LOF), One-Class Support Vector Machine (SVM), elliptic envelope, and Isolation Forest (iForest). When trained on standardized historical data from 2014 to 2018 and tested on labelled 2019 data collected at each buoy, the One-Class SVM and elliptic envelope models both achieve a maximum average F1 score of 0.86 among the four datasets. Therefore, One-Class SVM and elliptic envelope are promising algorithms for detecting potential HABs using fluorescence data only.

Cyanotoxins and Cyanobacteria Cell Accumulations in Drinking Water Treatment Plants with a Low Risk of Bloom Formation at the Source.

Toxic cyanobacteria have been shown to accumulate in drinking water treatment plants that are susceptible to algal blooms. However, the risk for plants that do not experience algal blooms, but that receive a low influx of cells, is not well known. This study determined the extent of cell accumulation and presence of cyanotoxins across the treatment trains of four plants in the Great Lakes region. Samples were collected for microscopic enumeration and enzyme-linked immunosorbent assay (ELISA) measurements for microcystins, anatoxin-a, saxitoxin, cylindrospermopsin, and ß-methylamino-L-alanine (BMAA). Low cell influxes (under 1000 cells/mL) resulted in significant cell accumulations (over 1 × 105 cells/mL) in clarifier sludge and filter backwash samples. Microcystins peaked at 7.2 µg/L in one clarifier sludge sample, exceeding the raw water concentration by a factor of 12. Anatoxin-a was detected in the finished drinking water of one plant at 0.6 µg/L. BMAA may have been detected in three finished water samples, though inconsistencies among the BMAA ELISAs call these results into question. In summary, the results show that plants receiving a low influx of cells can be at risk of toxic cyanobacterial accumulation, and therefore, the absence of a bloom at the source does not indicate the absence of risk.