Snapshot of cyanobacterial toxins in Pakistani freshwater bodies.

Cyanobacteria are known to produce diverse secondary metabolites that are toxic to aquatic ecosystems and human health. However, data about the cyanotoxins occurrence and cyanobacterial diversity in Pakistan's drinking water reservoirs is scarce. In this study, we first investigated the presence of microcystin, saxitoxin, and anatoxin in 12 water bodies using an enzyme-linked immunosorbent assay (ELISA). The observed cyanotoxin values for the risk quotient (RQ) determined by ELISA indicated a potential risk for aquatic life and human health. Based on this result, we made a more in-depth investigation with a subset of water bodies (served as major public water sources) to analyze the cyanotoxins dynamics and identify potential producers. We therefore quantified the distribution of 17 cyanotoxins, including 12 microcystin congeners using a high-performance liquid chromatography-high-resolution tandem mass spectrometry/mass spectrometry (HPLC-HRMS/MS). Our results revealed for the first time the co-occurrence of multiple cyanotoxins and the presence of cylindrospermopsin in an artificial reservoir (Rawal Lake) and a semi-saline lake (Kallar Kahar). We also quantified several microcystin congeners in a river (Panjnad) with MC-LR and MC-RR being the most prevalent and abundant. To identify potential cyanotoxin producers, the composition of the cyanobacterial community was characterized by shotgun metagenomics sequencing. Despite the noticeable presence of cyanotoxins, Cyanobacteria were not abundant. Synechococcus was the most abundant cyanobacterial genus found followed by a small amount of Anabaena, Cyanobium, Microcystis, and Dolichospermum. Moreover, when we looked at the cyanotoxins genes coverage, we never found a complete microcystin mcy operon. To our knowledge, this is the first snapshot sampling of water bodies in Pakistan. Our results would not only help to understand the geographical spread of cyanotoxin in Pakistan but would also help to improve cyanotoxin risk assessment strategies by screening a variety of cyanobacterial toxins and confirming that cyanotoxin quantification is not necessarily related to producer abundance.

Applying the modified UV-activated TOP assay to complex matrices impacted by aqueous film-forming foams.

Per- and polyfluoroalkyl substances (PFAS) are a large chemical family, and numerous chemical species can co-exist in environmental samples, especially those impacted by aqueous film-forming foams (AFFFs). Given the limited availability of chemical standards, capturing the total amount of PFAS is challenging. Thus, the total oxidizable precursor (TOP) assay has been developed to estimate the total amount of PFAS via the oxidative conversion of precursors into perfluorocarboxylic acids (PFCAs). This study aims to enhance the robustness of the TOP assay by replacing heat activation with UV activation. We evaluated the molar yields of known precursors in water in the presence of varying levels of Suwannee River natural organic matter (SRNOM) and in two soils. The impact of UV activation was also evaluated in two soils spiked with three well-characterized AFFFs, six AFFF-impacted field soils, and nine rinse samples of AFFF-impacted stainless-steel pipe. In the presence of 100 mg/L SNROM, 6:2 fluorotelomer sulfonate (FTS), 8:2 FTS, and N-ethyl perfluorooctane sulfonamidoacetic acid (N-EtFOSAA) in deionized water had good molar recovery as PFCAs (average of 102 ± 9.8 %); at 500 mg/L SNROM, the recovery significantly dropped to an average of 51 ± 19 %. In two soils (with 4 % and 8.8 % organic matter) with individual precursor spikes, the average molar recovery was 101 ± 9.4 %, except N-EtFOSAA, which had a reduced recovery in the soil with 8.8 % organic matter (OM). UV-activated assays outperformed heat-activated ones, especially in AFFF-impacted soils and pipe extract samples, with an average of 1.4-1.5× higher PFCA recovery. In almost all test samples, UV activation resulted in a notable shift towards longer PFCA chain lengths, particularly for samples with high OM content. The study confirmed the advantages of UV activation, including a significantly shortened exposure time (1 h vs. 6 h) and reduced matrix effects from OM due to the dual functions of UV in activating persulfate and photodegrading OM.

Improving water quality in a hypereutrophic lake and tributary through agricultural nutrient mitigation: A Multi-year monitoring analysis.

Anthropogenic eutrophication remains a critical global issue, significantly impacting surface water quality. Numerous regions have implemented beneficial management practices to combat agricultural nonpoint pollution, often evaluating efficacy at the field scale, but not downstream. In this study, we conducted an extensive, 11-year (2010-2020), all-season, weekly monitoring program in a small, shallow, hypereutrophic lake and main tributary located in a cold climate, northern temperate zone, within a predominantly agricultural-forested mesoscale watershed. The monitoring took place before and after the implementation of field-scale agricultural nutrient mitigation measures in the catchment, allowing assessment of changes over time in the downstream tributary and lake. We analyzed long-term trends and temporal change points for nitrogen and phosphorus concentrations, aquatic trophic status, and nutrient stoichiometric ratios. The results revealed significant reductions in nitrogen and phosphorus concentrations, improved lake trophic status from hypereutrophic to eutrophic, and an increase in total nitrogen : total phosphorus ratios following the implementation of field-scale agricultural nutrient mitigation measures. Notably, both the lake and its main tributary exhibited significant temporal change points for these parameters. Our findings offer evidence of a relatively rapid, positive effect of the implementation of field-scale agricultural nutrient mitigation measures contributing to subsequent improvements in downstream water quality.

ß-D-glucuronidase activity triggered monitoring of fecal contamination using microbial and chemical source tracking markers at drinking water intakes.

Intense rainfall and snowmelt events may affect the safety of drinking water, as large quantities of fecal material can be discharged from storm or sewage overflows or washed from the catchment into drinking water sources. This study used ß-d-glucuronidase activity (GLUC) with microbial source tracking (MST) markers: human, bovine, porcine mitochondrial DNA markers (mtDNA) and human-associated Bacteroidales HF183 and chemical source tracking (CST) markers including caffeine, carbamazepine, theophylline and acetaminophen, pathogens (Giardia, Cryptosporidium, adenovirus, rotavirus and enterovirus), water quality indicators (Escherichia coli, turbidity) and hydrometeorological data (flowrate, precipitation) to assess the vulnerability of 3 drinking water intakes (DWIs) and identify sources of fecal contamination. Water samples were collected under baseline, snow and rain events conditions in urban and agricultural catchments (Québec, Canada). Dynamics of E. coli, HF183 and WWMPs were similar during contamination events, and concentrations generally varied over 1 order of magnitude during each event. Elevated human-associated marker levels during events demonstrated that urban DWIs were impacted by recent contamination from an upstream municipal water resource recovery facility (WRRF). In the agricultural catchment, mixed fecal pollution was observed with the occurrences and increases of enteric viruses, human bovine and porcine mtDNA during peak contaminating events. Bovine mtDNA qPCR concentrations were indicative of runoff of cattle-derived fecal pollutants to the DWI from diffuse sources following rain events. This study demonstrated that the suitability of a given MST or CST indicator depend on river and catchment characteristics. The sampling strategy using continuous online GLUC activity coupled with MST and CST markers analysis was a more reliable source indicator than turbidity to identify peak events at drinking water intakes.

Global environmental and toxicological impacts of polybrominated diphenyl ethers versus organophosphate esters: A comparative analysis and regrettable substitution dilemma.

The prevalence of organophosphate esters (OPEs) in the global environment is increasing, which aligns with the decline in the usage of polybrominated diphenyl ethers (PBDEs). PBDEs, a category of flame retardants, were banned and classified as persistent organic pollutants (POPs) through the Stockholm Convention due to their toxic and persistent properties. Despite a lack of comprehensive understanding of their ecological and health consequences, OPEs were adopted as replacements for PBDEs. This research aims to offer a comparative assessment of PBDEs and OPEs in various domains, specifically focusing on their persistence, bioaccumulation, and toxicity (PBT) properties. This study explored physicochemical properties (such as molecular weight, octanol-water partition coefficient, octanol-air partition coefficient, Henry's law constant, and vapor pressures), environmental behaviors, global concentrations in environmental matrices (air, water, and soil), toxicities, bioaccumulation, and trophic transfer mechanisms of both groups of compounds. Based on the comparison and analysis of environmental and toxicological data, we evaluate whether OPEs represent another instance of regrettable substitution and global contamination as much as PBDEs. Our findings indicate that the physical and chemical characteristics, environmental behaviors, and global concentrations of PBDEs and OPEs, are similar and overlap in many instances. Notably, OPE concentrations have even surged by orders of several magnitude compared to PBDEs in certain pristine regions like the Arctic and Antarctic, implying long-range transport. In many instances, air and water concentrations of OPEs have been increased than PBDEs. While the bioaccumulation factors (BAFs) of PBDEs (ranging from 4.8 to 7.5) are slightly elevated compared to OPEs (-0.5 to 5.36) in aquatic environments, both groups of compounds exhibit BAF values beyond the threshold of 5000 L/kg (log10 BAF > 3.7). Similarly, the trophic magnification factors (TMFs) for PBDEs (ranging from 0.39 to 4.44) slightly surpass those for OPEs (ranging from 1.06 to 3.5) in all cases. Metabolic biotransformation rates (LogKM) and hydrophobicity are potentially major factors deciding their trophic magnification potential. However, many compounds of PBDEs and OPEs show TMF values higher than 1, indicating biomagnification potential. Collectively, all data suggest that PBDEs and OPEs have the potential to bioaccumulate and transfer through the food chain. OPEs and PBDEs present a myriad of toxicity endpoints, with notable overlaps encompassing reproductive issues, oxidative stress, developmental defects, liver dysfunction, DNA damage, neurological toxicity, reproductive anomalies, carcinogenic effects, and behavior changes. Based on our investigation and comparative analysis, we conclude that substituting PBDEs with OPEs is regrettable based on PBT properties, underscoring the urgency for policy reforms and effective management strategies. Addressing this predicament before an exacerbation of global contamination is imperative.

Tracking down pharmaceutical pollution in surface waters of the St. Lawrence River and its major tributaries.

A reconnaissance survey was undertaken to evaluate the occurrence and risks of 27 pharmaceuticals and metabolites in the St. Lawrence watershed. Surface water samples were collected over a five-year period (2017-2021) along a 700-km reach of the St. Lawrence River as well as 55 tributary rivers (overall N = 406 samples). Additionally, depth water samples and sediments were collected near a major wastewater effluent. Caffeine, diclofenac, and venlafaxine were the most recurrent substances (detection rates >80 %), and extremely high levels were found near a municipal effluent (e.g., ibuprofen (860 ng/L), hydroxyibuprofen (1800 ng/L) and caffeine (7200 ng/L)). Geographical mapping and statistical analyses indicated that the St. Lawrence River water mass after the Montreal City effluent was significantly more contaminated than the other water masses, and that contamination could extend up to 70 km further downstream. This phenomenon was repeatedly observed over the five years of sampling, confirming that this is not a random trend. A slight increase in contamination was also observed near Quebec City, but concentrations rapidly declined in the estuarine transition zone. Tributaries with the highest pharmaceutical levels (ΣPharmas ∼400-900 ng/L) included the Mascouche, Saint-Régis, and Bertrand rivers, all located in the densely populated Greater Montreal area. When flowrate was factored in, the top five tributaries in terms of mass load (ΣPharmas ∼200-2000 kg/year) were the Des Prairies, Saint-François, Richelieu, Ottawa, and Yamaska rivers. All samples met the Canadian Water Quality Guideline for carbamazepine. Despite the large dilution effect of the St. Lawrence River, a risk quotient approach based on freshwater PNEC values suggested that four compounds (caffeine, carbamazepine, diclofenac, and ibuprofen) could present intermediate to high risks for aquatic organisms in terms of chronic exposure.

High Persistence of Novel Polyfluoroalkyl Betaines in Aerobic Soils.

Some contemporary aqueous film-forming foams (AFFFs) contain n:3 and n:1:2 fluorotelomer betaines (FTBs), which are often detected at sites impacted by AFFFs. As new chemical replacements, little is known about their environmental fate. For the first time, we investigated the biotransformation potential of 5:3 and 5:1:2 FTBs and a commercial AFFF that mainly contains n:3 and n:1:2 FTBs (n = 5, 7, 9, 11, and 13). Although some polyfluoroalkyl compounds are precursors to perfluoroalkyl acids, 5:3 and 5:1:2 FTBs exhibited high persistence, with no significant changes even after 120 days of incubation. While the degradation of 5:3 FTB into suspected products such as fluorotelomer acids or perfluoroalkyl carboxylic acids (PFCAs) could not be conclusively confirmed, we did identify a potential biotransformation product, 5:3 fluorotelomer methylamine. Similarly, 5:1:2 FTB did not break down or produce short-chain hydrogen-substituted polyfluoroalkyl acids (n:2 H-FTCA), hydrogen-substituted PFCA (2H-PFCA), or any other products. Incubating the AFFF in four soils with differing properties and microbial communities resulted in 0.023-0.25 mol % PFCAs by day 120. Most of the products are believed to be derived from n:2 fluorotelomers, minor components of the AFFF. Therefore, the findings of the study cannot be fully explained by the current understanding of structure-biodegradability relationships.

Cyanotoxins dissipation in soil: Evidence from microcosm assays.

Cyanobacteria proliferate in warm, nutrient-rich environments, and release cyanotoxins into natural waters. If cyanotoxin-contaminated water is used to irrigate agricultural crops, this could expose humans and other biota to cyanotoxins. However, cyanotoxins may be degraded by the diverse microbial consortia, be adsorbed or otherwise dissipate in agricultural soil. This study investigates the disappearance and transformation of 9 cyanotoxins in controlled soil microcosms after 28 d. Six soil types were exposed to factorial combinations of light, redox conditions and microbial activity that influenced the recovery of anabaenopeptin-A (AP-A), anabaenopeptin-B (AP-B), anatoxin-a (ATX-a), cylindrospermopsin (CYN), and the microcystin (MC) congeners -LR, -LA, -LY, -LW, and -LF. Cyanotoxins estimated half-lives were from hours to several months, depending on the compound and soil conditions. Cyanotoxins were eliminated via biological reactions in aerobic and anaerobic soils, although anaerobic conditions accelerated the biological dissipation of ATX-a, CYN and APs. ATX-a was sensitive to photolytic degradation, but CYN, and MCs were not reduced through photochemical transformation. MC-LR and -LA were recovered after exposure to light, redox conditions and low microbial activity, suggesting that they persisted in extractable forms, compared to other cyanotoxins in soil. Cyanotoxin degradation products were identified using high-resolution mass spectrometry, revealing their potential degradation pathways in soil.

PFAS in fish from AFFF-impacted environments: Analytical method development and field application at a Canadian international civilian airport.

Methods targeting anionic per- and polyfluoroalkyl substances (PFAS) in aquatic biota are well established, but commonly overlook many PFAS classes present in aqueous film-forming foams (AFFFs). Here, we developed an analytical method for the expanded analysis of negative and positive ion mode PFAS in fish tissues. Eight variations of extraction solvents and clean-up protocols were first tested to recover 70 AFFF-derived PFAS from the fish matrix. Anionic, zwitterionic, and cationic PFAS displayed the best responses with methanol-based ultrasonication methods. The response of long-chain PFAS was improved for extracts submitted to graphite filtration alone compared with those involving solid-phase extraction. The validation included an assessment of linearity, absolute recovery, matrix effects, accuracy, intraday/interday precision, and trueness. The method was applied to a set of freshwater fish samples collected in 2020 in the immediate vicinity (creek, n = 15) and downstream (river, n = 15) of an active fire-training area at an international civilian airport in Ontario, Canada. While zwitterionic fluorotelomer betaines were major components of the subsurface AFFF source zone, they were rarely detected in fish, suggesting limited bioaccumulation potential. PFOS largely dominated the PFAS profile, with record-high concentrations in brook sticklebacks (Culaea inconstans) from the creek (16000-110,000 ng/g wet weight whole-body). These levels exceeded the Canadian Federal Environmental Quality Guidelines (FEQG) for PFOS pertaining to the Federal Fish Tissue Guideline (FFTG) for fish protection and Federal Wildlife Diet Guidelines (FWiDG) for the protection of mammalian and avian consumers of aquatic biota. Perfluorohexane sulfonamide and 6:2 fluorotelomer sulfonate were among the precursors detected at the highest levels (maximum of ∼340 ng/g and ∼1100 ng/g, respectively), likely reflecting extensive degradation and/or biotransformation of C6 precursors originally present in AFFF formulations.

Target and nontarget screening of PFAS in drinking water for a large-scale survey of urban and rural communities in Québec, Canada.

Limited monitoring data are available regarding the occurrence of emerging per- and polyfluoroalkyl substances (PFAS) in drinking water. Here, we validated an analytical procedure for 42 PFAS with individual detection limits of 0.001-0.082 ng/L. We also evaluated how different sample pH conditions, dechlorinating agents, and storage holding times might affect method performance. PFAS were analyzed in tap water samples collected at a large spatial scale in Quebec, Canada, covering 376 municipalities within 17 administrative regions. Target and nontarget screening revealed the presence of 31 and 23 compounds, respectively, representing 24 homolog classes. Overall, 99.3% of the tap water samples were positive for at least one PFAS, and the Æ©PFAS ranged from below detection limits to 108 ng/L (95th percentile: 13 ng/L). On average, Æ©PFAS was 12 times higher in tap water produced from surface water than groundwater; however, 6 of the top 10 contaminated locations were groundwater-based. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) had high detection rates (88% and 80%, respectively). PFOS (median: 0.15 ng/L; max: 13 ng/L) and PFOA (median: 0.27 ng/L; max: 8.1 ng/L) remained much lower than current Health Canada guidelines but higher than USEPA's interim updated health advisories. Short-chain (C3-C6) perfluoroalkyl sulfonamides were also recurrent, especially the C4 homolog (FBSA: detection rate of 50%). The 6:2 fluorotelomer sulfonyl propanoamido dimethyl ethyl sulfonate (6:2 FTSO2PrAd-DiMeEtS) was locally detected at ∼15 ng/L and recurred in 8% of our samples. Multiple PFAS that are most likely to originate from aqueous film-forming foams were also reported for the first time in tap water, including X:3 and X:1:2 fluorotelomer betaines, hydroxylated X:2 fluorotelomer sulfonates, N-trimethylammoniopropyl perfluoroalkane sulfonamides (TAmPr-FHxSA and TAmPr-FOSA), and N-sulfopropyl dimethylammoniopropyl perfluoroalkane sulfonamidopropyl sulfonates (N-SPAmP-FPeSAPS and N-SPAmP-FHxSAPS).

Impact of Stagnation on the Diversity of Cyanobacteria in Drinking Water Treatment Plant Sludge.

Health-related concerns about cyanobacteria-laden sludge of drinking water treatment plants (DWTPs) have been raised in the past few years. Microscopic taxonomy, shotgun metagenomic sequencing, and microcystin (MC) measurement were applied to study the fate of cyanobacteria and cyanotoxins after controlled sludge storage (stagnation) in the dark in a full-scale drinking water treatment plant within 7 to 38 days. For four out of eight dates, cyanobacterial cell growth was observed by total taxonomic cell counts during sludge stagnation. The highest observed cell growth was 96% after 16 days of stagnation. Cell growth was dominated by potential MC producers such as Microcystis, Aphanocapsa, Chroococcus, and Dolichospermum. Shotgun metagenomic sequencing unveiled that stagnation stress shifts the cyanobacterial communities from the stress-sensitive Nostocales (e.g., Dolichospermum) order towards less compromised orders and potential MC producers such as Chroococcales (e.g., Microcystis) and Synechococcales (e.g., Synechococcus). The relative increase of cyanotoxin producers presents a health challenge when the supernatant of the stored sludge is recycled to the head of the DWTP or discharged into the source. These findings emphasize the importance of a strategy to manage cyanobacteria-laden sludge and suggest practical approaches should be adopted to control health/environmental impacts of cyanobacteria and cyanotoxins in sludge.

Shotgun Metagenomic Sequencing to Assess Cyanobacterial Community Composition following Coagulation of Cyanobacterial Blooms.

The excessive proliferation of cyanobacteria in surface waters is a widespread problem worldwide, leading to the contamination of drinking water sources. Short- and long-term solutions for managing cyanobacterial blooms are needed for drinking water supplies. The goal of this research was to investigate the cyanobacteria community composition using shotgun metagenomics in a short term, in situ mesocosm experiment of two lakes following their coagulation with ferric sulfate (Fe2(SO4)3) as an option for source water treatment. Among the nutrient paramenters, dissolved nitrogen was related to Microcystis in both Missisquoi Bay and Petit Lac St. François, while the presence of Synechococcus was related to total nitrogen, dissolved nitrogen, dissolved organic carbon, and dissolved phosphorus. Results from the shotgun metagenomic sequencing showed that Dolichospermum and Microcystis were the dominant genera in all of the mesocosms in the beginning of the sampling period in Missisquoi Bay and Petit Lac St. François, respectively. Potentially toxigenic genera such as Microcystis were correlated with intracellular microcystin concentrations. A principal component analysis showed that there was a change of the cyanobacterial composition at the genus level in the mesocosms after two days, which varied across the studied sites and sampling time. The cyanobacterial community richness and diversity did not change significantly after its coagulation by Fe2(SO4)3 in all of the mesocosms at either site. The use of Fe2(SO4)3 for an onsite source water treatment should consider its impact on cyanobacterial community structure and the reduction of toxin concentrations.

Suspect screening of pharmaceuticals, illicit drugs, pesticides, and other emerging contaminants in Argentinean Piaractus mesopotamicus, a fish species used for local consumption and export.

The widespread distribution of contaminants of emerging concern (CECs) is a major concern due to their potential effects on human health and the environment. The insufficient sewage treatment plant infrastructures is a global problem most accentuated in less developed countries and results in the discharge of CECs to water bodies. Pacu (Piaractus mesopotamicus) is a ray-finned freshwater fish species native to the Paraná basin. It is also the most produced aquaculture fish species in Argentina since 2012. Though uninvestigated to date, the occurrence of CECs in pacu may be of high relevance due to production volumes and relevance to human exposure through fish consumption. In this study, we applied a high-resolution mass spectrometry screening method to qualitatively analyze over 100 CECs in pacu. Four extraction/cleanup methods were tested on pooled pacu fillet, including solid-phase extraction and QuEChERS. The method that produced the highest number of detections was selected for further analysis of pacu purchased in supermarkets and fish markets in Argentina between 2017 and 2020. Residues of pesticides, antibiotics, pharmaceuticals, personal care products, plasticizers, sweeteners, drug metabolites, stimulants, and illegal drugs were detected in the samples. A total of 38 CECs were detected, ranging between 24 and 35 CECs per individual sample. 100% of the samples had positive detections of caffeine, 1,7-dimethylxanthine, xanthine, benzoylecgonine, methylparaben, ethylparaben, bis(2-ethylhexyl) phthalate (DEHP), metolachlor, carbendazim, salicylic acid, 2,4-D, saccharin, cyclamate, and dodecanedioic acid. Mappings generated with correspondence analysis were used to explore similarities/dissimilarities among the detected compounds. To our knowledge this is the first report of saccharin, cyclamate, 2,4 - D, carbendazim, metolachlor, ethylparaben, propylparben, bisphenol A, DEHP, and benzotriazole in fish from Argentina, and the first report on the presence of lisinopril, metropolol acid and dodecanedioic acid in fish worldwide.

Targeted and Suspect Screening of Per- and Polyfluoroalkyl Substances in Cosmetics and Personal Care Products.

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals reported in cosmetics and personal care products as ingredients, possible impurities in the raw material manufacturing process, or degradation products. The purpose of this study was to further delineate contributions of these varying PFAS sources to these products. Thirty-eight cosmetics and personal care products were selected and analyzed for polyfluoroalkyl phosphates (PAPs), perfluoroalkyl carboxylic acids (PFCAs), fluorotelomer sulfonic acids (FTSAs), and perfluoroalkyl sulfonic acids (PFSAs) using targeted liquid chromatography tandem mass spectrometry (LC-MS/MS). A subset of products was also subjected to suspect screening using LC-high resolution mass spectrometry (HRMS) for >200 compounds. Results of LC-MS/MS and LC-HRMS indicated a predominant and ubiquitous presence of PAPs (detection frequency 99.7%, mean and median ΣPAPs 1 080 000 and 299 ng/g). Total median PFCA and PFSA concentrations were 3 and 38 times lower, respectively. There were significant correlations (Spearman's correlation coefficients = 0.60-0.81, p < 0.05) between 6:2 PAPs and their biotransformation products. Low levels of other PFAS classes were detected, including those previously measured in wastewater and human blood (e.g., hydrido-PFCAs), and five compounds associated with aqueous film-forming foams. Overall, these data highlight that cosmetics and personal care products can contain a breadth of PFAS at extremely high levels, leading to human and environmental exposure.

Early and late cyanobacterial bloomers in a shallow, eutrophic lake.

Cyanobacterial blooms present challenges for water treatment, especially in regions like the Canadian prairies where poor water quality intensifies water treatment issues. Buoyant cyanobacteria that resist sedimentation present a challenge as water treatment operators attempt to balance pre-treatment and toxic disinfection by-products. Here, we used microscopy to identify and describe the succession of cyanobacterial species in Buffalo Pound Lake, a key drinking water supply. We used indicator species analysis to identify temporal grouping structures throughout two sampling seasons from May to October 2018 and 2019. Our findings highlight two key cyanobacterial bloom phases - a mid-summer diazotrophic bloom of Dolichospermum spp. and an autumn Planktothrix agardhii bloom. Dolichospermum crassa and Woronichinia compacta served as indicators of the mid-summer and autumn bloom phases, respectively. Different cyanobacterial metabolites were associated with the distinct bloom phases in both years: toxic microcystins were associated with the mid-summer Dolichospermum bloom and some newly monitored cyanopeptides (anabaenopeptin A and B) with the autumn Planktothrix bloom. Despite forming a significant proportion of the autumn phytoplankton biomass (>60%), the Planktothrix bloom had previously not been detected by sensor or laboratory-derived chlorophyll-a. Our results demonstrate the power of targeted taxonomic identification of key species as a tool for managers of bloom-prone systems. Moreover, we describe an autumn Planktothrix agardhii bloom that has the potential to disrupt water treatment due to its evasion of detection. Our findings highlight the importance of identifying this autumn bloom given the expectation that warmer temperatures and a longer ice-free season will become the norm.

Bioaccumulation and trophic magnification of emerging and legacy per- and polyfluoroalkyl substances (PFAS) in a St. Lawrence River food web.

Research on per- and polyfluoroalkyl substances (PFAS) in freshwater ecosystems has focused primarily on legacy compounds and little is still known on the presence of emerging PFAS. Here, we investigated the occurrence of 60 anionic, zwitterionic, and cationic PFAS in a food web of the St. Lawrence River (Quebec, Canada) near a major metropolitan area. Water, sediments, aquatic vegetation, invertebrates, and 14 fish species were targeted for analysis. Levels of perfluorobutanoic acid (PFBA) in river water exceeded those of perfluorooctanoic acid (PFOA) or perfluorooctane sulfonate (PFOS), and a zwitterionic betaine was observed for the first time in the St. Lawrence River. The highest mean PFAS concentrations were observed for the benthopelagic top predator Smallmouth bass (Micropterus dolomieu, Σ60PFAS âˆ¼ 92 ± 34 ng/g wet weight whole-body) and the lowest for aquatic plants (0.52-2.3 ng/g). Up to 33 PFAS were detected in biotic samples, with frequent occurrences of emerging PFAS such as perfluorobutane sulfonamide (FBSA) and perfluoroethyl cyclohexane sulfonate (PFECHS), while targeted ether-PFAS all remained undetected. PFOS and long-chain perfluorocarboxylates (C10-C13 PFCAs) dominated the contamination profiles in biota except for insects where PFBA was predominant. Gammarids, molluscs, and insects also had frequent detections of PFOA and fluorotelomer sulfonates, an important distinction with fish and presumably due to different metabolism. Based on bioaccumulation factors >5000 and trophic magnification factors >1, long-chain (C10-C13) PFCAs, PFOS, perfluorodecane sulfonate, and perfluorooctane sulfonamide qualified as very bioaccumulative and biomagnifying. Newly monitored PFAS such as FBSA and PFECHS were biomagnified but moderately bioaccumulative, while PFOA was biodiluted.

Pharmaceutical pollution of hospital effluents and municipal wastewaters of Eastern Canada.

Quantification of drugs residues in wastewaters of different sources could help better understand contamination pathways, eventually leading to effluent regulation. However, limited data are available for hospital-derived wastewaters. Here, an analytical method based on automated on-line solid-phase extraction liquid chromatography tandem mass spectrometry (on-line SPE - UPLC-MS/MS) was developed for the quantification of multi-class pharmaceuticals in wastewaters. Filtrate phase and suspended solids (SPM) were both considered to evaluate the distribution of targeted analytes. Experimental design optimization involved testing different chromatographic columns, on-line SPE columns, and loading conditions for the filtrate phase, and different organic solvents and cleanup strategies for suspended solids. The selected methods were validated with suitable limits of detection, recovery, accuracy, and precision. A total of 30 hospital effluents and 6 wastewater treatment plants were sampled to evaluate concentrations in real field-collected samples. Certain pharmaceuticals were quantified at high levels such as caffeine at 670,000 ng/L in hospital wastewaters and hydroxyibuprofen at 49,000 ng/L in WWTP influents. SPM samples also had high contaminant concentrations such as ibuprofen at 31,000 ng/g in hospital effluents, fluoxetine at 529 ng/g in WWTP influents or clarithromycin at 295 ng/g in WWTP effluents. Distribution coefficients (Kd) and particle-associated fractions (Φ) indicate that pharmaceuticals tend to have better affinity to suspended solids in hospital wastewater than in municipal wastewaters. The results also bring arguments for at source treatment of these specific effluents before their introduction into urban wastewater systems.

Evidence-Based Framework to Manage Cyanobacteria and Cyanotoxins in Water and Sludge from Drinking Water Treatment Plants.

Freshwater bodies and, consequently, drinking water treatment plants (DWTPs) sources are increasingly facing toxic cyanobacterial blooms. Even though conventional treatment processes including coagulation, flocculation, sedimentation, and filtration can control cyanobacteria and cell-bound cyanotoxins, these processes may encounter challenges such as inefficient removal of dissolved metabolites and cyanobacterial cell breakthrough. Furthermore, conventional treatment processes may lead to the accumulation of cyanobacteria cells and cyanotoxins in sludge. Pre-oxidation can enhance coagulation efficiency as it provides the first barrier against cyanobacteria and cyanotoxins and it decreases cell accumulation in DWTP sludge. This critical review aims to: (i) evaluate the state of the science of cyanobacteria and cyanotoxin management throughout DWTPs, as well as their associated sludge, and (ii) develop a decision framework to manage cyanobacteria and cyanotoxins in DWTPs and sludge. The review identified that lab-cultured-based pre-oxidation studies may not represent the real bloom pre-oxidation efficacy. Moreover, the application of a common exposure unit CT (residual concentration × contact time) provides a proper understanding of cyanobacteria pre-oxidation efficiency. Recently, reported challenges on cyanobacterial survival and growth in sludge alongside the cell lysis and cyanotoxin release raised health and technical concerns with regards to sludge storage and sludge supernatant recycling to the head of DWTPs. According to the review, oxidation has not been identified as a feasible option to handle cyanobacterial-laden sludge due to low cell and cyanotoxin removal efficacy. Based on the reviewed literature, a decision framework is proposed to manage cyanobacteria and cyanotoxins and their associated sludge in DWTPs.

Removal of Zwitterionic PFAS by MXenes: Comparisons with Anionic, Nonionic, and PFAS-Specific Resins.

Zwitterionic per- and polyfluoroalkyl substances are increasingly detected in aquatic environments. The magnitude of their concentration and increased frequency of detection worldwide raise questions on their presence in drinking water and associated health risk. Scientific knowledge on the identification of treatment technologies to effectively capture such zwitterionic PFAS from contaminated water sources remains largely unknown. In this study, we investigated the application of anionic organic scavenger ion exchange (IX) resins (A860), nonionic IX resins (XAD 4 and XAD 7), PFAS-specific resins (A694 and A592), and Ti3C2 MXenes (novel two-dimensional metal carbides) for the removal of select fluorotelomer zwitterionic PFAS from natural waters. The cumulative removal of zwitterionic PFAS at pH ∼ 7 follows the order: Ti3C2 MXenes > A694 > A592 > A860 > XAD 4 ∼ XAD 7. Ti3C2 MXenes were able to capture >75% of the total influent zwitterionic PFAS and the performance remained consistent in natural and synthetic water. Ti3C2 MXenes also exhibited efficient regeneration (>90% recovery) with 0.4 M Na2SO3 solution, while the regeneration efficacy of other IX resins generally remained below 20%. Treatment with ∼180 J/cm2 UV dosage in the 0.4 M Na2SO3 regenerant brine solution yielded >99.9% reduction in the zwitterionic PFAS concentration indicating that UV-sulfite systems exhibit promising potential for the treatment of zwitterionic PFAS concentrates.