Aquatic toxicity and chemical fate of diluted bitumen spills in freshwater under natural weathering.

Increasing global demands for oils are fueling the production of diluted bitumen (DB) from Canada's oil sands region. More weathered than conventional crude (CC) oils, Alberta bitumen is often diluted with lighter petroleum oils to reduce density and viscosity to meet pipeline specifications for transportation. Being a heavy oil product that is transported in large volumes across Canada and the USA, there has been interest to compare its behavior and toxicity characteristics when spilled to those of CC. To determine the influence of environmental weathering upon DB following a freshwater spill, we conducted separate controlled spills of Cold Lake Blend DB and Mixed Sweet Blend light CC oil in a mesocosm spill-tank system at 24 °C with wave-action for 56 days. DB-contaminated waters remained acutely lethal for a period of 14 days to early life stage fathead minnows (Pimephales promelas) exposed during embryologic development, while CC was lethal for 1 day. However, concentrations of mono- and polycyclic aromatic compounds, often claimed to be principally responsible for the acute and chronic toxicity of crude oils, were consistently higher in CC water compared to DB. Elevated aromatic concentrations in CC water correlated with higher prevalences of developmental malformations, reduced heart and growth rates, and impacts on the aryl hydrocarbon receptor pathway. Organic acids were measured over the course of the studies and O2 containing naphthenic acids were present at greater relative abundances in DB- compared to CC-contaminated water, with their attenuation correlating with reduced acute and sublethal toxicity. Furthermore, organic acid degradation products accumulated with time and likely contributed to the consistently sublethal toxicity of the weathered oils throughout the experiment. Improved characterization of the fractions including organic acids and those organic compounds found within the unresolved complex mixture of fresh and weathered crude oils is necessary to adequately understand and prepare for the risks that accidental petroleum spills pose to aquatic resources.

Comparative Acute Toxicity Studies of Chlorpyrifos Technical Grade with its Emulsifiable Concentrate (20% EC) on Labeo rohita, a Freshwater Major Carp, and Mystus vittatus, a Freshwater Catfish.

Chlorpyrifos is widely used across the world as an organophosphate insecticide and frequently contaminates freshwater bodies through runoff from agricultural fields. In the laboratory, static bioassays were undertaken to examine differences in acute toxicity caused by exposure to the technical grade (94% a.i.) and an emulsifiable concentrate (20% EC) of chlorpyrifos to two species of freshwater fish, Labeo rohita and Mystus vittatus. The recovery of actual chlorpyrifos concentrations varied from 83% (technical grade, T) to 89% (emulsifiable concentrate, F) after two hours in water. The susceptibilities of the two fish species to the two types of chlorpyrifos varied. The 96-h LC50 values for T and F chlorpyrifos in L. rohita were 68 and 36 µg/L, respectively, and 120 and 62 µg/L in M. vittatus, respectively. As the exposure period was extended, the LC50 values gradually decreased. LC50 values between the technical grade and formulation were compared following the criteria of Mayer et al. (1986), Schmuck et al. (1994), APHA (1995), and Demetrio et al. (2014). It was concluded from the study that the emulsifiable concentrate (20% EC) of chlorpyrifos was more toxic than technical-grade chlorpyrifos.

Ecotoxicological assessment, in freshwater environment, of wastewater sludge coupled and uncoupled with micro-polyvinyl chloride on algae and water fleas.

In the frame of bioeconomy and circular economy, wastewater sludge (WS) could be a good candidate for its use in agriculture as fertilizer, due to its high content of organic matter, N and P, but on the other hand, it is full of toxicants such as heavy metal, microplastics, detergent, antibiotics, and so on that can reach groundwater and water bodies in leachate form. In this study, we have investigated different sludge concentrations in the eluate form, combined and not with PVC on two different freshwater organisms Selenastrum capricornutum and Daphnia magna, using ecotoxicity tests. At the endpoint, we have evaluated inhibition growth rate, oxidative stress, and pigments production for S. capricornutum, while in case of D. magna, we have assessed organism immobilization and development. From our results, it emerged that at the higher WS concentration, there was not inhibition growth rate, while at oxidative stress, it was higher in algae treated with WS and PVC. Higher Chl-a production was shown for algae treated with 0.3 g/L of sludge coupled with PVC, where higher phaeopigments production were recorded for algae treated with 0.3 g/L of WS. D. magna has shown an opposite trend when compared with algae, where at the highest WS concentrations supplied was corresponding to an increased mortality explaned as the highest immobility percentage. PRACTITIONER POINTS: Wastewater sludge is used in agriculture as fertilizer. PVC microplastic presence and associate ecotoxicity was tested. PVC presence increased oxidative stress in S. capricornutum. D. magna was significantly affected by sludge concentrations supplied.

Have per- and polyfluoroalkyl substances (PFAS) infiltrated Florida's freshwater springs?

The state of Florida contains over 1000 freshwater springs, fed by groundwater that provides 90 % of the drinking water for inhabitants. Freshwater springs are regarded as some of the cleanest water sources left on Earth, but recent studies regarding the extreme pervasiveness of per- and polyfluoroalkyl substances (PFAS) across the globe have called into question whether PFAS have infiltrated these vital water sources. In this study, 90 water samples (43 vents/40 runs/plus 7 additional surface samples) from 50 freshwater Florida springs were analyzed for the presence of 29 PFAS via ultra-high-performance liquid chromatography-tandem mass spectrometry. PFAS were detected in 63 % of the vent samples and 68 % of the run samples, with a total of 13 different quantifiable PFAS (>LOQ) present in at least one sample. Concentrations across samples ranged from 0.205 to 64.6 ng/L, with the most detected PFAS being perfluorobutanesulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonic acid (PFOS). This data highlights the presence of PFAS in Florida springs, representing a potential health concern for spring water users and drinking water consumers, and suggests the need for further research regarding the possible contamination pathways of Florida's freshwater springs.

Controls on the Barium and Strontium Isotopic Records of Water Chemistry Preserved in Freshwater Bivalve Shells.

Biogenic carbonates, including bivalve shells, record past environmental conditions, but their interpretation requires understanding environmental and biological factors that affect trace metal uptake. We examined stable barium (δ138Ba) and radiogenic strontium (87Sr/86Sr) isotope ratios in the aragonite shells of four native freshwater mussel species and two invasive species in five streams and assessed the effects of species identity, growth rate, and river water chemistry on shell isotopic composition. Shells were robust proxies for Sr, accurately reflecting 87Sr/86Sr ratios of river water, regardless of species or growth rate. In contrast, shell δ138Ba values, apart from invasive Corbicula fluminea, departed widely from those of river water and varied according to species and growth rate. Apparent fractionation between river water and the shell (Δ138Bashell-water) reached -0.86‰, the greatest offset observed for carbonate minerals. The shell deposited during slow growth periods was more enriched in lighter Ba isotopes than the rapidly deposited shell; thus, this phenomenon cannot be explained by aragonite precipitation kinetics. Instead, biological ion transport processes linked to growth rate may be largely responsible for Ba isotope variation. Our results provide information necessary to interpret water chemistry records preserved in shells and provide insights into biomineralization processes and bivalve biochemistry.

Review of the occurrence, treatment technologies, and detection methods for saxitoxins in freshwaters.

The increasing occurrence of saxitoxins in freshwaters is becoming a concern for water treatment facilities owing to its structural properties which make it resistant to oxidation at pH < 8. Hence, it is crucial to be able to monitor these toxins in surface and drinking water to protect public health. This review aims to outline the current state of knowledge related to the occurrence of saxitoxins in freshwaters and its removal strategies and provide a critical assessment of the detection methods to provide a basis for further development. Temperature and nutrient content are some of the factors that influence the production of saxitoxins in surface waters. A high dose of sodium hypochlorite with sufficient contact time or activated carbon has been shown to efficiently remove extracellular saxitoxins to meet the drinking water guidelines. While HILIC-MS has proven to be a powerful technology for more sensitive and reliable detection of saxitoxin and variants after solid phase extraction, ELISA is cost-effective and easy to use and is used by Ohio EPA for surveillance with a limit of detection of 0.015 µg/L. However, there is a need for the development of cost-effective and sensitive techniques that can quantify the variants of saxitoxin.

Ecotoxicity threshold values for 4-hydroxychlorothalonil, carbendazim, dimethoate and methoxyfenozide in fresh and marine waters: Part 1. Derivation of threshold values.

Pesticide active ingredients are frequently detected in the rivers, creeks, wetlands, estuaries, and marine waters of the Great Barrier Reef (GBR) region and are one of the main contributors to poor water quality. Pesticide concentrations detected in the environment through water quality monitoring programs can be compared against estimates of ecologically "safe" concentrations (i.e., water quality guidelines) to assess the potential hazard and risk posed to aquatic ecosystems. Water quality guidelines are also required to estimate the aquatic risk posed by pesticide mixtures, which is used for the Reef 2050 Water Quality Improvement Plan pesticide target. Seventy-four pesticide active ingredients and their degradates are frequently detected in GBR catchment waterways, however many do not have water quality guidelines in the Australian and New Zealand Guidelines for Fresh and Marine Water Quality. The current study derives ecotoxicity threshold values (ETVs) as unendorsed guideline values for active ingredients in two fungicides (4-hydroxychlorothalonil (fungicide degradate) and carbendazim) and two insecticides (dimethoate and methoxyfenozide) that are commonly detected in GBR catchment waterways. The proposed ETVs have been derived using species sensitivity distributions, as recommended in the Australian and New Zealand nationally endorsed method for deriving water quality guidelines for aquatic ecosystem protection. Four ETVs were derived for each chemical with values that should theoretically protect 99, 95, 90 and 80 % of species (i.e., PC99, PC95, PC90, PC80, respectively). The PC99 and PC95 values for 4-hydroxychlorothalonil, carbendazim, dimethoate and methoxyfenozide were 0.49 µg/L and 4 µg/L, 0.029 µg/L and 0.45 µg/L, 0.11 µg/L and 5.8 µg/L and 0.19 µg/L and 2 µg/L, respectively. The ETVs will be used in an ecological hazard and risk assessment across GBR waterways in part two of this study. The ETVs can also be used to assess potential risk across Australia and internationally where monitoring data are available.

Hotspots lurking underwater: Insights into the contamination characteristics, environmental fates and impacts on biogeochemical cycling of microplastics in freshwater sediments.

The widespread presence of microplastics (MPs) in aquatic environments has become a significant concern, with freshwater sediments acting as terminal sinks, rapidly picking up these emerging anthropogenic particles. However, the accumulation, transport, degradation and biochemical impacts of MPs in freshwater sediments remain unresolved issues compared to other environmental compartments. Therefore, this paper systematically revealed the spatial distribution and characterization information of MPs in freshwater (rivers, lakes, and estuaries) sediments, in which small-size (<1 mm), fibers, transparent, polyethylene (PE), and polypropylene (PP) predominate, and the average abundance of MPs in river sediments displayed significant heterogeneity compared to other matrices. Next, the transport kinetics and drivers of MPs in sediments are summarized, MPs transport is controlled by the particle diversity and surrounding environmental variability, leading to different migration behaviors and transport efficiencies. Also emphasized the spatio-temporal evolution of MPs degradation processes and biodegradation mechanisms in sediments, different microorganisms can depolymerize high molecular weight polymers into low molecular weight biodegradation by-products via secreting hydrolytic enzymes or redox enzymes. Finally, discussed the ecological impacts of MPs on microbial-nutrient coupling in sediments, MPs can interfere with the ecological balance of microbially mediated nutrient cycling by altering community networks and structures, enzyme activities, and nutrient-related functional gene expressions. This work aims to elucidate the plasticity characteristics, fate processes, and potential ecological impact mechanisms of MPs in freshwater sediments, facilitating a better understanding of environmental risks of MPs in freshwater sediments.

Impacts of salinity stress induced by ballast water discharge on the ecosystem of shanghai port, China.

Large quantities of marine ballast water discharged by ocean-going vessels can cause salinity increases in freshwater ports, which in turn negatively affects indigenous plankton in the ports. In this study, we investigated the impacts of marine ballast water discharge on the plankton community in a freshwater wharf through field surveys. It was found that salinity stress caused reductions in community indicators such as plankton community composition, abundance and diversity, thus threatening the structure and function of the plankton community in the wharf. In terms of the impact range, the salinity stress had a significant effect on all plankton in the waters near the discharge point and the phytoplankton in the waters 50 m from the discharge point, but had no significant effect on the plankton in the waters further away. Ballast water discharge also caused a significant decrease in the alpha diversity and richness of the plankton community but had no significant effect on the evenness of the plankton community. Moreover, phytoplankton were more tolerant of salinity changes than zooplankton in our study. This study provides an ecological reference for the scientific management of marine ballast water discharge and the risk of exogenous nutrient inputs to freshwater ecosystems.

Pharmaceutical Pollution Alters the Structure of Freshwater Communities and Hinders Their Recovery from a Fish Predator.

Freshwater ecosystems are under threat from rising pharmaceutical pollution. While such pollutants are known to elicit biological effects on organisms, we have limited knowledge on how these effects might cascade through food-webs, disrupt ecological processes, and shape freshwater communities. In this study, we used a mesocosm experiment to explore how the community impacts of a top-order predator, the eastern mosquitofish (Gambusia holbrooki), are mediated by exposure to environmentally relevant low (measured concentration: ∼10 ng/L) and high concentrations (∼110 ng/L) of the pervasive pharmaceutical pollutant fluoxetine. We found no evidence that exposure to fluoxetine altered the consumptive effects of mosquitofish on zooplankton. However, once mosquitofish were removed from the mesocosms, zooplankton abundance recovered to a greater extent in control mesocosms compared to both low and high fluoxetine-exposed mesocosms. By the end of the experiment, this resulted in fundamental differences in community structure between the control and fluoxetine-treated mesocosms. Specifically, the control mesocosms were characterized by higher zooplankton abundances and lower algal biomass, whereas mesocosms exposed to either low or high concentrations of fluoxetine had lower zooplankton abundances and higher algal biomass. Our results suggest that fluoxetine, even at very low concentrations, can alter aquatic communities and hinder their recovery from disturbances.

A novel pretreatment method for analysis the oxygen isotopic compositions of inorganic phosphorus pools in freshwater sediment.

Identifying the sources and cycling of phosphorus (P) is particularly important for formulating effective P management strategies in inland water. The oxygen isotopic compositions of phosphate (δ18OP) are recognized as a promising tool to solve this problem. However, the application of δ18OP in freshwater sediment is currently constrained by multiple difficulties. In this study, we presented a novel pretreatment method for δ18OP analysis of sediment inorganic P pools. Our results showed that the new method has advantages of simple operation, less time-consuming, and high P recovery rates. Specifically, we replaced the traditional Mg-induced co-precipitation (MAGIC) method by introducing Zr-Oxides gels with high selective adsorption function for phosphate. This made subsequent processing simpler and reduced the time consumption to ∼10 days, and the range of P recovery rates were from 88 % to 104 %. Furthermore, we emphasized the necessity of vacuum roasting following lyophilized Ag3PO4 to eliminate residual oxygen-containing impurities (e.g., NO3-, Ag2O, and organic matter). Additionally, evidences from microscopy and spectroscopy confirmed that this method ultimately yielded high-purity Ag3PO4 with the Ag:P molar ratios of 3.35:1. Importantly, combining direct synthesis Ag3PO4 between KH2PO4 and AgNO3 with the Ag3PO4 obtained by the method revealed no stark oxygen isotopic fractionation of phosphate during the pretreatment processes. The newly established δ18OP pretreatment methods here can also be extended to broader studies of the biogeochemical cycling of P in aquatic ecosystems, potentially advancing the understanding of the global P cycle.

Release kinetic study of microplastics from N95 face masks and consequent effects on freshwater alga Scenedesmus obliquus.

The uncontrolled disposal of N95 face masks, widely used during the recent COVID-19 pandemic can release significant amounts of microplastics and other additives into aquatic bodies. This study aimed to: (i) to quantify and analyze the released microplastics and heavy metals from N95 face masks weathered for various time periods (24, 48, 72, 96, 120, and 144 h) and (ii) to assess the cytotoxicity potential of the leachates on a model organism, freshwater alga Scenedesmus obliquus. The mask leachates contained microplastics, polypropylene in different shapes and sizes, and heavy metals like Cu, Cd, and Zn. The leachates significantly reduced cell viability and increased reactive oxygen species (ROS) generation, antioxidant enzyme activity, and membrane damage. The effects were also accompanied by a significant drop in the photosynthetic yield. All of the examined parameters indicated a dose-response relationship, with longer leaching periods resulting in higher microplastic concentrations. Mask leachates severely damaged the structural integrity of the algal cells, as seen in scanning electron microscopy images. The findings of our study confirm that the releases from disposable N95 face masks pose a severe threat to freshwater microalgae, and the cascading effects would harm the aquatic ecosystems.

Behavioral biomarkers in fishes: A non-lethal approach to assess the effects of chemical pollution on freshwater ecosystems.

The expansion of the human population and the escalating use of chemical products pose a considerable threat to aquatic biodiversity. Consequently, there is an imperative need for the implementation of non-lethal, cost-effective, and easily deployable biomonitoring tools. In this context, fish and their behavior as biomarkers have gained prominence in monitoring of freshwater ecosystems. The aim of this study was to assess the state of art in the use of behavioral biomarkers in ecotoxicology, emphasizing their role as informative tools for global environmental monitoring. Through a systematic literature search, ninety-two articles focusing on the evaluation of behavioral changes in freshwater fish in response to pollution were identified. The most prevalent keywords were "behavior" (7%) and "zebrafish" (6%). Experiments were conducted in countries with expansive territories, such as the United States (18%) and Brazil (17%). Exotic species were primarily employed (58%), with Danio rerio (26%) being the most frequently studied species. Among pollutants, pesticides (32%) and medicines (25%) were the most frequently studied, while locomotion (38%) and social behaviors (18%) were the most frequently evaluated behaviors. Across these studies, authors consistently reported significant changes in the behavior of fish exposed to contaminants, including decreased swimming speed and compromised feeding efficiency. The review findings affirm that evaluating behavioral biomarkers in freshwater fish offers an informative, non-lethal, cost-effective, and easily implementable approach to understanding pollution impacts on freshwater ecosystems. Although few studies on behavioral biomarkers were available to date, the number has rapidly increased in recent years. Furthermore, a variety of novel approaches and study models are being included. Research into behavioral biomarkers is crucial for understanding and managing environmental risks in freshwater ecosystems. Nevertheless, further studies are needed to enhance our understanding of behavioral toxicity indicators, considering factors such as life stage, sex, and breeding season in the tested species.

Eutrophication driven macrophyte-derived organic matter decomposition to methane emission relates to co-metabolism effect in freshwater sediments.

Lakes and wetlands play pivotal roles in global organic matter storage, receiving significant inputs of organic material. However, the co-metabolic processes governing the decomposition of these organic materials and their impact on greenhouse gas emissions remain inadequately understood. This study aims to assess the effects of mixed decomposition involving macrophytes and cyanobacteria on carbon emissions. A series of microcosms was established to investigate the decomposition of macrophyte residues and algae over a period of 216 days. A two-component kinetic model was utilized to estimate methane (CH4) production rates. Gas isotope technology was employed to discern the contributions of CH4 produced by macrophyte residues or algae. Quantitative PCR and analysis of 16S rRNA gene amplicons were employed to assess changes in functional genes and microbial communities. There were significant differences in the cumulative carbon release from the decomposition of different plant types due to the addition of carbon sources. After adding algae, the cumulative emission of CH4 increased significantly. The δ13C-CH4 partitioning indicated that CH4 originated exclusively from the fresh organic carbon of macrophyte residues, while it shifted to algae source after adding algae. The synergistic effect of the mixed decomposition on the CH4 emissions was greater than the sum of the individual decompositions. The microbial community richness was higher in the single plant residue treatment compared to the mixed treatment with algae addition, while microbial evenness in the sediment increased steadily in each treatment. Our findings emphasize the pronounced co-metabolic effect observed during the mixed decomposition of macrophytes and cyanobacteria.

Microplastic pollution differences in freshwater river according to stream order: Insights from spatial distribution, annual load, and ecological assessment.

Microplastic (MP) pollution has become a pressing concern in global freshwater ecosystems because rivers serve as essential channels for the transport of terrestrial debris to the ocean. The current researches mostly focus on the large catchments, but the impact on the small catchments remains underexplored. In this study, we employed Strahler's stream order classification to delineate the catchment structure of the Beijiang River in South China. The distribution pattern of MP contamination and the factors influencing the distribution pattern, were assessed across the streams at different orders. We found that the Beijiang River was moderately polluted compare to other rivers in China, with an average MP abundance of 2.15 ± 1.65 items/L. MP abundance ranged from 3.17 to 1.45 items/L in the streams at different orders, and significantly decreased with increasing stream order (R2 = 0.93). This highlights the key role of small rivers as the channels for the transport of MPs from watersheds to main streams. The high abundance of PP and PE fibers, the high correlation between the stream order and the resin proportion (R2 = 0.89), and the significant correlation between MP abundance and proximity to urban centers (P = 0.02), indicated that MP pollution across the streams at different orders was predominantly influenced by anthropogenic activities, rather than natural environmental factors. By integrating MP data with hydrographic information, the annual MP loads for the streams at Orders 1 to Order 5 were estimated to be 4.63, 39.38, 204.63, 503.06, and 1137.88 tons/yr, respectively. Additionally, an ecological risk assessment indicates that MP pollution led to a low risk in the Beijiang River. Our findings deepen the understanding of MP pollution within freshwater river networks, and emphasize the crucial role of tributary systems in transporting MPs to main river channels.

Docosahexaenoic acid-enriched diet improves the flesh quality of freshwater fish (Megalobrama amblycephala): Evaluation based on nutritional value, texture and flavor.

Docosahexaenoic acid (DHA) is a potential regulatory substance for flesh quality of fish, while the related evaluation is still barely. In this study, the effects of DHA-enriched diets on the flesh quality of freshwater fish (Megalobrama amblycephala) were investigated systematically. The sub-adult M. amblycephala were randomly fed with control diet (CON), 0.2% DHA diet (DL) or 0.8% DHA diet (DH). After 12-week feeding trial, the DH group flesh had higher concentrations of essential amino acids and polyunsaturated fatty acids compared to the CON group. Meanwhile, the hardness, springiness, shear force and moisture-holding capacity, as well as the values of umami, richness and sweetness were also improved by DH. The non-targeted metabolomics analysis revealed the key metabolites that may have significantly positive influence on flavor. Collectively, the diet supplementation with 0.8% DHA could achieve the improvement of the flesh quality in terms of nutritional value, texture and flavor in freshwater fish.

Preferential Partitioning of Per- and Polyfluoroalkyl Substances (PFAS) and Dissolved Organic Matter in Freshwater Surface Microlayer and Natural Foam.

Per- and polyfluoroalkyl substances (PFAS) are surfactants that can accumulate in the surface microlayer (SML) and in natural foams, with potential elevated exposure for organisms at the water surface. However, the impact of water chemistry on PFAS accumulation in these matrices in freshwater systems is unknown. We quantified 36 PFAS in water, the SML, and natural foams from 43 rivers and lakes in Wisconsin, USA, alongside measurements of pH, cations, and dissolved organic carbon (DOC). PFAS partition to foams with concentration ranging 2300-328,200 ng/L in waters with 6-139 ng/L PFAS (sum of 36 analytes), corresponding to sodium-normalized enrichment factors ranging <50 to >7000. Similar enrichment is observed for DOC (∼70). PFAS partitioning to foams increases with increasing chain length and is positively correlated with [DOC]. Modest SML enrichment is observed for PFOS (1.4) and FOSA (2.4), while negligible enrichment is observed for other PFAS and DOC due to low specific surface area and turbulent conditions that inhibit surfactant accumulation. However, DOC composition in the SML is distinct from bulk water, as assessed using high-resolution mass spectrometry. This study demonstrates that natural foams in unimpacted and impacted waters can have elevated PFAS concentrations, whereas SML accumulation in surface waters is limited.

Exploring spatial and temporal symptoms of the freshwater salinization syndrome in a rural to urban watershed.

The freshwater salinization syndrome (FSS), a concomitant watershed-scale increase in salinity, alkalinity, and major-cation and trace-metal concentrations, over recent decades, has been described for major rivers draining extensive urban areas, yet few studies have evaluated temporal and spatial FSS variations, or causal factors, at the subwatershed scale in mixed-use landscapes. This study examines the potential influence of land-use practices and wastewater treatment plant (WWTP) effluent on the export of major ions and trace metals from the mixed-use East Branch Brandywine Creek watershed in southeastern Pennsylvania, during the 2019 water year. Separate analysis of baseflow and stormflow subsets revealed similar correlations among land-use characteristics and streamwater chemistry. Positive associations between percent impervious surface cover, which ranged from 1.26 % to 21.9 % for the 13 sites sampled, and concentrations of Ca2+, Mg2+, Na+, and Cl- are consistent with road-salt driven reverse cation exchange and weathering of the built environment. The relative volume of upstream WWTP was correlated with Cu and Zn, which may be derived in part from corroded water-conveyance infrastructure; chloride to sulfate mass ratios (CSMR) ranged from ~6.3 to ~7.7× the 0.5 threshold indicating serious corrosivity potential. Observed exceedances of U.S. Environmental Protection Agency Na+ and Cl- drinking water and aquatic life criteria occurred in winter months. Finally, correlations between percent cultivated cropland and As and Pb concentrations may be explained by the persistence of agricultural pesticides that had been used historically. Study results contribute to the understanding of FSS solute origin, fate, and transport in mixed-use watersheds, particularly those in road salt-affected regions. Study results also emphasize the complexity of trace-metal source attribution and explore the potential for FSS solutes to affect human health, aquatic life, and infrastructure.

Multidirectional Fate Path Model to Connect Phosphorus Emissions with Freshwater Eutrophication Potential.

Excessive anthropogenic phosphorus (P) emissions put constant pressure on aquatic ecosystems. This pressure can be quantified as the freshwater eutrophication potential (FEP) by linking P emissions, P fate in environmental compartments, and the potentially disappeared fraction of species due to increase of P concentrations in freshwater. However, previous fate modeling on global and regional scales is mainly based on the eight-direction algorithm without distinguishing pollution sources. The algorithm fails to characterize the fate paths of point-source emissions via subsurface pipelines and wastewater treatment infrastructure, and exhibits suboptimal performance in accounting for multidirectional paths caused by river bifurcations, especially in flat terrains. Here we aim to improve the fate modeling by incorporating various fate paths and addressing multidirectional scenarios. We also update the P estimates by complementing potential untreated point-source emissions (PSu). The improved method is examined in a rapidly urbanizing area in Taihu Lake Basin, China in 2017 at a spatial resolution of 100 m × 100 m. Results show that the contribution of PSu on FEP (62.6%) is greater than that on P emissions (58.5%). The FEP is more spatially widely distributed with the improved fate modeling, facilitating targeted regulatory strategies tailored to local conditions.

Lethal and behavioral effects of semi-purified microcystins, Micropeptin and apolar compounds from cyanobacteria on freshwater microcrustacean Thamnocephalus platyurus.

The mass proliferation of cyanobacteria, episodes known as blooms, is a concern worldwide. One of the most critical aspects during these blooms is the production of toxic secondary metabolites that are not limited to the four cyanotoxins recognized by the World Health Organization. These metabolites comprise a wide range of structurally diverse compounds that possess bioactive functions. Potential human and ecosystem health risks posed by these metabolites and co-produced mixtures remain largely unknown. We studied acute lethal and sublethal effects measured as impaired mobility on the freshwater microcrustaceans Thamnocephalus platyurus for metabolite mixtures from two cyanobacterial strains, a microcystin (MC) producer and a non-MC producer. Both cyanobacterial extracts, from the MC-producer and non-MC-producer, caused acute toxicity with LC50 (24 h) values of 0.50 and 2.55 mgdw_biomass/mL, respectively, and decreased locomotor activity. Evaluating the contribution of different cyanopeptides revealed that the Micropeptin-K139-dominated fraction from the MC-producer extract contributed significantly to mortality and locomotor impairment of the microcrustaceans, with potential mixture effect with other cyanopeptolins present in this fraction. In the non-MC-producer extract, compounds present in the apolar fraction contributed mainly to mortality, locomotor impairment, and morphological changes in the antennae of the microcrustacean. No lethal or sublethal effects were observed in the fractions dominated by other cyanopetides (Cyanopeptolin 959, Nostoginin BN741). Our findings contribute to the growing body of research indicating that cyanobacterial metabolites beyond traditional cyanotoxins cause detrimental effects. This underscores the importance of toxicological assessments of such compounds, also at sublethal levels.