Exposure Assessment of Pesticides in Surface Waters of Ontario, Canada Reveals Low Probability of Exceeding Acute Regulatory Thresholds.

The objectives of this study were to: (1) characterize the exposure of aquatic ecosystems in Southern Ontario, Canada to pesticides between 2002 and 2016 by constructing environmental exposure distributions (EEDs), including censored data; and (2) predict the probability of exceeding acute regulatory guidelines. Surface water samples were collected over a 15-year period by Environment and Climate Change Canada. The dataset contained 167 compounds, sampled across 114 sites, with a total of 2,213 samples. There were 67,920 total observations of which 55,058 were non-detects (81%), and 12,862 detects (19%). The most commonly detected compound was atrazine, with a maximum concentration of 18,600 ngL- 1 and ~ 4% chance of exceeding an acute guideline (1,000 ngL- 1) in rivers and streams. Using Southern Ontario as a case study, this study provides insight into the risk that pesticides pose to aquatic ecosystems and the utility of EEDs that include censored data for the purpose of risk assessment.

Human health and environmental risk assessment of metals in community gardens of Winnipeg, Manitoba, Canada.

Fresh produce is an important component of maintaining cognitive and physical health, particularly for children. A mechanism to increase access to fresh produce is the construction of community gardens in urban centres. While reducing barriers to nutritious food, the soil of the community garden can contain contaminants (e.g. metals) depending on the location and how the garden was constructed. This study quantified, for the first time, seven metals (As, Cd, Cr, Cu, Pb, Mn, and Ni) in soil from 83 community gardens across the City of Winnipeg in Manitoba, Canada. Concentrations of metals in soil were used to create distributions for environmental exposure and estimated daily intake, which were then used to determine exceedances of soil quality guidelines and acceptable daily intakes, respectively. Raised garden beds and gardens further from roads had typically lower concentrations of metals in surface gardens and those nearer to roads. While some concentrations of metals exceeded CCME guidelines levels for the protection of environmental health, the vast majority represent a low risk. For human health, only As posed a quantifiable risk of exceeding the USEPA acceptable daily intake via the consumption of produce from gardens, though this was < 1.2% for the whole population and < 10.2% for children aged 1 to 2 years. Overall, this study is the first to show that the concentration of the metals in soil from gardens typically poses a low risk to environmental and human health. We recommend the use of raised gardens to further mitigate risk.

Occurrence and ecological risk assessment of organic UV filters in coastal waters of the Iberian Peninsula.

This study aimed to assess the presence of 21 UVFs and metabolites in coastal regions of the Iberian Peninsula, to evaluate their environmental risk, and identify possible influential factors affecting their measured concentrations. Sampling was carried out in spring and summer to assess possible seasonal variations. UVFs were detected in 43 of the 46 sampling sites. Only 5 were found above LOD: BP4, OC, BP3 and metabolites BP1 and BP8. Samples collected in Mar Menor had the greatest variety of compounds per sample and the highest cumulative concentrations. The risk was characterized using Risk Quotients (RQ). BP1 showed a Low environmental Risk in 2 sites while for OC the RQ indicated a Moderate Risk in 22 points. The variables that contribute most to the variation are population density, sampling season, whether it was an open bay or not, and level of urbanization. The presence of WWTPs had a lower influence.

Radio- and stable carbon isotope analysis reveals minimal assimilation of petrogenic carbon into an oligotrophic freshwater food web after experimental spills of diluted bitumen.

Following an oil spill into water, bacteria can biodegrade petroleum hydrocarbons which could lead to petrogenic carbon assimilation by aquatic biota. We used changes in the isotope ratios of radio- (Δ14C) and stable (δ13C) carbon to examine the potential for assimilation of petrogenic carbon into a freshwater food web following experimental spills of diluted bitumen (dilbit) into a boreal lake in northwestern Ontario, Canada. Different volumes (1.5, 2.9, 5.5, 18, 42, 82, and 180 L) of Cold Lake Winter Blend (a heavy crude blend of bitumen and condensate) dilbit were applied to seven 10-m diameter littoral limnocorrals (approximate volume of 100 m3), and two additional limnocorrals had no added dilbit to serve as controls. Particulate organic matter (POM) and periphyton from oil-treated limnocorrals had lower δ13C (up to 3.2‰ and 2.1‰ for POM and periphyton, respectively) than the control at every sampled interval (3, 6 and 10 weeks for POM and 6, 8 and 10 weeks for periphyton). Dissolved organic and inorganic carbon (DOC and DIC, respectively) had lower Δ14C in the oil-treated limnocorrals relative to the control (up to 122‰ and 440‰ lower, respectively). Giant floater mussel (Pyganodon grandis) housed for 25 days in aquaria containing oil-contaminated water from the limnocorrals did not show significant changes in δ13C values of muscle tissue compared to mussels housed in control water. Overall, the changes in δ13C and Δ14C observed indicated small amounts (up to 11% in DIC) of oil carbon incorporation into the food web. The combined δ13C and Δ14C data provide evidence for minimal incorporation of dilbit into the food web of this oligotrophic lake, suggesting that microbial degradation and subsequent incorporation of oil C into the food web may play a relatively small role in the ultimate fate of oil in this type of ecosystem.

Bioaccumulation and toxicokinetics of polycyclic aromatic compounds and metals in giant floater mussels (Pyganodon grandis) exposed to a simulated diluted bitumen spill.

Oil spills constitute a major risk to the environment and the bioaccumulation potential of the derived oil constituents will influence their impact on aquatic biota. Here we determined the bioaccumulation potential and toxicokinetic parameters of polycyclic aromatic compounds (PACs) and various selected metals in the giant floater mussels (Pyganodon grandis) following experimental oil spills in a freshwater lake. Specifically, these mussels were exposed ex situ for 25 days to water contaminated with naturally weathered diluted bitumen (dilbit), a form of oil commonly transported through pipelines. We detected greater concentrations of total PAC in mussels (∑PAC44) exposed to dilbit-contaminated water (25.92-27.79 µg g-1 lipid, n = 9, at day 25 of the uptake phase) compared to mussels from a control with no exposure to dilbit (average of 2.62 ± 1.95 µg g-1 lipid; ±SD, n = 17). This study demonstrates the importance of including alkylated PACs when assessing the impacts of an oil spill as the concentration of alkylated PACs in mussel tissue were an order of magnitude higher than their parent counterparts. However, metal accumulation in dilbit-exposed mussels did not exceed the unexposed controls, suggesting no excess metal accumulation by mussels from a 25-day dilbit exposure. From first-order one-compartment models, mean uptake rate constants (0.78-18.11 L g-1 day-1, n = 29) and bioconcentration factors (log values from 4.02 to 5.92 L kg-1, n = 87) for the 29 individual PACs that accumulated in mussels demonstrated that some alkylated PACs had greater bioaccumulation potential compared to their parent PAC counterpart but for the most part, alkylated and parent PACs had comparable BCF values. Results from this study also demonstrated that giant floater mussels could be used to biomonitor PAC contamination following oil spills as PACs accumulated in mussel tissue and some were still detectable following the 16-day depuration phase. This study provides the largest, most comprehensive set of toxicokinetic and bioaccumulation parameters for PACs and their alkylated counterparts (44 analytes) in freshwater mussels obtained to date.

Combustion of crude oil during in-situ burning can introduce polycyclic aromatic compounds (PACs) into small-scale freshwater systems.

In-situ burning (ISB) is the controlled combustion of an oil slick to remove large quantities of spilled oil from the aquatic environment. Prior to employing ISB as a remediation technique, an oil slick must often be corralled by physical or chemical means to achieve a sufficient thickness (typically >1 mm) for ignition. While ISB is an effective means to remove oil mass, less is known about the potential for ISB to mobilize polycyclic aromatic compounds (PACs) into the aquatic environment. The PACs are primary contaminants of concern in crude oil due to their environmental persistence and toxicity. We examined the potential for ISB to mobilize PACs into underlying waters in a series of small-scale burns conducted across a gradient of oil slick thicknesses (0-7 mm). Concentrations of PACs in underlying waters were evaluated and compared to reference conditions using an equivalent gradient of oil slick thicknesses that were not ignited. At thinner slick thicknesses (i.e. 0 - 4 mm) ISB enhanced the mobilization of total PACs, likely a result of heat transfer to underlying waters; this effect increased as slick thickness increased. Among thicker slicks (i.e. 4 - 7 mm), pyrogenic PACs became more prevalent and greater concentrations of 4-ring PACs were detected in underlying waters. The potential for PAC mobilization needs to be considered in scenarios where ISB may be the only viable oil spill remediation option (e.g. wetlands, marshes, or where oil is entrained) and in shallow systems susceptible to temperature changes.

Resilience of larval wood frogs (Rana sylvatica) to hydrocarbons and other compounds released from naturally weathered diluted bitumen in a boreal lake.

The risks to aquatic wildlife from spills of diluted bitumen (dilbit) into inland waters are poorly understood. In this paper, we describe the response of larval wood frogs (Rana sylvatica) to hydrocarbons and other compounds released from experimental spills of dilbit in a temperate boreal lake. To simulate a wide range of environmentally relevant oil spill scenarios, different volumes of Cold Lake Winter Blend dilbit (0, 1.5, 2.9, 5.5, 18, 42, 82, and 180 L) were added to 10 m diameter in-lake limnocorrals. Larvae (n = 360) were reared (from Gosner Stage (GS) 25 to ∼42) in land-based aquatic microcosms, where they were first exposed to clean water during a 2-week baseline phase, and then (at GS ∼30), to contaminated water withdrawn from the limnocorrals for 3 weeks. We observed no statistically significant trends in survival, growth, or development of larvae as a consequence of exposure to the chemical compounds released from naturally weathered dilbit. Likewise, neither cytochrome P450 1A biomarkers nor levels of thyroid hormones in wood frogs near metamorphic climax were significantly related to volume of the oil spills. However, there was a modest statistically significant decrease in larval activity (up to 8.7% relative to the control), but no change in other behavioral metrics (i.e., sociality or space use). Our work adds to the limited body of literature on the effects of unconventional oils on aquatic wildlife and helps to inform risk assessments regarding pipeline projects.

RNA metabarcoding helps reveal zooplankton community response to environmental stressors.

DNA metabarcoding can provide a high-throughput and rapid method for characterizing responses of communities to environmental stressors. However, within bulk samples, DNA metabarcoding hardly distinguishes live from the dead organisms. Here, both DNA and RNA metabarcoding were applied and compared in experimental freshwater mesocosms conducted for assessment of ecotoxicological responses of zooplankton communities to remediation treatment until 38 days post oil-spill. Furthermore, a novel indicator of normalized vitality (NV), sequence counts of RNA metabarcoding normalized by that of DNA metabarcoding, was developed for assessment of ecological responses. DNA and RNA metabarcoding detected similar taxa richness and rank of relative abundances. Both DNA and RNA metabarcoding demonstrated slight shifts in measured α-diversities in response to treatments. NV presented relatively greater magnitudes of differential responses of community compositions to treatments compared to DNA or RNA metabarcoding. NV declined from the start of the experiment (3 days pre-spill) to the end (38 days post-spill). NV also differed between Rotifer and Arthropoda, possibly due to differential life histories and sizes of organisms. NV could be a useful indicator for characterizing ecological responses to anthropogenic influence; however, the biology of target organisms and subsequent RNA production need to be considered.

Simulating diluted bitumen spills in boreal lake limnocorrals - Part 1: Experimental design and responses of hydrocarbons, metals, and water quality parameters.

Large-scale, in-lake enclosures (limnocorrals) were used to simulate spills of diluted bitumen (dilbit) in a boreal lake. In this study we use these simulated spills, which covered a range of sizes (oil:water ratio) representative of the upper 25% of onshore crude oil spills in North America (2008-2019), to assess the fate of dilbit-derived hydrocarbons and metals as well as the impacts of the spills on standard water quality parameters. The systems were monitored over 70 days following the application of dilbit amounts ranging between 1.5 and 179.8 L into 10-m diameter, ~100 m3 limnocorrals. The concentration of total petroleum hydrocarbons (TPH) in the water column increased rapidly over the first two weeks reaching a plateau that ranged between 200 µg/L and 2200 µg/L for the lowest and highest treatment respectively. The concentration of total polycyclic aromatic compounds (PACs) also increased over the first two weeks, prior to a slow decrease until day 70. The maximum measured concentrations in the highest treatment were 2858 ng/L for the sum of all 46 quantified PACs, 2716 ng/L for alkylated PACs and 154 ng/L for the 16 EPA priority PAHs. The concentrations of PACs in the sediment increased continuously over the study in the three highest treatments with maximum observed concentrations of 189 ng/g for ΣPAC46, 169 ng/g for ΣPACalk. No significant treatment-related changes in the 16 EPA priority PAHs were observed in the sediment. Of the 25 metals quantified in the water column, only manganese, molybdenum, and vanadium displayed a significant treatment effect with increases of 280, 76 and 25% respectively in the total fraction. These results can help us understand and predict the fate of oil-derived contaminants following a spill and characterize the exposure of freshwater organisms living within them. These results should help inform the risk assessment of future dilbit transportation projects.

Ecotoxicology of Glyphosate, Its Formulants, and Environmental Degradation Products.

The chemical and biological properties of glyphosate are key to understanding its fate in the environment and potential risks to non-target organisms. Glyphosate is polar and water soluble and therefore does not bioaccumulate, biomagnify, or accumulate to high levels in the environment. It sorbs strongly to particles in soil and sediments and this reduces bioavailability so that exposures to non-target organisms in the environment are acute and decrease with half-lives in the order of hours to a few days. The target site for glyphosate is not known to be expressed in animals, which reduces the probability of toxicity and small risks. Technical glyphosate (acid or salts) is of low to moderate toxicity; however, when mixed with some formulants such as polyoxyethylene amines (POEAs), toxicity to aquatic animals increases about 15-fold on average. However, glyphosate and the formulants have different fates in the environment and they do not necessarily co-occur. Therefore, toxicity tests on formulated products in scenarios where they would not be used are unrealistic and of limited use for assessment of risk. Concentrations of glyphosate in surface water are generally low with minimal risk to aquatic organisms, including plants. Toxicity and risks to non-target terrestrial organisms other than plants treated directly are low and risks to terrestrial invertebrates and microbial processes in soil are very small. Formulations containing POEAs are not labeled for use over water but, because POEA rapidly partitions into sediment, risks to aquatic organisms from accidental over-sprays are reduced in shallow water bodies. We conclude that use of formulations of glyphosate under good agricultural practices presents a de minimis risk of direct and indirect adverse effects in non-target organisms.

Surface-Dwelling Aquatic Insects in Low-Energy Freshwater Environments Are Highly Impacted by Oil Spills and the Surface Washing Agent Corexit EC9580A Used in Oil Spill Response.

Physical impacts of diluted bitumen (dilbit) and the application of surface washing agents (SWAs) in freshwater have not been characterized for aquatic invertebrates. These compounds are known to reduce surface tension in feather and fur microstructures of birds and mammals, and are thus likely to affect the buoyancy of surface-dwelling aquatic insects. We evaluated impacts of fresh dilbit and a SWA on water striders (Metrobates sp.), which are surface-dwelling organisms that rely on fine-hair microstructures to remain buoyant. We report nominal sheen thickness values that cause 50% immobility in 48 h as determined from exposure studies in outdoor tanks. A comparison of our data with those from historic oil spill volumes in Canada and the United States in the past 12 yr indicates that our reported nominal sheen thicknesses could have been reached or exceeded in 99% of historic spills when scaled to a small reference lake. The addition of Corexit EC9580A, a SWA approved for marine use in Canada, led to 100% immobility in striders within minutes, both in combination with oil and alone. Our study reveals an acute sensitivity to Corexit EC9580A and dilbit by surface-dwelling insects and may be driven by disruption of mechanisms of buoyancy. We highlight a need to evaluate physical impacts, typically excluded from standard toxicity testing, within the context of spill impact mitigation assessments. Environ Toxicol Chem 2021;40:1298-1307. © 2020 SETAC.

Use of Postregistration Monitoring Data to Evaluate the Ecotoxicological Risks of Pesticides to Surface Waters: A Case Study with Chlorpyrifos in the Iberian Peninsula.

Chemical monitoring data sets such as those provided by the implementation of the Water Framework Directive (WFD) offer opportunities to evaluate the ecological risks of pesticides under large spatiotemporal scales and to evaluate the protectiveness of the current prospective risk-assessment framework. As a case study, we used the monitoring data set for the insecticide chlorpyrifos to perform a probabilistic risk assessment for Iberian surface-water ecosystems. The specific objectives of the study were 1) to assess the occurrence of chlorpyrifos in relation to different agricultural production land uses, 2) to assess the spatiotemporal variation in the exceedance of the European WFD short- and long-term environmental quality standards (maximum allowable concentration environmental quality standard [MAC-EQS] and annual average [AA] EQS), and 3) to perform a probabilistic risk assessment for freshwater invertebrates. A database that contains chlorpyrifos concentrations from 14 600 surface water samples taken between 2012 and 2017 in the Iberian Peninsula (Spain and Portugal) was analyzed, and chlorpyrifos was detected in 21% of these samples. The MAC-EQS was exceeded in 2% of the cases, whereas the AA-EQS was exceeded in 18% of the cases. The majority of the exceedances took place in the littoral areas of the eastern and southeastern parts of the Iberian Peninsula, particularly in areas with dominant citrus production during late spring, late summer, and autumn. The present study indicates unacceptable risks posed by chlorpyrifos to Iberian surface waters over the study period, although it was approved for use in Europe. The present study supports the need to perform further postregistration monitoring assessments with other pesticides following similar approaches, which can help to identify possible pesticide-misuse practices and improvements of the prospective risk-assessment framework. Environ Toxicol Chem 2021;40:500-512. © 2020 SETAC.

Presence of pharmaceutical compounds, levels of biochemical biomarkers in seafood tissues and risk assessment for human health: Results from a case study in North-Western Spain.

This study assessed the presence of 27 pharmaceutically active compounds belonging to common therapeutic groups (cardiovascular, antiashmatic, psychoactive, diuretic, analgesic/anti-inflammatory, and antibiotic drugs) in the tissues of representative seafood species of bivalves, cephalopods, arthropods, and fish of high economic importance and consumption rates in North-Western Spain. Four pharmaceutical compounds, out of the 27 analyzed, were detected in the collected samples. The benzodiazepine citalopram was detected in the tissues of common octopus (14.1 ng g-1 dry weight) and pod razor (9.4 ng g-1 dw). The anxiolytic venlafaxine was detected in the tissues of common cockle (2.9 ng g-1 dw). The veterinary antiparasitic ronidazole was found in pod razor (2.3 ng g-1 dw) and, finally, the psychoactive compound alprazolam was also measured in common octopus (0.3 ng g-1 dw). Hazard quotients were calculated to assess the hazard posed by the consumption of the sampled seafoods. Octopus and pod razor tissues containing citalopram and alprazolam exceeded our chosen hazard limits (HQ > 0.1) for toddlers who are high consumers of seafood (HQ values between 0.18 and 0.27). A battery of biochemical biomarkers of effects (acetylcholinesterase, glutathione S-transferase; catalase, glutathione peroxidase and glutathione reductase enzymes activities and reduced/oxidized glutathione and malondialdehyde levels) was applied to samples of the study species with the aim of characterizing their basal levels and evaluating their suitability as a tool in the monitoring chronic exposure to environmental contaminants such as those analyzed in this study. According to the measured biomarkers, pod razor and cockles have the potential to be good bioindicator species, based on the observed among-site differences detected on acetylcholinesterase, glutathione S-transferase, catalase, glutathione peroxidase activities; reduced/oxidized glutathione and malondialdehyde levels.

Psychoactive pharmaceuticals and illicit drugs in coastal waters of North-Western Spain: Environmental exposure and risk assessment.

The knowledge on the presence of pharmaceutical compounds, and possible risks, in coastal and marine systems is still limited. This study represents the first attempt at monitoring psychoactive pharmaceuticals (PaPs) (benzodiazepines and anxiolytics) and illicit drugs (IDs) in the Rías Baixas coastal area of Northwestern Spain, an area of economic and ecological relevance, leader in shellfish production. Fourteen PaPs and 9 IDs were detected in the water samples with venlafaxine (59%), benzoylecgonine (40%), EDDP (40%), and citalopram (36%) showing the highest detection frequencies. The highest concentrations were measured for venlafaxine (291 ng L-1), benzoylecgonine (142 ng L-1), lorazepam (95.9 ng L-1), and citalopram (92.5 ng L-1). Risk assessment, based on hazard quotients suggested that venlafaxine, citalopram, sertraline, and EDDP were present in concentrations potentially able to cause chronic effects in exposed organisms. Based on the results obtained further monitoring of venlafaxine, citalopram, and EDDP in coastal waters is recommended.

[Wastewater-based epidemiology: applications towards the estimation of drugs of abuse consumption and public health in general. The Spanish network ESAR-Net]. / Análisis de aguas residuales con fines epidemiológicos: aplicaciones a la estimación del consumo de sustancias de abuso y en salud pública en general. Red española ESAR-Net.

This manuscript introduces Wastewater-Based Epidemiology (WBE) and its potential in the assessment of diverse aspects related to public health. This methodology can provide data in a relatively short temporal and local scale (typically dialy-weekly at the municipal level) on consumption patterns of illicit drugs (e.g. cocaine or cannabis), licit substances of abuse (e.g. alcohol) by measuring their consumption biomarkers (i.e. the original unmetabolized substance or some of its metabolite) in wastewater. Besides discussing the fundaments, advantages and shortcomings of WBE, it reviews some of the main precedents at international level and most remarkable activities that have been taken place in this field in Spain. Finally, the Spanish Network of Wastewater-Based Epidemiology (ESAR-Net) as is presented. ESAR-Net is an Excellence Network that sums up the efforts of the most relevant Spanish researchers in the field of WBE, aiming to investigate future perspectives of this methodology and its impact on Public Health competences in Spain.

En este artículo se presenta la metodología de análisis de aguas residuales con fines epidemiológicos (wastewater-based epidemiology, WBE) y su potencial para abordar diversos aspectos relacionados con la salud pública. Esta metodología permite obtener datos a una escala temporal y espacial relativamente pequeña (típicamente datos diarios-semanales sobre un municipio) de hábitos de consumo de sustancias de abuso, ilegales (como la cocaína o el cannabis) o legales (como el alcohol) a través de la determinación de biomarcadores de consumo (el compuesto original no metabolizado o alguno de sus metabolitos) en el agua residual. Aparte de discutir los fundamentos, ventajas y limitaciones de WBE, se comentan los precedentes más relevantes a nivel internacional, y las actividades más destacables en España en este ámbito. Finalmente, se exponen, los objetivos de la Red Española de Análisis de Aguas Residuales con Fines Epidemiológicos (ESAR-Net), una "Red de Excelencia" que agrupa a investigadores españoles con amplia experiencia en el área de WBE, así como las perspectivas de futuro de esta metodología puede tener para mejorar las competencias de la Salud Pública en España.

Analysis of lipid peroxidation in animal and plant tissues as field-based biomarker in Mediterranean irrigated agroecosystems (Extremadura, Spain).

The development of field-based biomarkers can allow for a more reliable assessment of the exposure of organisms to pollutants. Different sampling sites, along two streams running through an irrigable agricultural area, were selected to evaluate the effect of agrochemical load on the measured endpoints. The levels of lipid peroxidation were evaluated in several organs of Procambarus clarkii. The same method was applied to leaves of two woody species. Determining levels of MDA (malonaldehyde) by thiobarbituric acid reactive substances assay allows measuring the levels of lipid peroxidation. Differences in lipid peroxidation levels were observed in P. clarkii individuals collected at different sites; however, the patterns varied depending on the organ (when accounting for variations due to sex). The use of a MDA-gills/MDA-hepatopancreas index allowed for discrimination between reference and polluted sites. Significant differences in oxidative damage between sites were found in the leaves of Quercus rotundifolia but not in Salix sp. The lipid peroxidation of crayfish organs and holm oak leaves as a suitable biomarker of environmental pollution deserves further investigation.

Does the presence of caffeine in the marine environment represent an environmental risk? A regional and global study.

Caffeine is an emerging contaminant considered to be an indicator of human contamination that has been widely detected in various aquatic systems, especially in continental waters. Nevertheless, the extent of its possible environmental impact is yet to be determined. This study determined the presence of caffeine, and evaluated the environmental hazard posed by this substance, in the "Rías Gallegas", a series of costal inlets in north-west Spain which are of great ecological value and in which fishing and bivalve farming, are a significant source of income. Caffeine was found to be present at concentrations higher than the limit of quantification (LOQ=3.07ngL-1) in 15 of the 23 samples analysed, with the highest seawater concentration being 857ngL-1 (the highest measured in seawater in Spain). Six out of 22 seawater samples resulted in a hazard quotient (HQ) from chronic exposure higher than 1 with the highest being 17.14, indicating a high probability of adverse effects in the aquatic environment. Environmental Exposure Distributions (EEDs) generated from a literature review of caffeine levels reported previously in four out of the five continents, showed that 28% of all seawater samples, and 69% of all estuary water samples where caffeine has ever been measured resulted in HQ>1 for chronic exposure. Further studies into the potential adverse effects that may arise from exposure to caffeine in aquatic systems are still required. Indeed, the need to gain a more in-depth understanding of the long-term ecotoxicological effects of caffeine is essential to ensure the quality of our health and environment.

Dissipation of a commercial mixture of polyoxyethylene amine surfactants in aquatic outdoor microcosms: Effect of water depth and sediment organic carbon.

This study optimized existing analytical approaches and characterized the effect of sediment total organic carbon (0.05-2.05% TOC), and water depth (15, 30, and 90cm) on the fate of MON 0818, a commercial mixture of polyoxyethylene amine surfactants (POEAs), in outdoor microcosms. Mixtures of POEAs are commonly used as adjuvants in commercial herbicide formulations containing glyphosate. Until recently, analytical methods sensitive enough to monitor environmental concentrations of POEAs in aquatic systems were not available. After optimizing recently developed analytical methods, we found that the combined use of accelerated solvent extraction (ASE) and liquid chromatography-tandem mass spectrometry provided a reliable approach for determining the concentration of sediment-adsorbed POEAs. The surfactant showed strong affinity for sediment materials, with low maximum recoveries by ASE of 52%. Under microcosm conditions, water depth or sediment characteristics did not significantly affect the water-column half-life of POEA, which ranged from 3.2 to 5.3h. Binding of POEAs to suspended solids was observed, which dissipated via one- or two-phase exponential decay; when two-phase decay occurred, fast phase half-life values ranged from 0.71 to 1.3h and slow-phase values ranged from 18 to 44h. Concentrations of POEA increased in sediment shortly after application and decreased over the study period with a half-life of 5.8 to 71d. The concentrations of POEAs in the sediment of the shallow (15cm) ponds dissipated following a two-phase exponential decay model with an initial fast-phase half-life of 1.1 to 8.9d and a slower second-phase half-life of 21d. Our results suggest that aquatic organisms are unlikely to be exposed to POEAs in aqueous phase for periods of more than a few hours following an over-water application, and that sediment is a significant sink for POEAs in aquatic systems.

Toxicity of Cúspide 480SL® spray mixture formulation of glyphosate to aquatic organisms.

In 2011, an alternative formulation of glyphosate (Cúspide 480SL®) was chosen to replace Roundup-SL®, Fuete-SL®, and Gly-41® for the control of Erythroxylum coca, the source of cocaine, in Colombia. Cúspide 480SL contains the active ingredient glyphosate isopropylamine (IPA) salt, which is the same active ingredient used in previous formulations. However, Cúspide 480SL contains an alkyl polyglycoside surfactant rather than the polyethoxylated tallow amine (POEA) surfactant used in other formulations and known to be more toxic to nonprimary producing aquatic organisms than glyphosate itself. An adjuvant, Cosmo-Flux F411, and water also are added to the spray mixture before application. Aquatic ecosystems adjacent to the target coca fields might be exposed to the spray mix, placing aquatic organisms at risk. Because no toxicity data were available for spray mixture on aquatic organisms, acute toxicity tests were conducted on aquatic plants, invertebrates, and fish, by using the Cúspide 480SL spray mix as described on the label. Based on the median effective concentration (EC50) values for similar organisms, the spray mixture was less toxic to aquatic organisms than formulations previously used for the control of coca (i.e., Roundup-SL, Fuete-SL, and Gly-41). A physical effect induced by Cosmo-Flux F411 was observed in Daphnia magna, Ceriodaphnia dubia, and Hyalella azteca, causing the invertebrates to be trapped in an oily film that was present at the surface of the water. However, a hazard assessment for the Cúspide 480SL spray mix, using estimated worst-case exposure scenario concentrations and EC50 values from the toxicity tests, indicated de minimis hazard for the tested aquatic animals, with hazard quotients all <<1.