Influence of Salinity on the Partitioning Behavior of Six Commonly Used Pesticides in Fish Eggs.

Salinity has been reported to impact the octanol-water partition coefficient of organic contaminants entering aquatic ecosystems. However, limited data are available on the impacts of salinity on their partitioning from the aqueous phase to adjacent organic compartments. The pesticides bifenthrin, chlorpyrifos, dicloran, myclobutanil, penconazole, and triadimefon were used to investigate the effects of salinity on their partitioning to capelin (Mallotus villosus) eggs in 5 practical salinity units (PSU) versus 25 PSU artificial seawater (ASW). The partitioning coefficient was significantly higher in 25 versus 5 PSU ASW for bifenthrin, chlorpyrifos, dicloran, penconazole, and triadimefon by 31%, 28%, 35%, 28%, and 20%, respectively, while for myclobutanil there was no significant difference. Moreover, pesticide partitioning to store-bought capelin eggs was consistent with the partitioning observed for the standard assay species, inland silversides (Menidia beryllina) eggs, after partitioning between the eggs and exposure solution had reached a state of equilibrium. The present study illustrates the importance of considering the influence of salinity on the environmental partitioning and fate of hydrophobic organic contaminants in aquatic ecosystems. Environ Toxicol Chem 2024;43:299-306. © 2023 SETAC.

Impact of Reactive Oxygen Species Scavenging on the Intermediate Production of Anthracene and Anthraquinone in Fresh versus Saltwater Environments.

While salinity can alter the photodegradation of hydrophobic organic compounds (HOCs), the cause of their altered kinetics in seawater is not well understood. Because HOC intermediate photoproducts are often more toxic than their parent compounds, characterizing the generation of intermediates in saline environments is needed to accurately predict their health effects. The present study investigated the influence of salinity on the generation of anthraquinone through the photolysis of anthracene and the generation of anthrone and 1-hydroxyanthraquinone from the photolysis of anthraquinone as well as their reactivities with hydroxyl radicals. This was conducted by measuring the photolysis rates of anthracene and anthraquinone and characterizing their product formation in buffered deionized water, artificial seawater, individual seawater halides (bromide, chloride, and iodide), dimethyl sulfoxide, furfuryl alcohol, and solutions of hydrogen peroxide. Salinity enhanced the persistence of anthraquinone by a factor >10 and altered its product formation, including the generation of the suspected carcinogen 1-hydroxyanthraquinone. In part, this was attributed to reactive oxygen species (ROS) scavenging by the seawater constituents chloride and bromide. In addition, anthraquinone and its hydroxylated products were found to be moderately to highly reactive with hydroxyl radicals, further illustrating their tendency to react with ROS in aqueous environments. The present study emphasizes the importance of considering the effects of salinity on organic contaminant degradation; it can significantly enhance the persistence of HOCs and alter their intermediate formation, subsequently impacting chemical exposure times and potential toxic effects on estuarine/marine organisms. Environ Toxicol Chem 2023;42:1721-1729. © 2023 SETAC.

Assessment of risks to listed species from the use of atrazine in the USA: a perspective.

Atrazine is a triazine herbicide used predominantly on corn, sorghum, and sugarcane in the US. Its use potentially overlaps with the ranges of listed (threatened and endangered) species. In response to registration review in the context of the Endangered Species Act, we evaluated potential direct and indirect impacts of atrazine on listed species and designated critical habitats. Atrazine has been widely studied, extensive environmental monitoring and toxicity data sets are available, and the spatial and temporal uses on major crops are well characterized. Ranges of listed species are less well-defined, resulting in overly conservative designations of "May Effect". Preferences for habitat and food sources serve to limit exposure among many listed animal species and animals are relatively insensitive. Atrazine does not bioaccumulate, further diminishing exposures among consumers and predators. Because of incomplete exposure pathways, many species can be eliminated from consideration for direct effects. It is toxic to plants, but even sensitive plants tolerate episodic exposures, such as those occurring in flowing waters. Empirical data from long-term monitoring programs and realistic field data on off-target deposition of drift indicate that many other listed species can be removed from consideration because exposures are below conservative toxicity thresholds for direct and indirect effects. Combined with recent mitigation actions by the registrant, this review serves to refine and focus forthcoming listed species assessment efforts for atrazine.Abbreviations: a.i. = Active ingredient (of a pesticide product). AEMP = Atrazine Ecological Monitoring Program. AIMS = Avian Incident Monitoring SystemArach. = Arachnid (spiders and mites). AUC = Area Under the Curve. BE = Biological Evaluation (of potential effects on listed species). BO = Biological Opinion (conclusion of the consultation between USEPA and the Services with respect to potential effects in listed species). CASM = Comprehensive Aquatic System Model. CDL = Crop Data LayerCN = field Curve Number. CRP = Conservation Reserve Program (lands). CTA = Conditioned Taste Avoidance. DAC = Diaminochlorotriazine (a metabolite of atrazine, also known by the acronym DACT). DER = Data Evaluation Record. EC25 = Concentration causing a specified effect in 25% of the tested organisms. EC50 = Concentration causing a specified effect in 50% of the tested organisms. EC50RGR = Concentration causing a 50% reduction in relative growth rate. ECOS = Environmental Conservation Online System. EDD = Estimated Daily Dose. EEC = Expected Environmental Concentration. EFED = Environmental Fate and Effects Division (of the USEPA). EFSA = European Food Safety Agency. EIIS = Ecological Incident Information System. ERA = Environmental Risk Assessment. ESA = Endangered Species Act. ESU = Evolutionarily Significant UnitsFAR = Field Application RateFIFRA = Federal Insecticide, Fungicide, and Rodenticide Act. FOIA = Freedom of Information Act (request). GSD = Genus Sensitivity Distribution. HC5 = Hazardous Concentration for ≤ 5% of species. HUC = Hydrologic Unit Code. IBM = Individual-Based Model. IDS = Incident Data System. KOC = Partition coefficient between water and organic matter in soil or sediment. KOW = Octanol-Water partition coefficient. LC50 = Concentration lethal to 50% of the tested organisms. LC-MS-MS = Liquid Chromatograph with Tandem Mass Spectrometry. LD50 = Dose lethal to 50% of the tested organisms. LAA = Likely to Adversely Affect. LOAEC = Lowest-Observed-Adverse-Effect Concentration. LOC = Level of Concern. MA = May Affect. MATC = Maximum Acceptable Toxicant Concentration. NAS = National Academy of Sciences. NCWQR = National Center of Water Quality Research. NE = No Effect. NLAA = Not Likely to Adversely Affect. NMFS = National Marine Fisheries Service. NOAA = National Oceanic and Atmospheric Administration. NOAEC = No-Observed-Adverse-Effect Concentration. NOAEL = No-Observed-Adverse-Effect Dose-Level. OECD = Organization of Economic Cooperation and Development. PNSP = Pesticide National Synthesis Project. PQ = Plastoquinone. PRZM = Pesticide Root Zone Model. PWC = Pesticide in Water Calculator. QWoE = Quantitative Weight of Evidence. RGR = Relative growth rate (of plants). RQ = Risk Quotient. RUD = Residue Unit Doses. SAP = Science Advisory Panel (of the USEPA). SGR = Specific Growth Rate. SI = Supplemental Information. SSD = Species Sensitivity Distribution. SURLAG = Surface Runoff Lag Coefficient. SWAT = Soil & Water Assessment Tool. SWCC = Surface Water Concentration Calculator. UDL = Use Data Layer (for pesticides). USDA = United States Department of Agriculture. USEPA = United States Environmental Protection Agency. USFWS = United States Fish and Wildlife Service. USGS = United States Geological Survey. WARP = Watershed Regressions for Pesticides.

Salinity Alters Toxicity of Commonly Used Pesticides in a Model Euryhaline Fish Species (Menidia beryllina).

Changing salinity in estuaries due to sea level rise and altered rainfall patterns, as a result of climate change, has the potential to influence the interactions of aquatic pollutants as well as to alter their toxicity. From a chemical property point of view, ionic concentration can increase the octanol-water partition coefficient and thus decrease the water solubility of a compound. Biologically, organism physiology and enzyme metabolism are also altered at different salinities with implications for drug metabolism and toxic effects. This highlights the need to understand the influence of salinity on pesticide toxicity when assessing risk to estuarine and marine fishes, particularly considering that climate change is predicted to alter salinity regimes globally and many risk assessments and regulatory decisions are made using freshwater studies. Therefore, we exposed the Inland Silverside (Menidia beryllina) at an early life stage to seven commonly used pesticides at two salinities relevant to estuarine waters (5 PSU and 15 PSU). Triadimefon was the only compound to show a statistically significant increase in toxicity at the 15 PSU LC50. However, all compounds showed a decrease in LC50 values at the higher salinity, and all but one showed a decrease in the LC10 value. Many organisms rely on estuaries as nurseries and increased toxicity at higher salinities may mean that organisms in critical life stages of development are at risk of experiencing adverse, toxic effects. The differences in toxicity demonstrated here have important implications for organisms living within estuarine and marine ecosystems in the Anthropocene as climate change alters estuarine salinity regimes globally.

Potential toxic effects of 4-OH-chlorothalonil and photodegradation product on human skin health.

Chlorothalonil (CHT) is widely used in agriculture as a fungicide and has been detected in various ecosystems along with its degradation products. A primary intermediate product of degradation, 4-hydroxychlorothalonil (4-OH-CHT) has demonstrated toxic effects on aquatic organisms. However, the toxic effects of 4-OH-CHT on human health and the impacts of environmental factors on the toxicity remain unclear. To understand the environmental modification on the toxicity of 4-OH-CHT to human health, we used a three-dimensional human skin culture model. 4-OH-CHT and irradiated 4-OH-CHT were applied to the model for the dermatoxicity analyses. Although neither the 4-OH-CHT nor the irradiated 4-OH-CHT inhibited the cell proliferation, the 4-OH-CHT significantly attenuated the keratinocyte migration by 26% at a concentration of 20 ppb and by 44 % at 100 ppb. The 4-OH-CHT also demonstrated inhibitory effects on keratinocyte differentiation at both 20 ppb and 100 ppb. In contrast, photodegraded 4-OH-CHT did not show inhibitory effects on the migration and differentiation of the keratinocytes at any concentration. Similarly, the 4-OH-CHT treated 3D keratinocyte culture dramatically activated the co-cultured dermal fibroblast cells by increasing the production of α smooth muscle actin (α-SMA) and pro-Collagen Iα. The mRNA levels of these two proteins were upregulated by 1.13 and 10.97 folds with the stimulation of 100 ppb 4-OH-CHT. The protein level of pro-Collagen Iα in dermal fibroblast cells was increased by 68 % with 100 ppb 4-OH-CHT. The photodegraded 4-OH-CHT failed to activate the co-cultured fibroblast cells. The 4-OH-CHT also enhanced pro-inflammatory cytokine production in keratinocytes compared to the photodegraded products. These results suggest that exposure to environmental 4-OH-CHT could increase the risk of inflammatory skin diseases in humans.

Toward Sustainable Environmental Quality: Priority Research Questions for North America.

Anticipating, identifying, and prioritizing strategic needs represent essential activities by research organizations. Decided benefits emerge when these pursuits engage globally important environment and health goals, including the United Nations Sustainable Development Goals. To this end, horizon scanning efforts can facilitate identification of specific research needs to address grand challenges. We report and discuss 40 priority research questions following engagement of scientists and engineers in North America. These timely questions identify the importance of stimulating innovation and developing new methods, tools, and concepts in environmental chemistry and toxicology to improve assessment and management of chemical contaminants and other diverse environmental stressors. Grand challenges to achieving sustainable management of the environment are becoming increasingly complex and structured by global megatrends, which collectively challenge existing sustainable environmental quality efforts. Transdisciplinary, systems-based approaches will be required to define and avoid adverse biological effects across temporal and spatial gradients. Similarly, coordinated research activities among organizations within and among countries are necessary to address the priority research needs reported here. Acquiring answers to these 40 research questions will not be trivial, but doing so promises to advance sustainable environmental quality in the 21st century. Environ Toxicol Chem 2019;38:1606-1624. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Degradation of Dicloran in Irradiated Water-Sediment Systems.

Shallow water systems are uniquely susceptible to environmental processes such as photolysis and hydrolysis that can influence the dissipation of pesticides into sediments. The fungicide dicloran has previously been shown to undergo photolysis and is reported to dissipate in soils and sediments. The photodegradation and dissipation of dicloran in freshwater and seawater was monitored in a laboratory-simulated shallow water system. While no difference was observed between freshwater and seawater systems in the presence of simulated sunlight, the dissipation of dicloran in dark trial systems differed between salinities; 30% of the applied mass dissipated into the sediment in freshwater vs 22% in seawater, and the photodegradation rate and half-life were also impacted by the presence of sediment. The potential for dicloran to dissipate and photodegrade affects the overall behavior of dicloran between waters. Differences in chemical behavior with sediment presence and potential for photodegradation have the capacity to impact organisms within the ecosystem and suggest that these factors may need to be implemented into chemical exposure assessments dependent upon location.

Potential risk to human skin cells from exposure to dicloran photodegradation products in water.

Exposure to sunlight and certain pesticides can induce phototoxic responses. Long- and short-term exposure to the photoactivated pesticides can cause a variety of skin diseases. However, assessment of pesticide phototoxicity on human skin is difficult. In the present study, human skin keratinocytes were cultured in several forms: monolayer cell sheet, three-dimensional culture, and keratinocyte-fibroblast co-culture. A common fungicide, dicloran (DC, 2,6­dichloro­4­nitroaniline), was irradiated with simulated sunlight for 2 (DC-PD-2h) and 4 (DC-PD-4h) hours. Dicloran, and two purified intermediate photodegradation products, 2­chloro­1,4­benzoquinone (CBQ) and 1,4­benzoquinone (BQ), were applied in toxicity tests independently with the keratinocyte culture models. The cell migration, cell differentiation, pro-inflammatory molecule production, and dermal fibroblast cell activation were all measured in the keratinocytes treated with the chemicals described above. These parameters were used as references for dicloran phototoxicity assessment. Among all tested chemicals, the DC-PD-4h and BQ demonstrated elevated toxicities to the keratinocytes compared to dicloran based on our results. The application of DC-PD-4h or BQ significantly delayed the migration of keratinocytes in monolayer cell sheets, inhibited the keratinocyte differentiation, increased the production of pro-inflammatory molecules by 3D keratinocyte culture, and enhanced the ability of 3D cultured keratinocytes in the activation of co-cultured dermal fibroblast cells. In contrast, dicloran, DC-PD-2h, and CBQ showed minimal effects on the keratinocytes in all assays. The results suggested that the four-hour photodegraded dicloran was likely to induce inflammatory skin diseases in the natural human skin. The 1,4­benzoquinone, which is the predominant degradation product detected following 4 h of irradiation, was the main factor for this response. Photoactivation increased the risk of skin exposed to dicloran in nature. Our models provided an efficient tool in the assessment of toxicity changes in pesticide following normal use practices under typical environmental conditions.

Photodegradation of Dicloran in Freshwater and Seawater.

Dicloran appears to be a model pesticide for investigating photodegradation processes in surface waters. Photodegradation processes are particularly relevant to this compound as it is applied to crops grown in proximity to freshwater and marine ecosystems. The photodegradation of dicloran under simulated sunlight was measured in distilled water, artificial seawater, phosphate buffer, and filter-sterilized estuarine water to determine its half-life, degradation rate, and photodegradation products. The half-life was approximately 7.5 h in all media. There was no significant difference in the rate of degradation between distilled water and artificial seawater for dicloran. For the intermediate products, a higher concentration of 2-chloro-1,4-benzoquinone was measured in artificial seawater versus distilled water, while a slightly higher concentration of 1,4-benzoquinone was measured in distilled water versus artificial seawater. The detection of chloride and nitrate ions after 2 h of light exposure suggests photonucleophilic substitution contributes to the degradation process. Differences in product distributions between water types suggest that salinity impacts on chemical degradation may need to be addressed in chemical exposure assessments.

Evaluation of dicloran phototoxicity using primary cardiomyocyte culture from Crassostrea virginica.

Dicloran is a commonly used fungicide throughout the Southern and Western United States. Runoff of dicloran from agriculture systems to nearby waterbodies can accumulate in the organisms that inhabit those areas. Although severe damage of dicloran to ecological systems has not been reported, its toxicity has been modified by photodegradation. The objective of this study is to assess the changes of dicloran toxicities during photo exposure using a reliable in vitro biological model. In the present investigation, the photodegradation of dicloran in vitro showed over 90% of dicloran was degraded within 24h of UV exposure in water. Two major intermediate degradation products, 2-chloro-1,4-benzoquinone (CBQ) and 1,4-benzoquinone (BQ), were detected upon UV exposure of dicloran; however, they were rapidly degraded via photolysis. To estimate the impact of the phototoxicity of dicloran to aquatic organisms, we developed an in vitro cell culture system using the C. virginica cardiomyoctes (CvCMs) which were isolated from heart tissues and formed beating cell clusters. The CvCM clusters were treated with irradiated dicloran or the two intermediate standards, CBQ and BQ, and they showed up to 41% decrease in beating rates compared to control cell clusters. Expression levels of selected genes: def, hsp70, and cam, were upregulated in response to stimulations of UV irradiated dicloran and the two standard intermediates. The four-hour irradiated dicloran also resulted in more significant inhibition in the proliferation and small cardioactive peptide ß production of CvCMs than other treatment. Tested solutions of photolyzed dicloran showed elevated toxicities opposed to the standard intermediates, CBQ and BQ, suggesting additive toxicity of these dicloran products or toxicity due to other unidentified degradation products. Results of this study supported our hypothesis that the degradation of dicloran caused by photo irradiation results in an elevated toxicity which can be evaluated by the in vitro CvCM model.

Salinity impacts on water solubility and n-octanol/water partition coefficients of selected pesticides and oil constituents.

Salinity has been reported to influence the water solubility of organic chemicals entering marine ecosystems. However, limited data are available on salinity impacts for chemicals potentially entering seawater. Impacts on water solubility would correspondingly impact chemical sorption as well as overall bioavailability and exposure estimates used in the regulatory assessment. The pesticides atrazine, fipronil, bifenthrin, and cypermethrin, as well as the crude oil constituent dibenzothiophene together with 3 of its alkyl derivatives, all have different polarities and were selected as model compounds to demonstrate the impact of salinity on their solubility and partitioning behavior. The n-octanol/water partition coefficient (KOW ) was measured in both distilled-deionized water and artificial seawater (3.2%). All compounds had diminished solubility and increased KOW values in artificial seawater compared with distilled-deionized water. A linear correlation curve estimated salinity may increase the log KOW value by 2.6%/1 log unit increase in distilled water (R2 = 0.97). Salinity appears to generally decrease the water solubility and increase the partitioning potential. Environmental fate estimates based on these parameters indicate elevated chemical sorption to sediment, overall bioavailability, and toxicity in artificial seawater. These dramatic differences suggest that salinity should be taken into account when exposure estimates are made for marine organisms. Environ Toxicol Chem 2017;36:2274-2280. © 2017 SETAC.

The effects of fipronil and the photodegradation product fipronil desulfinyl on growth and gene expression in juvenile blue crabs, Callinectes sapidus, at different salinities.

Endocrine disrupting compounds (EDCs) are now widely established to be present in the environment at concentrations capable of affecting wild organisms. Although many studies have been conducted in fish, less is known about effects in invertebrates such as decapod crustaceans. Decapods are exposed to low concentrations of EDCs that may cause infertility, decreased growth, and developmental abnormalities. The objective herein was to evaluate effects of fipronil and its photodegradation product fipronil desulfinyl. Fipronil desulfinyl was detected in the eggs of the decapod Callinectes sapidus sampled off the coast of South Carolina. As such, to examine specific effects on C. sapidus exposed in early life, we exposed laboratory-reared juveniles to fipronil and fipronil desulfinyl for 96h at three nominal concentrations (0.01, 0.1, 0.5µg/l) and two different salinities (10, 30ppt). The size of individual crabs (weight, carapace width) and the expression of several genes critical to growth and reproduction were evaluated. Exposure to fipronil and fipronil desulfinyl resulted in significant size increases in all treatments compared to controls. Levels of expression for vitellogenin (Vtg), an egg yolk precursor, and the ecdysone receptor (EcR), which binds to ecdysteroids that control molting, were inversely correlated with increasing fipronil and fipronil desulfinyl concentrations. Effects on overall growth and on the expression of EcR and Vtg differ depending on the exposure salinity. The solubility of fipronil is demonstrated to decrease considerably at higher salinities. This suggests that fipronil and its photodegradation products may be more bioavailable to benthic organisms as salinity increases, as more chemical would partition to tissues. Our findings suggest that endocrine disruption is occurring through alterations to gene expression in C. sapidus populations exposed to environmental levels of fipronil, and that effects may be dependent upon the salinity at which exposure occurs.

Assessing the hydroxyl radical and volatilization roles in aquatic fate estimations of sulfur heterocycles: Dibenzothiophene derivatives.

Polycyclic aromatic sulfur heterocycles (PASHs) and their alkyl derivatives can be released into aquatic systems via crude oil spills or runoff from petroleum-treated areas, such as asphalt. Dibenzothiophene (DBT) and its derivatives (C1-DBT, C2-DBT, and C4-DBT) were chosen as model compounds to investigate the relative impact of volatilization and hydroxyl radical degradation on estimates of their overall dissipation after entry into aquatic ecosystems as a function of depth using the exposure analysis modeling system (EXAMS). The hydroxyl radical rate constant (K · OH ) and Henry's law constant of PASHs were determined in distilled water. The analogue C1-DBT reacted fastest with · OH relative to other PASHs. The C2-DBT and C4-DBT analogues had higher Henry's law constants compared with other derivatives. Steric hindrance by alkyl substituents on the sulfur moiety most strongly impacted measured rate and Henry's law constants between DBT and individual alkyl derivatives. These steric effects do not appear to be considered in the physical property estimation software EPI Suite. Simulated dissipation of PASHs using EXAMS suggests that volatilization is a dominant fate pathway for the higher molecular weight and less polar C2-DBT and C4-DBT at all depths and DBT and C1-DBT at 0.1-m. However, model scenarios suggest that hydroxyl radical degradation may significantly contribute to the degradation of more polar DBT and C1-DBT at 1-m and 2-m depths. Environ Toxicol Chem 2017;36:1998-2004. © 2017 SETAC.

Organic contaminants of emerging concern in sediments and flatfish collected near outfalls discharging treated wastewater effluent to the Southern California Bight.

To investigate the occurrence and bioaccumulation of organic contaminants of emerging concern (CECs) near four major wastewater ocean outfalls in the Southern California Bight, more than 75 pharmaceutical and personal care products, current-use pesticides, and industrial/commercial chemicals were analyzed in sediment and liver tissues of hornyhead turbot (Pleuronichthys verticalis) using gas and liquid chromatography-mass spectrometry. Although most CECs targeted were infrequently detected or not detectable, triclosan, 4-nonylphenol (4-NP) and bis(2-ethylhexylphthalate) were detected in all sediments at median (maximum) concentrations of 5.1 (8.6), 30 (380), and 121 (470) µg/kg, respectively. In the liver, 4-NP and polybrominated diphenyl ether (PBDE) congeners 47 and 99 were detected in >90% of samples at median (maximum) concentrations of 85 (290) and 210 (480) µg/kg, respectively. The sedative diazepam was detected in all liver samples, but was infrequently detected in sediments. Sediment and liver concentrations across outfall locations ranged over several orders of magnitude and were elevated relative to a reference site. Relative to sediment, accumulation in liver of PBDEs 47 and 99 was comparable to that for legacy organochlorines, confirming their high bioaccumulation potential and suggesting their inclusion in future tissue monitoring studies. Mean tissue PBDE and diazepam concentrations were higher in livers from male versus female P. verticalis, suggesting that gender differences also be considered in designing such studies.

Transformation of triclosan and triclocarban in soils and biosolids-applied soils.

Triclosan (TCS) and triclocarban (TCC), widely used as antibacterial agents, have been frequently detected in biosolids. Biosolids land application may introduce pharmaceuticals and personal care products (PPCPs) such as TCS and TCC into the environment. Microcosm studies were conducted to investigate TCS and TCC transformation in Marietta fine loam and McLaurin coarse loam. Both compounds were spiked into the soils with and without biosolids amendment under non-sterilized and sterilized conditions and incubated aerobically at 30 degrees C for up to 100 d. In both soils, transformation of TCS followed second-order reaction kinetics, with estimated reaction rate constants of (5.27 +/- 0.920) x 10(-1) and (9.13 +/- 1.58) x 10(-2) (mg kg(-1))(-1) d(-1) for Marietta fine loam and McLaurin coarse loam, respectively. Transformation of TCC in both soils was slower than that for TCS. After 100 d, 53 +/- 1% and 71 +/- 2% of the initially added TCC and only 2.8 +/- 0.35% and 6.2 +/- 0.80% of initially added TCS remained in Marietta fine loam and McLaurin coarse loam, respectively. The transformation of both compounds were faster in the Marietta fine loam (pH 7.8; 1.8% organic matter) than in the McLaurin coarse loam (pH 4.7; 0.65% organic matter). Our result suggests that biotic processes are more of a controlling factor affecting TCS transformation, whereas abiotic processes may affect TCC transformation more significantly. Addition of biosolids to the two soils slowed the transformation of both compounds, indicating interactions between both compounds and biosolids may adversely affect their transformation in soils, an important factor that must be included in models predicting environmental fate of biosolids-associated PPCPs.

Assessment of the toxicological interaction of sertraline with cholinesterase inhibiting insecticides in aquatic insects using the black fly, Simulium vittatum IS-7.

Sertraline is a selective serotonin reuptake inhibitor (SSRI) prescribed as an antidepressant. Although SSRIs are known to block serotonin reuptake sites on cell membranes, they also have been shown to inhibit acetylcholinesterase (AChE) activity. Thus, the interaction of these chemicals with other AChE inhibitors, namely, organophosphate and carbamate insecticides, is of interest. In addition, these insecticides have been shown to interact with serotonergic neuronal pathways creating questions as to how these chemicals might interact. In this study, the interactive effect of sertraline (SSRI) in binary combinations with carbaryl (carbamate insecticide) and diazinon (organophosphate insecticide) was assessed using a 48-h acute toxicity test with black fly larvae, Simulium vittatum IS-7. Results showed that observed mortality was bracketed by the independent action model and concentration addition model with the independent action model slightly underestimating mortality and the concentration addition model slightly overestimating mortality. Varying the concentration of the chemicals in the mixture did not indicate that sertraline was interacting with the insecticides to make them more toxic or vice versa. These results indicate that sertraline and the insecticides are likely eliciting toxicity at separate neuronal pathways since no interaction was observed.

Growth and development of tadpoles (Xenopus laevis) exposed to selective serotonin reuptake inhibitors, fluoxetine and sertraline, throughout metamorphosis.

Selective serotonin reuptake inhibitors (SSRIs) are widely prescribed drugs that are present in sewage effluents and surface waters. The objective of the present study was to determine whether low environmentally relevant concentrations of the SSRIs fluoxetine and sertraline could impair growth and development in tadpoles of the African clawed frog (Xenopus laevis) and to evaluate if such effects may be caused by a disruption of the neuroendocrine system. Tadpoles were exposed to SSRIs at concentrations of 0.1, 1, and 10 microg/L for 70 d throughout metamorphosis. No effects on deformities were observed. Tadpoles exposed to fluoxetine (10 microg/L) and sertraline (0.1, 1, and 10 microg/L) exhibited reduced growth at metamorphosis. Tadpoles exposed to sertraline (0.1 and 1 microg/L) exhibited an acceleration of development as indicated by an increase in the time to tail resorption. The effects of SSRIs on growth and development in tadpoles were likely driven by reduced food intake. Reduced feeding rates were observed in SSRI-exposed tadpoles, and nutritional status can influence growth and development in amphibians via effects on the neuroendocrine system. Only sertraline was capable of causing developmental toxicity in tadpoles at environmentally relevant concentrations. These data warrant additional research to characterize the risks to human health and wildlife from pharmaceutical exposures.

Determination of 17alpha-ethynylestradiol, carbamazepine, diazepam, simvastatin, and oxybenzone in fish livers.

A method using liquid chromatography/tandem mass spectrometry (LC/MS/MS) was developed for the determination of 17alpha-ethynylestradiol in fish liver; a second method using LC/MS was developed for the determination of carbamazepine, diazepam, simvastatin, and oxybenzone in fish liver. The fish liver samples were extracted and cleaned up by using liquid-liquid extraction and solid-phase extraction before the extracts were analyzed by LC/MS or LC/MS/MS with electrospray negative and positive ionization. Recoveries of the 5 target compounds from spiked catfish liver ranged from 72 +/- 2 to 100 +/- 3%. Limits of quantification for the 5 compounds were between 4.2 and 12.3 ng/g (wet weight). Ten turbot (Pleuronichthys verticalis) liver samples were analyzed; levels of 17alpha-ethynylestradiol, carbamazepine, simvastatin, and oxybenzone were below the detection limits. Diazepam was detected in all 10 fish liver samples at concentrations ranging from 23 to 110 ng/g (wet weight).

Aqueous solubility, n-octanol-water partition coefficient, and sorption of five selective serotonin reuptake inhibitors to sediments and soils.

Aqueous solubilities (S (w)) and n-octanol-water partition coefficients (K (ow)) of five selective serotonin reuptake inhibitors (SSRIs) were measured and sorption to two sediments and three soils with organic matter contents ranging from 0.16% to 1.77% and pH ranging between 5.0 and 7.8 was investigated using a batch equilibrium method. SSRIs had high S (w) (3,022-15,460 mg/l) and relatively low log K (ow) (1.12-1.39). Sorption isotherms followed the Freundlich equation. All SSRIs had sorption capacities of greater than 91% except fluvoxamine with a minimum capacity of 73%. Organic matter contents partly affected sorption, however no correlation between sorption characteristics and cation exchange capacity (CEC) or clay content was observed for any SSRI or adsorbent. Values of K (f), K (d), and log K (oc) ranged from 39 to 18,342, from 60 to 42,579, and 3.35 to 6.02 for the SSRIs. SSRIs likely exhibit mixed mechanisms of sorption such as ionic binding in addition to hydrophobic interactions.

Laboratory persistence and fate of fluoxetine in aquatic environments.

The persistence and fate of fluoxetine, a selective serotonin reuptake inhibitor, has been investigated in laboratory-scale experiments, including studies with various aqueous solutions, water/sediment systems, and activated sludge-amended medium. The samples were placed in the dark and/or in a growth chamber fitted with fluorescent lamps simulating the ultraviolet output of sunlight. Over a period of 30 d, fluoxetine was hydrolytically and photolytically stable in all aqueous solutions except synthetic humic water (pH 7), in which the degradation rate was increased by approximately 13-fold in comparison with buffered solutions at the same pH. Fluoxetine rapidly dissipated from the aqueous phase in water/sediment systems, primarily because of distribution to sediments. The dissipation rate from the aqueous phase was similar between light and dark systems, indicating a low contribution of photodegradation to the dissipation of fluoxetine in this system. The potential impact of fluoxetine in aquatic environments would be decreased because of adsorption to sediments. Based on results of ready-biodegradability investigations, fluoxetine would not be expected to rapidly biodegrade in wastewater treatment plants. A photoproduct was detected only in a sample of synthetic humic water and was identified as norfluoxetine formed by demethylation. Results indicate that fluoxetine is relatively recalcitrant to hydrolysis, photolysis, and microbial degradation and that it is rapidly removed from surface waters by adsorption to sediment, where it appears to be persistent.