Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Fate of hydrophobic organic pollutants in the aquatic environment: a review

The fate of hydrophobic organic pollutants in the aquatic environment is controlled by a variety of physical, chemical and biological processes. Some of the most important are physical transport, chemical and biological transformations, and distribution of these compounds between the various environmental compartments (atmosphere, water, sediments and biota). The major biogeochemical processes that control the fate of hydrophobic organic compounds in the aquatic environment are reviewed. These processes include evaporation, solubilization, interaction with dissolved organic matter, sediment-water partitioning, bioaccumulation and degradation. Physico-chemical parameters used to predict the aquatic fate of such compounds are also discussed.     

Photolysis of beta-blockers in environmental waters

Many drugs such as beta-blockers have been shown to occur in aquatic environments. Even if adequate ecotoxicity data are not available, it is of primary importance to get informations about their fate in environmental waters, particularly about their photofate in sewage treatment plant effluents (STP). The main difficulties when studying pharmaceutical photochemical behaviour in environmental waters, are linked to the very low environmentally relevant concentrations (ng L(-1) to microg L(-1)) which can generate problems in terms of analytical sensitivity. Moreover, the complexity of environmental matrices can modify micropollutants degradation kinetics. The photodegradation of beta-blockers has been compared at two concentration levels (10 microg L(-1) and 10 mg L(-1)) and in two different matrices (pure water and STP effluent). It has been shown that the concentration does not influence beta-blockers degradation pathways, thus allowing the identification of degradation compounds using the 10 mg L(-1) solutions. Although environmental waters speed up the degradation process, the same photoproducts were appeared in both matrices. Using LC-MS/MS, hydroxyl radical additions have been identified as an important degradation pathway for especially pindolol, propranolol and timolol, leading to several positional isomers, corresponding to mono-, di- or tri-hydroxylations. Kinetics of appearance/disappearance of these photoproducts have been studied in STP effluents.     

Occurrences and potential risks of 16 fragrances in five German sewage treatment plants and their receiving waters

Fragrances are used in a wide array of everyday products and enter the aquatic environment via wastewater. While several musk compounds have been studied in detail, little is known about the occurrence and fate of other fragrances. We selected 16 fragrance compounds and scrutinized their presence in Bavarian sewage treatment plants (STP) influents and effluents and discussed their ecological risks for the receiving surface waters. Moreover, we followed their concentrations along the path in one STP by corresponding time-related water sampling and derived the respective elimination rates in the purification process. Six fragrance substances (OTNE, HHCB, lilial, acetyl cedrene, menthol, and, in some grab samples, also methyl-dihydrojasmonate) could be detected in the effluents of the investigated sewage treatment plants. The other fragrances under scrutiny were only found in the inflow and were eliminated in the purification process. Only OTNE and HHCB were found in the receiving surface waters of the STP in congruent concentrations, which exceeded the preliminary derived environmental thresholds by a factor of 1.15 and 1.12, respectively, indicating potential risks. OTNE was also detected in similar concentration ranges as HHCB in muscles and livers of fish from surface waters and from ponds that are supplied with purified wastewater. The findings show that some fragrance compounds undergo high elimination rates, whereas others—not only musks—are present in receiving surface water and biota and may present a risk to local aquatic biota. Hence, our results suggest that the fate and potential effects of fragrance compounds in the aquatic environment deserve more attention.     

An examination of the physical properties,fate, ecotoxicity and potential environmental risks for a series of propylene glycol ethers

Propylene glycol ethers (PGEs) are comprised of mono-, di- and tri-PGEs and several of their acetate esters. The nature of the range of applications that use PGEs suggests that there is a potential for both intentional and unintentional entry of the materials into the environment. Selected physical/chemical properties, fate characteristics, aquatic toxicity data and calculated environmental concentrations were used to assess potential risks from the manufacture, handling, use, and disposal of PGEs. In general, the PGEs are low to moderately volatile, have high aqueous solubilities, low octanol-water partition coefficients (Kow), and bioconcentration factor values of <10, which indicate they are unlikely to accumulate in aquatic food chains. Both abiotic and biological degradation processes reduce environmental concentrations of PGEs. In air, vapor-phase PGEs react with photo-chemically produced hydroxyl radicals and have half-lives ranging from 5.5 to 34.4 h. A variety of ready and inherent biodegradation test methods, as well as tests that simulate biodegradation in wastewater treatment plants, surface water and soil have been conducted on PGEs. Significant aerobic biodegradation was generally observed, with a range of biodegradation half-lives on the order of 5-25 d. Acute aquatic toxicity studies with PGEs resulted in LC50 values ranging from approximately >100 to >20,000 mg/l for freshwater fish, the pelagic invertebrate Daphnia magna, green algae Selenastrum capricornutum (now called Pseudokirchneriella capricornutum) and bacteria. Level 3 multi-media modeling (EQC model of Mackay) was used to simulate regional-scale concentrations of PGEs in air, soil, water, and sediment. Toxicity thresholds were then compared with regional-scale water, soil and sediment concentrations to determine hazard quotients. Based upon this analysis, concentrations of PGEs are unlikely to pose adverse risks to the environment.     

Assessment of the environmental fate and effects of the PPARgamma receptor agonist, pioglitazone

The environmental fate and effects of pioglitazone prescribed for the treatment of type 2 diabetes were evaluated in an environmental risk assessment following the European Medicines Agency (EMA) "Guideline on the Environmental Risk Assessment of Medicinal Products for Human Use"; EMEA/CHMP/SWP/4447/00. A predicted environment concentration (PEC) for surface water was estimated at 0.023μgL(-1), (action limit of 0.01μgL(-1)) triggering a comprehensive battery of laboratory evaluations. Pioglitazone and its major metabolites were determined not to significantly adsorb to sewage solids, were not persistent in the aquatic environment, did not bioaccumulate and were non-toxic to aquatic organisms. Pioglitazone does not pose an unacceptable risk to groundwater supplies, with concentrations not anticipated to be a risk to aquatic organisms or human drinking water supplies. Pioglitazone does not pose a risk of secondary poisoning.     

Do tubificid worms influence the fate of organic matter and pollutants in stormwater sediments?

In urban area, management of stormwater leads to the accumulation of polluted sediments at the water-sediment interface of various aquatic ecosystems. In many cases, these sediments are colonised by dense populations of tubificid worms. However, the influence of tubificid worms on the fate of stormwater sediments has never been tackled. The aim of this study was to measure in sediment columns the influence of tubificid worms on sediment reworking, organic matter processing (O(2) uptake and release of NH(4)(+), NO(3)(-), PO(4)(3-), and dissolved organic carbon), release of hydrocarbons and heavy metals, and microbial characteristics. Results showed that tubificid worms increased the release of NH(4)(+), PO(4)(3-), and dissolved organic carbon by 2-, 4-, and 3-fold, respectively. O(2) uptake also increased by more than 35% due to tubificid activity. The increase in the percentages of active bacteria and hydrolytic activity in the presence of worms indicated that the higher sediment respiration was caused by the stimulation of microbial communities. A reduction of the number of sulphate-reducing bacteria in the uppermost layers of the sediment was attributed to the penetration of O(2) due to worm activity. These significant effects of tubificid worms were probably linked to the dense network of burrows, which enhanced the exchange surface between the water column and the sediment. No release of heavy metals and hydrocarbons to the water phase was detected in the sediment columns. Understanding the fate and effect of organic stormwater sediments in the natural environment requires the integration of the role of bioturbation in urban pollution studies.     

Microbial ecotoxicity and mutagenicity of 1-hydroxypyrene and its photoproducts.

1-Hydroxypyrene (1-HP) is a carcinogenic and slightly water-soluble polycyclic aromatic hydrocarbon. Ecotoxicity and mutagenicity of 1-HP and its photoproducts, and the effect of Mn2+ and Cu2+ on their mutagenicity were measured with microbial assay in this study. The assay includes spread plate counting, direct counting, microbial mineralization of 14C-UL-D-glucose and Mutatox Test. At the concentration examined (0.8 microM), the photoproducts (after 1.5 h solar irradiation) of 1-HP inhibited microbial glucose mineralization activity (by 64%) after microbial assemblages of a local reservoir site were exposed for 1 day. However, heterotrophic bacteria were able to utilize 1-HP photoproducts as the growth substrates and increase viability counts by up to 4.75-folds. 1-HP exhibited positive response to Mutatox Test in both direct medium and S-9 medium, with the lowest observable effective concentration of 0.625 microM in the test with direct medium. After photolysis, 1-HP decreased its mutagenicity. Mn2+ (312.5 microM-5 mM) and Cu2+ (6.25-100 microM) themselves are not mutagenic. However, addition of the metal ions before or after photolysis modifies the light readings of 1-HP during the test. Therefore, presence of metal ions could affect the genotoxicity of 1-HP in aquatic environments, depending on timing of the addition.     

Biodegradability of some antibiotics, elimination of the genotoxicity and affection of wastewater bacteria in a simple test

Most antibiotics and their metabolites are excreted by humans after administration and therefore reach the municipal sewage with the excretions. Only little is known about their biodegradability in aquatic environments. It was recognised that genotoxic substances may represent a health hazard to humans but also may affect organisms in the environment. Therefore, the biodegradability of some clinically important antibiotic drugs (ciprofloxacin, ofloxacin, metronidazole) and hereby the elimination of their genotoxicity was investigated as the first step of an environmental risk assessment using the Closed Bottle test (CBT) (OECD 301 D) and the SOS chromotest. Additionally, to assess toxicity of the antibiotics tested against aquatic bacteria (i) a growth inhibition test (GIT) with Pseudomonas putida was conducted, (ii) a toxicity control was used in the CBT and (iii) the colony forming units (CFUs) were monitored in the test vessels. Worst case concentrations of the antibiotics in hospital effluents were estimated and compared with minimum inhibitory concentrations for susceptible pathogenic bacteria and with the genotoxic potency in the SOS chromotest. Both the concentrations calculated for hospital effluents and the adverse effects in bacteria were in the same order of magnitude. None of the test compounds were biodegraded. The genotoxicity was not eliminated.     

Phototransformation products of tamoxifen by sunlight in water. Toxicity of the drug and its derivatives on aquatic organisms

Transformation of tamoxifen has been observed in water by prolonged sunlight irradiation. The main photoproducts, isolated by chromatographic techniques, have been identified by spectroscopic means. Photoisomerization, photocyclization and, to a lesser extent, photooxygenation appear to be involved in the degradation of the drug. The acute and chronic toxicity of the parent drug and its photoproducts were tested on non-target aquatic organisms (Brachionus calyciflorus, Thamnocephalus platyurus, Daphnia magna and Ceriodaphnia dubia). Exposure to all the compounds induced mainly chronic effects without significant differences among the parental and derivative compounds.     

Review of recent advances in research on the toxicity,detection, occurrence and fate of cyclic volatile methyl siloxanes in the environment

The fate and behavior of cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in the environment were reviewed. We evaluated their usage data and patterns, physico-chemical properties, toxicology, partitioning and degradation, methods of detection, and concentrations. The use of cVMS as an intermediate in the formation of silicone polymers, personal care and household products has resulted in their widespread environmental exposure; they have been detected in biogas, air, water, soil, biosolid, sediment, and biota samples. Modeled and experimental results suggest that cVMS may be subject to long-range atmospheric transport, but have low potential to contaminate the Arctic. For D4 and D5, there was no evidence of trophic biomagnification in aquatic food webs, while some aquatic organisms demonstrated a high degree of bioconcentration and bioaccumulation. High concentrations of cVMS observed in indoor air and biosolids resulted from point sources. Concentrations of cVMS in water, sediment, and soil were all below their no-observed-effect-concentrations.     

Fate, effects and potential environmental risks of ethylene glycol: a review

The fate, effects, and potential environmental risks of ethylene glycol (EG) in the environment were examined. EG undergoes rapid biodegradation in aerobic and anaerobic environments (approximately 100% removal of EG within 24 h to 28 days). In air, EG reacts with photo-chemically produced hydroxyl radicals with a resulting atmospheric half-life of 2 days. Acute toxicity values (LC(50)s and EC(50)s) were generally >10,000 mg/l for fish and aquatic invertebrates. The data collectively show that EG is not persistent in air, surface water, soil, or groundwater, is practically non-toxic to aquatic organisms, and does not bioaccumulate in aquatic organisms. Potential long-term, quasi-steady state regional concentrations of EG estimated with a multi-media model for air, water, soil, and sediment were all less than predicted no effect concentrations (PNECs).     

The toxicity of antibiotic agents to the luminescent bacterium Vibrio fischeri.

Despite their common use the fate and effects of antibiotics in the environment are largely unknown. These compounds may enter the environment through different pathways, resulting in the contamination of waste water or fresh water, where bacteria are most likely the primarily affected organisms. In this paper the toxicity of several drugs, reflecting the most important groups of antibiotics and chemotherapeutics, towards Vibrio fischeri are presented. The chronic bioluminescence inhibition assay with Vibrio fischeri is shown to be sensitive against many of the high volume antibiotics used for veterinary purposes and in aquaculture. Thus the assay may be a valuable tool for an effects assessment and biomonitoring of these xenobiotics. The available data for both parts of the risk assessment procedure--exposure assessment and effects assessment--have to be regarded as insufficient for most antibiotics. When the available data about environmental concentrations of antibiotics are compared with their toxicity towards Vibrio fischeri, direct effects on natural microbial communities are to be expected.     

Photolysis of fluometuron in the presence of natural water constituents

Phototransformation of the herbicide fluometuron (1 microM) in natural sunlight was investigated in neutral Milli-Q water and in synthetic waters containing either fulvic acids, nitrate ions or both in order to mimic reactions taking place in aquatic environments. Fluometuron degradation followed a pseudo-first order kinetics. The reaction was faster in synthetic than in Milli-Q water. Fulvic acids (10 mg l(-1)) increased the rate of fluometuron photolysis by a factor 2.5 and nitrates (25 mg l(-1)) by a factor 15. Identification of major photoproducts was conducted under laboratory conditions using LC-ESI-MS. Numerous photoproducts were detected and tentatively characterized. In the presence of nitrates, hydroxylation of the aromatic ring with or without hydrolysis of CF(3) into CO(2)H and oxidation of the urea chain leading to demethylation were observed. In the presence of fulvic acids, hydroxylation of the aromatic ring was the major reaction route.     

Colloids as a sink for certain pharmaceuticals in the aquatic environment

Background, aim, and scope  

The occurrence and fate of pharmaceuticals in the aquatic environment is recognized as one of the emerging issues in environmental chemistry and as a matter of public concern. Existing data tend to focus on the concentrations of pharmaceuticals in the aqueous phase, with limited studies on their concentrations in particulate phase such as sediments. Furthermore, current water quality monitoring does not differentiate between soluble and colloidal phases in water samples, hindering our understanding of the bioavailability and bioaccumulation of pharmaceuticals in aquatic organisms. In this study, an investigation was conducted into the concentrations and phase association (soluble, colloidal, suspended particulate matter or SPM) of selected pharmaceuticals (propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid) in river water, effluents from sewage treatment works (STW), and groundwater in the UK.     

Removal of sulfadimethoxine in soil mediated by extracellular oxidoreductases

Sulfadimethoxine (SDM) is an antibiotic commonly used in concentrated animal feeding operations and released into the environment via manure application on agricultural lands. Transformation of antibiotics in soil impacts the likelihood of their entry to water bodies, uptake by plants, and thus their effect on terrestrial and aquatic organisms. We conducted experiments to incubate SDM in a sandy loam soil in the presence of humification enzymes commonly found in natural soil, laccase, horseradish peroxidase, and lignin peroxidase. Incubation with the enzymes led to significant reduction in the fraction of SDM extractable from soil, indicating the formation of bound residues. Such transformation was enhanced when the organic matter content in soil is increased or when certain chemical mediators were used along with laccase. The study provided a basis for understanding the environmental fate of sulfonamides and help with the development of remediation methods to mitigate the release of sulfonamides from soil to water.     

Pesticide fate in tropical wetlands of Brazil: an aquatic microcosm study under semi-field conditions

A contamination of off-site aquatic environments with pesticides has been observed in the tropics, yet only sparse information exists about pesticide fate in such ecosystems. The objective of our semi-field study was to elucidate the fate of alachlor, atrazine, chlorpyrifos, endosulfan, metolachlor, profenofos, simazine, and trifluralin in the aqueous environment of the Pantanal wetland (MT, Brazil). To this aim, water and water/sediment microcosms of two sizes (0.78 and 202 l) were installed in the outskirts of this freshwater lagoon environment and pesticide dissipation was monitored for up to 50 d after application. The physical-chemical water conditions that developed in the microcosms were reproducible among field replicates for both system sizes. Pesticide dissipation was substantially enhanced for most pesticides in small microcosms relative to the large ones (reduced DT(50) by a factor of up to 5.3). The presence of sediment in microcosms led to increased persistence of chlorpyrifos, endosulfan, and trifluralin in the test systems, while for polar pesticides (alachlor, atrazine, metolachlor, profenofos, and simazine) a lesser persistence was observed. Atrazine, simazine, metolachlor, and alachlor were identified as the most persistent pesticides in large water microcosms (DT(50) > or = 47 d); in large water/sediment systems endosulfan beta, atrazine, metolachlor, and simazine showed the slowest dissipation (DT(50) > or = 44 d). A medium-term accumulation in the sediment of tropical ecosystems can be expected for chlorpyrifos and endosulfan isomers (11-35% of applied amount still extractable at 50 d after application). We conclude that the persistence of the studied pesticides in aquatic ecosystems of the tropics is not substantially lower than during summer in temperate regions.     

An environmental fate, exposure and risk assessment of ethylene oxide from diffuse emissions

Ethylene oxide (EO) is mainly used as a chemical intermediate and as a fumigant and sterilizing agent. Through its manufacturing and intended uses, EO may be released into the environment. Therefore, an assessment of the environmental significance of those potential emissions was conducted. Data were collected describing pertinent physical properties, degradation and other loss mechanisms that control the fate of EO in the environment. Available aquatic and terrestrial ecotoxicity data were assembled and used as the basis of calculating critical toxicity values to characterize hazard. Environmental compartment concentrations of EO were calculated using Level III fugacity-based modeling. Six scenarios were developed to account for different climatic conditions in various portions of the US. Finally, potential regional-scale risks to aquatic and terrestrial wildlife were determined. In the conceptual model that was developed in this assessment, EO diffuses into air, partitions between environmental compartments, is transported out of the different compartments via advection, and undergoes abiotic and biological degradation within each compartment. All known emissions within the continental USA were assumed to enter a modeled region roughly the size of the State of Ohio. Organisms (receptors) were assumed to dwell in both terrestrial and aquatic compartments. Receptors were assumed to include small mammals, soil invertebrates, water column (pelagic) organisms, and sediment benthos. The goal of this assessment was to characterize any potential adverse risks to terrestrial and aquatic wildlife populations. Hazard Quotients (HQ) were calculated by dividing predicted concentrations of EO in air, water, sediment, and soil by their critical toxicity values. Maximum calculated HQ values in air were 1.52x10(-7), in water were 1.17x10(-5), in sediment were 2.25x10(-4), and in soil were 1.37x10(-5). The results of this assessment suggest that EO as currently manufactured and used does not pose adverse risks to aquatic or terrestrial wildlife. In all cases, the HQ values were much less than the maximum desired HQ value of 1.0 (4,400-6,600,000 times), indicating that the potential for diffuse emissions of EO to pose adverse environmental risks is quite low.     

Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).     

Gram-negative bacteria responsible for insoluble technetium formation and the fate of insoluble Tc in the water column above flooded paddy soil

We studied the characteristic gram-stain of Tc insolubilizing bacteria using various antibiotics, and the fate of insoluble Tc in a water column above flooded paddy soil to clarify Tc behavior in paddy fields. The formation of insoluble Tc in water column samples was inhibited by the addition of antibiotics, especially reagents against gram-negative bacteria. For a sample without antibiotics, insoluble Tc formation increased with time, and the maximum amount of insoluble Tc was observed on day 4 of incubation with (95m)Tc. In contrast, concentrations of ferrous ion decreased with time. These results suggested that gram-negative bacteria were mainly responsible for insoluble Tc formation, and that these bacteria were able to transform soluble Tc to insoluble forms under oxidizing conditions.