Selected Transformation Products Research Articles

Cardiovascular Drugs as Water Contaminants and Analytical Challenges in the Evaluation of Their Degradation

Cardiovascular drugs have been a burning topic in the field of environmental analytical chemistry in the last few decades. Growing modern healthcare has led to the widespread use of pharmaceuticals. Among these, antihypertensives (sartans, angiotensin-converting enzyme inhibitors) and lipid-regulating drugs (fibrates and statins) are the most frequently consumed and, thus, excreted into wastewater. Their chemical fate during conventional and advanced wastewater treatment, such as ozonation, remains unclear. Analytical chemistry, providing sample pretreatment followed by instrumental analysis, has a tremendous role in water treatment evaluation, mostly from the perspective of parent contaminants’ removals and also assessment of transformation pathways. Ultrasensitive liquid chromatography–mass spectrometry (LC-MS) systems provide many opportunities. By carefully using planned workflows for chromatographic and mass-spectrometric data processing, i.e., suspect and non-target screening approaches, LC-MS allows for the identification and structural elucidation of unknown, predicted, suspected or selected transformation products. Accordingly, some examples and case studies on selected cardiovascular drugs in this review are presented to show the applicability of the used analytical approaches and workflows.

The Impact of Weather Conditions on Biocides in Paints.

Weather conditions affect biocides on exposed outer surfaces on constructions. Contact with water causes hydrolysis and leaching of substances. Ultraviolet radiation may induce photolysis. As a result, a mixture of biocidal active substances and transformation products can be emitted into the environment. In a semi-field study, leaching of the biocidal active substances terbutryn, diuron, octylisothiazolinone, carbendazim, and selected transformation products was observed for two paints containing either a white or a red pigment. Painted test panels were exposed to natural weathering for about 1.5 years. Runoff samples were analyzed during the course of the experiment. At the end of the study, residues of biocidal active substances and transformation products were determined in sections of the test panels. Emissions of substances were mainly observed during the first few months of the experiments. Increased emissions of transformation products were observed during periods of increased global radiation and subsequent periods with relatively high amounts of driving rain. Different patterns of transformation products were observed, especially for terbutryn, both for paints containing different pigments and in experiments that were started in different periods of the year, as well as during different periods of the experiments.

Occurrence and ecological risk assessment of neonicotinoids and related insecticides in the Bohai Sea and its surrounding rivers, China

Systemic insecticides like neonicotinoids and the phenylpyrazole insecticide fipronil are the most widely applied insecticides around the world. Multiple studies analyzed insecticide residues in freshwater systems, but data on seawater contamination levels are scarce. This study investigates the spatiotemporal distribution and ecological risk assessment of fipronil, neonicotinoids, sulfoxaflor and selected transformation products (TPs) in the Chinese Bohai Sea and its surrounding rivers. Well-established neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid and thiamethoxam) and TPs of fipronil and imidacloprid were frequently detected (detection frequency (DF): 42-100%) in freshwater. The median total insecticide concentration in freshwater was significantly higher in summer (72.4 ng•L-1) than in fall (23.4 ng•L-1), with major contributions from neonicotinoids, suggesting that pollution originates mostly from diffuse sources. In 2018, acetamiprid, desnitro-imidacloprid, fipronil-desulfinyl and thiacloprid were abundant in seawater (DF: 47–100%), indicating a high stability of acetamiprid and thiacloprid and a rapid photodegradation of fipronil and imidacloprid in surface waters. These results indicate that the continued use of these parent compounds may lead to their accumulation and/or of their TPs in shallow coastal seas. Consequently, this may lead to their transport to open seas, increasing their potential risk to marine organisms. Similarities between contaminant fingerprints in freshwater and seawater strongly suggest riverine discharges as main pollution source of adjacent coastal areas. This is the first study to perform an ecological risk assessment of fipronil, neonicotinoids, sulfoxaflor and selected TPs on marine ecosystems. Fipronil and its TPs demonstrated to be environmentally relevant with potential high risks for aquatic species. Our study provides novel insights into the fate and ecological risk of fipronil, neonicotinoids, sulfoxaflor and their TPs to marine species in shallow coastal seas.

Selected transformation products of neonicotinoid insecticides (other than imidacloprid) in drinking water

Several transformation products (or metabolites) of neonicotinoid insecticides (NNIs) have been detected in drinking water, such as desnitro-imidacloprid and imidacloprid-urea. However, data on the occurrences of the metabolites of NNIs (mNNIs) in drinking water are mainly limited to the imidacloprid metabolites. To identify whether the potential metabolites of other widely used NNIs (such as acetamiprid, clothianidin, and thiamethoxam) occur in drinking water and to characterize their distribution profiles, twelve selected (mainly urea and desnitro/decyano) metabolites of NNIs were measured in drinking water samples (n = 884, including n = 789 for tap water, and n = 95 for shallow groundwater) that were collected from 32 provinces in mainland China and Hong Kong. Nearly 90% of the drinking water samples contained the detected mNNI residues. Among the selected mNNIs, thiamethoxam-urea (THM-urea: 76%) and decyano-acetamiprid (decyano-ACE: 73%) were frequently detected (median: 0.94 and 0.25 ng/L, respectively), which were followed by clothianidin-urea (CLO-urea: 45%), desnitro-thiamethoxam (DN-THM: 38%), and other mNNIs (detected in less than 30% of the water samples). Surface-water-sourced tap water had an approximately 8–10 times higher median cumulative concentration (ng/L) of the selected mNNIs (ΣmNNIs: 3.88) than the deep groundwater-sourced tap water (0.53) and groundwater that was directly used as drinking water (0.38). Higher ratios of THM-urea accounted for ΣTHM in north and northwest China than in south China could be partly explained by the decreasing soil pH values from north to south in China. The higher ratios of decyano-ACE accounted for ΣACE in south China than in north and northwest China could be attributable to the lower soil pH levels, higher temperatures, and greater light intensities in south China. The THM-urea, decyano-ACE, and ΣmNNIs levels in cities were found to be significantly higher than those in nonurban areas. The THM-urea levels in seven drinking water samples from Guangxi and Henan Provinces exceeded the guideline limit (100 ng/L) of the European Union. This is the first study to identify THM-urea, decyano-ACE, CLO-urea, and DN-THM in drinking water. To better assess the mass loadings of NNIs in drinking water, mNNIs should be considered in further studies.

Leaching and Transformation of Film Preservatives in Paints Induced by Combined Exposure to Ultraviolet Radiation and Water Contact under Controlled Laboratory Conditions

Stormwater from urban areas can transport biocidally active substances and related transformation products from buildings into the environment. The occurrence of these substances in urban runoff depends on the availability of water, and on ultraviolet radiation exposure that causes photolytic reactions. In a systematic laboratory study, painted test specimens were exposed to either ultraviolet radiation, water contact, or a combination of both. Leaching of the biocidally active substances carbendazim, diuron, octylisothiazolinone, terbutryn, and selected transformation products of terbutryn and diuron were observed under various exposure conditions. Remaining concentrations of these substances in the paint were quantified. It was demonstrated that the distribution of active substances and transformation products in eluates and in the coatings themselves differs with exposure conditions. Strategies for environmental monitoring of biocide emissions need to consider the most relevant transformation products. However, environmental concentrations of biocidally active substances and transformation products depend on earlier exposure conditions. As a consequence, monitoring data cannot describe emission processes and predict expected leaching of biocidally active substances from buildings if the data are collected only occasionally.

Microalgae-based removal of contaminants of emerging concern: Mechanisms in Chlorella vulgaris and mixed algal-bacterial cultures

Incomplete removal of contaminants of emerging concern (CECs) has been reported for conventional wastewater treatment technologies. Microalgae-based treatment has recently gained interest thanks to simultaneous removal capacity of organic and inorganic compounds and potentially CECs. In this study, a lab-scale monoculture of Chlorella vulgaris and mixed microalgal-bacterial culture were compared in terms of removal of 28 CECs (bisphenols, 2018 EU Watch List substances, including neonicotinoids, pharmaceuticals, selected transformation products). The removal pathways in light and dark abiotic controls were also studied. Batch photobioreactors were run at hydraulic retention times of 11–12 days and CECs spiked at environmentally relevant concentrations (1–20 μg L−1). The mixed culture was better at removing bisphenols, compared to C. vulgaris. Bisphenols’ log Kow was significant in removal pathways, where bisphenols with high log Kow were removed abiotically while bisphenols with low log Kow were mainly biodegraded. The removal degrees and the pathways of pharmaceuticals and EU Watch List substances were comparable between both cultures, showing no impact of log Kow for most compounds; however, the removal with C. vulgaris was faster for some. High log Kow was associated with high removal of estradiol in abiotic controls, showing the importance of adsorption onto biomass and suspended matter.

Novel Organophosphate Esters in Airborne Particulate Matters: Occurrences, Precursors, and Selected Transformation Products.

Organophosphate esters (OPEs) represent an important group of industrial additives with broad applications. However, their occurrences and fate in the atmospheric environment have not been sufficiently investigated. Our study focused on four novel OPEs, including tris(2,4-di-tert-butylphenyl) phosphate (AO168 = O), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphate, triisodecyl phosphate, and trisnonylphenol phosphate, and characterized their organophosphite antioxidant (OPA) precursors and selected transformation products, in airborne fine particles from South China. House dust from South China was also studied for comparison. Among these four OPEs, exceedingly high concentrations were determined for AO168 = O (i.e., median: 25 500 ng/g in PM2.5, 52 900 ng/g in PM1.0, and 10 700 ng/g in indoor dust), reaching 1 order of magnitude greater than those of traditional OPEs. Their OPA precursors were not detectable in airborne particles but hypothesized as one of the sources for airborne OPEs. In addition, potential transformation products of AO168 = O, including bis(2,4-di-tert-butylphenyl) phosphate (B2,4DtBPP) and 2,4-di-tert-butylphenol (2,4DtBP), also exhibited broad distributions. The levels of 2,4DtBP even surpassed those of AO168 = O in particles. The links between OPAs, OPEs, and other transformation products indicate the complexity of OPE-related chemicals in atmospheric environments. These links should be taken into consideration for a better characterization of OPEs' environmental and health risks.

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H2O2. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC50 and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.

Wastewater alters feeding rate but not vitellogenin level of Gammarus fossarum (Amphipoda)

Wastewater treatment plant (WWTP) effluents release complex mixtures of organic and inorganic micropollutants, including endocrine disrupting compounds, into receiving water bodies. These substances may cause adverse effects in aquatic communities as well as in ecosystem functions they provide. The aim of this study was to determine the potential impact of secondary treated wastewater released into a small Swiss stream on leaf litter decomposition based on feeding rates of the amphipod shredder Gammarus fossarum measured in situ. Additionally, endocrine disrupting effects downstream of the WWTP were investigated by measuring vitellogenin (vg) induction in male gammarids exposed in situ, as well as estrogen receptor activation using the Yeast Estrogen Screen (YES) involving passive sampler and grab water sample extracts. Extracts were also analysed for 424 organic micropollutants and selected transformation products. Gammarid feeding rate was significantly reduced 100, 200 and 400 m downstream of the WWTP effluent relative to the upstream site. While YES results showed significantly elevated estrogenicity at downstream sites, vg production in male gammarids was not induced. A laboratory experiment, in which gammarids were exposed to WWTP effluent, supported this observation. These results, hence, suggest that treated wastewater released into aquatic ecosystems impairs the ecosystem function of leaf litter decomposition. Vg levels in male gammarids measured by UPLC-MS/MS did, however, not alter.

Development of a solid phase extraction method for agricultural pesticides in large-volume water samples

An analytical method using solid phase extraction (SPE) and analysis by gas chromatography/mass spectrometry (GC-MS) was developed to determine trace levels of a variety of 41 agricultural pesticides and selected transformation products in high-elevation surface waters. Large-volume water sampling (up to 100L) was employed because it was anticipated that pesticide contamination, if present, would be at very low levels. The target compounds comprise pesticides (and selected oxygen transformation products) known to have been extensively used in agriculture in the San Joaquin Valley, CA, USA. Solid phase extraction using the polymeric resin Abselut Nexus was optimized to extract the pesticide analytes from water samples. A single determinative method using GC-MS with electron ionization was used for all the analytes. Recoveries from 100L of reagent water at 100pg/L and 1ng/L concentrations were generally greater than 75%, although dimethoate, disulfoton, and phorate were not recovered. Analysis of the extracts without cleanup yielded detection limits for the remaining 38 analytes between 0.1 and 30ng/L. A silica cleanup with separate analysis of 3 eluant fractions improved detection limits for 37 of the compounds to between 6 and 600pg/L in high-elevation surface waters.

Determination of vapor pressure-temperature relationships of current–use pesticides and transformation products

Sub-cooled liquid vapor pressures (PL 0) of current–use organochlorine and organophosphate pesticides (chlorothalonil, chlorpyrifos methyl, diazinon, fipronil) and selected transformation products (chlorpyrifos oxon, heptachlor epoxide, oxychlordane, 3,5,6-trichloro-2-pyridinol) were determined at multiple temperatures using the gas chromatography retention time technique. Results were utilized to determine vapor pressure-temperature relationships and to calculate enthalpies of vaporization (ΔHvap). While results for chlorothalonil and diazinon were comparable with published values, the measured value for fipronil (1.82 × 10− 6 Pa) is almost an order of magnitude higher than the reported literature value (3.7 × 10− 7 Pa). The availability of vapor pressure temperature relationships for these chemicals will aid in pesticide risk assessment development and improve the effectiveness of mitigation and remediation efforts.

Relative risks of transformation products of pesticides for aquatic ecosystems

In this study, the availability of physico-chemical and ecotoxicological information on 78 transformation products for 20 regularly used pesticides in the open literature is evaluated. Based on this information, it is attempted to predict the relative risk for the aquatic environment of each transformation product in comparison to its parent pesticide. It is concluded that for the 78 transformation products selected, the data set on physico-chemical and ecotoxicological behaviour is not very large. Measured log K ow values and other physico-chemical properties are known for only 30–40% of the selected transformation products. The overall reliability of the collected physico-chemical values is considered to be moderate to slight, while for the ecotoxicological data set, reliability is considered to be sufficient. In many cases, there is a need for more information especially on the persistency and no-observed-effect concentrations of the pesticide's transformation products. In general, over 50% of the transformation products of triazines, carbamates and phenoxypropionic acids pose, in theory, a similar to higher risk than their parent pesticide, while over 50% of the transformation products of synthetic pyrethroids, organophosporous pesticides and dithiocarbamates probably pose less risk. High risk was expected for products with high accumulation or persistency in sediment and/or high toxicity together with considerable bioaccumulation (potential) or relatively high concentrations or persistency in water. A generalization of the joint features that caused an increased risk for ecosystems could not be made for most pesticide classes. Exceptions are the synthetic pyrethroids, for which transformation products with a similar or even higher log K ow than the parent pesticide caused an increased potential risk, while for the carbamates the presence of the carbamate group in the transformation product was the joint characteristic of chemicals with predicted increased risk. For three transformation products, monitoring data based on concentrations measured in surface water in The Netherlands were compared with maximum permissible concentrations. This comparison indicated that two of these compounds pose a potential risk of adverse effects in the field situation in Dutch aquatic ecosystems. For all other transformation products, the potential risk in the field situation could not be established because of the absence of monitoring data.

Effect of selected transformation products of phenolic antioxidants on tetralin oxidation at 65 °C

Effect of selected transformation products of phenolic antioxidants on tetralin oxidation at 65 °C