Main Transformation Products Research Articles

Migration and transformation of 1,1-dimethylhydrazine in peat bog soil of rocket stage fall site in Russian North

An ingress of highly toxic rocket fuel 1,1-dimethylhydrazine (UDMH) and its transformation products into environment represents a serious negative impact on the ecosystem, as well as human health. The present research demonstrates the first data on the spatial distribution and quantification of UDMH and its main transformation products (methylhydrazine, hydrazine, 1,1,4,4-tetramethyltetrazene, formaldehyde, acetaldehyde and furaldehyde N,N-dimethylhydrazones, 1-formyl-2,2-dimethylhydrazine, N,N-dimethylformamide, N-nitrosodimethylamine, and 1-methyl-1H-1,2,4-triazole) in the peat bog soil of the fall site in subarctic region. One hundred samples of peat bog soil and one sample of surface water were analyzed by the developed earlier methodology.The considerable amounts of UDMH and most of its transformation products were found at distances of not >10 m from the center of the fall site. The maximum concentration of UDMH was found near the center, where maximal permissible concentration (MPC) was exceeded 2400-fold. The greatest pollution was observed in the surface soil layer, while methylhydrazine, 1-methyl-1H-1,2,4-triazole, 1-formyl-2,2-dimethylhydrazine, formaldehyde and acetaldehyde N,N-dimethylhydrazones, and N,N-dimethylformamide were the major UDMH transformation products. With increasing distance from the center, the composition of the transformation products changes in favor of the last three compounds. Formaldehyde N,N-dimethylhydrazone and N,N-dimethylformamide are present in all soil samples and can be considered as reliable markers of contamination with rocket fuel. The surface water of the peat bog contained four UDMH transformation products in considerable concentrations, including extremely toxic N-nitrosodimethylamine.The processes of migration and transformation of UDMH in peat bog soil differ considerably from those in sandy soils. This is due to cold climate of subarctic zone, the reducing environment of peat bog, and strong binding of hydrazines to organic matter of peat, which prevents migration of pollutants and contributes to the long-term maintenance of high levels of soil pollution.

The enhanced degradation and detoxification of chlortetracycline by Chlamydomonas reinhardtii.

Nowadays, numerous studies have focused on the newly developed technologies for the thorough removal of tetracyclines (TCs). However, it is often ignored that the parent TCs have limited stability in aquatic environments. Thus, this study selected green alga Chlamydomonas reinhardtii with high chlorophyll content to rapidly degrade chlortetracycline (CTC) into products with low toxicity. As the results shown, the half-life times of CTC (1×10-6mol/L) decreased from 10.35h to 2.55h by the presence of C. reinhardtii at 24±1°C with 12/12h dark/light cycle. The main transformation products were iso-chlortetracycline (ICTC), 4-epi-iso-chlortetracycline (EICTC), and other degradation products with lower molecular weight. The toxicity evaluation shows that the negative effects of CTC on growth rate and soluble protein content of green algae were significantly alleviated after the enhanced degradation treatment, while the generation of reactive oxygen species (ROS) and antioxidant response in algal cells returned to normal levels. The chlorophyll of algae played an important role of photosensitizer, which catalyzed the photo-induced electron/energy transfer of CTC degradation. The ROS generation of algae also was also inseparable from the enhanced degradation of CTC, especially when the chlorophyll was damaged at the high CTC concentration. Based on these results, we can better select suitable algal species to further strengthen the degradation of antibiotics and effectively reduce the environmental risk of CTC in aqueous system.

Fate of Grape-Derived Terpenoids in Model Systems Containing Active Yeast Cells.

Terpenes are important contributors to wine aroma. Free and glycosidically bound terpenes are primarily formed in grapes. During fermentation, they undergo important transformation catalyzed by yeast, so that the terpene profile of grape is substantially different from that of the corresponding wine. The present paper assessed the ability of a Saccharomyces cerevisiae strain to transform 17 different terpenes. Biotransformation was performed by placing target compounds in incubation with resting cells. Volatile compounds produced were extracted by solid-phase extraction and analyzed by gas chromatography-mass spectrometry. Geranyl acetate, neryl acetate, citronellyl acetate, and menthyl acetate were formed from the corresponding terpene alcohols. β-Citronellol was the main product of geraniol transformation; geranial, an intermediate of this pathway, has also been detected. Limonene was hydroxylated by yeast to form carveol, trans-2,8-menthadien-1-ol, and cis-2,8-menthadien-1-ol. Moreover, yeast cells were found to be able to adsorb a significant portion of the terpenes present in the reaction batches, with the extent of this phenomenon being linked to terpene hydrophobicity.

Analysis of the aerobic biodegradation of glucocorticoids: Elucidation of the kinetics and transformation reactions

Glucocorticoids (GCs) are one of the most prescribed pharmaceutical classes worldwide. They have reached the focus as environmental pollutants in the current scientific research, due to their potential risks to aquatic organisms even in the lower ng L−1 range. The objective of this study was to determine the kinetic behavior of selected GCs and to identify their main transformation products (TPs) in lab scaled biodegradation experiments. Therefore, we analyzed the removal of 13 GCs in aerated incubation experiments with activated sludge taken from a German municipal wastewater treatment plant (WWTP) as inoculum. For all steroids, an exponential decrease of the concentrations was observed, which was modelled by pseudo-first order kinetics. Overall, the rate constants kbiol. ranged from 0.07 L gss−1 d−1 (triamcinolone acetonide) to 250 L gss−1 d−1 (prednisolone). These results emphasize the broad variation in the biodegradability and recalcitrance of certain GCs. The selection of the studied GCs enabled a deduction of microbiological stability related to functional groups. Based on the identified TPs, a variety of enzymatically mediated reactions were postulated. Moreover, the identified TPs are characterized by an intact steroid core structure. Thus residual endocrine activity cannot be ruled out. The main observed reactions were regioselective hydrogenation of carbon double-bonds, degradation of the steroid C17 side-chain, ester hydrolysis and oxidative hydroxylation. In total, 41 TPs were tentatively identified and 22 of them were unambiguously confirmed via reference standards. Additionally, 12 TPs were detected in the effluents of municipal WWTPs and, to the best of our knowledge, the occurrence of eight of these TPs has been shown for the first time. These TPs might significantly contribute to the detected residual endocrine activities in the aquatic environments. Therefore, there is a strong need for efficient removal strategies, in particular for persistent steroid hormones with elevated potencies.

Ozonation of rivaroxaban production waste water and comparison of generated transformation products with known in vivo and in vitro metabolites

During production of rivaroxaban, an orally administrated anticoagulant, process waste water is generated at several stages of manufacturing. Due to low biodegradability in conventional waste water treatment plants, it is currently incinerated. Thus, new pre-treatment methods for rivaroxaban-containing waste water could facilitate its subsequent biological processing. In this study, ozonation was investigated as the pre-treatment method, with special emphasis on the elimination of the target compound and the generation of its main transformation products. These were determined by high performance liquid chromatography – high resolution mass spectrometry (HPLC-HRMS). Our results show that the concentration of rivaroxaban in the ozonated waste water can be effectively reduced (below detection limit) under acidic conditions, whereas neutral or basic reaction environment proved less suitable. Four main transformation products were identified and their concentrations determined. Rivaroxaban and its most prominent transformation product acetoxamide were elucidated in multiple-stage mass spectrometry (MSn) experiments. Transformation products derived from the degradation of rivaroxaban were then compared to its natural (animal and human) metabolites as well as other known derivatives. In contrast to previously published rivaroxaban-derived metabolites, the presented ozonation experiments resulted in new transformation products.

Fate of priority pharmaceuticals and their main metabolites and transformation products in microalgae-based wastewater treatment systems

The present study evaluates the removal capacity of two high rate algae ponds (HRAPs) to eliminate 12 pharmaceuticals (PhACs) and 26 of their corresponding main metabolites and transformation products. The efficiency of these ponds, operating with and without primary treatment, was compared in order to study their capacity under the best performance conditions (highest solar irradiance). Concentrations of all the target compounds were determined in both water and biomass samples. Removal rates ranged from moderate (40–60 %) to high (>60 %) for most of them, with the exception of the psychiatric drugs carbamazepine, the β-blocking agent metoprolol and its metabolite, metoprolol acid. O-desmethylvenlafaxine, despite its very low biodegradability in conventional wastewater treatment plants, was removed to certain extent (13–39 %). Biomass concentrations suggested that bioadsorption/bioaccumulation to microalgae biomass was decisive regarding the elimination of non-biodegradable compounds such as venlafaxine and its main metabolites. HRAP treatment with and without primary treatment did not yield significant differences in terms of PhACs removal efficiency. The implementation of HRAPs as secondary treatment is a feasible alternative to CAS in terms of overall wastewater treatment, including organic micropollutants, with generally higher removal performances and implying a green, low-cost and more sustainable technology.

Susceptibility of atrazine photo-degradation in the presence of nitrate: Impact of wavelengths and significant role of reactive nitrogen species

The role of reactive nitrogen species (RNS) formed from nitrate photolysis has aroused interests in transformation of contaminants of emerging concern. This study investigated the influence of UV wavelengths (255, 285 and 365 nm) on photolysis of nitrate for degradation of atrazine (ATZ). The UV285/nitrate system showed the fastest rate constant for degradation of ATZ with kobs of 0.0022 cm2 mJ−1. UV photolysis, RNS, and hydroxyl radical (HO) were identified as main contributors to ATZ degradation in UV/nitrate system. Among the contributors, RNS made the major contribution to degradation of ATZ in UV285/nitrate system, while HO is the predominant specie in UV255/nitrate system. Variance decomposition analysis showed that degradation of ATZ was slightly impacted by natural organic matter and carbonate/bicarbonate in UV285/nitrate system but was dramatically affected in UV255/nitrate system. Main transformation products of ATZ in UV285/nitrate system were identified and possible pathways were proposed. RNS were confirmed to be favorable for acceleration of ATZ photolysis through further reaction of RNS with hydroxyatrazine (with electron-rich moieties). Our study provides deep insights on the influence of UV wavelength on nitrate photolysis and ATZ degradation, and provides a novel method for remediation of water co-contaminated by nitrate and organic contaminants.

Genesis of authigenic kaolinite and its indicative significance to secondary pores in petroliferous basins: A case study in the Dongying Sag, Bohai Bay Basin, Eastern China

Porosity of sandstone generally declines as the formation burial depth rises, during which transformation of unstable minerals (e.g. feldspar) in sandstone significantly contributes to abnormally high porosity zones. It is still controversial that whether transformation of feldspar being massive in sandstone can lead to formation of considerable secondary pores. As the main diagenetic product of feldspar transformation, namely authigenic kaolinite, in terms of the physical and chemical features, acts as indicators of the transformation process of feldspar and the consequent formation of secondary pores. In this study, a series of analyses are implemented on sandstone samples collected from the Dongying Sag, Bohai Bay Basin, Eastern China, including microscopic observation, SEM, EDX, XRD, isotope, and fluid inclusion analysis, with specific attention to genesis and formation process of authigenic kaolinite as well as their indicative significance to secondary pores. It is demonstrated that there are mainly three types of authigenic kaolinite (denoted as K1, K2, and K3), the occurrence and geochemical characteristics of which are greatly different. Based on contact relationship between authigenic kaolinite and other diagenetic products, the three authigenic kaolinite are distinguished into two stages, namely the first-stage K1and the second-stage K2 and K3, which are of obviously different genesis. Specifically, K1 is formed under the effect of acidic fluids that are rich in carboxylic acids. In contrast, K2 and K3 are formed under the effect of acidic fluids that are rich in CO2. During formation of K1, plagioclase dissolution pores are formed and well preserved, and carbonate cements get well preserved, showing no sign of dissolution. During formation of K2 and K3, K-feldspar is kaolinitized as K2, and a small amount of Si and Al elements migrates with short-distance and precipitates as K3 in the vicinity of K2. During this process, K-feldspar is transformed into kaolinite, accompanied by dissolution of carbonate cements and massive formation of secondary pores.

Bioconcentration and bioaccumulation of C60 fullerene and C60 epoxide in biofilms and freshwater snails (Radix sp.)

Fullerenes are carbon nanomaterials that have awaken a strong interest due to their adsorption properties and potential applications in many fields. However, there are some gaps of information about their effects and bioconcentration potential in the aquatic biota. In the present work, freshwater biofilms and snails (Radix sp.) were exposed to fullerene C60 aggregates, at concentrations in the low μg/L order, in mesocosms specifically designed to mimic the conditions of a natural stream. The bioconcentration factors of C60 fullerene and its main transformation product, [6,6]C60O epoxide, were studied to the mentioned organisms employing analyses by liquid chromatography coupled to high-resolution mass spectrometry.Our results show that C60 fullerene and its [6,6]C60O present a low bioconcentration factor (BCF) to biofilms: BCFC60 = 1.34 ± 0.95 L/kgdw and BCFC60O = 1.43 ± 0.72 L/kgdw. This suggests that the sorption of these aggregates to biota may be less favoured than it would be suggested by its hydrophobic character. According to our model, the surface of fullerene aggregates is saturated with [6,6]C60O molecules, which exposes the polar epoxide moieties in the surface of the aggregates and decreases their affinity to biofilms. In contrast, freshwater snails showed a moderate capacity to actively retain C60 fullerenes in their organism (BAFC60 = 2670 ± 3070 L/kgdw; BAFC60O = 1330 ± 1680 L/kgdw), probably through ingestion. Our results indicate that the bioaccumulation of these carbon nanomaterials can be hardly estimated using their respective octanol-water partition coefficients, and that their colloidal properties, as well as the feeding strategies of the tested organism, play fundamental roles.

Transformation of atenolol by a laccase-mediator system: Efficiencies, effect of water constituents, and transformation pathways

In this study, we investigated the transformation of atenolol (ATL) by the naturally occurring laccase from Trametes versicolor in aqueous solution. Removal efficiency of ATL via laccase-catalyzed reaction in the presence of various laccase mediators was examined, and found that only the mediator 2, 2, 6, 6-tetramethyl-1-piperidinyloxy (TEMPO) was able to greatly promote ATL transformation. The influences of TEMPO concentration, laccase dosage, as well as solution pH and temperature on ATL transformation efficiency were tested. As TEMPO concentrations was increased from 0 to 2000 μM, ATL transformation efficiency first increased and then decreased, and the optimal TEMPO concentration was determined as 500 μM. ATL transformation efficiency was gradually increased with increasing laccase dosage. ATL transformation was highly pH-dependent with an optimum pH of 7.0, and it was almost constant over a temperature range of 25–50 °C. Humic acid inhibited ATL transformation through competition reaction with laccase. The presence of anions HCO3− and CO32− reduced ATL transformation due to both anions enhanced solution pHs, while Cl−, SO42−, and NO3− at 10 mM showed no obvious influence. The main transformation products were identified, and the potential transformation pathways were proposed. After enzymatic treatment, the toxicity of ATL and TEMPO mixtures was greatly reduced. The results of this study might present an alternative clean strategy for the remediation of ATL contaminated water matrix.

Effects of guanylurea, the transformation product of the antidiabetic drug metformin, on the health of brown trout (Salmo trutta f. fario).

BackgroundGuanylurea is the main transformation product of the antidiabetic drug metformin, which is one of the most prescribed pharmaceuticals worldwide. Due to the high rate of microbial degradation of metformin in sewage treatment plants, guanylurea occurs in higher concentrations in surface waters than its parent compound and could therefore affect aquatic wildlife. In this context, data for fish are scarce up to now which made us investigate the health of brown trout (Salmo trutta f. fario) in response to guanylurea.MethodsIn two experiments, eggs plus developing larvae and juvenile brown trout were exposed to three different concentrations of guanylurea (10, 100 and 1,000 µg/L) and, as a negative control, filtered tap water without this compound. Low internal concentrations were determined. The investigated parameters were mortality, length, weight, condition factor, tissue integrity of the liver and kidney, levels of stress proteins and lipid peroxides, as well as behavioural and developmental endpoints. It was found that guanylurea did not significantly change any of these parameters in the tested concentration range.ResultsIn conclusion, these results do not give rise to concern that guanylurea could negatively affect the health or the development of brown trout under field conditions. Nevertheless, more studies focusing on further parameters and other species are highly needed for a more profound environmental risk assessment of guanylurea.

Bioaccumulation and biochemical effects of ethylhexyl methoxy cinnamate and its main transformation products in zebrafish

The purpose of this study was to investigate the bioaccumulation and biochemical responses exposed to one of the main organic ultraviolet (UV) pollutants in the environment, ethylhexyl methoxy cinnamate (EHMC), and its main transformation product, either alone or in combination in zebrafish (Danio rerio). Four-month-old zebrafish were exposed to EHMC (34.4, 344 nmol/L) solution for 14 days, the species and contents of EHMC transformation products in zebrafish were determined and 3,5-dichloro-2-hydroxyacetophenone (3,5DCl2HAcP) was the one with the highest concentration in transformation products. Then, zebrafish were exposed to EHMC, 3,5DCl2HAcP alone and mixed solution for 21 days. At 7, 14 and 21 d, the related indexes of antioxidant defense system were determined. Results showed that both EHMC and 3,5DCl2HAcP can lead to the increase of malondialdehyde (MDA) and glutathione (GSH) contents, superoxide dismutase (SOD), catalase (CAT) and glutathione reductase (GR) activities in visceral mass compared with the corresponding control group, thus produced oxidative stress effect in organism and 3,5DCl2HAcP even showed stronger oxidative stress than EHMC. The effects of the two lower concentration co-exposure groups were similar and more significant to that of single exposure groups, while excessive oxidative stress occurred at the highest co-exposure group indicated by the decrease of GSH content, SOD, CAT, GR activities and the continued increase of MDA content. At 21 d, estradiol (E2), vitellogenin (Vtg) and testosterone (T) contents, estrogen receptor (Esr), progesterone receptor (Pgr), androgen receptor (Ar), Vtg1, P450 aromatase (Cyp19a1) and 17β-hydroxysteroid dehydrogenase (Hsd17b3) expression were all significantly increased when exposed to 3,5DCl2HAcP alone, showing complex estrogen and androgen effects. When exposed to EHMC alone, E2 and Vtg contents, Esr, Pgr, Vtg1, Cyp19a1 and Hsd17b1 gene expression levels decreased significantly, and T content and Ar and Hsd17b3 expression increased significantly, indicated that EHMC can produce anti-estrogen and androgen effect. Last, the decrease of estrogen effect and increase of androgen effect in co-exposure group suggested that 3,5DCl2HAcP might weaken the estrogen effect and promote the androgen effect of EHMC.

Sulfamethoxazole persistence in a river water ecosystem and its effects on the natural microbial community and Lemna minor plant

Sulfamethoxazole (SMX) is a sulfonamide antibiotic commonly used in human and veterinary medicine and frequently detected in surface water as a micro-contaminant. The presence of this antibiotic and its main transformation product N4-acetyl-sulfamethoxazole (Ac-SMX) was evaluated in an Italian river water by Solid Phase Extraction (SPE) and subsequent LC MS/MS determination.River water microcosm experiments were set up in the presence and absence of duckweed (Lemna minor L.) adding SMX (500 μg L−1) with the aim of evaluating the persistence of antibiotic and its effects on both the microbial community naturally occurred in a river and the plant. The concentrations of SMX and Ac-SMX were measured at fixed times over a period of 28 days. The microbial abundance, intI1 gene and plant morpho-physiological analyses were also conducted.In the river water samples, SMX was not detected as a parent compound, but its acetylate metabolite Ac-SMX was found as a micro-contaminant. The results of the microcosm experiment showed that SMX did not substantially degrade, except in the presence of L. minor where a slight decrease (17%) was observed. The river residual concentration of Ac-SMX remained quite constant during the experimental period. The river microbial community was initially affected by adding the antibiotic with a decrease in its abundance; however, although it was not able to degrade SMX, it displayed an overall antibiotic resistance. In fact, the intI1 gene was found throughout the entire experimental period. Finally, SMX did not cause evident inhibition or suffering symptoms for the plant.

Transformation of roxarsone during UV disinfection in the presence of ferric ions

The transformation of roxarsone (ROX) during UV disinfection with Fe(III) has been investigated. Fe(OH)2+, as the main Fe(III) species at pH = 3, produces HO under UV irradiation leading to the oxidation of ROX. Dissolved oxygen plays a very important role in the continuous conversion of generated Fe2+ to Fe3+, which ensures a Fe(III)-Fe(II) cycle in the system. The presence of Cl−/HCO3−/NO3− has little influence on the ROX transformation, whereas PO43− achieves an obvious inhibitory effect. The transformation of ROX leads to the formation of inorganic arsenic consisting of a much higher amount of As(V) than As(III). LC-MS analysis shows that phenol, o-nitrophenol and arsenic acid were the main transformation products. Both the radical scavenger experiment and electron spin resonance data confirm that the HO is responsible for ROX transformation. The toxic transformation products are found to have potential environmental risks for the natural environment, organisms and human beings.

Degradation of α-terpineol in aqueous solution by UV/H2O2: kinetics, transformation products and pathways.

The monoterpene alcohol α-terpineol is extensively used as the foaming agent in mineral processing and can be released to environment along with the wastewater. This study evaluated the feasibility of eliminating α-terpineol in water by ultraviolet irradiation (UV) in combination with hydrogen peroxide (H2O2). Within an H2O2 dose of 10 mg/L and an UV fluence of 64.8 J/cm2, more than 95% of the α-terpineol can be removed. The reactions fitted well to pseudo-first-order kinetics, and the apparent rate constant was 0.0678 min-1. The effects of matrix species including various anions and humic acid (HA), were evaluated. The degradation rate decreased significantly with the addition of bicarbonate and HA. Further verification was carried out with three types of real water samples. In the ground water and the surface water, the degradation rate decreased likely due to the presence of natural organic matter. Finally, possible degradation pathways were proposed based on the identification of transformation products, and the occurrence of two main transformation products were monitored. This study demonstrated that the UV/H2O2 is an effective technology for the degradation of α-terpineol in water.

Determination of pesticide levels in wastewater from an agro-food industry: Target, suspect and transformation product analysis.

Agriculture is considered as the main source of water contamination by pesticides. However, food packaging or processing industries are also recognised as relevant point sources of contamination by these compounds, not yet investigated in depth. The objective of this work has been to improve current knowledge about the presence and concentration of pesticides in the effluent of a food processing industry, as well as to investigate their main transformation products (TPs). An analytical strategy combining target and suspect analysis has been applied to provide an evaluation of the effluents. The methodology involves solid-phase extraction (SPE) of wastewater samples followed by (i) liquid chromatography quadrupole-linear ion trap tandem mass spectrometry (LC-QqLIT-MS/MS) for quantitative target analysis and (ii) liquid chromatography coupled to quadrupole-time-of-flight high resolution mass spectrometry (LC-QTOF-HRMS) to identify non-target pesticides and possible TPs. The results revealed the presence of 17 of the target pesticides analysed and 3 additional ones as a result of the suspect screening performed by HRMS. The TPs were investigated for the pesticides found at the highest concentrations: imazalil (7038-19802 ng/L), pyrimethanil (744-9591 ng/L) and thiabendazole (341-926 ng/L). Up to 14 TPs could be tentatively identified, demonstrating the relevance of this type of studies. These data provide a better understanding of the occurrence of pesticides and their TPs in agro-food industrial effluents.

Response Surface Analysis of Fenobucarb Removal by Electrochemically Generated Chlorine

The aim of the present study was to investigate the electrochemical formation of active chlorine and its subsequent use for the degradation of the pesticide fenobucarb. Initially, the process of electrochemical active chlorine production was investigated using an electrochemical flow-cell with a Ti/RuO2 plate electrode. The contribution of four main factors (chloride concentration, current density, the retention time of chloride in the cell (flow rate), and initial pH of inlet solution) to form active chlorine was determined by a central composite design (CCD). The influence of the four variables was statistically significant, and the contributions of flow rate, chloride concentration, pH, and current density were found to be 37.2%, 33.59%, 18.28%, and 10.93%, respectively. A mathematical model was established to predict and optimize the operating conditions for fenobucarb removal in the NaCl electrolysis process. The main transformation products (seven compound structures) were detected by liquid chromatography coupled with high-resolution mass spectrometry (LC–HRMS). The results of the model and transformation products indicated that fenobucarb was degraded due to direct oxidation on the electrode surface, and indirectly by active chlorine and other radicals present during the NaCl electrolysis process.

Impact of the Antidiabetic Drug Metformin and Its Transformation Product Guanylurea on the Health of the Big Ramshorn Snail (Planorbarius corneus)

Pharmaceuticals can enter surface waters via sewage treatment plants. In the environment, the substances and their transformation products, formed by degradation of the parent compounds, may affect aquatic wildlife including freshwater invertebrates. However, research on pharmaceutical-induced effects in feral freshwater organisms other than fish is still scarce to date. In our study, we therefore investigated the impact of the highly consumed antidiabetic drug metformin and its main transformation product guanylurea on the health of a freshwater gastropod – the big ramshorn snail (Planorbarius corneus) with respect to biochemical and cellular stress responses and apical parameters. The snails were exposed to different concentrations of the drug (0, 10, 100, 1000, 10 000, 100 000 µg/L) and its transformation product (0, 100, 10 000, 100 000 µg/L). The examined parameters were mortality, weight, tissue integrity of the hepatopancreas and the levels of stress proteins and lipid peroxides. Mortality and the levels of stress proteins and lipid peroxides were not influenced by the two substances. In response to the highest concentrations of both chemicals, the weight of the snails was slightly but not significantly reduced. The histopathological investigation of the hepatopancreas revealed a significant effect of guanylurea at a concentration of 100 000 µg/L with an increased number of symptoms of cellular responses in the tissue (e.g. dilated lumen, disturbed compartmentation of the digestive cells, nucleus deformation, hyperplasia and hypertrophy of crypt cells). For the parent compound, a similar trend was also revealed for the highest concentration. Overall, the observed effects did not occur at environmentally relevant concentrations, but at concentrations which were 10 000 times higher than these. Thus, the results did not give rise to major concern that metformin and guanylurea may pose a risk to the big ramshorn snail in the environment.

Photodegradation of tefuryltrione in water under UV irradiation: Identification of transformation products and elucidation of photodegradation pathway

Photodegradation is an important abiotic degradation process in the aquatic environment. In this study, the photodegradation of tefuryltrione in aqueous solution was investigated under UV–Visible irradiation. Effects of carbonate (CO32−), bicarbonate (HCO3−), nitrate (NO3−), hydrogen phosphate (HPO42−), potassium (K+), and ammonium (NH4+) on the photodegradation kinetics of tefuryltrione were evaluated. Results showed that tefuryltrione photodegradation was increased by HCO3−, CO32−, and NO3− in the range of 0.1–10 mmol L−1; decreased by HPO42−; and insignificantly affected by K+ and NH4+. Twelve main transformation products (TPs) were separated and identified on the basis of mass spectrum data assigned by elemental-composition calculations, comparison of structural analogs, and available literature. A tentative photodegradation pathway was further proposed depending on the identified TPs and their kinetic evolutions. Results indicated that TP 1 was generated by the hydroxyl that substituted for chlorine, TP 2 was formed by the cleavage of the ether bond of tefuryltrione, and TPs 3–6 were formed by the breakage of the CC bond of the keto moiety of tefuryltrione. Further, TPs 9–12 were formed by the rearrangement of tefuryltrione-photodegradation products. These findings are highly important for elucidating the environmental fate of tefuryltrione in aquatic ecosystems.

Feruloyloacetone can be the main curcumin transformation product

Curcumin is a phenolic compound produced by some plants, among which Curcuma longa is the reachest in this principal curcuminoid. At elevated temperature curcumin degrades to trans-6-(4′-hydroxy-3′-methoxyphenyl)-2,4-dioxo-5-hexenal, vanillin, ferulic acid and feruloylmethane, however, the formation of feruloyloacetone ((5E)-6-(4-hydroxy-3-methoxyphenyl)hex-5-ene-2,4-dione) in the curcumin degradation process has not been reported yet. As results from experiments, even 28.8% or 20.6% of the degraded curcumin is transformed to feruloyloacetone during 2 h heating of alkaline or acidic curcumin solution, respectively. The structure of the identified feruloyloacetone was confirmed by MSn, HRMS and NMR data. The presented results are important for food processing as feruloyloacetone is formed during food products preparation and its biological activity has not been fully recognized.