Biodegradation of Photocatalytic Degradation Products of Sulfonamides: Kinetics and Identification of Intermediates.

Sulfonamides can be effectively removed from wastewater through a photocatalytic process. However, the mineralization achieved by this method is a long-term and expensive process. The effect of shortening the photocatalytic process is the partial degradation and formation of intermediates. The purpose of this study was to evaluate the sensitivity and transformation of photocatalytic reaction intermediates in aerobic biological processes. Sulfadiazine and sulfamethoxazole solutions were used in the study, which were irradiated in the presence of a TiO2-P25 catalyst. The resulting solutions were then aerated after the addition of river water or activated sludge suspension from a commercial wastewater treatment plant. The reaction kinetics were determined and fifteen products of photocatalytic degradation of sulfonamides were identified. Most of these products were further transformed in the presence of activated sludge suspension or in water taken from the river. They may have been decomposed into other organic and inorganic compounds. The formation of biologically inactive acyl derivatives was observed in the biological process. However, compounds that are more toxic to aquatic organisms than the initial drugs can also be formed. After 28 days, the sulfamethoxazole concentration in the presence of activated sludge was reduced by 66 ± 7%. Sulfadiazine was practically non-biodegradable under the conditions used. The presented results confirm the advisability of using photocatalysis as a process preceding biodegradation.

Degradation of veterinary antibiotics by the ozonation process: Product identification and ecotoxicity assessment.

The purpose of the study was to evaluate the effects of using of ozonation to remove antibiotics used, among others, in veterinary medicine, from the aqueous environment. The effect of this process on the degradation, mineralisation and ecotoxicity of aqueous solutions of ampicillin, doxycycline, tylosin, and sulfathiazole was investigated. Microbiological MARA® bioassay and two in silico methods were used for the ecotoxicity assessment. Ozonation was an effective method for the degradation of the antibiotics studied and the reduction in ecotoxicity of the solutions. However, after ozonation, the solutions contained large amounts of organic products, including compounds much less susceptible to ozonation than the initial antibiotics. Structures of 14, 12, 40 and 10 degradation products for ampicillin, doxycycline, tylosin, and sulfathiazole, respectively, were proposed. It was confirmed that ozone plays a greater role than hydroxyl radicals in the degradation of these antibiotics, with the exception of TYL. The use of ozonation to obtain a high degree of mineralisation is unfavourable and it is suggested to combine ozonation with biodegradation. The pre-ozonation will cause decomposition of antibiotic pharmacophores, which significantly reduces the risk of spread of antimicrobial resistance in the active biocenosis of wastewater treatment plants.

Degradation of veterinary antibiotics by Fenton process: Products identification and toxicity assessment.

The aim of the work was primarily to determine the relationship between the doses of Fenton's reagents and the effectiveness of the ecotoxicity removal of aqueous solutions containing selected antibiotics. The degradation process of ampicillin, doxycycline, and tylosin in an acidic environment in the presence of H2O2 and FeSO4 was studied. The effect of reagent doses on the degree of degradation and identification of antibiotic transformation products was measured by the UPLC qTOF method. The degree of mineralisation was determined based on changes in the concentration of total organic carbon. The ecotoxicity of products was determined with commercial MARA® and MICROTOX® bioassays, as well as against unselected microorganisms from polluted rivers and wastewater treatment plant effluent. It was found that the complete degradation of antibiotics and the simultaneous elimination of the toxicity of the Fenton process products required the use of a precisely defined amount of reagents. When an insufficient dose of reactants was used, the post-reaction solutions contained antibiotic derivatives showing antimicrobial activity. On the other hand, the toxicity of the post-reaction solution against to microbiocenoses was observed when too high doses of H2O2 were used in the process. This effect resulted from the presence of unreacted reagent or other unidentified peroxides.

Degradation of the Selected Antibiotic in an Aqueous Solution by the Fenton Process: Kinetics, Products and Ecotoxicity.

Sulfonamides used in veterinary medicine can be degraded via the Fenton processes. In the premise, the process should also remove the antimicrobial activity of wastewater containing antibiotics. The kinetics of sulfathiazole degradation and identification of the degradation products were investigated in the experiments. In addition, their toxicity against Vibrio fischeri, the MARA® assay, and unselected microorganisms from a wastewater treatment plant and the river was evaluated. It was found that in the Fenton process, the sulfathiazole degradation was described by the following kinetic equation: r0 = k CSTZ-1 or 0 CFe(II)3 CH2O20 or 1 CTOC-2, where r0 is the initial reaction rate, k is the reaction rate constant, C is the concentration of sulfathiazole, Fe(II) ions, hydrogen peroxide and total organic carbon, respectively. The reaction efficiency and the useful pH range (up to pH 5) could be increased by UVa irradiation of the reaction mixture. Eighteen organic degradation products of sulfathiazole were detected and identified, and a possible degradation mechanism was proposed. An increase in the H2O2 dose, to obtain a high degree of mineralization of sulfonamide, resulted in an increase in the ecotoxicity of the post-reaction mixture.

Influence of pH on the Kinetics and Products of Photocatalytic Degradation of Sulfonamides in Aqueous Solutions.

The aims of the study were to determine the kinetics of the photocatalytic degradation of six sulfonamides in the presence of TiO2-P25 in acidic, neutral, and alkaline solutions and to identify the structures of the stable products. It was stated that the pH of the solution significantly affected the photocatalytic degradation rate of sulfonamides in acidic and alkaline environments, and the effect likely depended on the susceptibility of sulfonamides to attack by hydroxyl radicals. In the post-reaction mixture, we identified the compounds resulting from the substitution of the aromatic rings with a hydroxyl group; the amide hydrolysis products; the hydroxylamine-, azo, and nitro derivatives; and the compounds formed via the elimination of the sulfone group. Moreover, previously unknown azo compounds were detected. Some degradation products of sulfonamides may exhibit marked bacteriostatic activity and high phytotoxicity. The azo and nitro compounds formed in an acidic environment may be potentially more toxic to aquatic ecosystems than the initial compounds.

A New Mechanism of the Selective Photodegradation of Antibiotics in the Catalytic System Containing TiO2 and the Inorganic Cations.

The mechanism of sulfisoxazole (SFF) selective removal by photocatalysis in the presence of titanium (IV) oxide (TiO2) and iron (III) chloride (FeCl3) was explained and the kinetics and degradation pathways of SFF and other antibiotics were compared. The effects of selected inorganic ions, oxygen conditions, pH, sorption processes and formation of coordination compounds on the photocatalytic process in the presence of TiO2 were also determined. The Fe3+ compounds added to the irradiated sulfonamide (SN) solution underwent surface sorption on TiO2 particles and act as acceptors of excited electrons. Most likely, the SFF degradation is also intensified by organic radicals or cation organic radicals. These radicals can be initially generated by reaction with electron holes, hydroxyl radicals and as a result of electron transfer mediated by iron ions and then participate in propagation processes. The high sensitivity of SFF to decomposition caused by organic radicals is associated with the steric effect and the high bond polarity of the amide substituent.

The remediation of sulfonamides from the environment by Pleurotus eryngii mycelium. Efficiency, products and mechanisms of mycodegradation.

The objective of the study was to assess the applicability of the mycelium obtained from the in vitro cultures of nontoxic bracket fungus, Pleurotus eryngii, to sulfonamides mycodegradation. Samples containing one of the six selected sulfonamides, sulfanilamide derivatives, were incubated with the mycelium of P. eryngii for 7 and 14 days in vitro. Subsequently, change in the sulfonamide concentration was assessed in the samples using the UPLC-QTof. The transformation products were identified based on monoisotopic molecular mass and fragmentation spectra. The studied sulfonamides did not inhibit the growth of P. eryngii mycelium in the in vitro cultures. In addition, a considerable reduction of sulfonamide concentration was observed in all the incubated samples (from 73.7 ± 8.3% to 99.8 ± 0.3%). In the case of three sulfonamides, the reduction in concentration >90% occurred after 7 days of incubation. However, the transformation of sulfonamides was partially caused by their degradation to simpler organic compounds. After incubation, the products of condensation of sulfonamides with formyl, acyl, and sugar groups, and amino acid-derived compounds were identified in the samples. This indicated the partially reversible nature of the mycodegradation process.

The influence of waste from electronic cigarettes, conventional cigarettes and heat-not-burn tobacco products on microorganisms.

Tobacco smoking, especially conventional cigarettes, is widespread throughout the world. Simultaneously, there is a growing interest in new alternative products that allow delivering nicotine to the users' organisms, including electronic cigarettes and heat-not-burn tobacco products. However, there are few scientific reports regarding the effect of waste generated from the above-mentioned products on microorganisms. The aim of the manuscript was to investigate the influence of substances leached from conventional cigarette butts, butts from heat-not-burn tobacco products, cartridges and e-liquids for electronic cigarettes on microorganisms. The commercial multispecies MARA (microbial assay for risk assessment) test and non-selected microorganisms from the Brynica River (Poland), as well as an effluent from the wastewater treatment plant (Sosnowiec-Zagórze, Poland), were used in the ecotoxicity assessment of the investigated waste. The results of the experiments revealed that the waste from electronic cigarettes, i.e. cartridges and e-liquids, does not pose a considerable threat to the microbiocenosis. On the other hand, a particularly strong ecotoxic effect on the investigated microorganisms has been reported for leachate from smoked cigarette butts and butts from heat-not-burn tobacco products. Their high ecotoxicity combined with a high supply is worrying and it can require interventions to protect the aquatic environment. The retention of the waste can have an adverse effect on microorganisms in reservoirs surface waters or a sludge activity in wastewater treatment plants.

Removal of veterinary antibiotics from wastewater by electrocoagulation.

The aim of this study was to assess the effectiveness of veterinary antibiotic removal from wastewater using an electrocoagulation method. The removal efficiency of ampicillin, doxycycline, sulfathiazole and tylosin; the antibiotic degradation degree after electrolysis; and the toxicity and qualitative composition of antibiotic solutions after electrocoagulation were determined in the experiments. HPLC-QTOF was used for quantitative and qualitative determination. The eco-toxicity was assessed using the MARA® assay. After electrocoagulation, the concentration of ampicillin, doxycycline, sulfathiazole and tylosin in wastewater decreased 3.6 ± 3.2%, ∼100%, 3.3 ± 0.4% and 3.1 ± 0.3%, respectively. Doxycycline was the only antibiotic effectively removed from wastewater during electrocoagulation. Simultaneously, part of this antibiotic underwent oxidative degradation. As a result of this process, the eco-toxicity in the reaction environment decreased.

Assessment of the biodegradability of selected sulfa drugs in two polluted rivers in Poland: Effects of seasonal variations, accidental contamination, turbidity and salinity.

The aim of our study was to assess the aerobic biodegradation of four selected sulfonamides (sulfanilamide, sulfamethoxazole, sulfadiazine and sulfathiazole) using water samples drawn from highly polluted rivers. Additionally, we aimed to identify the factors that have a significant effect on the process efficiency. The 19 water samples were collected from Brynica and Czarna Przemsza rivers (in Poland) at the same location at approximately monthly intervals. A characteristic feature of the results is the presence of significant differences between the rates of sulfonamides biodegradation in particular samples. The sulfonamide most resistant to biodegradation was sulfamethoxazole, whereas sulfathiazole was most biodegradable. Seasonal variations and related microbial population changes had the most significant effects on sulfonamides biodegradation, e.g., the studied process was highly inhibited during wintertime. A decrease in the biodegradation rate in the river water could be caused by an accidental water pollution by industrial wastewater with heavy metals, an increase in salinity and a decrease in pH, and turbidity.

Effects of the presence of sulfonamides in the environment and their influence on human health.

World production and consumption of pharmaceuticals has been steadily increasing. Anti-infectives have been particularly important in modern therapy of microbial infection. Sulfonamides have been widely used for a long time as anti-infectives and are still widely prescribed today. This review presents the most common types of sulfonamides used in healthcare and veterinary medicine and discusses the problems connected with their presence in the biosphere. Based on the analysis of over 160 papers, it was found that small amounts of sulfonamides present in the environment were mainly derived from agricultural activities. These drugs have caused changes in the population of microbes that could be potentially hazardous to human health. This human health hazard could have a global range, and administrative activities have been ineffective in risk reduction.

In vitro and in vivo effects of fluoride ions on enzyme activity.

RESULTS: This work presents mechanisms by which interaction of fluoride ions with enzymes can take place. The effects of fluoride on enzymes participating in cellular metabolic pathways, like energy formation and carbohydrate and lipid turnover, are discussed. A list of enzymes which are inhibited or activated in vivo and in vitro by fluoride ions is provided, together with information on species and organs of origin, fluoride concentration, and extent of inhibition or activation.

The results of the interference of nitrates and vitamin E in the metabolism in the connective tissue of rat's liver.

We examined 72 female Wistar rats which were divided into 6 groups. The animals were administered sodium nitrate (V), vitamin E or both compounds at the same time. In order to estimate the interference of nitrates in the presence of vitamin E with the metabolism of rat's liver, we determined the composition and the amount of glycosoaminoglycans (GAGs). It was stated that the total amount of GAGs increased in livers of all rats. Basing on all fractions of the examined GAGs it was determined that the most significant differences between individual groups appeared in the amount of heparane sulphate (HS). The results obtained confirmed the fact of the changes taking place in the picture of liver GAGs in the process of ageing of the examined animals. The results obtained, however, allowed to state the normalising influence of vitamin E on the quantitative composition of GAGs of rats which drank nitrates.