Captopril and its dimer captopril disulfide: photodegradation, aerobic biodegradation and identification of transformation products by HPLC-UV and LC-ion trap-MS(n)

In some countries effluents from hospitals and households are directly emitted into open ditches without any further treatment and with very little dilution. Under such circumstances photo- and biodegradation in the environment can occur. However, these processes do not necessarily end up with the complete mineralization of a chemical. Therefore, the biodegradability of photoproduct(s) by environmental bacteria is of interest. Cardiovascular diseases are the number one cause of death globally. Captopril (CP) is used in this study as it is widely used in Egypt and stated as one of the essential drugs in Egypt for hypertension. Three tests from the OECD series were used for biodegradation testing: Closed Bottle test (CBT; OECD 301 D), Manometric Respirometry test (MRT; OECD 301 F) and the modified Zahn-Wellens test (ZWT; OECD 302 B). Photodegradation (150 W medium-pressure Hg-lamp) of CP was studied. Also CBT was performed for captopril disulfide (CPDS) and samples received after 64 min and 512 min of photolysis. The primary elimination of CP and CPDS was monitored by LC-UV at 210 nm and structures of photoproducts were assessed by LC-UV-MS/MS (ion trap). Analysis of photodegradation samples by LC-MS/MS revealed CP sulfonic acid as the major photodegradation product of CP. No biodegradation was observed for CP, CPDS and of the mixture resulting from photo-treatment after 64 min in CBT. Partial biodegradation in the CBT and MRT was observed in samples taken after 512 min photolysis and for CP itself in MRT. Complete biodegradation and mineralization of CP occurred in the ZWT.     

Laboratory simulation of biodegradation of chemicals in surface waters: closed bottle and respirometric test

Microbial degradation is the most dominant elimination mechanism of organics from the environment. For evaluation of biodegradability of pure chemicals many standardized tests are available, but no standardized procedure for assessment of biodegradability of chemicals in surface water is agreed upon. Rates of in-situ biodegradation are usually estimated in laboratory simulation where environmental factors are reproduced to some extent. The aim of our study was to compare standardised ready biodegradability assessment, test (Closed bottle test) and its modifications employing the basic agreements on test conditions to simulate biodegradation in surface water. Standard test was modified using various natural river waters to simulate the natural environment in a simplified way. The impact of different types and amounts of nutrients and microorganisms on biodegradation was confirmed. The conditions in the recipient should be examined to extrapolate the results from ready biodegradability tests to real surface water.     

Assessment of the interrelation between photooxidation and biodegradation of selected polyesters after artificial weathering

Three commercially available biodegradable polymers, two different aromatic-aliphatic copolyesters and polylactic acid, intended for the fabrication of agricultural mulching films, in addition to other applications, were subjected to a series of tests with the aim of studying the relationship between their photooxidation and biodegradation. Photooxidation resulted in the rearrangement of polymeric chains, in the case of both copolyesters the events led to polymeric chain crosslinking and the formation of insoluble polymeric gel. The tendency was significantly more pronounced for the copolyester with the higher content of the aromatic constituent. As regards polylactic acid photochemical reactions were not accompanied by crosslinking but instead provoked chain scissions. A biodegradation experiment showed that, despite marked structural changes, the extent of photooxidation was not the decisive factor, which significantly modified the rate of biodegradation in all three materials investigated. The specific surface area of the sample specimens was shown to be more important.     

Biological and photochemical degradation rates of diethylenetriaminepentaacetic acid (DTPA) in the presence and absence of Fe(III)

The environmental fate of ethylenediaminetetraacetic acid (EDTA) has been extensively studied, while much less is known about the environmental behaviour of diethylenetriaminepentaacetic acid (DTPA). In this study, it was confirmed that DTPA is persistent toward biodegradation. The biodegradability of DTPA was investigated in the absence and in the presence of Fe(III) by using CO2 evolution test and Manometric respirometry test. The CO2 evolution and oxygen uptake of iron-free (DTPA was added as free acid) and Fe(III)DTPA were less than in inoculum blank. Possible inhibitor effect was analysed by testing biodegradation of sodium benzoate with and without iron-free or Fe(III)DTPA in the Manometric respirometry test. Only slight inhibition was observed when DTPA was added as free acid. Photodegradation of iron-free DTPA and Fe(III)-DTPA complex was studied by using sunlight and UV radiation at the range 315-400 nm emitted by black light lamps. The results indicate that DTPA added as free acid degrades photochemically in humic lake water. Fe(III)DTPA was shown to be very photolabile in humic lake water in the summer; the photochemical half-life was below one hour. Photodegradation products were identified by the mass spectrometric technique (GC-MS). It was shown that photodegradation of Fe(III)DTPA does not result in total mineralization of the compound. Diethylenetriaminetetraacetic acid, diethylenetriaminetriacetic acid, ethylenediaminetriacetic acid, N,N'- and/or N,N-ethylenediaminediacetic acid, iminodiacetate, ethylenediaminemonoacetic acid and glycine were identified as photodegradation products of Fe(III)DTPA. Based on these observations, we propose a photodegradation pathway for Fe(III)DTPA.     

紫外光照射与生物降解耦合用于PCBs降解的研究

介绍了PCBs紫外光降解的机理及研究进展 ,讨论了影响PCBs光降解的主要因素 ,即环上的氯原子数目、取代位置及所处的微环境均显著地影响PCBs的光降解速率。简述了PCBs生物降解的研究进展 ,重点概述了好氧降解、厌氧降解及好氧厌氧协同作用的机理及特点。最后 ,讨论了PCBs生物降解和光降解的互补性 ,介绍了最近的研究进展 ,指出光降解和生物降解耦合将加快PCBs的移走速率 ,提出了PCBs污染土壤原位修复需要进一步解决的问题。     

Application of the headspace CO2 method (ISO 14 593) to the assessment of the ultimate biodegradability of surfactants: results of a calibration exercise

In the recent review of the control of marketing surfactants used in detergents, the EU decided to increase the severity of the testing procedure by using the criterion of ultimate biodegradability (mineralization) rather than primary biodegradation (removal of the parent molecule) to ensure that possible harmful organic metabolites do not reach the environment. The relatively new ISO headspace CO2 test, considered to be an improvement on the OECD 301B (Sturm CO2) test was chosen. The method was subjected to a ring test by 11 laboratories using one of each of four classes of surfactants plus a poorly degradable reference surfactant; all laboratories satisfactorily applied the method. The necessary addition of silica gel to the medium containing the cationic surfactant, known as a class to be more inhibitory than other classes, was confirmed as a technique for avoiding inhibition of the inoculum. The biodegradability of the surfactants was in general agreement with results reported in the literature and the often reported variable values of % inorganic carbon (IC) produced of the theoretical was found. The anionic and cationic surfactants were readily biodegradable (%IC > 60), the non-ionic surfactant was well below the pass value, while the amphoteric was borderline. The IC production by the blank controls, one of the validity criteria, was about 0.3 mg C/100 ml test medium, equivalent to 3 mg C/l, as recommended in the ISO text. Mild conditions of pre-exposure of the inoculum to the test surfactant did not produce consistent worthwhile effects on either the percentage biodegradation or on its variability.     

Toxicity and biodegradability of sulfonamides and products of their photocatalytic degradation in aqueous solutions

The photocatalytic degradation of sulfacetamide, sulfathiazole, sulfamethoxazole and sulfadiazine in water solutions during their illumination of UV radiation (lambda(max) 366 nm) with TiO2 catalyst was examined. The growth-inhibition effect of sulfonamides and intermediate products theirs photodegradation was investigated in aqueous solution with the green alga Chlorella vulgaris. The biodegradability of the investigated compounds was determined in the illuminated solutions and is expressed as Biochemical Oxygen Demand. It was found that all of the investigated sulfonamides in the initial solutions were resistant to biodegradation and were toxic relative to C. vulgaris. The toxicity (EC50 values) relative to C. vulgaris increased in the following order sulfacetamide, sulfathiazole, sulfamethoxazole, sulfadiazine. All of the investigated sulfonamides undergo photocatalytic degradation. The toxicity of intermediate products of the sulfonamides degradation was significantly lower than the toxicity of sulfonamides in the initial solutions and was dependent on illumination time and degradation rate. The intermediate products of photocatalysis in contrast to the initial sulfonamides, might be mineralized using biological methods.     

Microbial degradation of phthalic acid esters under anaerobic digestion of sludge

The microbial degradation by anaerobic sludge of three phthalates, priority pollutants, listed by both China National Environmental Monitoring Center and the U.S.EPA, namely, dimethyl (DMP), di-n-butyl (DBP) and di-n-octyl (DOP) phthalates was investigated. The experimental results indicated that the biodegradation rate and the biodegradability of three phthalates under anaerobic conditions appeared to be related to the length of the alkyl-side chains. More than 90% of DMP and DBP with the short alkyl-side chain phthalates can be degraded, whereas the DOP degradation appeared to be relatively slow under the same experimental conditions. The quantity of methane produced was measured and the results showed that both the ester groups and the phthalate ring were mineralized at a significant rate. The kinetics study demonstrated that the biodegradation of three phthalates conformed to the first-order model with respect to their concentrations.     

太阳光对湖泊中有机污染物降解的研究进展

论述了太阳光对湖泊水体中有机污染物降解作用的研究,就其降解机理、动力学特征、作用对象及降解产物等作了逐一介绍.阐明了太阳光对生物降解湖泊水体中有机污染物具有协同作用,也概述了光降解作用受pH、溶解性有机物(DOM)、水深与水体运动、地理、水文、水质与气候等因素的影响.并对实验室模拟条件下的降解与自然条件下的降解进行对比,提出今后该领域的发展前景与研究方向.     

Biodegradation of polystyrene-graft-starch copolymers in three different types of soil

Materials based on polystyrene and starch copolymers are used in food packaging, water pollution treatment, and textile industry, and their biodegradability is a desired characteristic. In order to examine the degradation patterns of modified, biodegradable derivates of polystyrene, which may keep its excellent technical features but be more environmentally friendly at the same time, polystyrene-graft-starch biomaterials obtained by emulsion polymerization in the presence of new type of initiator/activator pair (potassium persulfate/different amines) were subjected to 6-month biodegradation by burial method in three different types of commercially available soils: soil rich in humus and soil for cactus and orchid growing. Biodegradation was monitored by mass decrease, and the highest degradation rate was achieved in soil for cactus growing (81.30 %). Statistical analysis proved that microorganisms in different soil samples have different ability of biodegradation, and there is a significant negative correlation between the share of polystyrene in copolymer and degree of biodegradation. Grafting of polystyrene on starch on one hand prevents complete degradation of starch that is present (with maximal percentage of degraded starch ranging from 55 to 93 %), while on the other hand there is an upper limit of share of polystyrene in the copolymer (ranging from 37 to 77 %) that is preventing biodegradation of degradable part of copolymers.     

Comparison of biodegradation of surfactants in soils and sludge-soil mixtures by use of 14C-labelled compounds and automated respirometry

The biodegradability of dodecyl benzene sulphonate (LAS), nonylphenol-di-ethoxylate (NP2EO) and tridecyl-tetra-ethoxylate (LAE) in soil was examined by use of 14C experiments at two concentrations (10 and 400 mg/kg). Increasing the concentration of test chemical from 10 to 400 mg/kg resulted in a decrease in the relative maximum mineralization rate and an increase in the estimated lag times of a factor of approximately 3.5. In sludge-amended soil, the highest expected environmental concentration (just after sludge application) will be around 10 mg/kg for linear alkylbenzene sulphonate (LAS), while the concentration of NP2EO and linear alcohol ethoxylates (LAE) will be much lower. However, when using a respirometric method it is necessary to use a higher concentration of test substance in order to detect biodegradation. In our experiment, amendment with anaerobically digested sludge resulted in a decrease in the mineralization of LAS, NP2EO and LAE for all soils. Respirometric experiments were carried out at 400 mg/kg and could be used for estimation of biodegradation potential of LAS, NP2EO and LAE in soil and sludge-amended soil. For LAS, the results obtained from the respirometric experiments were similar to the results obtained in the 14C experiments, whereas NP2EO and LAE showed a faster degradation in the respirometric experiments.     

Contamination characteristics and degradation behavior of low-density polyethylene film residues in typical farmland soils of China

Low-density polyethylene (LDPE) film residues left in farmlands due to agricultural activities were extensively investigated to evaluate the present pollution situation by selecting the typical areas with LDPE film application, including Harbin, Baoding, and Handan of China. The survey results demonstrated that the film residues were ubiquitous within the investigated areas and the amount reached 2,400-8,200 g ha(-1). Breakage rates of the film residues were almost at the same level in the studied fields. There were relatively small amounts of film residues remaining in neighboring farmland fields without application of LDPE film. The studies showed that the sheets of LDPE residues had the same oxidative deterioration, which was probably due to photodegradation instead of biodegradation. The higher molecular weight components of the LDPE film gradually decreased, which were reflected by the appearance of some small flakes detached from the film bodies. LDPE films in the investigated fields gradually deteriorated and the decomposing levels developed with their left time increasing. The degradation behaviors of LDPE films were confirmed by using Fourier transform infrared (FTIR), scanning electron microscopic (SEM), and gel permeation chromatography analyses.     

Combined UV-biological degradation of PAHs

The UV-photolysis of PAHs was tested in silicone oil and tetradecane. In most cases, the degradation of a pollutant provided within a mixture was lower than when provided alone due to competitive effects. With the exception of anthracene, the larger pollutants (4- and 5-rings) were always degraded first, proving that UV-treatment preferentially acts on large PAHs and thereby provides a good complement to microbial degradation. UV-photolysis was also found to be suitable for treatment of soil extract from contaminated soils. The feasibility of UV-biological treatment was demonstrated for the removal of a mixture of phenanthrene and pyrene in silicone oil. UV-irradiation of the silicone oil led to 83% pyrene removal but no phenanthrene photodegradation. Subsequent treatment of the oil in a two-phases partitioning bioreactor (TPPB) system inoculated with Pseudomonas sp. was followed by complete phenanthrene biodegradation but no further pyrene removal. Totally, the combined process allowed 92% removal of the PAH mixture. Further work should focus on characterizing the photoproducts formed and studying the influence of the solvent on the photodegradation process.     

4种脂肪酸浮选捕收剂的生物降解性能研究

在好氧的条件下,以活性污泥为接种体,使用改良斯特姆法测试脂肪酸浮选捕收剂(油酸钠、9-羟基硬脂酸钠、硬脂酸钠、蓖麻油酸钠)的生物降解性能,并与利用BOD5/COD进行的可生化评价方法进行比较。结果表明:(1)油酸钠、蓖麻油酸钠的BOD5/COD分别为0.54、0.63,属易生物降解物质;9-羟基硬脂酸钠、硬脂酸钠的BOD5/COD分别为0.36、0.37,属可生物降解物质。(2)油酸钠、9-羟基硬脂酸钠、蓖麻油酸钠28d的生物降解率分别为88.6%、62.2%、100.0%,达到了经济合作与发展组织的OECD-301B生物降解性能实验标准,属于易生物降解物质;硬脂酸钠28d的生物降解率为49.8%,没有达到OECD-301B生物降解性能实验标准,属难生物降解物质。4种脂肪酸浮选捕收剂的生物降解性能依次为:蓖麻油酸钠油酸钠9-羟基硬脂酸钠硬脂酸钠。(3)当有机酸中存在碳碳双键和羟基时,有机酸的生物降解性能都会提高,并且碳碳双键的影响要大于羟基的影响;当二者同时存在时,生物降解性能会大幅度提高。     

Photocatalytic degradation of an organophosphorus pesticide phosalone in aqueous suspensions of titanium dioxide

The present work deals with photocatalytic degradation of an organophosphorus pesticide, phosalone, in water in the presence of TiO2 particles under UV light illumination (1000 W). The influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO2, irradiation time, stirring rate, and distance from UV source, on the photodegradation efficiency of phosalone was investigated. The degradation rate of phosalone was not high when the photolysis was carried out in the absence of TiO2 and it was negligible in the absence of UV light. The half-life (DT50) of a 20 ppm aqueous solution of phosalone was 15 min in optimized conditions. The plot of lnC (phosalone) vs. time was linear, suggesting first order reaction (K=0.0532 min(-1)). The half-life time of photomineralization in the concentration range of 7.5-20 ppm was 13.02 min. The efficiency of the method was also determined by measuring the reduction of Chemical Oxygen Demand (COD). During the mineralization under optimized conditions, COD decreased by more than 45% at irradiation time of 15 min. The photodegradation of phosalone was enhanced by addition of proper amount of hydrogen peroxide (150 ppm).     

Direct VUV photodegradation of gaseous α-pinene in a spiral quartz reactor: intermediates, mechanism, and toxicity/biodegradability assessment

Photodegradation of gaseous α-pinene by a vacuum ultraviolet (VUV) in a spiral reactor was investigated under various gaseous reaction media and residence time, and their respective effects on types and biodegradability of the intermediates were studied. Analysis of carbon amounts showed that about 33% and 43% of total carbon were converted to soluble organic carbon in the air medium with a relative humidity (RH) of 35-40% at empty bed residence times (EBRTs) of 18 and 45 s. Based on the identified intermediates by GC/MS and IC, a photodegradation pathway was proposed by the combined roles of photolysis, OH. photooxidation and O? photooxidation. Biodegradability to active sludge, toxicity to Chlorella vulgaris and 96-well microplates showed that α-pinene could be largely converted to more biodegradable and less toxic compounds through photodegradation in the air reaction medium with a RH of 35-40% at an EBRT of 18s, in which the initial concentration was 600 mg m?3. Therefore, VUV photodegradation could be applied as an effective pre-treatment method for detoxification and biodegradability improvement under the optimized photodegradation conditions. Such results supported the potential use of VUV photodegradation to improve the removal capacity of conventional biological treatments for hydrophobic and poorly biodegradable compounds.     

Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters

This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L^?1, are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.     

Degradation of organophosphoric esters in leachate from a sea-based solid waste disposal site

Degradation of organophosphoric esters (OPEs) in leachate from a sea-based solid waste disposal site was investigated by laboratory experiment. Aryl-phosphates, tricresyl phosphate and triphenyl phosphate, in leachate rapidly decreased to less than the detection limit within 20 days under aerobic condition, suggesting high biodegradability. These phosphates also decreased in sterilized leachate, which suggested a contribution to degradation by reactions (adsorption and chemical degradation) with chemicals in the leachate. Concerning alkyl-phosphates, tributyl phosphate decreased rapidly after one week, which is considered to have been caused by biodegradation. Tris-2-ethylhexyl phosphate and tris-2-butoxyethyl phosphate decreased slowly in all samples but that of sterilized distilled water. This however, suggested contribution of biodegradation because the velocity of decrease in the leachate was higher than in control samples. Among chloro alkylphosphates, decrease of tris-2-chloroethyl phosphate and tris-dichloropropyl phosphate were observed though it was not obvious whether by biodegradation or not. Decrease of tris-2-chloropropyl phosphate (TCPP) was not observed for 80 days suggesting that TCPP remains in the leachate over a long period of time. Except for aryl-phosphates decrease of OPEs was not observed under anaerobic condition. It was considered that the composition ratio and the behavior of OPEs in leachate in the field reflects the biological and chemical degradation as well as the chemical properties of OPEs.     

TiO2膜光催化降解4，4’-二溴联苯的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中4,4’-二溴联苯（4,4’-DBB）的效果,考察了溶液pH值和4,4’-DBB初始浓度等对TiO2膜光催化降解4,4’-DBB的影响,探讨了降解机理。结果表明,TiO2膜光催化降解水中4,4’-DBB的效果良好,紫外光照射8h,初始浓度为4mg／L的4,4’-DBB的降解率高达94％,降解速率随着4,4’-DBB初始浓度的增大而下降。在溶液pH：1时,4,4’-DBB的降解效率最高。超声的加入使降解反应的速率加快。经拟合发现4,4’-DBB的降解符合拟一级反应规律,并推导出动力学方程。