Formation of mutagens by photochemical reaction of biphenyl in nitrate aqueous solution

Biphenyl was found to be converted to mutagenic compounds by UV irradiation with a high-pressure mercury lamp in nitrate aqueous solution under neutral conditions. The mutagenicity of the reaction mixture increased in proportion to the nitrate ion concentration. The most mutagenic product was dinitro dihydroxy biphenyl, and the main products in this reaction were 2-hydroxy-3-nitrobiphenyl and 4-hydroxy-3-nitrobiphenyl.     

Destruction of phenol aqueous solution by photocatalysis or direct photolysis

The photodegradation of phenol has been investigated under a high-pressure mercury lamp with a kind of jacket (glass or quartz) depending on used UV light range and a variety of experimental conditions: UV (lambda > 200 nm) with oxygen or with TiO2 and oxygen or with N2; UV (lambda > 330 nm) with oxygen or with TiO2 and oxygen or with N2. Photocatalysis and direct photolysis of phenol have different reaction pathways. Direct photolysis of phenol yielded a brown-yellow complex organic polymer in both aerobic and anaerobic environments. The polymer cannot be mineralized in an anaerobic environment. The effects of catalyst amount and oxygen concentration in the reaction atmosphere on the destruction of phenol were studied. The results prove that an appropriate catalyst amount can avoid direct photolysis and increase the mineralization rate of phenol.     

Photochemical nitrosation of dimethylamine in aqueous solution containing nitrite

Dimethylamine was found to be nitrosated photochemically in aqueous solution containing nitrite both by the irradiation with a high pressure mercury lamp and by the exposure to sunlight to give nitrosodimethylamine, a well-known carcinogen. The nitrosation occurred more readily at alkaline pH than at acidic and neutral pH. These findings suggest that nitrosodimethylamine is produced photochemically under natural environmental conditions.     

Hydrolysis and photolysis of oxytetracycline in aqueous solution

Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day^{? 1} were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 10² to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca^{2 +} made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day^{? 1}, which is comparable to that of hydrolysis at 60°C. The presence of Ca^{2 +} accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca^{2 +}. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.     

双系统离子色谱同时测定河流中氨氮、亚硝酸盐和硝酸盐的含量

水样经o.22μm微孔滤膜过滤后,通过双系统离子色谱,分别以氢氧化钾和甲烷磺酸作为流动相,抑制电导检测,成功建立了同时、准确、快速测定河流中氨氮、亚硝酸盐和硝酸盐的方法.结果表明,该方法检出限o.001～0.002 mg/L,相对标准偏差1.2％～1.9％,加标回收率89.6％～101.5％.该方法操作简便、快速、选择性好,检出限可满足环境水质分析的要求.     

中性红在柚子皮上的吸附机制研究

采用柚子皮作为生物吸附材料吸附去除中性红。研究了中性红的初始浓度、吸附时间及反应温度对吸附效果的影响。结果表明,当中性红溶液从100 mg/L升高到250 mg/L时,反应95 min后,柚子皮对中性红的吸附量从16.80 mg/g增加到40.00mg/g。中性红在柚子皮上的吸附在60 min内基本上可以达到平衡,且柚子皮对中性红的吸附过程为放热过程;二级吸附动力学方程能更好地描述中性红在柚子皮上的吸附行为;中性红在柚子皮孔隙中的扩散不是唯一的吸附速率控制步骤,这个吸附过程可能受多个步骤共同控制;柚子皮对中性红的吸附是自发吸附,Langmuir、Freundlich和Temkin吸附等温式能很好地拟合柚子皮对中性红的吸附过程,拟合相关系数分别达到了0.991 8、0.993 4、0.989 0。     

Photolytic degradation of fluoroquinolone carboxylic acids in aqueous solution

Subsequent to irradiation with a xenon lamp simulating sunlight, fluoroquinolone carboxylic acids in aqueous solution form polar pyridone dicarboxylic and tricarboxylic acids. After liquid/liquid partition with chloroform/water these substances can be isolated by ion exchange chromatography of the aqueous phase. They can be regarded as intermediate compounds on the route to a complete photomineralization. The structural elucidation is performed by such mass spectroscopic methods as MS, GC/MS and HPLC/MS, whereby HPLC/MS shows the highest reliability. Additionally¹H- and¹³C-NMR measurements confirm the structure of the main polar degradation product.     

Degradation of bisphenol A in aqueous solution by persulfate activated with ferrous ion

Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO₄ ^?·), which was generated by the activation of persulfate (S₂O₈ ^2?) with ferrous ion (Fe²⁺). S₂O₈ ^2? was activated by Fe²⁺ to produce SO₄ ^?·, and iron powder (Fe⁰) was used as a slow-releasing source of dissolved Fe²⁺. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S₂O₈ ^2? or Fe²⁺ concentrations and then decreased with excess Fe²⁺ concentration. The adding mode of Fe²⁺ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe²⁺, while complete degradation was observed with continuous diffusion of Fe²⁺, and the latter achieved higher TOC removal rate. When Fe⁰ was employed as a slow-releasing source of dissolved Fe²⁺, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe⁰–S₂O₈ ^2? system, Fe⁰ as the activator of S₂O₈ ^2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe⁰–S₂O₈ ^2? system has perspective for future works.     

Nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution

This paper studies the nitration and hydroxylation of benzene in the presence of nitrite/nitrous acid in aqueous solution, both in the dark upon addition of hydrogen peroxide and under 360 nm irradiation. In both cases the detected transformation intermediates were phenol (P), nitrobenzene (NB), 2-nitrophenol (2NP) and 4-nitrophenol (4NP). P and NB directly form from benzene, and the initial formation rate of P is at least an order of magnitude higher than that of NB. In our experiments nitrophenols arise from P nitration, as can be inferred by their time evolution and isomer ratio (2NP:4NP=60:40, 3NP below detection limit). Nitrophenols may also form upon hydroxylation of NB, but in a different ratio (2NP:3NP:4NP=45:30:25). The detection of 3NP is thus a marker for the hydroxylation of NB, since this isomer is not formed in P nitration processes. The formation rates of P and NB increase with decreasing pH, both in the presence of HNO₂ + H₂O₂ in the dark (which produce HOONO) and in the presence of NO₂⁻/HNO₂ under irradiation. In the former case the pH dependence reflects the formation rate of HOONO. In the case of the irradiation experiments the pH effect can be accounted for by the higher molar absorbivity and photolysis quantum yield of nitrous acid when compared with nitrite. Interestingly, benzene does not react with HNO₂ alone in the dark. An important feature of benzene nitration in the presence of NO₂⁻/HNO₂ under irradiation is that the process is not inhibited by the addition of hydroxyl scavengers, differently from the case of phenol nitration. This finding indicates that nitrite irradiation might lead to the nitration of certain aromatic compounds in natural waters even in the presence of natural hydroxyl scavenging agents, which are usually thought to limit the environmental role of many photochemical processes.     

Photocatalytic oxidation of nitrite in water to nitrate

It is found that the nitrite in water is converted into nitrate by irradiation in the presence of oxygen and titanium dioxide which acts as a catalyst. As nitrate is a less hazardous contaminant, this method might be worth investigating further for the treatment of water.     

Formation of nitrophenols upon UV irradiation of phenol and nitrate in aqueous solutions and in TiO2 aqueous suspensions.

The formation of nitrophenols was studied as a consequence of ultra violet (UV) irradiation of aqueous solutions of phenol and nitrate in the range of pH 1-12. The study was performed both in homogeneous phase and in the presence of water-suspended TiO2. The effects of pH, dissolved oxygen and 2-propanol as .OH scavenger have been evaluated. A reaction mechanism is proposed, based on the experimental results.     

The effects of pH, bromide and nitrite on halonitromethane and trihalomethane formation from amino acids and amino sugars

In this study, the effects of pH, bromide and nitrite on the formation of halonitromethanes (HNMs) and trihalomethanes (THMs) from eight amino acids (glycine, alanine, serine, cysteine, aspartic acid, glutamic acid, lysine and histidine) and four amino sugars (glucosamine, galactosamine, N-acetylglucosamine and N-acetylneuraminic acid) were examined for chlorination and ozonation followed by chlorination. During ozonation-chlorination, two amino acids, glycine and lysine, exhibited distinctly higher HNM formation than the other compounds. The formation of HNMs was higher at pH 8 than 6. Glycine and lysine also produced higher levels of THMs than the other compounds at pH 8. The presence of nitrite resulted in an increase in HNM formation. The presence of bromide increased the HNM formation, especially brominated HNM species. Bromine incorporation factors of trihalogenated HNMs were higher than those of THMs. For chlorination alone, HNM levels were about the detection limit (4 nM or 0.7 μg L⁻¹) at pH 6 and 8, and in the presence of bromide or nitrite. Amino acids and amino sugars tested, except glycine and lysine, showed relatively low levels of THM (∼15 μg L⁻¹) formation.     

丙酮酸钠光解引发染料水溶液的脱色

对丙酮酸钠紫外光解所引发的染料橙黄Ⅱ的脱色进行了研究,讨论了pH值、丙酮酸钠初始浓度、染料初始浓度及外加Fe(Ⅲ)对橙黄Ⅱ光致脱色的影响,比较了4种染料的脱色效果,并对反应机理进行了初步探讨.实验表明,丙酮酸盐对染料有较高的光降解脱色效率;pH为3.0～8.0的范围内,橙黄Ⅱ都有很高的脱色率;丙酮酸盐的初始浓度越大,橙黄Ⅱ脱色率和反应初始速率越大;橙黄Ⅱ浓度越大,其脱色率越低,但反应初始速率变化不大;外加Fe(Ⅲ)会抑制橙黄Ⅱ脱色;Fe(Ⅲ)-丙酮酸在水体中也能产生·OH;橙黄Ⅱ的脱色是由丙酮酸钠光解产生的活性自由基等所致,但不是·OH.     

Visual determination of nitrite and nitrate in waters by color band formation method

A spot test for aqueous nitrate and nitrite for controlling nitrogen removal performance in small-scale wastewater treatment facilities is proposed. In this method, NO(2)(-) ion in water samples was allowed to react with sulfanilic acid and 1-naphthol to form an anionic azo dye. The resulting colored solution was introduced onto a mini column (similar to a gas detecting tube) packed with PVC particles coated with benzyl cetyl dimethyl ammonium chloride (BCDMA) and biphenyl. The NO(2)(-)-N concentration was determined visually by measuring the color band length (CBL) in the column. The CBL correlates linearly with nitrite concentration in the 4-20 mg-N l(-1) range. The concentration of nitrite+nitrate was determined after reduction to nitrite with zinc. The concentration of NO(3)(-)-N species was calculated by difference. This method was used to visually determine the concentrations of NO(2)(-)-N and (NO(2)(-)+NO(3)(-))-N in domestic wastewater samples with maximum suspended solid (SS) and chemical oxygen demand (COD) concentrations of 114 mg l(-1) and 73.9 mg l(-1), respectively.     

Direct and indirect photolysis of cyhalofop in aqueous systems

The photodegradation of the aryloxyphenoxy propionic herbicide cyhalofop-butyl (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]butylpropanoate (CyB), and of its primary metabolite (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CyA) was studied in water at different irradiation wavelengths. The sunlight irradiation was investigated also in the presence of humic acid (HA), Fe oxide, titanium dioxide (TiO₂) and zinc oxide (ZnO) as photocatalysts.CyB and CyA were rapidly degraded by UV irradiation. CyB afforded the butyl ester of 2-[3-(4-cyano-2-fluorophenyl)-4-hydroxy-phenoxy]propanoic acid (CyI), a metabolite arising from a photo-Fries rearrangement. Instead, CyA yielded (R)-2-4-(4-carboxyl-2-fluorophenoxy)phenoxypropanoic acid (CyD), a dicarboxylic acid arising from the photo-hydrolysis of cyano group via amide. CyB was stable in simulated sunlight also in the presence of the catalysts tested.The irradiation of a CyA solution, in the presence of HA or Fe oxide, with simulated sunlight did not produce any significant degradation. In the same experimental conditions, CyA was totally mineralized in the presence of TiO₂ and ZnO.     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl(-) increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl(-) at total mineralization was detected when initial diuron concentration was 13.8 mg L(-1). For N species, the final concentrations of NO3(-) and NH4+ after 60 min of reaction time were 0.28 and 0.19 mg L(-1), respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na2CO3, additive NaHCO3 and additive H2O2 were all advantageous to improve the degradation efficiency of diuron.