Photolysis of fluometuron in the presence of natural water constituents

Phototransformation of the herbicide fluometuron (1 microM) in natural sunlight was investigated in neutral Milli-Q water and in synthetic waters containing either fulvic acids, nitrate ions or both in order to mimic reactions taking place in aquatic environments. Fluometuron degradation followed a pseudo-first order kinetics. The reaction was faster in synthetic than in Milli-Q water. Fulvic acids (10 mg l(-1)) increased the rate of fluometuron photolysis by a factor 2.5 and nitrates (25 mg l(-1)) by a factor 15. Identification of major photoproducts was conducted under laboratory conditions using LC-ESI-MS. Numerous photoproducts were detected and tentatively characterized. In the presence of nitrates, hydroxylation of the aromatic ring with or without hydrolysis of CF(3) into CO(2)H and oxidation of the urea chain leading to demethylation were observed. In the presence of fulvic acids, hydroxylation of the aromatic ring was the major reaction route.     

Photo-induced degradation of diuron in aqueous solution by nitrites and nitrates: kinetics and pathways

The photo-induced degradation of diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea) in aqueous solution under simulated solar irradiation has been investigated in the presence of NO3-/NO2- ions. The degradation rates were compared by varying environmental parameters including substrate and inducer concentrations, oxygen content and pH. The photoproducts were identified by extensive LC-ESI-MS and LC-ESI-MS-MS studies after SPE preconcentration on prepacked cartridges. In both NO3- and NO2- conditions, oxidation of the N-(CH3)2 terminus group is the main process leading to the N-monodemethylated (NHCH3), N-formyl (N(CH3)CHO) and the uncommon and unstable carbinolamine (N(CH3)CH2OH) by-products. Cl/OH substituted and nitrated phenylureas are formed minorily. Degradation pathways involving OH* and NO2* (or dimer) radicals as reactive species are proposed.     

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.     

Sonochemically induced decomposition of energetic materials in aqueous media

This study demonstrates that ultrasound rapidly degrades the energetic compounds RDX (cyclo-1,3,5-trinitramine-2,4,6-trimethylene) and ADN (ammonium dinitramide) in aqueous microheterogeneous media. The conditions for effective degradation of these nitramines, as monitored by UV absorption spectroscopy, were determined by varying sonication time, the heterogeneous phase and its suspension density, and the concentration of NaOH. In the presence of 5 mg/ml of aluminum powder and at pH approximately 12 (10 mM NaOH), 74% of the RDX and 86% of the ammonium dinitramide (ADN) in near-saturated solutions decompose within the first 20 min of sonication (20 kHz; 50 W; < or =5 degrees C). Sonication without Al powder and base yields minimal degradation of either RDX and ADN (approximately 5-10%) or the nitrite/nitrate ions that are expected byproducts during RDX and ADN degradation. Sonication at high pH in the presence of dispersed aluminosilicate zeolite, alumina, or titanium dioxide also yields minimal degradation. Preliminary electrochemical studies and product analyses indicate that in situ ultrasonic generation of metallic aluminum and/or aluminum hydride drives reductive denitration of the nitramines. Sonochemical treatment in the presence of a reductant offers an effective and rapid waste remediation option for energetic waste compounds.     

微波辅助法合成纳米ReFeO3光催化剂

以稀土金属硝酸盐La（NO3）3、Sm（NO3）3、Eu（NO3）3、Gd（NO3）3和Fe（NO3）3.9H2O为原材料,以活性炭为模板剂,聚乙烯醇（PVA）和尿素分别用作阻聚剂和均相沉淀剂,在微波辐照下制得纳米钙钛矿型化合物ReFeO3（Re：La,Sm,Eu,Gd）。用X射线粉末衍射仪（XRD）、UV-vis漫反射仪（DRS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）对产物组成、结构、颗粒大小、形貌等进行了表征,结果表明产物均为单一钙钛矿结构的纳米颗粒。以产物为光催化剂,在可见光照射下对罗丹明B水溶液进行光催化降解实验,发现该类化合物均具有较好的光催化活性,180 min内对罗丹明B的脱色率均达到85%以上。     

Mineralization of C.I. Reactive Yellow 84 in aqueous solution by sonolytic ozonation

The operational parameters and mechanism of mineralization of C.I. Reactive Yellow 84 (RY84), one of the azo dyes, in aqueous solution were investigated using sonolytic ozonation (US/O(3) oxidation). Of the pseudo-first-order degradation rate constants of TOC reduction, 9.0 x 10(-4), 7.3 x 10(-3) and 1.8 x 10(-2)min(-1) were observed with US, O3, and a combination of US and O3, respectively. These results illustrate that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone without considering the operating costs. With the initial pH value at 10.0, the ozone dose at 4.5 g h(-1), the energy density of ultrasound at 176 W l(-1), and the initial concentration of RY84 at 100 mg l(-1), the extent of mineralization measured as TOC loss was maximized. The variation of the concentrations of related ions (oxalate, formate, acetate, NO3(-), NO2(-), NH4(+), Cl(-), and SO4(2-)) during the reaction process was monitored. Other organic intermediates detected by GC/MS were N-methyleneaniline, phthalic acid, 4-hydroxyphthalic acid, isocyanatobenzene, aniline, 4-iminocyclohexa-2,5-dien-1-one, butene diacid and urea. Based on these findings, a tentative degradation pathway was proposed.     

Responses of greening bean seedling leaves to nitrogen dioxide and nutrient nitrate supply

Phaseolus vulgaris cv. Kinghorn Wax seedlings grown in darkness at 25 degrees C for 7 days with half strength Hoagland's nutrient solution containing no nitrogen, were transferred to lit continuous stirred tank reactors (CSTRs) in atmospheres containing 0 or 0.3 ppm NO(2) and irrigated with a nutrient solution containing 0 or 5 mm nitrate as sole nitrogen source and allowed to grow for a period of up to 5 days in a 14 h photoperiod. Exposure to NO(2) increased total Kjeldahl nitrogen in the leaves. Further, the exposure to NO(2) increased chlorophyll content from day 3 onwards and inhibited the leaf dry weight substantially on days 4 and 5. The primary leaves of the seedlings exposed to 0.3 ppm NO(2) and supplied with nitrate accumulated some nitrite after 5 days of exposure. Some of the seedlings were returned from CSTRs to growth chambers and allowed to grow for a further period of 5 days in a 14 h photoperiod without NO(2). The growth which developed after the NO(2) exposure growth period, as measured by fresh and dry weights of the leaves, was significantly less in NO(2)-exposed plants than in nitrate-grown plants. The experiments demonstrate that the leaves of greening seedlings are able to assimilate NO(2) and that a reduction in leaf dry weight by prolonged NO(2) exposure in the presence of nutrient nitrate can be associated with nitrite accumulation, and that NO(2) has a carry-over effect beyond the duration of NO(2) exposure. It is apparent that NO(2) induces some durable biochemical or cytological aberration in the presence of nutrient nitrate, which adversely affects subsequent leaf growth.     

Effects of various ions on the dechlorination kinetics of hexachlorobenzene by nanoscale zero-valent iron

The effect of several anions and cations normally co-present in soil and groundwater contamination sites on the degradation kinetics and removal efficiency of hexachlorobenzene (HCB) by nanoscale zero-valent iron (NZVI) particles was examined. The degradation kinetics was not influenced by the HCO(3)(-), Mg(2+), and Na(+) ions. It was enhanced in the presence of the Cl(-) and SO(4)(2-) ions due to their corrosion promotion. The NO(3)(-) competes with HCB so it inhibits the degradation reaction. The Fe(2+) ions would inhibit the degradation reaction due to passivation layer formed, while it was enhanced in the presence of Cu(2+) ions resulted from the reduced form of copper on NZVI surfaces. These observations lead to a better understanding of HCB dechlorination with NZVI particles and can facilitate the remediation design and prediction of treatment efficiency of HCB at remediation sites.     

Enhanced photoelectrocatalytic performance of Zn-doped WO(3) photocatalysts for nitrite ions degradation under visible light

WO(3) and Zn-doped WO(3) thin films were prepared on indium-tin oxide glass by a dip-coating. The composite films were characterized by UV-Vis absorption spectra, X-ray diffraction and scanning electron microscope. The effect of preparation conditions (concentration of Zn, annealing temperature, number of layers) on the photocurrent was studied. It was found that the photocurrent under visible light displayed the highest value for 2% Zn-WO(3) films annealed at 400 degrees C. The photocatalytic activity of the Zn-doped WO(3) was evaluated in terms of decay rate of nitrite ions under visible light. The influence of applied potential, initial pH and nitrite concentration on the reaction rate was studied. The experiments demonstrated that NO(2)(-) could be efficiently degraded on the doped photoanode that showed a higher activity than the undoped WO(3) especially under high anodic potential (>0.7 V). The rate of degradation was enhanced in aqueous NaCl solutions. Furthermore, it was demonstrated that the photodegradation mechanism of NO(2)(-) proceeded mainly indirectly via OH radicals. The possible reason of enhancement of reaction rate was also discussed.     

Nitrification in polluted soil fertilized with fast- and slow-releasing nitrogen: a case study at a refinery landfarming site

The nitrifying activity and the effect of fertilization with urea and methylene urea were studied in a landfarming site. The site has been operative over 20 years and maintained by heavy nitrogen fertilization. The landfarming soil contained 4-6% (w/w) oil. The nitrate accumulation was 20-50mg NO3-N day(-1)kg(-1) observed after methylene urea fertilization of 889 g Nm(-2). Nitrification ex situ (in laboratory conditions) was 8.8 mg NO3-N day(-1) kg(-1) in the presence of 380 mg kg(-1) NH4+-N. The half-saturation concentration of nitrification was more than 200 mg NH4+-N kg(-1). The results show that nitrification was active in soil with high oil concentration. Urea fertilization of 893 g Nm(-2) caused an increase of soil NH4+-N concentration up to 5500 mg kg(-1) and pH>8.5. This led to inhibition of nitrification, which persisted after NH4+ concentration decreased below 200mg NH4+ kg(-1).     

An anaerobic continuous-flow fixed-bed reactor sustaining a 3-chlorobenzoate-degrading denitrifying population utilizing versatile electron donors and acceptors

An anaerobic continuous-flow fixed-bed column reactor capable of degrading 3-chlorobenzoate (3-CBA) under denitrifying conditions was established, and its rate reached 2.26 mM d(-1). The denitrifying population completely degraded 3-CBA when supplied at 0.1-0.54 mM, but its activity was partly suppressed when 3-CBA was supplied at 0.89 mM. Nitrate was concomitantly consumed throughout the operation of the reactor, the amount of which was similar to or up to 35% higher than the theoretical stoichiometric value that was calculated by assuming that 3-CBA degradation is coupled with denitrification. Batch incubation experiments proved that nitrate is strictly required for 3-CBA degradation in the absence of molecular oxygen. The population also degraded 3-CBA aerobically. Benzoate and 4-CBA were degraded under denitrifying conditions as well as 3-CBA, but 2-CBA was not. Considering that the previously reported denitrifying 3-CBA-degrading cultures do not exhibit 4-CBA degradation under denitrifying conditions, nor aerobic 3-CBA degradation [FEMS Microbiol. Lett. 144 (1996) 213, Appl. Environ. Microbiol. 66 (2000) 3446], the microbial population developed in this experiment was physiologically versatile with respect to the utilization of both electron donors and electron acceptors.     

HPLC determination of chlorate metabolism in bovine ruminal fluid

Salmonella and Escherichia coli are two bacteria that are important causes of human and animal disease worldwide. Chlorate is converted in the cell to chlorite, which is lethal to these bacteria. An HPLC procedure was developed for the rapid analysis of chlorate (ClO(3)(-)), nitrate (NO(3)(-)), and nitrite (NO(2)(-)) ions in bovine ruminal fluid samples. Standard curves for chlorite, nitrite, nitrate, and chlorate were well defined linear curves with R(2) values of 0.99846, 0.99106, 0.99854, and 0.99138, respectively. Concentrations of chlorite could not be accurately determined in bovine ruminal fluid because chlorite reacts with or binds a component(s) or is reduced to chloride in bovine ruminal fluid resulting in low chlorite measurements. A standard curve ranging from 25 to 150 ppm ClO(3)(-) ion was used to measure chlorate fortified into ruminal fluid. The concentration of chlorate was more rapidly lowered (P < 0.01) under anaerobic compared to aerobic incubation conditions. Chlorate alone or chlorate supplemented with the reductants sodium lactate or glycerol were bactericidal in anaerobic incubations. In anaerobic culture, the addition of sodium formate to chlorate-fortified ruminal fluid appeared to decrease chlorate concentrations; however, formate also appeared to moderate the bactericidal effect of chlorate against E. coli. Addition of the reductants, glycerol or lactate, to chlorate-fortified ruminal fluid did not increase the killing of E. coli at 24 h, but may be useful when the reducing equivalents are limiting as in waste holding reservoirs or composting systems required for intense animal production.     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Enhancement by anthraquinone-2-sulphonate of the photonitration of phenol by nitrite: implication for the photoproduction of nitrogen dioxide by coloured dissolved organic matter in surface waters

Anthraquinone-2-sulphonate (AQ2S) under UVA irradiation is able to oxidise nitrite to (·)NO(2) and to induce the nitration of phenol. The process involves the very fast reactions of the excited triplet state (3)AQ2S(*) and its 520-nm absorbing exciplex with water, at different time scales (ns and μs, respectively). Quinones are ubiquitous components of coloured dissolved organic matter (CDOM) in surface waters and AQ2S was adopted here as a proxy of CDOM. Using a recently developed model of surface-water photochemistry, we found that the oxidation of nitrite to (·)NO(2) by (3)CDOM(*) could be an important (·)NO(2) source in water bodies with high [NO(2)(-)] to [NO(3)(-)] ratio, for elevated values of column depth and NPOC.     

Photocatalytic degradation of pesticides in pure water and a commercial agricultural solution on TiO2 coated media

Heterogeneous photocatalysis of pesticides is an effective process for removing pesticides from pure water. With a view to treating real agricultural effluents, this paper deals with the degradation of the chlortoluron and cyproconazole pesticides in pure water and the treatment of commercial solutions by photocatalysis on TiO2 coated media. The process was effective in degrading and mineralizing the pesticides. The changes of the fate of heteroatoms showed that during irradiation of the chlortoluron and cyproconazole, NH4+ and NO3(-) ions were produced. A release of chloride ions was observed from the beginning of the irradiation and stoichiometry was achieved. The photodegradation of chlortoluton and cyproconazole in commercial solutions was studied. For the degradation of chlortoluton in a commercial solution, the mineralization was completely achieved whereas in the case of the commercial cyproconazole solution, the degradation kinetic was lower. These results highlight the fact that the chemical nature of the additives in the commercial pesticide solutions does significantly affect the degradation yield of the target compound by photocatalysis.     

Phenol nitration upon oxidation of nitrite by Mn(III,IV) (hydr)oxides

An interesting aspect of the chemistry of nitrite is the possibility for this compound to interact with other environmental factors and many oxidising species, which results in the oxidation of nitrite to nitrogen dioxide. This is a potentially interesting process that can lead to the formation of nitroaromatic compounds in the environment. In previous papers we have shown that nitrite can interact with dissolved Fe(III) and nitrate under irradiation, Fenton and heterogeneous photo-Fenton reagents, and semiconductor oxides such as TiO2, alpha-Fe2O3, and beta-FeOOH under irradiation. This paper reports on the interaction between nitrite/nitrous acid and the Mn(III,IV) (hydr)oxides beta-MnO2 and gamma-MnOOH, both in neutral solution under irradiation and in acidic conditions in the dark. beta-MnO2 and gamma-MnOOH originate from the oxidation of Mn(II) and play a key role in the redox cycling of manganese in the environment. These Mn(III,IV) (hydr)oxides show some photocatalytic activity, and they can act as thermal oxidants at acidic pH. The photoinduced oxidation of nitrite and the thermal oxidation of nitrous acid by Mn(III,IV) (hydr)oxides yield nitrogen dioxide and lead to the formation of nitrophenols in the presence of phenol. These processes can take place at the water-sediment or water-colloid interface in natural waters and on the surface of atmospheric particulate. Furthermore, the phenol/gamma-MnOOH/HNO2 system in dark acidic solution is an interesting model due to the formation of phenoxyl radical upon phenol monoelectronic oxidation by gamma-MnOOH. The kinetics of nitrophenol generation under such conditions indicates that phenol nitration is unlikely to take place upon reaction between phenoxyl and *NO2 and suggests a solution to a literature debate on the subject.     

Electrocatalytic reduction of nitrate ions from water using polyaniline nanofibers modified gold electrode

Polyaniline (PANI) nanofibers were electrochemically synthesized on gold electrode using ethanol as soft template by the cyclic voltammetry technique. The PANI nanofibers were characterized by Fourier transform infrared spectroscopy, UV-visible spectroscopy, and scanning electron microscopy. Linear sweep voltammetry was used to investigate electrocatalytic activity of the PANI nanofibers modified electrode toward the reduction of nitrate ions. Results showed that the electroreduction process strongly depends on the applied potential. At the potential value of about -0.8 V vs Ag/AgCl, the electroreduction of nitrate anions to nitrite anions was identified as the rate-determining step of the electroreduction process. In the potential range of -0.8 to -1.0 V, reduction of nitrite to hydroxylamine occurs, followed by the reduction to ammonia. At potentials more negative than -1.0 V, nitrite is directly reduced to ammonia. This study demonstrates the effectiveness of PANI nanofibers modified electrode in the electroreduction of nitrate ions compared to traditional reduction methods.     

Ammonium, nitrate and nitrite nitrogen and nitrate reductase enzyme activity in groundnut (Arachis hypogaea L.) fields after diazinon, imidacloprid and lindane treatments

Impacts of diazinon (O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate), imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] and lindane (1,2,3,4,5.6-hexachlorocyclohexane) treatments on ammonium, nitrate, and nitrite nitrogen and nitrate reductase enzyme activities were determined in groundnut (Arachis hypogaea L.) field for three consecutive years (1997 to 1999). Diazinon was applied for both seed- and soil-treatments but imidacloprid and lindane were used for seed treatments only at recommended rates. Diazinon residues persisted for 60 days in both the cases. Average half-lives (t1/2) of diazinon were found 29.3 and 34.8 days respectively in seed and soil treatments. In diazinon seed treatment, NH4(+), NO3(-), and NO2(-) nitrogen and nitrate reductase activity were not affected. Whereas, diazinon soil treatment indicated significant increase in NH4(+)-N in a 1-day sample, which continued until 90 days. Some declines in NO3(-)N were found from 15 to 60 days. Along with this decline, significant increases in NO2(-)N and nitrate reductase activity were found between 1 and 30 days. Imidacloprid and lindane persisted for 90 and 120 days with average half-lives (t1/2) of 40.9 and 53.3 days, respectively. Within 90 days, imidacloprid residues lost by 73.17% to 82.49% while such losses for lindane residues were found 78.19% to 79.86 % within 120 days. In imidacloprid seed-treated field, stimulation of NO3(-)N and the decline in NH4+NO2(-)-N and nitrate reductase enzyme activity were observed between 15 to 90 days. However, lindane seed treatment indicated significant increases in NH4(+)-N, NO2(-)-N and nitrate reductase activity and some adverse effects on NO3(-)N between 15 and 90 days.     

Studies on nitric oxide (NO) formation by the green alga Scenedesmus obliquus and the diazotrophic cyanobacterium Anabaena doliolum.

This study provides preliminary evidence that NO production could be a general attribute of algae. Anabaena doliolum was found to be a better NO producer than Scenedesmus and Synechoccocus. Experiments conducted with inhibitors of photosynthesis (DCMU), ATP synthesis (DCCD), and the uncoupler (2,4-DNP) and its analog arsenate clearly revealed that inhibition of nitrite assimilation through the blockage of nitrite reductase (NiR) is primarily responsible for NO emission. A linear relationship between nitrite concentration in the culture medium and NO in the exhaust gas supports the view that accumulation of nitrite is responsible for NO formation. A failure of Scenedesmus, grown in the medium substituted with W for Mo, to produce either NO/NO-2 in light or a 'light-off' peak, and a resumption of these activities upon the addition of Mo proved beyond doubt that a functional nitrate reductase (NR) is necessary for the production of nitrite and NO by algae grown on nitrate as the nitrogen source. Moreover, the appearance of a NO peak immediately after nitrite supplementation under dark conditions in W-substituted cultures with or without glucose ruled out an enzymatic role of NR in NO emission.     

MnOx／Al-SBA-15催化剂低温NH3选择性催化还原NO的原位红外研究

用原位红外分别进行了MnOx／Al-SBA-15催化剂上NH3和NO＋O2的吸附态和瞬态实验以及NH3＋NO＋02反应的稳态实验。结果表明,催化剂上存在着L酸位和B酸位,NH3吸附在催化剂上形成配位态的NH3和NH4＋,配位态的NH3能脱氢形成-NH2活性中间态。NO＋O2在催化剂上吸附形成硝酸盐类、硝基类和亚硝酸盐类。将NO＋O2通入预吸附NH3的催化剂中时,表面的配位态的NH3、NH4＋和-NH2都会减少直至消失,SCR反应显著。而将NH3通人预吸附NO＋O2的催化剂中时,只有硝基类和亚硝酸盐类减少,硝酸盐类基本不发生变化,SCR反应微弱。NH3＋NO＋O2稳态反应中,催化剂表面稳定存在着NH4＋和硝酸盐类,SCR反应显著。