Kinetics and hydrolysis of fenamiphos, fipronil, and trifluralin in aqueous buffer solutions.

Hydrolyses of fenamiphos, fipronil, and trifluralin were studied in aqueous buffer solutions of pH 4.1, 7.1, and 9.1 at different temperatures, 5, 22 +/- 1, 32 +/- 1, and 50 +/- 1 degrees C. Fenamiphos, fipronil, and trifluralin were found to be more stable in acidic and neutral buffer solutions at temperatures of 5 and 22 +/- 1, and dissipation is rapid at 50 +/- 1 degrees C. In basic buffer and at higher temperature, degradation of fenamiphos was found to be very rapid when compared with fipronil and trifluralin. The rate constants calculated at 32 degrees C for fenamiphos were 2349.4 x 10(-)(8) (pH 4.1), 225.2 x 10(-)(8) (pH 7.1), and 30476.0 x 10(-)(8) (pH 9.1); for fipronil 1750.0 x 10(-)(8) (pH 4.1), 3103.0 x 10(-)(8) (pH 7.1), and 3883.0 x 10(-)(8) (pH 9.1); and for trifluralin 2331.0 x 10(-)(8) (pH 4.1), 2360.0 x 10(-)(8) (pH 7.1), and 3188.0 x 10(-)(8) (pH 9.1). On the basis of rate constant values, these pesticides appeared to be more susceptible to hydrolysis than synthetic organophosphorus compounds such as chlorpyriphos, diazinon, malathion, and ronnel. DT(50) values calculated at 32 degrees C were 228 (pH 4.1), 5310.24 (pH 7.1), and 37.68 (pH 9.1) h for fenamiphos; 608.6 (pH 4.1), 373.9 (pH 7.1), and 270.2 (pH 9.1) h for fipronil; and 502.1 (pH 4.1), 496.8 (pH 7.1), and 355.7 (pH 9.1) h for trifluralin.     

Kinetics and mechanism of the primary steps of degradation of carotenoids by acid in homogeneous solution

The kinetics of reaction between trifluoroacetic acid as an acid of medium strength and the carotenoids beta-carotene, zeaxanthin, canthaxanthin, and astaxanthin has been examined in detail including the effects of dioxygen, acid concentration, and carotenoid structure. Reaction between acid and carotenoid leads to species absorbing in the red and near-infrared (NIR) spectral regions, intermediates that subsequently disappear. ESR experiments clearly show that these species are not carotenoid radicals, although their NIR absorption is similar to the absorption of carotenoid radical cations. Under most reaction conditions, the disappearance of carotenoids follows pseudo-zero-order kinetics, whereas the reaction order is >1 with respect to acid, and the long-lived (hours) intermediates are suggested to be mono- (700 nm) and diprotonated carotenoid ( approximately 950 nm). Acid induces cis/trans-isomerization via the protonated intermediates, which also decay to nonradical species with shorter conjugated systems-most probably carotenoid esters. Slow protonization of the methine carbon is the primary step in the degradation, but dioxygen increases the rate as a result of formation of a charge-transfer complex with the carotenoids as indicated by a red-shift of the NIR absorption bands. Carotenoids with carbonyl groups (astaxanthin and canthaxanthin) have slower rates of degradation than beta-carotene and zeaxanthin, indicating preferential nondegradative protonation of the carbonyl groups.     

Kinetics and products of photo-Fenton degradation of triazophos

Triazophos is a contaminant of wastewater at manufacturing facilities, and remediative treatment may be needed. While toxicity and persistence limit the effectiveness of biological and physicochemical methods, photo-Fenton processes are promising. UV-Fenton and solar-Fenton processes were applied to degrade triazophos. The optimum parameters were 50 mmol/L H(2)O(2), 0.3 mmol/L FeSO(4), and pH 3.0. The decomposition of triazophos by a photo-Fenton process followed first-order kinemics. At 30 degrees C, the half-life of triazophos in a UV-Fenton process ranged from 9.1 min at 2.0 x 10(5) Lx to 27.3 min at 1.0 x 10(5) Lx. At 35 degrees C and with solar irradiation luminance, it ranged within 1.0 x 10(5) -1.2 x 10(5) Lx; the half-life of triazophos in the solar-Fenton process was 11.2 min. Five major degradation products, O,O-diethyl phosphorothioic acid, monoethyl phosphorothioic acid, phosphorothioic acid, 1-phenyl-3-hydroxy-1,2,4-triazole, and phenylsemicarbazine, were tentatively identified as their corresponding trimethylsilyl derivatives with a gas chromatography-mass spectrometer. The possible degradation pathway of triazophos was proposed. The results indicate the potential use of a solar-Fenton treatment for triazophos-contaminated water.     

Kinetics and mechanism of imazosulfuron hydrolysis

Knowledge of the kinetics and pathways of hydrolytic degradation is crucial to the prediction of the fate and transport mechanism of chemicals. This work first describes the kinetics of the chemical hydrolysis of imazosulfuron, a new sulfonylurea herbicide, and evaluates the results to propose a degradation pathway. The hydrolysis of imazosulfuron has been studied in aqueous buffers both within the pH range 1.9-12.3 at ambient temperature (thermostated at 25 +/- 2 degrees C) and at pH 3.6 within the temperature range of 15-55 degrees C. The hydrolysis rate of imazosulfuron was characterized by a first-order kinetics, pH- and temperature-dependent, and accelerated by acidic conditions and higher temperatures. The calculated half-lives at pH 4.5 and 5.9 were 36.5 and 578 days, respectively. At pH 6.6, 7.4, 9.2, and 12.3 no significant change in imazosulfuron concentration was observed after 150 days. Half-lives were much lower at pH <4 (= imazosulfuron pK(a)), at which they ranged from 3.3 to 6.3 days. Moreover, a change in temperature from 15 to 25 degrees C in acidic conditions (pH 3.6) decreased the half-life of imazosulfuron by a factor of approximately 4.0; in any case, a 3-5-fold increase in the rate of hydrolysis was found for each 10 degrees C increase in temperature. In acidic conditions the only hydrolysis products were the two molecules resulting from the cleavage of the sulfonylurea bridge.     

Kinetics and mechanism of lactosylation of alpha-lactalbumin

The lactosylation of alpha-lactalbumin in aqueous solution was followed at pH(c) = 6.0, 6.3, 7.0, 7.3, and 7.9 and constant ionic strength (I = 0.080) at 50-60 degrees C by reversed-phase high-performance liquid chromatography (RP-HPLC) and electrospray mass spectrometry (MS). The rate of the lactosylation reaction increased with increasing pH and with temperature most significantly at lower pH. The rate of lactosylation could be described by an acid dissociation curve corresponding to pK(a) of the epsilon-amino group of lysine in alpha-lactalbumin. From initial rates for conditions of excess of lactose, pseudo-first-order rate constants were calculated and further transferred into second-order rate constants by dividing with the lactose concentration. Second-order rate constants for protonated and unprotonated lysine in alpha-lactalbumin both showed Arrhenius behavior, and using transition-state theory, DeltaH# = 31 +/- 2 kJ/mol and DeltaS# = -266 +/- 48 J/(mol . K) were determined for the unprotonated form and DeltaH# = 158 +/- 49 kJ/mol and DeltaS# = 80 +/- 150 J/(mol . K) for the protonated form, respectively. On the basis of the marked differences in activation parameters, initial formation of a lactosylamine is suggested as rate-determining for reaction between lactose and a protonated lysine in alpha-lactalbumin, while subsequent water elimination to form a Schiff base becomes rate-determining for the unprotonated form.     

Degradation of flumorph in soils, aqueous buffer solutions, and natural waters

Flumorph is an oomycete fungicide that is now used extensively in China. A residue analysis method for the determination of flumorph in environmental samples was developed with solid-phase extraction (SPE) for sample preparation and high-performance liquid chromatographic (HPLC) for separation. An environmental fate study was performed concerning the degradation of flumorph in soils, aqueous buffer solutions, and natural waters under laboratory-controlled conditions. The degradation of flumorph in three Chinese soil samples followed a first-order kinetics, with half-lives all longer than 100 days. No degradation of flumorph occurred in aqueous buffer solutions having different pH values or in natural waters with different physical and chemical properties. The data generated from this study could be helpful for risk assessment studies of the pesticide in the environment.     

猕猴桃果浆中叶绿素和颜色的热降解动力学

为了研究猕猴桃果浆加工中叶绿素和绿色的热降解规律,测定了不同温度(70、80、90℃)和pH值(pH值3.3、6.0、8.0)对猕猴桃果浆叶绿素含量和色差的影响。结果表明,猕猴桃叶绿素a、b和绿色值(-a*)的热降解属一级动力学反应;在相同pH值条件下,随温度升高,叶绿素a、b和绿色值(-a*)的反应速率常数(k)降低,半衰期(t1/2)缩短;随pH值增加,叶绿素a的活化能(Ea)变化范围为14.69～66.02kJ/mol,叶绿素b为40.88～54.64kJ/mol,绿色值(-a*)为48.55～64.14kJ/mol;pH值3.3时叶绿素a、b的降解和绿色值(-a*)相关性较好。猕猴桃果浆加工中适量提高pH值可减少叶绿素和绿色的损失。     

Kinetics of chlorophyll degradation and color loss in heated broccoli juice

Degradation of chlorophyll in broccoli juice occurred at temperatures exceeding 60 degrees C. Chemical analysis revealed that degradation of chlorophyll a and b to pheophytin a and b, respectively, followed first-order kinetics and that chlorophyll a was more heat sensitive than chlorophyll b. Temperature dependencies of chlorophyll a and b degradation rate constants could be described by Arrhenius equations with activation energies (E(a)) of 71.04 +/- 4.89 and 67.11 +/- 6.82 kJ/mol, respectively. Objective greenness measurements, using the -a value as the physical property, together with a fractional conversion kinetic analysis, indicated that green color degradation followed a two-step process. Kinetic parameters for the first degradation step were in accordance with the kinetic parameters for pheophytinization of the total chlorophyll content, as determined by chemical analysis (E(a) approximately 69 kJ/mol). The second degradation step, that is, the subsequent decomposition of pheophytins, was characterized by an activation energy of 105.49 +/- 4.74 kJ/mol.     

Semi-mechanistic partial buffer approach to modeling pH, the buffer properties, and the distribution of ionic species in complex solutions

In many biological science and food processing applications, it is very important to control or modify pH. However, the complex, unknown composition of biological media and foods often limits the utility of purely theoretical approaches to modeling pH and calculating the distributions of ionizable species. This paper provides general formulas and efficient algorithms for predicting the pH, titration, ionic species concentrations, buffer capacity, and ionic strength of buffer solutions containing both defined and undefined components. A flexible, semi-mechanistic, partial buffering (SMPB) approach is presented that uses local polynomial regression to model the buffering influence of complex or undefined components in a solution, while identified components of known concentration are modeled using expressions based on extensions of the standard acid-base theory. The SMPB method is implemented in a freeware package, (pH)Tools, for use with Matlab. We validated the predictive accuracy of these methods by using strong acid titrations of cucumber slurries to predict the amount of a weak acid required to adjust pH to selected target values.     

Kinetics of maneb degradation during thermal treatment of tomatoes

The kinetics of maneb degradation in tomato homogenates at high temperatures and at two pH values (4 and 9) and the rate of formation of the toxic metabolite, ethylenethiourea (ETU), were studied. Maneb was measured as carbon disulfide by headspace gas-chromatography and ETU by high-performance liquid chromatography with photodiode array detection. First-order kinetics adequately described the degradation of maneb in tomato homogenates. The degradation rate constants exhibited an Arrhenius temperature dependence in the range from 50 to 90 degrees C and the apparent activation energy (E(a)) was calculated to be 36 KJ mol(-1) in homogenates with natural pH (4). Raising temperature from 60 to 75 and to 90 degrees C, ETU formation was significantly increased. Interestingly, the selectivity toward ETU showed a downward trend when the total conversion increased at longer heating times. When the pH of the tomato homogenates was adjusted to 9, the degradation of maneb proceeded faster at both 60 and 90 degrees C. The combination of alkaline pH and the highest temperature (90 degrees C) resulted in the maximum ETU conversion rates. The results of the present study on the fate of maneb and ETU residues during tomato processing, may prove valuable in estimating potential risk from dietary exposure.     

Kinetics and products of the degradation of chitosan by hydrogen peroxide

Low concentrations of hydrogen peroxide induced random degradation of partially deacetylated chitin and chitosan. Average molecular weight decreased in accordance with first-order kinetics. The degradation rate was much faster than that of the ultrasonic degradation, and it was comparable to that of the enzymatic hydrolysis of chitosan. Chain-end scissions occurred after chitosan was degraded severely and produced significant amounts of oligosaccharides at temperatures > or =80 degrees C. Universal calibration moderated the change in molecular weight more closely than that calculated by the usual calibration using pullulan standards. Trace amounts of transition metal ions and the amino groups in chitosan were critical to the breakdown of the beta-1,4 glycosidic linkages. HPLC results of glucosamine and chito-oligosaccharides could be characterized by correlating the logarithmic values of retention time with the degrees of polymerization. The formation of glucosamine and chito-oligosaccharides depended on the concentration of H(2)O(2), temperature, and the physicochemical property of chitin/chitosan.     

石油烃类污染物降解动力学和微生物群落多样性分析

为了探讨不同初始浓度石油污染土壤堆腐化修复机制,以石油降解菌剂和腐熟鸡粪为调理剂,研究了初始浓度分别为5 000（T1）、10 000（T2）和50 000 mg/kg（T3）的石油污染土壤堆腐化修复过程石油烃类污染降解动力学特征和微生物群落多样性。结果表明：堆腐化修复过程石油烃类污染物降解符合一级反应动力学,反应常数分别为0.012、0.094和0.050 d-1,半衰期分别为6.79、7.37和13.86 d。整个堆腐过程石油烃类污染物平均降解速率分别为112.08、230.05和887.93 mg/(kg·d)。3个处理的孔平均颜色变化率（average well color development）和碳源利用率（除芳香烃类化合物外）随堆腐进程的推进逐渐升高,在堆腐中、后期达到最大,T3处理显著高于T1、T2处理。多聚物类和糖类代谢群是堆腐体系中的优势菌群。主成分分析表明3个处理的微生物群落差异显著（除第9天外）,起分异作用的碳源主要是糖类和羧酸类。微生物群落的丰富度指数和均一度指数随堆腐进程的推进逐渐升高并在堆腐后期达到最大,与T1处理相比,T3处理分别高了0.21%和17.64%,差异达到显著水平（P<0.05）。微生物群落优势度指数在中期达到最大,T1处理分别比T2、T3处理高2.12%和9.44%,3个处理间差异不显著（P>0.05）。堆肥结束时3个处理的种子发芽指数（seed germination index, SGI）分别比堆腐初期提高了18.26%、20.42%和36.41%。该研究结果为黄土高原不同程度石油污染土壤堆腐化修复的应用提供参考依据和理论基础。     

Characterization of metabolites of fungicidal cymoxanil in a sensitive strain of Botrytis cinerea

The metabolism of cymoxanil [1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea] by a very sensitive strain of Botrytis cinerea toward this fungicide was studied by using [2-(14)C]-cymoxanil. Labeled cymoxanil was added either in a culture of this strain or in its enzymatic extract. The main metabolites, detected in biological samples, were isolated and identified by mass and NMR spectrometry. Their identification allowed us to show that this strain quickly metabolized cymoxanil according to at least three enzymatic pathways: (i) cyclization leading, after hydrolysis, to ethyl parabanic acid, (ii) reduction giving demethoxylated cymoxanil, and (iii) hydrolysis and reduction followed by acetylation leading to N-acetylcyanoglycine. In a cell-free extract of the same strain, only the first and the second enzymatic reactions, quoted above, occurred. Biological tests showed that, among all the metabolites, only N-acetylcyanoglycine is fungitoxic toward this sensitive strain.     

两株蜡状芽孢杆菌对毒死蜱的降解动力学研究

利用微生物消除农药污染是一项安全、经济、有效的方法,降解动力学模型的构建有助于理解污染物的生物降解行为和估测系统中特征污染物的浓度变化,菌株对高浓度污染物的降解效果是降解菌在受污染水体中实际应用的关键。本研究采用基础培养基中定量添加毒死蜱和定时取样分析毒死蜱残留浓度的方法,探讨两株蜡状芽孢杆菌(HY-1和HY-2)的接种体培养时间、接种量和降解菌对毒死蜱的降解动力学,同时研究了降解菌对高浓度毒死蜱的降解率。结果表明:HY-1和HY-2最适接种体培养时间分别为10 h和19 h,接种体培养时间对菌株降解毒死蜱的影响较大。两菌株最适接菌量为8%(v/v),接种量从4%增至8%时,接种量对HY-1降解毒死蜱的影响大于HY-2。当毒死蜱的初始浓度为40 mg.L 1、80 mg.L 1、100 mg.L 1和120 mg.L 1时,一级动力学方程ln(C0/Ct)=kt可以用来拟合两菌株对毒死蜱的降解动力学及确定降解动力学参数,当毒死蜱初始浓度再次增加时,仅HY-2对毒死蜱的降解符合一级动力学方程。当毒死蜱初始浓度为40~120 mg.L 1时,菌株HY-1对毒死蜱的降解速率常数分布在0.013 5~0.015 7;当毒死蜱初始浓度为40~200 mg.L 1时,菌株HY-2的降解速率常数分布在0.008 0~0.015 3。菌株HY-2比HY-1可以在较高的毒死蜱浓度下发挥降解作用,且降解率较高。因此,两菌株在毒死蜱污染水体的净化去毒方面具有重要意义。     

渭北果园土壤物理退化特征及其机理研究

【目的】针对我国渭北苹果主产区出现的随植果年限增加,果园土壤质量严重退化,树势衰弱、树体过早衰老、抗性降低、腐烂病及早期落叶病频繁发生,果品产量与品质下降等问题,开展了渭北苹果园土壤物理质量退化特征、退化机理及危害程度等问题的研究,以期查明制约果业可持续发展的因素,为果园土壤科学管理提供依据。【方法】在渭北黄土塬区选取了10 a、10 20 a、20 a 3个园龄段果园各4个,并以土壤条件相同的农田作对照,在果树冠层投影范围内距树干2/3处采取土样,测定土壤剖面不同层次容重、紧实度、孔隙度、饱和导水率、粘粒含量等物理性指标。【结果】渭北果园土壤容重和紧实度随园龄和土层深度的增加而增大,尤其在表层(20 cm)以下,土壤容重已经达到了1.45 1.61 g/cm3,紧实度达到933 2433 k Pa,严重超出果树健康生长的阈值。土壤孔隙度仅在0—20 cm土层能够保持在50%以上,属于良好状态,而20—60 cm土层维持在40%46%,已处于紧实和严重紧实状态。土壤饱和导水率在果园表层和紧实层均表现出随植果园龄的增大而减小的趋势,尤其是10 20 a和20 a的果园亚表层土壤饱和导水率低至46.88 cm/d和20.89 cm/d,制约着降水入渗和土壤蓄墒。3个园龄段果园土壤剖面上粘粒含量随土层深度呈递增趋势,且在0—30 cm土层随园龄的增加而明显减少,而在30 cm以下则随园龄的增加而呈递增趋势。进一步分析发现,粘粒含量与土壤容重、紧实度以及孔隙度之间呈极显著的相关关系。以压实密度(PD)为指标,对渭北果园土壤压实程度进行评估,发现渭北果园20 cm土层以下的土壤压实密度都在1.40 g/cm3以上,均达到了中度压实的程度,严重影响果树根系的健康生长及对养分的吸收。【结论】渭北果园20 cm以下的亚表层土壤孔隙密实、容重和紧实度增大,土壤饱和导水率递减是其土壤物理性质退化的主要特征,表层土壤粘粒的深层移动与淀积是土壤物理退化的主要过程和机理,果园土壤翻耕扰动少、对物理退化干预少是其土壤物理退化程度逐渐加剧的外在原因,土壤团聚体稳定性差是土壤物理状态退化的根本原因。     

Kinetics of hydrolysis of fructooligosaccharides in mineral-buffered aqueous solutions: influence of pH and temperature

High-performance anion exchange chromatography coupled with a pulsed amperometric detection system (HPAEC-PAD) was used to evaluate the extent of chemical hydrolysis of three fructooligosaccharides (FOS) including 1-kestose (beta-D-Fru-(2-->1)(2)-alpha-D-glucopyranoside, GF2), nystose (beta-D-Fru-(2-->1)(3)-alpha-D-glucopyranoside, GF3), and fructofuranosylnystose (beta-D-Fru-(2-->1)(4)-alpha-D-glucopyranoside, GF4). A kinetic study was carried out at 80, 90, 100, 110, and 120 degrees C in aqueous solutions buffered at pH values of 4.0, 7.0, and 9.0. Under each experimental condition, the determination of the respective amounts of reactants and hydrolysis products showed that FOS hydrolysis obeyed pseudo-first-order kinetics as the extent of hydrolysis, which decreased at increasing pH values, increased with temperature. The three oligomers were found to be degraded mainly under acidic conditions, and at the highest temperature value (120 degrees C), a quick and complete acid degradation of each FOS was observed. Using the Arrhenius equation, rate constants, half-life values, and activation energies were calculated and compared with those obtained from sucrose under the same experimental conditions. It appeared that the hydrolysis of FOS took place much more easily at acidic pH than at neutral or basic pH values.     

Yeast-induced inhibition of (+)-catechin and (-)-epicatechin degradation in model solutions

(+)-catechin and (-)-epicatechin degradation in water-alcohol solutions containing Fe2+ and tartaric acid was studied in the presence and absence of yeasts. On the basis of the results, yeast partially inhibited the degradation of both flavans, with much slower formation of browning products absorbing at 420 and 520 nm. In comparative terms, yeast was found to be more efficient toward the degradation products of (+)-catechin absorbing at the latter wavelength. Likewise, the presence of yeast decreased the yield of a group of colored compounds eluting at high retention times in HPLC and indicated these as important contributors to color darkening in white wines. This inhibitory effect may in part account for the resistance to browning observed over periods of several years in sherry wines subjected to biological aging under flor yeast.     

Extraction,molecular fractionation and enzyme degradation of organically associated phosphorus in soil solutions

The concentrations and chemical composition of water-extractable P were compared in four soil types from NE Scotland. All sites were sampled during the early establishment phase of a spring barley (Hordeum vulgare) crop. The quantity of total soluble P extracted ranged from <2.0 to 10 mg P kg soil^-1, of which up to 50% was classified as being organically associated. Sample fractionation showed that both orthophosphate inorganic P and organic P were associated with a wide molecular-size range of organic material. A strong positive correlation was readily apparent between P and the sum of Fe + Al in the fractionated samples. The extent of enzymatic hydrolysis of organic P varied between soil samples and the type of enzyme. Phytase consistently produced the greatest degree of hydrolysis.     

Development of a gas chromatographic method for fungicide cymoxanil analysis in dried hops

An analytical method for detecting cymoxanil [2-cyano-N-[(ethylamino)carbonyl]-2-(methoxyimino)acetamide] residues in dried hops was developed utilizing liquid-liquid partitioning, automated gel permeation chromatography (GPC), solid phase extraction (SPE) cleanup, and gas chromatography (GC). Method validation recoveries from dried hops were 96 +/- 12, 108 +/- 11, and 136 +/- 8% over three levels of fortification (0.05, 0.5, and 1.0 ppm, respectively). The hop samples from three field sites, which were treated with cymoxanil, had residue levels ranging from 0.146 to 0.646 ppm. The detection limit and the quantitation limit of the method developed in the present study were 0.022 and 0.050 ppm, respectively.     

Kinetics of Fe(III) reduction by ascorbic acid in aqueous solutions

The reaction of Fe(III) and ascorbic acid (AA) in food products and digestive tracts affects the efficiency and uptake of these two nutrients. We investigated the kinetics of Fe(III) reduction by AA at pH 5 and 6 in a model system at 25 degrees C. The results indicate that the reduction of Fe(III) by AA is of zero order with respect to AA. The reaction order with respect to Fe(III) cannot be represented by a simple kinetic model at pH 5 or 6. The major stage of the reduction (about 80%, stoichiometrically), however, could be represented by a general equation of -d[Fe(III)]/dt = k[Fe(III)],(1. 811) where k is a rate constant and [Fe(III)] is the total ferric concentration. The rate constant decreased 1 order of magnitude as pH increased from 5 to 6. Aging of Fe(III) solution slows its reduction rate at pH 6 but not at pH 5.