Photolysis pathway of imazapic in aqueous solution: ultrahigh resolution mass spectrometry analysis of intermediates

Direct degradation of imazapic, an herbicide of the imidazoline family, has been investigated in aqueous solution at different concentrations, pH values, and temperatures. The efficiency of the photodegradation process has been evaluated through degradation rate constants that could be fitted best with pseudo-first-order kinetics ( Ct = C0 e(- kt )). Ultrahigh resolution mass spectrometry (FTICR/MS) was used in electrospray ionization mode as a tool to study the photolysis process on a molecular level, whereas UV-vis and high-performance liquid chromatography/mass spectrometry analysis were used to follow, by time, the evolution of the intermediates. Taking advantage of the high resolving power of FTICR/MS to perform precise formula assignments taking account of the natural abundance of isotopes, we herein propose and demonstrate an approach using 2D-derived van Krevelen visualization (O/C, H/C, m/z) to confirm the formation of imazapic intermediates. Such an approach allows a qualitative analysis of intermediates and elucidates the plausible reaction pathways of the photolysis process. More than eight photoproducts were separated and identified as a phototransformation of the imidazole ring. A mechanistical pathway was proposed.     

The effect of titanium dioxide alumina beads on the photocatalytic degradation of picloram in water

Photocatalytic degradation of pesticides with titanium dioxide (TiO(2)) and other catalysts has shown promise as a potential water remediation method. Titanium-based powders have been used in photocatalytic degradation studies but have limitations. The objective of this study was to determine picloram degradation in water using various UV light sources and low-pressure metal organic chemical vapor deposition titanium dioxide alumina beads (TDABs) as a catalyst. A triple-annular, flow-through photoreactor was used as a degradation chamber. A picloram test solution of 50 microg/mL was introduced to the photoreactor inlet and recycled for 10 h at a flow rate of 50 mL/min. Three ultraviolet light sources were compared for their photocatalytic capacity (UV-A, UV-B, and UV-C) both with and without TDABs. TDABs were added to the photoreactor at 1.8 g/cm(3). Dark treatments with and without TDABs were included to quantify hydrolysis or adsorption. A 500-microL aliquot was taken from the test solution 14 times during the 10-h recycling period. Sampling times ranged from 0 to 600 min (10 h). These aliquots were placed in a vial and analyzed by high performance liquid chromatography equipped with a photodiode array detector. Picloram was not significantly hydrolyzed or adsorbed to TDABs during the experiment. The picloram degradation rate with UV-A and TDABs (t(1/2) = 119.5 min) was greater than the degradation rate of UV-A alone (t(1/2)=2288 min). Picloram degradation was not enhanced by the presence of TDABs with either UV-B or UV-C. This may be attributed to inadequate TDAB densities and/or poor light penetration in the photoreactor. Rapid picloram degradation occurred with both UV-B and UV-C, regardless of the presence of TDABs with mean half-lives ranging from 7 to 18 min. These rates were 8 to 16 times faster than picloram degradation using UV-A with TDABs. TDABs' greatest photocatalytic effect was with the lowest energy light source (UV-A). However, picloram degradation was not enhanced when TDABs were combined with more powerful, shorter wavelength light.     

Microbial degradation of penoxsulam in flooded rice field soils

The degradation of penoxsulam [2-(2,2-difluoroethoxy)-N-5,8-dimethoxy[1,2,4]triazolo[1,5-C]pyrimidin-2-yl-6-(trifluoromethyl)benzene-sulfonamide] was studied in flasks simulating flooded rice field conditions using four representative rice field soils from the Sacramento Valley. Degradation half-lives (t(1/2) values) ranged between 2 and 13 days. Increased degradation rates were observed in flask systems with steeper redox gradients between the flooded soil layer and the overlaying water. Two transient metabolites were identified that were temporarily formed in amounts exceeding 5% of the total initial mass of penoxsulam. The results of high-performance liquid chromatography/(14)C radiodetection studies indicate that the degradation of the triazolopyrimidine system and its substituents is the main pathway of microbial transformation processes. Microbial activity, as measured by dehydrogenase activity, was not affected by penoxsulam concentrations corresponding to the proposed maximum annual use rate of 40 g active ingredient/ha.     

Estimated Quantities and Trends of Cadmium, Lead, and Mercury in US Municipal Solid Waste Based on Analysis of Incinerator Ash

The degradation of diethyl phthalate (DEP) in aqueous solution by titanium dioxide (TiO₂) photocatalysis has been investigated in our research. DEP was completely removed in the solution by 50-min irradiation. Results show that DEP degradation rate was affected by initial DEP concentration, photocatalyst amount, light intensity, and pH. Photocatalytic degradation intermediates were identified by gas chromatography-mass spectrometry intermediates were identified by gas chromatography-mass spectrometry. The major intermediates are methyl benzoate, ethyl benzoate, and carboxylic derivatives. The photocatalytic degradation process was found to obey first-order reaction. Consequently, the result of photocatalytic degradation could be an efficient method of DEP removal from wastewater.     

Biotreatment of Melanoidin-Containing Distillery Spent Wash Effluent by Free and Immobilized Aspergillus oryzae MTCC 7691

Humic acids (HA) are known as the precursors of carcinogenic compounds formed by the disinfection of drinking water. While conventional treatments were found to be inefficient HA removal processes in drinking water, advanced oxidation processes have been proven to have a significant effect in the treatment of HA. The degradation of HA was investigated using nano-sized zinc oxide (ZnO)/laponite composite (NZLC). The reactions occurred in a UVC reactor by considering following variables: pH, initial HA concentration, catalyst loading, addition of hydrogen peroxide (H₂O₂), and catalyst reuse. Water samples containing HA were analysed by ultraviolet/visible spectrophotometer and high-performance size-exclusion chromatography. Initial HA concentrations were tested by the Langmuir–Hinshelwood model with k and K _ads values, determined to be 0.126 mg/L.min and 0.0257 L/mg, respectively. The change in pH affected the HA degradation efficiency by the photocatalytic activity where it was higher under acidic conditions rather than alkaline ones. Optimal catalyst loading was proved to be a constrained factor in influencing the photocatalytic efficiency: the increase of catalyst concentration enhanced the HA decomposition efficiency up to an optimum value of 20 g/L, where there was no further degradation with excess loading. The addition of H₂O₂ was investigated through homogenous and heterogeneous photocatalysis, and, heterogeneous photocatalysis showed higher removal efficiency due to the combined effect of both catalysts and H₂O₂. Finally, NZLC was effective for reuse and exhibited an excellent stability after six times of usage.     

Visible Light Induced Photocatalytic Degradation of Methyl Orange by Polythiophene/TiO2 Composite Particles

The adsorption and photocatalytic degradation of methyl orange (MO) aqueous solution under visible light illumination by polythiophene/titanium dioxide (PTh/TiO₂) composite particles were studied. The experimental observations from UV–vis spectrophotometer indicate that MO molecules were degraded in a different degree during the visible light-induced photocatalysis reaction. We propose a new degradation mechanism of MO during the photocatalytic reaction, based on blue shift of UV–vis absorption spectra of MO solution and other researches. The data from total organic carbon analyzer definitely prove that MO can be mineralized to CO₂ and H₂O, and some intermediate products are generated during the photocatalysis degradation of MO.     

Isolation of oligopeptides from the water-soluble extract of goat cheese and their identification by mass spectrometry

A procedure for the separation and identification of small peptides from the water-soluble fraction of a goat cheese was developed. The water-soluble extract was ultrafiltered (1000 Da membrane cutoff), and peptides were isolated by sequential chromatography: size exclusion chromatography (HPLC-grade water), anion exchange chromatography (phosphate buffer gradient), and semipreparative reverse-phase high-performance liquid chromatography (water/acetonitrile gradient). The fractions obtained were analyzed by combined mass spectrometry methods including electrospray ionization, liquid secondary ionization, and tandem mass spectrometry to identify and to confirm the sequences of 28 tri- to octapeptides naturally appearing in goat cheese during ripening. Among these peptides, 26 are produced by degradation of caseins but do not correspond to the known specific cleavages due to chymosin. Only low correlation was found between hydrophobicity of peptides and HPLC elution time with acetonitrile gradient.     

Degradation studies on benzoxazinoids. Soil degradation dynamics of (2R)-2-O-beta-D-glucopyranosyl-4-hydroxy-(2H)- 1,4-benzoxazin-3(4H)-one (DIBOA-Glc) and its degradation products, phytotoxic allelochemicals from Gramineae

Wheat (Triticum aestivum L.) has been found to possess allelopathic potential and studies have been conduced to apply wheat allelopathy for biological weed control. 2,4-Dihydroxy-(2H)-1,4-benzoxazin-3(4H)-one (DIBOA) is a common product found in wheat, corn, and rye exudates and it can be released to the environment by that way. In this report, the stability of DIBOA is studied in two soils from crop lands of wheat cv. Astron and cv. Ritmo. These varieties were selected by their concentrations of DIBOA and 2,4-dihydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA) from aerial parts and by the bioactivities of their aqueous extracts in the growth of wheat coleoptile sections. The degradation rate of DIBOA in these soils was measured in laboratory tests during 90 h by high-pressure liquid chromatography methods. These analyses demonstrate that DIBOA was transformed primarily into 2-benzoxazolinone (BOA). This transformation was similar in both soil types with an average half-life of 43 h. The degradation studies for BOA show its biotransformation to 2-aminophenoxazin-3-one (APO) with a half-life of 2.5 days. Therefore, BOA is an intermediate product in the biotransformation from DIBOA to APO in these wheat crop soils and is consistent with previous findings. APO was not degraded after three months in soil, suggesting that its degradation rate in soil is very slow.     

UV-TiO2 Photocatalytic Degradation of Landfill Leachate

Mature landfill leachate contains some macromolecular organic substances that are resistant to biodegradation. The photocatalytic process helps to enhance biodegradability of landfill leachate. Batch experiments were employed to determine the optimum conditions for removal of organic matter by UV-TiO₂ photocatalysis. Under optimum conditions, the removal of chemical oxygen demand (COD), dissolved organic carbon (DOC), biological oxygen demand (BOD), and color was determined. Moreover, gas chromatography coupled with mass spectrometry (GC/MS) was used to analyze the organic matter in the treated leachate before and after treatment by the photocatalysis. The experimental results indicated that the removal of COD, DOC, and color by UV-TiO₂ photocatalysis could reach above 60%, 70% and 97%, respectively. Under optimal conditions, the ratio of biological oxygen demand (BOD)/chemical oxygen demand (COD) was elevated from 0.09 to 0.39, representing substantial improvement in biodegradability. GC/MS analysis revealed that 37 out of 72 kinds of organic pollutants in the leachate remained after 72 h treatment. Esters were produced during photocatalytic process and ketones, hydrocarbons, aromatic hydrocarbons, hydroxybenzenes, and acids were easier to be degraded during photocatalytic oxidation processes. The UV-TiO₂ photocatalysis systems proposed may be a cost-effective approach for pre-treatment of landfill leachate.     

Improved method to track chlorophyll degradation

An analytical method capable of identifying >30 chlorophyll-related compounds in plant extracts has been developed. The method employs liquid chromatography coupled to UV-vis, MS, and MS/MS detection. It can be applied without modification to analyze natural chlorophyll degradation products and other metalloporphyrines. It was successfully applied to identify chlorophyll derivatives found in rehydrated spinach powder and conventionally canned and Veri-Green-processed beans. In the Veri-Green-processed beans several degradation products were identified that are zinc-containing analogues to the chlorophyll derivatives found in vegetables after conventional canning. They have been characterized by liquid chromatography and mass spectrometry.     

Reverse phase liquid chromatographic determination of bisacodyl in dosage forms

A method is described for the determination of bisacodyl in enteric-coated tablets and suppositories by liquid chromatography (LC). The method will also determine the hydrolysis degradation products monoacetylbisacodyl and desacetylbisacodyl. The sample is dissolved in 2-propanol, and the extract is diluted with the mobile phase and injected into a liquid chromatograph fitted with a mu Bondapak C18 column and an ultraviolet detector set at 254 nm. The column is eluted with methanol-acetonitrile-0.01M citric acid (25 + 25 + 50). The pooled mean recovery value for bisacodyl from commercial enteric-coated tablets and suppositories was 99.7% with a pooled coefficient of variation (CV) of 0.72%. For content uniformity assays, the CVs were 0.7 and 1.0% for groups of 10 individual commercial suppositories and tablets, respectively. Differences between assay values by the LC and USP XX methods were 0.2% of declared for enteric-coated tablets (n = 5) and 1.0% of declared for suppositories (n = 2). The LC method can determine as little as 0.015 microgram of the monoacetyl or desacetyl degradation product.     

Heat-induced, metal-catalyzed oxidative degradation of quercetin and rutin (Quercetin 3-O-rhamnosylglucoside) in aqueous model systems

The oxidative degradation of quercetin and rutin in phosphate buffer solutions, pH 8.0, at 97 degrees C, was studied by means of UV-vis spectroscopy and reversed-phase high-performance liquid chromatography (HPLC). The effect of the transition metal ions Fe(2+) and Cu(2+) on degradation rate and browning development was also assessed. It was shown that both flavonols are very labile to thermally induced degradation under oxidative conditions. Fe(2+) and Cu(2+) caused an increase in the degradation rate, as well as an increase in browning (A(420)). Significant differences were observed in the degradation mechanisms, as implied by HPLC analyses. It is postulated that metal ions promote flavonol oxidation through reactive oxygen species formation, whereas increases in browning could be ascribed to oxidation and metal-polyphenol interactions.     

Use of a stopped-flow pneumatic mixing module to analyze dinitrophenol pesticides. Simultaneous determination of dinoseb and dinobuton.

A kinetic study of the degradation of dinobuton in an alkaline medium has been undertaken by using a stopped-flow pneumatic system. A semiautomatic method for determining dinobuton is proposed for the first time. A detection limit of 0.40 microg mL(-)(1) was calculated. Simultaneous determination of dinobuton and dinoseb can be made by combination of equilibrium and kinetic measurements. The proposed method has been applied to analyze binary mixtures of dinobuton and dinoseb samples with the amount of both components simulating the composition of one undegraded and several degraded dinobuton samples. Also, the procedure has been tested in the analysis of a commercial formulation of dinobuton and the results validated with high-performance liquid chromatography (HPLC).     

Determination of total riboflavin in cooked sausages.

A simple and rapid method for determining riboflavin content in cooked sausages by ion-pair reversed-phase liquid chromatography has been set up. Samples were subjected to acid and enzymatic hydrolysis. Sample extracts were directly chromatographed, avoiding purification and concentration treatment. Final determination was performed by high-performance liquid chromatography with fluorescence detector (excitation, 227 nm; emission, 520 nm), on a 25 cm x 4 mm i.d. Spherisorb ODS-2 cartridge using a mixture of 5 mM heptanesulfonic acid adjusted to pH 2.7 with phosphoric acid and acetonitrile (75:25, v/v) as mobile phase. Precision of the method was 1.3% (within a day) and 2.6% (between days). The detection limit was 0.015 mg/100 g. The recovery was >95%.     

Isomerization and degradation kinetics of hop (Humulus lupulus) acids in a model wort-boiling system

The rate of isomerization of alpha acids to iso-alpha acids (the compounds contributing bitter taste to beer) was determined across a range of temperatures (90-130 degrees C) to characterize the rate at which iso-alpha acids are formed during kettle boiling. Multiple 12 mL stainless steel vessels were utilized to heat samples (alpha acids in a pH 5.2 buffered aqueous solution) at given temperatures, for varying lengths of time. Concentrations of alpha acids and iso-alpha acids were quantified by high-pressure liquid chromatography (HPLC). The isomerization reaction was found to be first order, with reaction rate varying as a function of temperature. Rate constants were experimentally determined to be k1 = (7.9 x 10(11)) e(-11858/T) for the isomerization reaction of alpha acids to iso-alpha acids, and k2 = (4.1 x 10(12)) e(-12994/T) for the subsequent loss of iso-alpha acids to uncharacterized degradation products. Activation energy was experimentally determined to be 98.6 kJ per mole for isomerization, and 108.0 kJ per mole for degradation. Losses of iso-alpha acids to degradation products were pronounced for cases in which boiling was continued beyond two half-lives of alpha-acid concentration.     

UV Light-Assisted Degradation of Methyl Orange,Methylene Blue,Phenol, Salicylic Acid,and Rhodamine B: Photolysis Versus Photocatalyis

Methyl orange (MO), methylene blue (MB), phenol (F), salicylic acid (SA), and rhodamine B (ROD) were used as substrates during the photodegradation experiments in the absence and in the presence of nanostructured Ag/titania-silica. The catalyst was characterized by scanning electron microscopy (SEM), scanning transmission electron microscope high-angle annular dark field (STEM-HAADF), stereological analysis, nitrogen adsorption-desorption, and X-ray photoelectron spectroscopy (XPS) measurements. The results were fitted on pseudo-first and pseudo-second kinetic order models. The film diffusion was also determined. The photolysis degrades MO and F to a greater extent than the photocatalysis. The degradation of SA occurred at the same rate either by photolysis or by photocatalysis. MB was best removed by photocatalysis. With regard to the photocatalysis, the highest rates of film diffusion were obtained for MB, F, and ROD, meaning that these molecules crossed the film to arrive at the catalyst surface more rapidly than the others. For MO and MB, the results followed the pseudo-first-order kinetic model while for SA, F, and ROD, the pseudo-second-order kinetic model was more appropriate.     

解淀粉芽孢杆菌NS2降解玉米赤霉烯酮的研究

为了丰富玉米赤霉烯酮(ZEN)解毒菌种库,通过采集湖南省邵阳市等7个省市粮食样品,筛选获得1株能够高效降解ZEN的解淀粉芽孢杆菌NS2。采用高效液相色谱法检测降解前后ZEN的含量发现,液态发酵72 h,该菌对5 mg·L^-1 ZEN标准品的降解率高达96.0%,固态发酵72 h,菌株对玉米粉中2.5 mg·L^-1 ZEN标准品的降解率高达88.2%。采用高效液相色谱与四级杆飞行时间质谱联用技术检测该菌处理后的ZEN降解产物,未检测出具有毒性作用的α-玉米赤霉烯醇(α-ZOL)、β-玉米赤霉烯醇(β-ZOL)等ZEN的类似物。此外,抗菌活性试验与木聚糖酶、纤维素酶和蛋白酶活性试验显示降解菌NS2还能通过产生具有抗菌作用的次生代谢产物,抑制病原微生物大肠杆菌和鼠伤寒沙门氏菌的生长。上述结果表明,解淀粉芽孢杆菌NS2可以高效降解ZEN,具有潜在应用前景,为ZEN解毒产品的开发与应用奠定了材料基础。     

Persistence of simazine and terbuthylazine in a semiarid soil after organic amendment with urban sewage sludge

The persistence of two herbicides, simazine and terbuthylazine, and appearance of their principal dealkylated chloro-s-triazine metabolites have been studied in agricultural soil after the addition of urban sewage sludge as organic amendment. Both herbicides and metabolites were monitored during long-term laboratory incubation (140 days) and analyzed by gas chromatography with a nitrogen-phosphorus detector (GC-NPD). Residues were confirmed by gas chromatography with a mass selective detector (GC-MSD). A sonication microextraction method was used to extract the compounds. The organic amendments used were urban sewage sludge and the humic fraction of this sludge, to increase the organic matter content of the soil from 1% to 2%. For both compounds, simazine and terbuthylazine, the degradation began earlier in the amended soils. Simazine showed a higher dissipation rate than terbuthylazine, the percentage of the former at the end of the experiment being lower than 2% in all cases, while for terbuthylazine the corresponding percentage ranged from 5% to 46%. Organic amendment, mainly its humic fraction, caused a certain stabilization of terbuthylazine in the soil, but did not greatly influence the residual amount of simazine at the end of the experiment. The periodic aeration of the soil caused a greater degradation in the case of terbuthylazine. Only mono-deethylsimazine and deethylterbuthylazine were isolated from the soil during the time the experiment lasted, while the di-deethylated metabolite of simazine was not found.     

Biodegradation of buprofezin by Rhodococcus sp. strain YL-1 isolated from rice field soil

A buprofezin-degrading bacterium, YL-1, was isolated from rice field soil. YL-1 was identified as Rhodococcus sp. on the basis of the comparative analysis of 16S rDNA sequences. The strain could use buprofezin as the sole source of carbon and nitrogen for growth and was able to degrade 92.4% of 50 mg L(-1) buprofezin within 48 h in liquid culture. During the degradation of buprofezin, four possible metabolites, 2-tert-butylimino-3-isopropyl-1,3,5-thiadiazinan-4-one, N-tert-butyl-thioformimidic acid formylaminomethyl ester, 2-isothiocyanato-2-methyl-propane, and 2-isothiocyanato-propane, were identified using gas chromatography-mass spectrometry (GC-MS) analysis. The catechol 2,3-dioxygenase activity was strongly induced during the degradation of buprofezin. A novel microbial biodegradation pathway for buprofezin was proposed on the basis of these metabolites. The inoculation of soils treated with buprofezin with strain YL-1 resulted in a higher degradation rate than that observed in noninoculated soils, indicating that strain YL-1 has the potential to be used in the bioremediation of buprofezin-contaminated environments.     

Modification of IgE binding to beta-lactoglobulin by fermentation and proteolysis of cow's milk

The effect of fermentation by Lactobacilli and of proteolytic hydrolysis of whole milk on the IgE binding ability of beta-lactoglobulin was studied using an ELISA inhibition assay. Sera from nine adult milk allergic patients were tested. The individual sera showed a similar inhibition pattern in the changes during fermentation and proteolysis. The degradation of beta-lactoglobulin was studied with liquid chromatography. In general, fermentation with Lactobacilli gave little effect on IgE binding, even though chromatography data showed a gradual degradation of beta-lactoglobulin. Proteolysis with trypsin, however, gave extensive degradation of beta-lactoglobulin and strongly decreased IgE binding. In addition, we measured the inhibition pattern of beta-lactoglobulin in various selected commercially available fermented milk products. These showed an IgE binding capacity similar to that of nonfermented high pasteurized milk.