Comparative electrochemical degradation of salicylic and aminosalicylic acids: Influence of functional groups on decay kinetics and mineralization.

Solutions of 100 mL with 1.20 mM of salicylic acid (SA), 4-aminosalicylic acid (4-ASA) or 5-aminosalicylic acid (5-ASA) have been comparatively degraded by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were carried out with a stirred tank reactor with a BDD anode and an air-diffusion cathode for continuous H2O2 production. A marked influence of the functional groups of the drugs was observed in their decay kinetics, increasing in the order SA < 5-ASA < 4-ASA in AO-H2O2 and 5-ASA < SA < 4-ASA in EF and PEF, due to the different attack of OH generated at the BDD surface and in the bulk from Fenton's reaction, respectively. This effect was clearly observed when varying the current density between 16.7 and 100 mA cm(-2). The relative mineralization power of the processes always followed the sequence: AO-H2O2 < EF < PEF. The three drugs underwent analogous mineralization abatement up to 88% by AO-H2O2 at 100 mA cm(-2). The mineralization rate in EF and PEF grew in the order: 4-ASA < 5-ASA < SA. The most powerful process was PEF, attaining >98% mineralization for all the drugs at 100 mA cm(-2). Oxalic and oxamic acids were detected as final short-linear aliphatic carboxylic acids by ion-exclusion HPLC, allowing the fast photolysis of their Fe(III) complexes by UVA light to justify the high power of PEF.

Selectively light scattering spectrometric detection of copper (II) based on a new synthesized oxamide ligand.

Light scattering (LS) signals have been applied for analytical detections, but the selectivity is poor. In order to improve the selectivity, pre-separation or new machines are generally considered. Differing from these methods, we synthesized a highly selective oxamide ligand, N',N'-bis (2-aminophenyl) oxamide (NAPO). It was found that the LS signals of NAPO, measured with a common spectrofluorometer, could be selectively enhanced by copper ion in neutral medium. Thus, a new highly selective detection method for copper ion could be developed over the range of 0.9-31.0 microM with the limit of determination of 97.6 nM (3sigma). Foreign ions including Cd(II), Al(III) could be allowed even if present at the level of 7-fold more than that of Cu(2+), avoiding pre-separation procedures from complicated samples such as real wastewater samples. Mechanism studies showed that the reaction between NAPO and copper ion could form some kinds of clusters and induce the enhanced LS signals.

Direct aqueous injection LC-ESI/MS/MS analysis of water for 11 chloro- and thiomethyltriazines and metolachlor and its ethanesulfonic and oxanilic acid degradates.

A multianalyte method is reported for the determination of atrazine, simazine, propazine, and their respective dealkylated chlorotriazine metabolites; ametryn and prometryn and their respective dealkylated thiomethyltriazine metabolites; and S-metolachlor and its ethanesulfonic and oxanilic acid degradates in deionized, ground, surface, and finished drinking water. Water samples are analyzed using direct aqueous injection (DAI) liquid chromatography-electrospray ionization/mass spectrometry/mass spectrometry (LC-ESI/MS/MS). No preanalysis sample manipulation is required other than transfer of a small portion of sample to an injection vial. The lower limit of the method validation is 0.050 microg/L (ppb) for all analytes except 2,4-diamino-6-chloro- s-triazine (didealkylatrazine, DDA, or G-28273). For this compound the LLMV is 0.50 microg/L (ppb). The overall mean procedural recoveries (and percent relative standard deviations) for all water types for all analytes ranged from 95 to 101% (4.5-11%). The method validation was conducted under U.S. EPA FIFRA Good Laboratory Practice Guidelines 40 CFR 160.

Development of EPA method 535 for the determination of chloroacetanilide and other acetamide herbicide degradates in drinking water by solid-phase extraction and liquid chromatography/tandem mass spectrometry.

U.S. Environmental Protection Agency (EPA) Method 535 has been developed in order to provide a method for the analysis of "Alachlor ESA and other acetanilide degradation products," which are listed on EPA's 1998 Drinking Water Contaminant Candidate List. Method 535 uses solid-phase extraction with a nonporous graphitized carbon sorbent to extract the ethane sulfonic acid (ESA) and oxanilic acid degradates of propachlor, flufenacet, dimethenamid, alachlor, acetochlor, and metolachlor from finished drinking water matrixes. Separation and quantitation of the target analytes are achieved with liquid chromatography/tandem mass spectrometry. Dimethachlor ESA and butachlor ESA were chosen during the method development as the surrogate and internal standard. Drinking water samples were dechlorinated with ammonium chloride without adversely affecting the analyte recoveries. Typical mean recoveries of 92-116% in deionized water and 89-116% in ground water were observed with relative standard deviations of <5%.

Are neutral chloroacetamide herbicide degradates of potential environmental concern? Analysis and occurrence in the upper Chesapeake Bay.

Although laboratory studies have revealed that many different neutral degradates of chloroacetamide herbicides can form during thermochemical, biological, and photochemical transformations, relatively few have been sought in the environment, despite their likely generation in appreciable amounts, relative persistence, and known or potential toxicity. The present paper describes a GC/ MS method for the analysis of 20 neutral chloroacetamide degradates, along with the four parent compounds, three triazine herbicides, and two neutral triazine degradates. Using large volume injections and 300:1 concentration via solid phase extraction, detection limits for most neutral chloroacetamide degradates were in the hundreds of pg/L range (low ng/L range for degradates possessing a hydroxy group). In a depth profile taken in midsummer from the upper Chesapeake Bay, 19 of the 20 neutral chloroacetamide degradates of interest were detected, along with three ionic oxanilic acid derivatives. Of those degradates encountered, eight do not appear to have been previously reported in natural or affected environmental samples. Concentrations of most neutral chloroacetamide degradates exceeded those of the parent compounds, while the total concentration of the neutral chloroacetamide degradates was 20-30 times that of the parents. These micropollutants therefore merit more detailed attention as contaminants of potential environmental concern.

Degradation of metolachlor in bare and vegetated soils and in simulated water-sediment systems.

A study was conducted to determine the half-life (t1/2), degradation rate, and metabolites of metolachlor in a water-sediment system and in soil with and without switchgrass. Metolachlor degradation in a laboratory was determined in sediment from Bojac sandy loam soil incubated at 24 degrees C. The study also was conducted in a greenhouse on tilted beds filled with Bojac soil and planted with switchgrass. In both experiments, samples were collected at days 0, 7, 14, 28, 42, 56, and 112 and analyzed for metolachlor and its major metabolites. The water-sediment oxidation-reduction potential took 28 d to reach -371 mV and the pH increased from 5.6 to 6.5 by the last sampling day (day 112). The average soil temperature of the tilted beds with or without switchgrass during the study was 21degrees C and the soil moisture content was 23% by volume. The t1/2 of metolachlor was 34 d in sediment and 8 d in the water phase. The t1/2 of metolachlor in soil from the switchgrass filter strip (6 d) was not different from that in soil without grass (9.6 d). The metolachlor metabolites ethanesulfonic acid (ESA) and oxanilic acid (OA) were detected in the water-sediment system and in soil from tilted beds. In both sediment and soil from tilted beds, the two metabolites peaked by day 56 of incubation and declined after that, indicating transformation to other products. In the water-sediment system, greater quantities of OA and ESA were detected in sediment than in the aqueous phase. The production of OA and ESA in the watersediment system occurred in the first 28 d, when the system was at an aerobic redox state. Metolachlor can degrade in sediment and the relatively high soil temperature and moisture level accelerated its breakdown in beds with and without switchgrass. Under warm and moist soil conditions, the presence of switchgrass has no effect on the degradation of metolachlor.

Vibrational characterization of the peptide bond.

This article describes the complete vibrational analysis of N,N'-dimethyloxamide, CH3HNCOCONHCH3, on basis of the infrared and Raman spectra of four isotopes (H, D, CH3, CD3). Force field calculations on the monomers and multimers (n = 5) combined with solid state spectra in the -196 to +100 degrees C temperature range have been used to obtain a better understanding of the influence of hydrogen bonding on the typical amide fundamentals. The cooperative effect in de series monomer --> multimers --> solid state at decreasing temperatures has been demonstrated. Nine typical so-called 'amide bands' have been further characterized and special attention has been given to the Amide IV mode. The influence of the CH and CD vibrations on the amide fundamentals, has been studied by comparison with the calculated and experimental fundamentals and P.E.D. values of the CH3 and CD3 isotopes. The most important amide bands have further been assigned in X-CONHCH3 molecules where X = methyl, amide, thioamide, ester, salt, cyanide and acid functional groups.

24-well plate spectrophotometric assay for preliminary screening of metabolic activity.

A 90-min assay using 24-well plates was developed for screening overall metabolic effects of toxic chemicals by measuring extracellular acidification rate of mammalian cells. During the 90-min test, the pH of each well of a 24-well plate is monitored by measuring the absorbance of phenol red using a spectrophotometric plate reader. The acidification rate is then calculated from the change in pH divided by the time interval and cell density, which is also estimated non-invasively by spectroscopy. The assay was verified by testing the effects of five well-characterized chemical toxins on fibroblast cell cultures. As expected, the responses of the fibroblasts were dependent on the dose and type of toxin. They also corresponded with the established mechanisms of the toxins and with measured lactate production rates. The set-up is simple, inexpensive, and amenable to being automated. The method is easy to perform and rapid. Uses include screening compounds for gross metabolic effects in mammalian cell lines, determining preliminary metabolic dose-response curves for guiding further research, and designing and optimizing media for in vitro systems utilizing cell cultures.

Determination of oxanilic and sulfonic acid metabolites of acetochlor in soils by liquid chromatography-electrospray ionisation mass spectrometry.

An analytical method is presented that describes the extraction and quantification of oxanilic and sulfonic acid metabolites of the herbicide acetochlor in soil samples. Experiments were performed on 50 g of soil using a solvent extraction technique with an acetonitrile-water (60:40) mixture in an acidic medium. Analysis was carried out by reversed-phase liquid chromatography and detection by electrospray ionisation mass spectrometry in single ion monitoring and negative modes. Four different soil matrices were spiked in triplicate with standards of each degradation compound at three concentration levels between 2 and 80 microg/kg. The average recoveries range from 90 to 120% for both the metabolites, with relative standard deviations lower than 15%. The limits of quantification are about 1 and 2 microg/kg for the ethanesulfonic acid and the oxanilic acid metabolites, respectively. The method has been applied to soils and solids recovered from the deeper unsaturated zone of a small French catchment closely monitored as part of the European project "Pesticides in European Groundwaters: detailed study of Aquifers and Simulation of possible Evolution scenarios (PEGASE)".

Analysis and detection of the herbicides dimethenamid and flufenacet and their sulfonic and oxanilic acid degradates in natural water.

Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufenacet [N-(4-fluorophenyl)-N-(1-methylethyl)-2-(5-(trifluoromethyl)-1,3,4-thiadiazol-2-yl)oxy] were isolated by C-18 solid-phase extraction and separated from their ethanesulfonic acid (ESA) and oxanilic acid (OXA) degradates during their elution using ethyl acetate for the parent compound, followed by methanol for the polar degradates. The parent compounds were detected using gas chromatography-mass spectrometry in selected-ion mode. The ESA and OXA degradates were detected using high-performance liquid chromatography--electrospray mass spectrometry (HPLC-ESPMS) in negative-ion mode. The method detection limits for a 123-mL sample ranged from 0.01 to 0.07 microg/L. These methods are compatible with existing methods and thus allow for analysis of 17 commonly used herbicides and 18 of their degradation compounds with one extraction. In a study of herbicide transport near the mouth of the Mississippi River during 1999 and 2000, dimethenamid and its ESA and OXA degradates were detected in surface water samples during the annual spring flushes. For flufenacet, the only detections at the study site were for the ESA degradates in samples collected at the peak of the herbicide spring flush in 2000. The low frequency of detections in surface water likely is due to dimethenamid and flufenacet being relatively new herbicides. In addition, detectable amounts of the stable degradates have not been detected in ground water.

Finding minimal herbicide concentrations in ground water? Try looking for their degradates.

Extensive research has been conducted regarding the occurrence of herbicides in the hydrologic system, their fate, and their effects on human health and the environment. Few studies, however, have considered herbicide transformation products (degradates). In this study of Iowa ground water, herbicide degradates were frequently detected. In fact, herbicide degradates were eight of the 10 most frequently detected compounds. Furthermore, a majority of a herbicide's measured concentration was in the form of its degradates--ranging from 55 to over 99%. The herbicide detection frequencies and concentrations varied significantly among the major aquifer types sampled. These differences, however, were much more pronounced when herbicide degradates were included. Aquifer types presumed to have the most rapid recharge rates (alluvial and bedrock/karst region aquifers) were those most likely to contain detectable concentrations of herbicide compounds. Two indirect estimates of ground-water age (depth of well completion and dissolved-oxygen concentration) were used to separate the sampled wells into general vulnerability classes (low, intermediate, and high). The results show that the herbicide detection frequencies and concentrations varied significantly among the vulnerability classes regardless of whether or not herbicide degradates were considered. Nevertheless, when herbicide degradates were included, the frequency of herbicide compound detection within the highest vulnerability class approached 90%, and the median total herbicide residue concentration increased over an order of magnitude, relative to the parent compounds alone, to 2 microg/l. The results from this study demonstrate that obtaining data on herbicide degradates is critical for understanding the fate of herbicides in the hydrologic system. Furthermore, the prevalence of herbicide degradates documented in this study suggests that to accurately determine the overall effect on human health and the environment of a specific herbicide its degradates should also be considered.

Determination of chloroacetanilide herbicide metabolites in water using high-performance liquid chromatography-diode array detection and high-performance liquid chromatography/mass spectrometry.

Analytical methods using high-performance liquid chromatography-diode array detection (HPLC-DAD) and high-performance liquid chromatography/mass spectrometry (HPLC/MS) were developed for the analysis of the following chloroacetanilide herbicide metabolites in water: alachlor ethanesulfonic acid (ESA); alachlor oxanilic acid; acetochlor ESA; acetochlor oxanilic acid; metolachlor ESA; and metolachlor oxanilic acid. Good precision and accuracy were demonstrated for both the HPLC-DAD and HPLC/MS methods in reagent water, surface water, and ground water. The average HPLC-DAD recoveries of the chloroacetanilide herbicide metabolites from water samples spiked at 0.25, 0.5 and 2.0 microg/l ranged from 84 to 112%, with relative standard deviations of 18% or less. The average HPLC/MS recoveries of the metabolites from water samples spiked at 0.05, 0.2 and 2.0 microg/l ranged from 81 to 118%, with relative standard deviations of 20% or less. The limit of quantitation (LOQ) for all metabolites using the HPLC-DAD method was 0.20 microg/l, whereas the LOQ using the HPLC/MS method was at 0.05 microg/l. These metabolite-determination methods are valuable for acquiring information about water quality and the fate and transport of the parent chloroacetanilide herbicides in water.

The determination of oxalic acid, oxamic acid, and oxamide in a drug substance by ion-exclusion chromatography.

Oxalic acid, oxamic acid and oxamide are potential impurities in some active pharmaceutical ingredients (API). The retention and separation of oxalic and oxamic acids are particularly challenging using conventional reversed-phase HPLC due to their high polarity. An ion-exclusion chromatography (IEC) method has been shown to provide good separation and sensitivity for the three oxalate-related impurities in a hydrophobic API matrix. The method uses a Dionex IonPac ICE-ASI column with 95/5 (v/v) 0.1% sulfuric acid/acetonitrile as the mobile phase and UV detection at 205 nm. Development and validation of this method are described.

Simultaneous quantification of acetanilide herbicides and their oxanilic and sulfonic acid metabolites in natural waters.

This paper describes a procedure for simultaneous enrichment, separation, and quantification of acetanilide herbicides and their major ionic oxanilic acid (OXA) and ethanesulfonic acid (ESA) metabolites in groundwater and surface water using Carbopack B as a solid-phase extraction (SPE) material. The analytes adsorbed on Carbopack B were eluted selectively from the solid phase in three fractions containing the parent compounds (PCs), their OXA metabolites, and their ESA metabolites, respectively. The complete separation of the three compound classes allowed the analysis of the neutral PCs (acetochlor, alachlor, and metolachlor) and their methylated OXA metabolites by gas chromatography/mass spectrometry. The ESA compounds were analyzed by high-performance liquid chromatography with UV detection. The use of Carbopack B resulted in good recoveries of the polar metabolites even from large sample volumes (1 L). Absolute recoveries from spiked surface and groundwater samples ranged between 76 and 100% for the PCs, between 41 and 91% for the OXAs, and between 47 and 96% for the ESAs. The maximum standard deviation of the absolute recoveries was 12%. The method detection limits are between 1 and 8 ng/L for the PCs, between 1 and 7 ng/L for the OXAs, and between 10 and 90 ng/L for the ESAs.

Identification of bis(agmatine)oxalamide in venom from the primitive hunting spider, Plectreurys tristis (Simon).

N, N'-bis(4-guanidinobutyl)oxalamide, a novel bis(agmatine)oxalamide, is identified as a major component (8 micrograms/microliters) and the predominant acylpolyamine in venom from the primitive hunting spider, Plectreurys tristis. The function of this compound is unknown since it does not confer insecticidal or fungicidal activity in the systems examined.

Estudio de algunos factores que influyen en la concentración de ácido orálico en equisetum bogotense KBH "cola de caballo" zea mays L. "maiz". Solanum tuberosum L. "papa" y su cuantificación por lo métodos de titulación permanganometrica y de absorción atómica / Some factors study of Oralic acid in equisetum bogotense KBH \"cola de caballo\", zea mays L. \"maiz\" Solanum tuberosum L. \"papa\" y su cuantification by the methods of permanganometric titulation by atomic absortion

Se usaron 3 plantas diuréticas. Determinar ácido oxálico en las diferentes drogas tanto crudas como cocidas en forma individual y combinado, usando los métodos de la ADAC. La edad de la planta, es determinante en el contenido de ácido oxálico. Las muestras crudas lanzaron mayor porcentaje de ácido oxálico. Se comprobó que existen algunos factores determinantes que influyen directa o indirectamente en la concentración de ácido oxálico en los vegetales.

Effects of ethyl N-N-benzyl-methyl-oxamate in Meriones unguiculatus infected with Echinococcus multilocularis metacestodes. Biochemical and ultrastructural observations.

Ethyl N-N-benzyl-methyl-oxamate is a N-substituted derivative of the oxamic acid, well-known as inhibitor of the lactate dehydrogenase activity. The biochemical and ultrastructural effects of this drug in Echinococcus multilocularis metacestodes and the repercussions in the livers of receptive host, Meriones unguiculatus, were investigated. This compound decreased the specific activity of the lactate dehydrogenase in the metacestodes and the host liver by 81 and 86.8%, respectively. This N-methyl compound has shown an important repercussion on the lactate dehydrogenase activity due to its greater lipophilicity and thus allows a better penetration of the molecule. In the host liver, a fall of the alkaline and acid phosphatases activity was observed. The glucose and glycogen concentrations were also decreased. The ultrastructural study provided an alteration of the tegument of the metacestodes and damages of the muscular system. The parenchyma was disorganized. In conclusion, these biochemical and ultrastructural data obtained with ethyl-N-N-benzyl-methyl oxamate in E. multilocularis metacestodes show clearly the importance of the lactate dehydrogenase activity in the metacestodes.

Analysis of the variance components in a pharmaceutical aerosol product: lodoxamide tromethamine.

The contributions of several components to the variance in lodoxamide delivery from lodoxamide tromethamine metered-dose aerosol containers have been estimated. Two aerosol lots, manufactured with mean diameters of 2.3 and 7.2 micron, exhibited approximately equal variances. The variance was apportioned to the following components: container-to-container, 27%; mouthpiece-to-mouthpiece 18%; valve-to-valve, 11%; assay, 6%. The largest single contribution to the variance (38%) is attributed to unassignable variations which include within-container variations in the dose; quality improvement efforts should concentrate on this area. Little effort should be expended to minimize the assay, valve delivery, or mouthpiece variation as their contribution to lodoxamide dose variation is small. Likewise, the bulk drug particle size did not contribute appreciably to within-lot dose variation.