Photolysis of 14C-sulfadiazine in water and manure

Photolysis of 14C-sulfadiazine in aqueous solution under simulated sunlight followed first-order kinetics. The impact of H2O2, humic acid, fulvic acid and acetone to enhance the photodegradation of sulfadiazine (SDZ) was studied. Six photoproducts, 4-OH-SDZ, 5-OH-SDZ, N-formyl-SDZ, 4-[2-iminopyrimidine-1(2H)-yl] aniline, 2-aminopyrimidine, and aniline were identified. Extrusion of SO2 was found to be the main degradation process during irradiation. These photoproducts can occur in water and soil upon sunlight exposure, when soil is treated with SDZ contained in manure. Due to photodegradation the experimental half-life of the SDZ in water was 32h and in the presence of photosensitizers the half-life values were 19.3-31.4h, 17.2-31.4h, 12.6-29.8h, and 3.8-30.7h for H2O2, humic acid, fulvic acid, and acetone, respectively depending on the concentration of the photosensitizers. The presence of photosensitizers markedly reduced SDZ persistence, indicating that indirect photolytic processes are important factors governing the photodegradation of SDZ in aqueous environments. Investigation revealed further persistence behavior of SDZ in manure. The half-life value of SDZ in manure was 158h.     

Benzoic acid, a stimulant of odorant receptors of Bombyx mori, is rapidly metabolized to N-benzoylserine on the antennae

Summary. Benzoic acid is a known stimulant of olfactory receptor cells in trichoid sensilla on the antennae of adult females of Bombyx mori. Exposure of freshly excised antennae, from B. mori females and males, to vapours of [¹⁴C]-benzoic acid revealed that the adsorbed acid is rapidly metabolized (15% conversion in 10 s), suggesting the presence of a highly active enzymatic system. The major product could be identified as N-benzoylserine by use of [²H₅]-benzoic acid, and mass spectrometry linked to a gas chromatograph (GC-MS) or a liquid chromatograph (LC-MS), for analysis of the metabolites. The conjugation of benzoic acid with an amino acid apparently represents a novel mode for the rapid deactivation of odorant molecules. Received 26 March 2001.     

Uranyl–water-containing complexes: solid-state UV-MALDI mass spectrometric and IR spectroscopic approach for selective quantitation

Since primary environmental concept for long storage of nuclear waste involved assessment of water in uranium complexes depending on migration processes, the paper emphasized solid-state matrix-assisted laser desorption/ionization (MALDI) mass spectrometric (MS) and IR spectroscopic determination of UO₂(NO₃)₂·6H₂O; UO₂(NO₃)₂·3H₂O, α-, β-, and γ-UO₃ modifications; UO₃·xH₂O (x?=?1 or 2); UO₃·H₂O, described chemically as UO₂(OH)₂, β- and γ-UO₂(OH)₂ modifications; and UO₄·2H₂O, respectively. Advantages and limitation of vibrational spectroscopic approach are discussed, comparing optical spectroscopic data and crystallographic ones. Structural similarities occurred in α–γ modifications of UO₃, and UO₂(OH)₂ compositions are analyzed. Selective speciation achieved by solid-state mass spectrometry is discussed both in terms of its analytical contribution for environmental quality assurance and assessment of radionuclides, and fundamental methodological interest related the mechanistic complex water exchange of UO₃·H₂O forms in the gas phase. In addition to high selectivity and precision, UV-MALDI-MS, employing an Orbitrap analyzer, was a method that provided fast steps that limited sample pretreatment techniques for direct analysis including imaging. Therefore, random and systematic errors altering metrology and originating from the sample pretreatment stages in the widely implemented analytical protocols for environmental sampling determination of actinides are significantly reduced involving the UV-MALDI-Orbitrap-MS method. The method of quantum chemistry is utilized as well to predict reliably the thermodynamics and nature of U–O bonds in uranium species in gas and condensed phases.     

Point- and nonpoint-source pesticide contamination in the Zwester Ohm catchment, Germany

Reducing pesticide loads in surface waters implies identifying the pathways responsible for the pollution. The current study documents the pesticide contamination of the river Zwester Ohm, a 4917-ha catchment in Germany with 41% of the land used for crop production. Discharges and concentrations of 19 pesticides were measured continuously at three locations for 15 mo. The load detected at the outlet of the catchment amounted to 9048 g a.i. The losses represent 0.22% of the pesticides applied by the farmers. The contamination showed a seasonal pattern following the pesticide application times. The wastewater treatment plant system (WWTPS) in the catchment (two wastewater treatment plants [WWTP], 14 combined sewer overflows (CSO), four CSO tanks) emits during dry weather periods purified sewage and during storm events sewage mixed with stormwater runoff into the river. The contribution by the WWTPS to the pesticide load was defined as point-source pollution (PSP). The load was dominated by PSP with at least 77% of the total pollution. No significant interdependencies between intrinsic properties of the pesticides, hydrometeorological factors, and the loads occurring in the stream could be found. Therefore, it is not possible to predict PSP for other catchments based on the results from this study. Whereas 65% of the total load entered the river via the WWTP, a portion of 12% was attributed to the CSO. The study points out that the influence of CSO on PSP should be taken into account in future catchment studies in areas with comparable agricultural structure.     

Environmental modeling of uranium interstitial compositions of non-stoichiometric oxides: experimental and theoretical analysis

Study of uranium interstitial compositions of non-stoichiometric oxides UO_2+x (x ∈ 0.1–0.02) in gas and condense phases has been presented, using various soft-ionization mass spectrometric methods such as ESI-, APCI-, and MALDI-MS at a wide dynamic temperature gradient (∈ 25–300 °C). Linearly polarized vibrational spectroscopy has been utilized in order to assign unambiguously, the vibrational frequencies of uranium non-stoichiometric oxides. Experimental design has involved xUO_2.66·yUO_2.33, xUO_2.66·yUO_2.33/SiO₂, xUO_2.66·yUO_2.33/SiO₂ (NaOH) and SiO₂/x′NaOH·y′UO₂(NO₃)₂·6H₂O, multicomponent systems (x = 1, y ∈ 0.1–1.0 and x′ = 1, y′ ∈ 0.1–0.6) as well as phase transitions UO₂(NO₃)₂·6H₂O → {U₄O₉(UO_2.25)} → U₃O₇(UO_2.33) → U₃O₈(UO_2.66) → {UO₃}, thus ensuring a maximal representativeness to real environmental conditions, where diverse chemical, geochemical and biochemical reactions, including complexation and sorption onto minerals have occurred. Experimental factors such as UV-irradiation, pH, temperature, concentration levels, solvent types and ion strength have been taken into consideration, too. As far as uranium speciation represents a challenging analytical task in terms of chemical identification diverse coordination species, mechanistic aspects relating incorporation of oxygen into UO _2+x form the shown full methods validation significantly impacts the field of environmental radioanalytical chemistry. UO₂ is the most commonly used fuel in nuclear reactors around the globe; however, a large non-stoichiometric range ∈ UO_1.65–UO_2.25 has occurred due to radiolysis of water on UO₂ surface yielding to H₂O₂, OH^·, and more. Each of those compositions has different oxygen diffusion. And in this respect enormous effort has been concentrated to study the potential impact of hazardous radionuclide on the environment, encompassing from the reprocessing to the disposal stages of the fuel waste, including the waste itself, the processes in the waste containers, the clay around the containers, and geological processes. In a broader sense, thereby, this study contributes to field of environmental analysis highlighting the great ability of various soft-ionization MS methods, particularly, MALDI-MS one, for direct assay of complex multicomponent heterogeneous mixtures at fmol–attomol concentration ranges, along with it the great instrumental features allowing, not only meaningful quantitative, but also structural information of the analytes, thus making the method indispensable for environmental speciation of radionuclides, generally.     

Photolytic degradation of fluoroquinolone carboxylic acids in aqueous solution

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

Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5.