A comparison between flow-through cathode and mixed tank cells for the electro-Fenton process with conductive diamond anode.

This work focusses on the production of hydrogen peroxide and in the removal of bromacil by the electro-Fenton process using two different electrochemical cells: mixed tank cell (MTC) and flow-through cell (FTC). Both cells use boron doped diamond (BDD) as anode and carbon felt as cathode to promote the formation of hydrogen peroxide. In the case of the MTC, two surface area ratios, Acathode/Aanode, have been used. Results show that the H2O2 produced by MTC and FTCPSC increases with the time until a stabilization state. For the FTCPSC, the average hydrogen peroxide concentration produced increases progressively with the current, while for MTC the maximum values are found in applying very low current densities. In addition, the FTCPSC provides higher concentrations of hydrogen peroxide for the same current density applied. Regarding the MTC, it can be stated that the higher the area of the cathode, the higher is the amount of H2O2 produced and the lower is the cell voltage (because of a more efficient current lines distribution). The initial oxidation of bromacil is very efficiently attained being rapidly depleted from wastewater. However, the higher production of hydrogen peroxide obtained by the FTCPSC cell does not reflect on a better performance of the electro-Fenton process. Thus, bromacil is better mineralized using the MTC cell with the lowest cathode area. This observation has been explained because larger concentrations of produced hydrogen peroxide seems to benefit the oxidation of intermediates and not the mineralization.

On the Cooperativity Effect in Watson and Crick and Wobble Pairs for a Halouracil Series and Its Potential Quantitative Application Studied through Surface-Enhanced Raman Spectroscopy.

The nature of the cooperativity effect of hydrogen bonds in Watson and Crick and wobble base pairs formed with thymine, uracil, and its 5-halogenated derivatives (5-fluoro, -chloro, and -bromouracil) has been studied through SERS and by using chemometric tools to process data and extract relevant information. Remarkable differences between the two kinds of pairs were clearly observed, and the behavior correlated to the withdrawing character of different substituents at the 5-position of uracil was verified. Multivariate analyses have also unveiled information about the pair's stability, and a stronger cooperativity effect seems to rule the Watson and Crick pairs when compared to wobble pairs. Defined patterns in the behavior of Watson and Crick pairs allowed the design of an indirect methodology for quantifying 5-bromouracil using a partial least squares (PLS) method with variable selection. Limit of detection (LOD) values of 0.037 and 0.112 mmol L-1 in the absence and presence of structurally similar interferences were reached, while its direct surface-enhanced Raman spectroscopy (SERS) quantification is only possible at ∼45 mmol L-1.

Use of quadrupole time-of-flight mass spectrometry to determine proposed structures of transformation products of the herbicide bromacil after water chlorination.

The herbicide bromacil has been extensively used in the Spanish Mediterranean region, and although plant protection products containing bromacil have been withdrawn by the European Union, this compound is still frequently detected in surface and ground water of this area. However, the fast and complete disappearance of this compound has been observed in water intended for human consumption, after it has been subjected to chlorination. There is a concern about the possible degradation products formed, since they might be present in drinking water and might be hazardous. In this work, the sensitive full-spectrum acquisition, high resolution and exact mass capabilities of hybrid quadrupole time-of-flight (QTOF) mass spectrometry have allowed the discovery and proposal of structures of transformation products (TPs) of bromacil in water subjected to chlorination. Different ground water samples spiked at 0.5 µg/mL were subjected to the conventional chlorination procedure applied to drinking waters, sampling 2-mL aliquots at different time intervals (1, 10 and 30 min). The corresponding non-spiked water was used as control sample in each experiment. Afterwards, 50 µL of the water was directly injected into an ultra-high-pressure liquid chromatography (UHPLC)/electrospray ionization (ESI)-(Q)TOF system. The QTOF instrument enabled the simultaneous recording of two acquisition functions at different collision energies (MS(E) approach): the low-energy (LE) function, fixed at 4 eV, and the high-energy (HE) function, with a collision energy ramp from 15 to 40 eV. This approach enables the simultaneous acquisition of both parent (deprotonated and protonated molecules) and fragment ions in a single injection. The low mass errors observed for the deprotonated and protonated molecules (detected in LE function) allowed the assignment of a highly probable molecular formula. Fragment ions and neutral losses were investigated in both LE and HE spectra to elucidate the structures of the TPs found. For those compounds that displayed poor fragmentation, product ion scan (MS/MS) experiments were also performed. On processing the data with specialized software (MetaboLynx), four bromacil TPs were detected and their structures were elucidated. To our knowledge, two of them had not previously been reported.

Modelling the dissipation kinetics of six commonly used pesticides in two contrasting soils of New Zealand.

We used three non-linear bi-phasic models, bi-exponential (BEXP), first-order double exponential decay (FODED), and first-order two-compartment (FOTC), to fit the measured degradation data for six commonly used pesticides (atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone) in two New Zealand soils. Corresponding DT(50) and DT(90) values for each compound were numerically obtained and compared against those estimated by simple first-order kinetic (SFOK) model. All 3 non-linear models gave good fit of the measured data under both soil depths and were well supported by the values obtained for the respective statistical indices (RMSE, CRM and r(2)). The FOTC model gave by far the best fit for most compounds, followed by the FODED and BEXP models. Overall, DT(50) values derived by non-linear models for the six compounds in soils from both sites were lower than the values obtained by the SFOK model. Differences in the SFOK and the three non-linear models derived DT(90)were, however, an order of magnitude higher for some compounds, while for others differences were very small. Although all three non-linear models described most data by giving excellent fits, in a few instances > 5-10% asymptotes hindered the estimation of DT(90) values. This work shows that when degradation deviates from first-order kinetic, application of non-linear decay models to describe the kinetics of degradation becomes important in order to derive the true end-points for pesticides in soil.

Evaluation of sources and loading of pesticides to the Sacramento River, California, USA, during a storm event of winter 2005.

A monitoring study was conducted in the tributaries and main stem of the Sacramento River, California, USA, during the storm event of January 26 to February 1, 2005. The purpose of the study was to evaluate the sources and loading of pesticides in the Sacramento River watershed during the winter storm season. A total of 26 pesticides or pesticide degradates were analyzed, among which five pesticides and one triazine degradate were detected. Diuron, diazinon, and simazine were found in all streams with a total load of 110.4, 15.4, and 15.7 kg, respectively, in the Sacramento River over the single storm event. Bromacil, hexazinone, and the triazine degradate diaminochlorotriazine were only detected in two smaller drainage canals with a load ranged from 0.25 to 7 kg. The major source of pesticides detected in the main stem Sacramento River was from the most upstream subbasin, the Sacramento River above Colusa, where detected pesticides either exceeded or were close to those at the main outlet of the Sacramento River at Alamar Marina. The higher precipitation in this subbasin was partly responsible for the greater contribution of pesticides observed. Diazinon was the only pesticide with concentrations above water quality criteria, indicating that additional mitigation measures may be needed to reduce its movement to surface water.

Groundwater contamination by chlorinated naphthalenes and related substances caused by activities of a former military base.

Water samples derived from two different aquifer layers of six sampling sites were analysed by GC/MS in order to characterize a groundwater contamination caused by chemicals used for wood impregnation. Mono- and dichlorinated naphthalenes, chlorobenzo(b)thiophene, 1-chloro-4-naphthol, 1-chloronaphthoic acid, acenaphthene and methyled naphthalenes were identified as the main pollutants and quantified. 1-Chloro-4-naphthol and 1-chloronaphthoic acid are discussed as possible indicators for anaerobic degradation processes. Results of inorganic and compound specific stable carbon isotope analyses revealed only a minor degree of microbiological transformation. Thus, sorption was characterized as the main attenuation process within the aquifer affecting the contamination described.

EPR studies of 5-bromouracil crystal after irradiation with X rays in the bromine K-edge region.

Radicals induced in a single crystal of 5-bromouracil (BrUra) by synchrotron soft X rays in the bromine K-edge region (13.461-13.482 keV) were investigated using the X-band EPR method. The crystal was irradiated at three peak energies of the absorption spectrum at room temperature or at 80 K. A hydrogen abstraction radical derived from N1 of the pyrimidine ring was commonly observed for all of the energies used, though with some variation in quantity. Similar characteristics were also observed in the EPR signal for the off-K-edge low-energy (13.42 keV) and (60)Co gamma rays used for comparison. When irradiated at 80 K, a much larger exposure (roughly 10 times) of soft X rays was needed to obtain the same signal intensity as that observed at room temperature. EPR signals were not detectable with gamma irradiation at liquid nitrogen temperature.

Analysis of herbicide Krovar I by liquid chromatography with atmospheric pressure chemical ionization mass spectrometry.

A simple, very efficient method is presented for routine analysis of herbicide Krovar I (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid-liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 microg L(-1) and for diuron 0.03 microg L(-1). Method detection limit for soil samples is 0.01 microg g(-1) dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.

Interlaboratory comparison of extraction efficiency of pesticides from surface and laboratory water using solid-phase extraction disks.

A continuation of an earlier interlaboratory comparison was conducted (1) to assess solid-phase extraction (SPE) using Empore disks to extract atrazine, bromacil, metolachlor, and chlorpyrifos from various water sources accompanied by different sample shipping and quantitative techniques and (2) to compare quantitative results of individual laboratories with results of one common laboratory. Three replicates of a composite surface water (SW) sample were fortified with the analytes along with three replicates of deionized water (DW). A nonfortified DW sample and a nonfortified SW sample were also extracted. All samples were extracted using Empore C(18) disks. After extraction, part of the samples were eluted and analyzed in-house. Duplicate samples were evaporated in a 2-mL vial, shipped dry to a central laboratory (SDC), redissolved, and analyzed. Overall, samples analyzed in-house had higher recoveries than SDC samples. Laboratory x analysis type and laboratory x water source interactions were significant for all four compounds. Seven laboratories participated in this interlaboratory comparison program. No differences in atrazine recoveries were observed from in-house samples analyzed by laboratories A, B, D, and G compared with the recovery of SDC samples. In-house atrazine recoveries from laboratories C and F were higher when compared with recovery from SDC samples. However, laboratory E had lower recoveries from in-house samples compared with SDC samples. For each laboratory, lower recoveries were observed for chlorpyrifos from the SDC samples compared with samples analyzed in-house. Bromacil recovery was <65% at two of the seven laboratories in the study. Bromacil recoveries for the remaining laboratories were >75%. Three laboratories showed no differences in metolachlor recovery; two laboratories had higher recoveries for samples analyzed in-house, and two other laboratories showed higher metolachlor recovery for SDC samples. Laboratory G had a higher recovery in SW for all four compounds compared with DW. Other laboratories that had significant differences in pesticide recovery between the two water sources showed higher recovery in DW than in the SW regardless of the compound. In comparison to earlier work, recovery of these compounds using SPE disks as a temporary storage matrix may be more effective than shipping dried samples in a vial. Problems with analytes such as chlorpyrifos are unavoidable, and it should not be assumed that an extraction procedure using SPE disks will be adequate for all compounds and transferrable across all chromatographic conditions.

Phagocytes produce 5-chlorouracil and 5-bromouracil, two mutagenic products of myeloperoxidase, in human inflammatory tissue.

Oxidative damage to DNA has been implicated in carcinogenesis during chronic inflammation. Epidemiological and biochemical studies suggest that one potential mechanism involves myeloperoxidase, a hemeprotein secreted by human phagocytes. In this study, we demonstrate that human neutrophils use myeloperoxidase to oxidize uracil to 5-chlorouracil in vitro. Uracil chlorination by myeloperoxidase or reagent HOCl exhibited an unusual pH dependence, being minimal at pH approximately 5, but increasing markedly under either acidic or mildly basic conditions. This bimodal curve suggests that myeloperoxidase initially produces HOCl, which subsequently chlorinates uracil by acid- or base-catalyzed reactions. Human neutrophils use myeloperoxidase and H2O2 to chlorinate uracil, suggesting that nucleobase halogenation reactions may be physiologically relevant. Using a sensitive and specific mass spectrometric method, we detected two products of myeloperoxidase, 5-chlorouracil and 5-bromouracil, in neutrophil-rich human inflammatory tissue. Myeloperoxidase is the most likely source of 5-chlorouracil in vivo because halogenated uracil is a specific product of the myeloperoxidase system in vitro. In contrast, previous studies have demonstrated that 5-bromouracil could be generated by either eosinophil peroxidase or myeloperoxidase, which preferentially brominates uracil at plasma concentrations of halide and under moderately acidic conditions. These observations indicate that the myeloperoxidase system promotes nucleobase halogenation in vivo. Because 5-chlorouracil and 5-bromouracil can be incorporated into nuclear DNA, and these thymine analogs are well known mutagens, our observations raise the possibility that halogenation reactions initiated by phagocytes provide one pathway for mutagenesis and cytotoxicity at sites of inflammation.

Movement of bromacil and hexazinone in soils of Hawaiian pineapple fields.

Bromacil and hexazinone have been heavily used to control weeds in the pineapple fields in central Oahu, Hawaii, USA, since 1970s and 1980s, respectively. The last application prior to this study was at a rate of 0.6 kg active ingredient (a.i.) ha(-1) for hexazinone and 1.8 or 3.4 kg (a.i.) ha(-1) for bromacil in the six study fields during June-October 1998. Soils were collected from 0 to 1860 cm below the surface in January-May 1999 to survey the residue profiles of the two herbicides. Stratoprobe sampling showed to be an efficient and convenient method for deep soil cores. Bromacil was detected in all the soil samples above 60 cm (105-1338 ng g(-1) dry weight) and in 74% of the samples above 400 cm (26-473 ng g(-1)). Trace amounts of bromacil (90-113 ng g(-1)) were detected in some of the samples collected from as deep as 1540 cm. Hexazinone was detected in three of the six fields at 0-60 cm only (86-107 ng g(-1) dry weight). The more frequent detection of bromacil at higher concentrations than hexazinone is related to the prolonged higher application rates of bromacil in the fields and its higher persistence and mobility in soil.

Recovery of atrazine, bromacil, chlorpyrifos, and metolachlor from water samples after concentration on solid-phase extraction disks: interlaboratory study.

An interlaboratory comparison was conducted in 1997 and 1998 to examine the feasibility of using C18 solid-phase extraction disks (Empore) to simultaneously determine the herbicides atrazine, bromacil, and metolachlor and the insecticide chlorpyrifos in water samples. A common fortification source and sample processing procedure were used to minimize variation in initial concentrations and operator inconsistencies. The protocol consisted of paired laboratories in different locations coordinating their activities and shipping fortified water samples (deionized or local surface water) or Empore disks on which the pesticides had been retained and then quantitating the analytes by a variety of gas chromatographic methods. Average recoveries from all laboratories were >80% for atrazine, bromacil, and metolachlor, and >70% for chlorpyrifos. Detection of bromacil was unachievable at some locations because of chromatographic problems. Shipping samples between cooperating laboratories did not affect the recovery of atrazine, chlorpyrifos, or metolachlor in either matrix. Recoveries tended to be higher from disks shipped to cooperating laboratories compared with those from fortified water. Shipping disks eliminated many problems associated with the shipment of water samples, such as bottle breakage, higher shipping cost, and possible pesticide degradation. Recoveries of bromacil and metolachlor were lower from fortified surface water samples than from fortified deionized water samples. This collaborative research demonstrated that pesticides in water samples can be concentrated on solid-phase extraction disks at one location and quantitated under diverse analytical conditions at another location. The extraction efficiencies of the disks were comparable with or better than the recoveries obtained from the shipped water samples, and the problems associated with shipping water samples were eliminated by using the disks.

Determination of selected herbicides and phenols in water and soils by solid-phase extraction and high-performance liquid chromatography.

A high-performance liquid chromatography procedure or the determination of the herbicides simazine, propazine, bromacil, metoxuron, and hexazinone is elaborated. Stationary phases RP8 and RP18 and mixtures of methanol-water (2:1 and 1:1, v/v) as a mobile phase are applied for this purpose. The conditions for solid-phase extraction are established, allowing the separation of phenols and herbicides in their mixtures and the extraction of phenols (from river and coke plant water) and herbicides (from the soil samples).

Gas chromatographic method for determination of uracil herbicides in roots of Echinacea angustifolia Moench (Asteraceae).

A GC/NPD method and a rapid screening TLC method were developed for the simultaneous determination of uracil herbicide residues (bromacil, lenacil, terbacil) in the roots of Echinacea angustifolia Moench (Asteraceae). The uracil herbicide residues were extracted into acetone. After evaporation of acetone from the acetone-water extract the residue was dissolved in water-methanol (5:1 v/v). Cyclohexane was used for removal of the non-polar co-extractives in the sample matrix. After separation of the cyclohexane phase the uracil herbicide residues were extracted into chloroform. This extract was purified on a Florisil column, and residues were eluted with dichloromethane-acetone (9:1, v/v). The cleaned up extract was analysed by the GC/NPD method on a capillary column DB-1 using atrazine as internal standard. A minimum recovery of 70% was attained for contamination levels of 0.02-0.40 mg kg(-1).

Combination of solid-phase extraction and field-amplified concentration for trace analysis of organonitrogen pesticides by micellar electrokinetic chromatography.

An analytical method based on the combination of solid-phase extraction (SPE) and field-amplified concentration (FAC), with micellar electrokinetic chromatography (MEKC) was developed to extract, concentrate, separate, and quantitate six organonitrogen pesticides (metribuzin, bromacil, terbacil, hexazinone, triadimefon, and DEET) in drainage water. The recovery of the first five pesticides was over 85%, and the limit of detection was 0.8 ppb. Four advantages (enhanced enrichment and recoveries, reduced extraction time and interferences) of combining SPE with FAC for trace analysis of pesticides at the ppb level were demonstrated.

Rapid extraction and capillary gas chromatography for diazine herbicides in human body fluids.

A simple and rapid method for the extraction of four diazine herbicides (terbacil, bromacil, norflurazon and PAC) from human whole blood, plasma and urine with use of Bond Elut C18 cartridges is presented. Whole blood, plasma and urine samples containing the herbicides, after mixing with distilled water, were loaded on Bond Elut C18 cartridges and the herbicides were eluted with chloroform/methanol (9:1). They were detected by capillary gas chromatography with flame ionization detection (FID) with splitless injection. Separation of the four diazine herbicides from each other and from impurities was generally satisfactory with the use of an intermediately polar DB-17 capillary column. The recovery of all compounds, which had been added to whole blood, plasma and urine, was > 89%. The calibration curve for the herbicides, which has been added to whole blood, plasma and urine, showed linearity in the range 1.6-100 ng on column. Their detection limits were 1.2-1.4 ng on column for whole blood and plasma, and 1.1-1.2 ng on column for urine.