Electron-beam treatment of aromatic hydrocarbons that can be air-stripped from contaminated groundwater. 2. Gas-phase studies

The electron-beam (EB) degradation of volatile aromatics (benzene, toluene, ethylbenzene, xylenes: BTEX) in groundwater strip gas, which in the present work has been modeled by the introduction of the desired aromatic(s) to a stream of air or another gas, such as oxygen, is initiated essentially by the addition of *OH radicals to the aromatic ring, giving rise to hydroxycyclohexadienyl radicals, which form the corresponding peroxyl radicals upon addition of oxygen. As studied in some detail with benzene as a BTEX representative, various reactions of these lead to numerous oxidation products in a cascade of reactions, including the decomposition of products under the prevailing conditions of high turnover of the initial aromatic. Importantly, hydroxycyclohexadienylperoxyl radical formation is partly reversible, and the reactions of the hydroxycyclohexadienyl radicals, which thus have a significant presence in these systems, must therefore also be taken into consideration. In the gas phase, in contrast to the aqueous phase (see Part 1), the reactions of the hydroxycyclohexadienyl radicals lead to oligomeric products that appear to contribute, in addition to ionic clusters, to nucleation for the aerosols observed. Various nitrated products, among them nitrophenols, are observed when air is used for the stripping. However, these studies did not clear the pilot plant stage, since BTEX degradation using a bioreactor carried out in parallel was so successful that the EB technology was judged to be noncompetitive. As for the latter, expensive equipment consisting of a stripper, the EB machine, and an aerosol precipitator would be required. The condensed aerosols are biorefractory and would require further treatment for detoxification.     

Concentration and distribution of heavy metals in urban airborne particulate matter in Frankfurt am Main, Germany

Heavy metal concentrations were measured in airborne dust collected at three sites with different traffic densities from August 2001 to July 2002 in the Frankfurt am Main area. Bulk samples of particulate matter (PM) with an aerodynamic equivalent diameter of <22 microm were collected on cellulose nitrate filters using air filtration devices. Fractionated samples of PM with an aerodynamic equivalent diameter of <10 microm were collected using an eight-stage Andersen impactor. Pb, Cd, Mn, Ni, Zn, V, As, Sb, Cu, Cr, Co, and Ce were determined by inductively coupled plasma sector field mass spectrometry, Pt and Rh were determined by adsorptive voltammetry, and Pd was determined by total reflection X-ray fluorescence analysis. The results show that the highest airborne heavy metal concentrations occurred at the main street with a large volume of traffic. With the exception of Co, V, Ce, and Mn, the heavy metals had an elevated enrichment factor compared to their concentrations in the continental crust. The main street site was especially contaminated with Sb, Zn, Cu, V, and Ni. Motor vehicles are the likely source of emissions. With the exception of Cr, Cu, and Zn, most of the airborne heavy metal concentrations determined for impactor samples deviate slightly from the results for total airborne dust. Heavy metal particle size distributions can be divided into three groups. For metals such as As, Cd, Pb, and V, the main fraction can be found in fine particles with a diameter of <2.1 microm, whereas Ce, Cr, Co, and Ni occur mainly in coarse particles with a diameter of >2.1 microm. Cu, Mn, Sb, Zn, Pt, Pd, and Rh occur in high concentrations in the medium range of the impactor stages (particle diameters of 1.1-4.7 microm). Metal concentrations in fine dust particles are needed to assess the human health risks of their inhalation.     

Transport of chemical and microbial compounds from known wastewater discharges: potential for use as indicators of human fecal contamination

The quality of drinking and recreational water is currently (2005) determined using indicator bacteria. However, the culture tests used to analyze forthese bacteria require a long time to complete and do not discriminate between human and animal fecal material sources. One complementary approach is to use chemicals found in human wastewater, which would have the advantages of (1) potentially shorter analysis times than the bacterial culture tests and (2) being selected for human-source specificity. At 10 locations, water samples were collected upstream and at two successive points downstream from a wastewaster treatment plant (WWTP); a treated effluent sample was also collected at each WWTP. This sampling plan was used to determine the persistence of a chemically diverse suite of emerging contaminants in streams. Samples were also collected at two reference locations assumed to have minimal human impacts. Of the 110 chemical analytes investigated in this project, 78 were detected at least once. The number of compounds in a given sample ranged from 3 at a reference location to 50 in a WWTP effluent sample. The total analyte load at each location varied from 0.018 microg/L at the reference location to 97.7 microg/L in a separate WWTP effluent sample. Although most of the compound concentrations were in the range of 0.01-1.0 microg/L, in some samples, individual concentrations were in the range of 5-38 microg/L. The concentrations of the majority of the chemicals present in the samples generally followed the expected trend: they were either nonexistent or at trace levels in the upstream samples, had their maximum concentrations in the WWTP effluent samples, and then declined in the two downstream samples. This research suggests that selected chemicals are useful as tracers of human wastewater discharge.     

Interactions of fluoroquinolone antibacterial agents with aqueous chlorine: reaction kinetics, mechanisms, and transformation pathways

Kinetics, products, and mechanistic aspects of reactions between free available chlorine (HOCl/OCl-), ciprofloxacin (CF), and enrofloxacin (EF) were extensively investigated to elucidate the behavior of fluoroquinolone antibacterial agents during water chlorination processes. Although the molecular structures of these two substrates differ only with respect to degree of N(4) amine alkylation, CF and EF exhibit markedly different HOCl reaction kinetics and transformation pathways. HOCI reacts very rapidly at CF's secondary N(4) amine, forming a chloramine intermediate that spontaneously decays in aqueous solution by concerted piperazine fragmentation. In contrast, HOCl reacts relatively slowly at EF's tertiary N(4) amine, apparently forming a highly reactive chlorammonium intermediate (R3N-(4)Cl+) that can catalytically halogenate EF or other substrates present in solution. Flumequine, a fluoroquinolone that lacks the characteristic piperazine ring, exhibits no apparent reactivity toward HOCI but appears to undergo facile halodecarboxylation in the presence of R3N(4)-Cl+ species derived from EF. Measured reaction kinetics were validated in real water matrixes by modeling CF and EF losses in the presence of free chlorine residuals. Combined chlorine (CC) kinetics were determined under selected conditions to evaluate the potential significance of reactions with chloramines. CF's rapid kinetics in direct reactions with HOCl, and relatively high reactivity toward CC, indicate that secondary amine-containing fluoroquinolones should be readily transformed during chlorination of real waters, whether applied chlorine doses are present as free or combined residuals. However, EF's slower HOCl reaction kinetics, recalcitrance toward CC, and participation in the catalytic halogenation cycle described herein suggest that tertiary amine-containing fluoroquinolones will be comparatively stable during most full-scale water chlorination processes.     

Kinetic and mechanistic investigations of the oxidation of tramadol by ferrate and ozone

The kinetics and oxidation products (OPs) of tramadol (TRA), an opioid, were investigated for its oxidation with ferrate (Fe(VI)) and ozone (O(3)). The kinetics could be explained by the speciation of the tertiary amine moiety of TRA, with apparent second-order rate constants of 7.4 (±0.4) M(-1) s(-1) (Fe(VI)) and 4.2 (±0.3) × 10(4) M(-1) s(-1) (O(3)) at pH 8.0, respectively. In total, six OPs of TRA were identified for both oxidants using Qq-LIT-MS, LTQ-FT-MS, GC-MS, and moiety-specific chemical reactions. In excess of oxidants, these OPs can be further transformed to unidentified OPs. Kinetics and OP identification confirmed that the lone electron pair of the amine-N is the predominant site of oxidant attack. An oxygen transfer mechanism can explain the formation of N-oxide-TRA, while a one-electron transfer may result in the formation of N-centered radical cation intermediates, which could lead to the observed N-dealkylation, and to the identified formamide and aldehyde derivatives via several intermediate steps. The proposed radical intermediate mechanism is favored for Fe(VI) leading predominantly to N-desmethyl-TRA (ca. 40%), whereas the proposed oxygen transfer prevails for O(3) attack resulting in N-oxide-TRA as the main OP (ca. 90%).     

An 8-hour system for Salmonella detection with immunomagnetic separation and homogeneous time-resolved fluorescence PCR

We describe a system consisting of rapid sample enrichment and homogeneous end-point PCR analysis that enables the detection of Salmonella in various food matrices in 8 h. Sample preparation starts with 6 h enrichment step in supplemented broth, after which Salmonella cells are collected with immunomagnetic particles. The particles are washed and dispensed to ready-to-use PCR reaction vessels, which contain dried assay-specific reagents and an internal amplification control. PCR is performed with a novel instrument platform utilising the sensitive label technology of time-resolved fluorometry. Qualitative assay results are automatically interpreted and available in 45 min after sample addition. The overall accuracy, sensitivity and specificity of the Magda CA Salmonella system were 99.1%, 98.4% and 100.0%, respectively, based on the evaluation of 107 samples (beef, pork, poultry and ready-to-eat meals) artificially contaminated with sub-lethally injured Salmonella cells.     

Short communication: Feeding method affects the feeding behavior of growing dairy heifers

There is limited information available on what is the most appropriate feeding method for growing dairy heifers. The objective of this study was to determine the effect of feeding method on the feeding behavior and diet selection of growing dairy heifers. Six prepubescent Holstein heifers (158.2 ± 4.0 d old, weighing 168.2 ± 15.7 kg), fed once per day for 1.0 kg/d of growth, were subjected to each of 3 treatments in 3 successive 7-d treatment periods using a replicated 3 × 3 Latin square design. Treatments consisted of feeding 2.02 kg/d dry matter of grain concentrate and ad libitum chopped grass hay as: 1) choice (grain concentrate and hay in separate feed bins), 2) top-dressed ration (grain concentrate placed on top of the hay in one feed bin), and 3) total mixed ration (TMR, grain concentrate mixed with hay in one feed bin). Dry matter intake (DMI) and feeding behavior were monitored for 7 d for each animal on each treatment, and feed sorting was monitored for the last 3 d of each treatment period. The provision of grain concentrate and hay in either a choice or top-dressed situation resulted in young dairy heifers rapidly consuming the grain concentrate portion of their ration in very few, large meals before consuming the hay portion of their ration. The provision of the 2 ration ingredients as a TMR increased the distribution of DMI over the day and reduced the amount of sorting (against long forage particles, and for short grain concentrate particles) by heifers. These results suggest that the provision of a TMR to growing dairy heifers, as opposed to feeding concentrate and hay as either a choice or top-dressed, promotes a more balanced intake of nutrients across the day.     

Temporal feed restriction and overstocking increase competition for feed by dairy cattle

Dairy cows are often overstocked. Some managers are now using “slick bunk” (i.e., feeding for 0% orts) management to save on feed costs, but this reduces the time that cows have access to feed. Both practices may increase competition and affect feeding behavior in dairy cows. The aim was to determine the effects of temporal and spatial restrictions on the feeding and competitive behavior of group-housed cows. Treatments were 2 levels of stocking (2:1 versus 1:1 cows:feed bin) and 2 levels of feed access time (14 versus 24 h/d access). Eight groups (each of 6 cows) were tested on each of the 4 treatment combinations for 1 wk, with treatment order assigned using a replicated 4 × 4 Latin square design. Dry matter intake (DMI), feeding time, and feeding rate were measured for the last 4 d of each week, and data were summarized daily and for the 2-h period immediately after the morning feeding. Displacements were recorded for 2 h after the delivery of morning feed (peak feeding period) and 2 h following the afternoon milking. The DMI did not decline when temporal access was restricted (27.0 vs. 25.7 ± 0.5 kg/d), and was not affected by overstocking (26.4 ± 1.9, mean ± SD). Cows with restricted temporal access spent less time feeding (190.9 vs. 207.9 ± 6.1 min). Overstocked cows that were temporally restricted had greater feeding rates during the day (156 vs. 137 ± 4 g/min) and especially during the peak feeding period (175 vs. 146 ± 4 g/min) compared with cows that were not restricted. In the peak feeding period, overstocked cows had reduced DMI (3.0 vs. 3.4 ± 0.1 kg/h) and feeding times (20.8 vs. 25.8 ± 1.0 min/h) and increased feeding rates (161 vs. 138 ± 4 g/min). Cows with restricted temporal access had greater DMI (3.9 vs. 2.6 ± 0.2 kg/h) and time spent feeding (27.3 vs. 19.2 ± 1.3 min/h) during the peak feeding period compared with cows that had continuous access to feed. Restricting temporal access in conjunction with overstocking resulted in the greatest increase in daily displacements (15.0 vs. 3.8 ± 1.4 displacements/d); the majority of these occurred during the peak feeding period. Adequate space and time to access feed is essential to minimize feed bunk competition in indoor group housing systems.     

A New Access to Piperidino-cyclopiperidinecarboxamides – constrained analogues of a pharmaceutical used diaminic building block

6-Piperidino-3-azabicyclo[3.1.0]hexane-6-carboxamide diastereomers 1a and 2a represent conformationally rigid analogues of 3a which is a building block in some pharmaceutical compounds. A new access to these compounds 1a and 2a was found via the cleavage of bicyclic N,N-acetal 6 with hydrocyanic acid as the stereodetermining step. Reaction of derivatives 1a and 2a with bromodiphenyl-butyronitrile 14 gave cyclopiritramide isomers 1c and 2c , respectively. Qualitative preliminary investigations showed different affinities of 1c and 2c to the opiate-μ receptor. These results were discussed on the basis of an X-ray structural analysis of cyclopiritramide isomer 2c . 1-Benzylcyclopiperidine derivatives 1d and 2d were used as model systems for studying the conformation of cyclopiritramide isomer 1c and 2c , respectively.