Free radical chemistry of disinfection byproducts. 2. Rate constants and degradation mechanisms of trichloronitromethane (chloropicrin)

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, *OH, and hydrated electron, e(aq)-, reactions were (4.97 +/- 0.28) x 10(7) M(-1) s(-1) and (2.13 +/- 0.03) x 10(10) M(-1) s(-1), respectively. It appears that the *OH adds to the nitro-group, while the e(aq)- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance of the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.     

Tubular membrane cathodes for scalable power generation in microbial fuel cells

One of the greatest challenges for using microbial fuel cells (MFCs) for wastewater treatment is creating a scalable architecture that provides large surface areas for oxygen reduction at the cathode and bacteria growth on the anode. We demonstrate here a scalable cathode concept by showing that a tubular ultrafiltration membrane with a conductive graphite coating and a nonprecious metal catalyst (CoTMPP) can be used to produce power in an MFC. Using a carbon paper anode (surface area Aan = 7 cm2, surface area per reactor volume Aan,s = 25 m2/m3), an MFC with two 3-cm tube cathodes (Acat = 27 cm2, Acat,s = 84 m2/m3) generated up to 8.8 W/m3 (403 mW/m2) using glucose [0.8 g/L in a 50 mM phosphate buffer solution (PBS)], which was only slightly less than that produced using a carbon paper cathode with a Pt catalyst (9.9 W/m3, 394 mW/m2; Acat= 7 cm2, Acat,s= 25 m2/m3). Coulombic efficiencies (CEs) with carbon paper anodes were 25-40% with tube cathodes (CoTMPP), compared to 7-19% with a carbon paper cathode. When a high-surface-area graphite brush anode was used (Aan = 2235 cm2, Aan,s = 7700 m2/m3) with two tube cathodes placed inside the reactor (Acat = 27 cm2, Acas, = 93 m2/m3), the MFC produced 17.7 W/m3 with a CE = 70-74% (200 mM PBS). Further increases in the surface area of the tube cathodes to 54 cm2 (120 m2/m3) increased the total power output (from 0.51 to 0.83 mW), but the increase in volume resulted in a constant volumetric power density (approximately 18 W/m3). These results demonstrate that an MFC design using tubular cathodes coated with nonprecious metal catalysts, and brush anodes, is a promising architecture that is intrinsically scalable for creating larger systems. Further increases in power output will be possible through the development of cathodes with lower internal resistances.     

Electricity generation from synthetic acid-mine drainage (AMD) water using fuel cell technologies

Acid-mine drainage (AMD) is difficult and costly to treat. We investigated a new approach to AMD treatment using fuel cell technologies to generate electricity while removing iron from the water. Utilizing a recently developed microbial fuel cell architecture, we developed an acid-mine drainage fuel cell (AMD-FC) capable of abiotic electricity generation. The AMD-FC operated in fed-batch mode generated a maximum power density of 290 mW/m2 at a Coulombic efficiency greater than 97%. Ferrous iron was completely removed through oxidation to insoluble Fe(III), forming a precipitate in the bottom of the anode chamber and on the anode electrode. Several factors were examined to determine their effect on operation, including pH, ferrous iron concentration, and solution chemistry. Optimum conditions were a pH of 6.3 and a ferrous iron concentration above approximately 0.0036 M. These results suggest that fuel cell technologies can be used not only for treating AMD through removal of metals from solution, but also for producing useful products such as electricity and recoverable metals. Advances being made in wastewater fuel cells will enable more efficient power generation and systems suitable for scale-up.     

Effect of level of oil inclusion in the diet of dairy cows at pasture on animal performance and milk composition and properties

The effect of including additional oil, incorporated as whole rapeseeds, in the diet of 64 Holstein–Friesian dairy cows (32 mid‐ and 32 late‐lactation) at pasture on animal performance and milk fat composition and properties was followed over a continuous trial of 20 weeks duration. Within two stages of lactation (mid, 130 ± 16.2 days, or late, 231 ± 58.9 days), cows were allocated to concentrate treatments representing four levels of rapeseed oil inclusion, 0 (control), 200, 400 and 600 g oil day^?1. Oil inclusion had little effect on milk yield but decreased milk fat content significantly (P < 0.01), with a mean depression of 0.40% at the highest level of oil inclusion. The content of milk protein also decreased with increasing addition of oil, but the decrease was smaller than the milk fat depression and was not statistically significant. Increasing the level of rapeseed oil in the diet to 600 g oil day^?1 resulted in linear changes in milk fat and protein concentrations which were described by regression equations. For each 100 g of rapeseed oil added to the diet, milk fat content decreased by 0.068% in mid‐lactation cows and 0.061% in late‐lactation cows, while protein content decreased by 0.026% in mid‐lactation cows and 0.028% in late‐lactation cows. Total unsaturated fatty acid content of milk fat also increased in a linear fashion with increased level of oil addition, from 345.7 g kg^?1 total fatty acids in control milk fat to 459.3 g kg^?1 total fatty acids at 600 g oil day^?1, while total saturated fatty acids decreased in the same milk fats from 640.7 to 522.2 g kg^?1 total fatty acids. These changes were reflected in lower solid fat contents (SFC) in the milk fat at the lower temperatures of measurement, eg 41% SFC at 5 °C at the highest level of oil inclusion compared with 52% in the control milk fat. However, SFC at 20 °C showed little difference with increasing level of dietary oil addition, an important factor in maintaining product integrity at room temperatures. The relatively high content of the monounsaturated fatty acid C18:1 (345.5 g kg^?1 total fatty acids at 600 g oil day^?1) and low content of polyunsaturated fatty acids (total C18:2 and C18:3 <40 g kg^?1 total fatty acids at 600 g oil day^?1) ensured that the oxidative stability of the treatment and control milk fats did not differ significantly. Stage of lactation had an unexplained effect of consistent magnitude on milk fat composition throughout the trial period, with late‐lactation animals producing milk fats containing a significantly (P < 0.001) higher proportion of unsaturated fatty acids than the mid‐lactation animals. Changes in the proportions of unsaturated fatty acids in milk fat, as reflected by changes in iodine value, were established within 2 weeks of the trial commencing and persisted over the 20 weeks of the trial duration. No adverse effect on animal health from this type of dietary manipulation was identified. Copyright © 2004 Society of Chemical Industry     

Gene expression profiles for detecting and distinguishing potential endocrine-disrupting compounds in environmental samples

Industrial and municipal processes may produce and release endocrine-disrupting compounds (EDCs) into the environment, but the exact nature of their effects is difficult to investigate. EDCs typically exert their effect by affecting gene expression aberrantly. To determine if gene expression profiles could be used to detect and distinguish estrogenic EDCs, an estrogen receptor positive human breast cancer cell line (MCF-7) was exposed to known estrogenic compounds, suspected EDCs, and extracts from three effluent samples. A set of specifically estrogen-regulated genes was identified by microarray analysis. Nine estrogen up-regulated genes (IGFBP4, HSPA8, B4GALT1, XBP1, KRT8, GTPBP4, HNRPAB, SLC2A1, and CALM1) and two estrogen down-regulated genes (ID2 and ZNF217) were consistently detectable in response to estrogen and other estrogenic compounds. Gene expression patterns in cells that were exposed to effluent sample extracts were compared to gene expression patterns in cells that were exposed to known endocrines. Using this technique, two of the effluent samples were shown to have estrogenic activity. This approach could easily be extended to screen for other types of receptor-mediated endocrine disruption. For example, cells expressing androgen or aryl hydrocarbon receptors could be used in gene expression profiling assays to detect androgenic effects or for the presence of bioactive aromatic hydrocarbons. Gene expression profiling is emerging as a sensitive and specific method to screen complex samples for endocrine disrupting activity.     

Continuous electricity generation from domestic wastewater and organic substrates in a flat plate microbial fuel cell

A microbial fuel cell (MFC) is a device that converts organic matter to electricity using microorganisms as the biocatalyst. Most MFCs contain two electrodes separated into one or two chambers that are operated as a completely mixed reactor. In this study, a flat plate MFC (FPMFC) was designed to operate as a plug flow reactor (no mixing) using a combined electrode/proton exchange membrane (PEM) system. The reactor consisted of a single channel formed between two nonconductive plates that were separated into two halves by the electrode/PEM assembly. Each electrode was placed on an opposite side of the PEM, with the anode facing the chamber containing the liquid phase and the cathode facing a chamber containing only air. Electricity generation using the FPMFC was examined by continuously feeding a solution containing wastewater, or a specific substrate, into the anode chamber. The system was initially acclimated for 1 month using domestic wastewater orwastewater enriched with a specific substrate such as acetate. Average power density using only domestic wastewater was 72+/-1 mW/m2 at a liquid flow rate of 0.39 mL/min [42% COD (chemical oxygen demand) removal, 1.1 h HRT (hydraulic retention time)]. At a longer HRT = 4.0 h, there was 79% COD removal and an average power density of 43+/-1 mW/m2. Power output was found to be a function of wastewater strength according to a Monod-type relationship, with a half-saturation constant of Ks = 461 or 719 mg COD/L. Power generation was sustained at high rates with several organic substrates (all at approximately 1000 mg COD/L), including glucose (212+/-2 mW/ m2), acetate (286+/-3 mW/m2), butyrate (220+/-1 mW/ m2), dextran (150+/-1 mW/m2), and starch (242+/-3 mW/ m2). These results demonstrate the versatility of power generation in a MFC with a variety of organic substrates and show that power can be generated at a high rate in a continuous flow reactor system.     

Transdermal nicotine use in postmenopausal women: does the treatment efficacy differ in women using and not using hormone replacement therapy?

This study of postmenopausal female smokers (N = 94) asked: During short-term smoking abstinence, do the beneficial effects of transdermal nicotine replacement therapy (NRT) on acute symptomatology (i.e., withdrawal, cigarette craving, smoking urges, mood, depressive symptoms, motor speed, and reaction time) differ in women who use and do not use hormone replacement therapy (HRT)? Participants were recruited according to HRT and non-HRT use (self-selecting), then randomized within strata to active nicotine or placebo nicotine patch. After 1 baseline week of smoking, participants quit smoking for 2 weeks. Women received cessation counseling and were monitored for abstinence. Dependent measures were collected during five clinic visits. Two-way analysis of covariance (ANCOVA) were run on change scores for dependent variables, with nicotine patch group (active/placebo) and HRT group (HRT/non-HRT) as independent variables and age as a covariate. No interactions were found between HRT and patch condition, but both showed specific effects. During the first abstinent week, women on active nicotine patch (compared with placebo) experienced less severe withdrawal, greater reductions in cigarette cravings, and lower (more favorable) Factor 1 scores on the Questionnaire of Smoking Urges. During the second abstinent week, women using HRT (compared with the non-HRT group) exhibited better mood (Profile of Mood States scores) and less depression (Beck Depression Inventory scores). These results suggest the following: First, the efficacy of transdermal nicotine replacement is not adversely modified by women's HRT use; second, ovarian hormones might influence women's responses to smoking cessation, and thus should be considered in developing effective strategies for women to quit smoking.     

Adaptation of the ToxRTool to Assess the Reliability of Toxicology Studies Conducted with Genetically Modified Crops and Implications for Future Safety Testing

To determine the reliability of food safety studies carried out in rodents with genetically modified (GM) crops, a Food Safety Study Reliability Tool (FSSRTool) was adapted from the European Centre for the Validation of Alternative Methods’ (ECVAM) ToxRTool. Reliability was defined as the inherent quality of the study with regard to use of standardized testing methodology, full documentation of experimental procedures and results, and the plausibility of the findings. Codex guidelines for GM crop safety evaluations indicate toxicology studies are not needed when comparability of the GM crop to its conventional counterpart has been demonstrated. This guidance notwithstanding, animal feeding studies have routinely been conducted with GM crops, but their conclusions on safety are not always consistent. To accurately evaluate potential risks from GM crops, risk assessors need clearly interpretable results from reliable studies. The development of the FSSRTool, which provides the user with a means of assessing the reliability of a toxicology study to inform risk assessment, is discussed. Its application to the body of literature on GM crop food safety studies demonstrates that reliable studies report no toxicologically relevant differences between rodents fed GM crops or their non-GM comparators.