Kinetics and mechanistic aspects of As(III) oxidation by aqueous chlorine, chloramines, and ozone: relevance to drinking water treatment

Kinetics and mechanisms of As(III) oxidation by free available chlorine (FAC-the sum of HOCl and OCl-), ozone (O3), and monochloramine (NH2Cl) were investigated in buffered reagent solutions. Each reaction was found to be first order in oxidant and in As(III), with 1:1 stoichiometry. FAC-As(III) and O3-As(III) reactions were extremely fast, with pH-dependent, apparent second-order rate constants, k'app, of 2.6 (+/- 0.1) x 10(5) M(-1) s(-1) and 1.5 (+/- 0.1) x 10(6) M(-1) s(-1) at pH 7, whereas the NH2Cl-As(III) reaction was relatively slow (k'app = 4.3 (+/- 1.7) x 10(-1) M(-1) s(-1) at pH 7). Experiments conducted in real water samples spiked with 50 microg/L As(III) (6.7 x 10(-7) M) showed that a 0.1 mg/L Cl2 (1.4 x 10-6 M) dose as FAC was sufficient to achieve depletion of As(III) to <1 microg/L As(III) within 10 s of oxidant addition to waters containing negligible NH3 concentrations and DOC concentrations <2 mg-C/L. Even in a water containing 1 mg-N/L (7.1 x 10(-5) M) as NH3, >75% As(III) oxidation could be achieved within 10 s of dosing 1-2 mg/L Cl2 (1.4-2.8 x 10(-5) M) as FAC. As(III) residuals remaining in NH3-containing waters 10 s after dosing FAC were slowly oxidized (t1/2 > or = 4 h) in the presence of NH2Cl formed by the FAC-NH3 reaction. Ozonation was sufficient to yield >99% depletion of 50 microg/L As(III) within 10 s of dosing 0.25 mg/L O3 (5.2 x 10(-6) M) to real waters containing <2 mg-C/L of DOC, while 0.8 mg/L O3 (1.7 x 10(-5) M) was sufficientfor a water containing 5.4 mg-C/L of DOC. NH3 had negligible effect on the efficiency of As(III) oxidation by O3, due to the slow kinetics of the O3-NH3 reaction at circumneutral pH. Time-resolved measurements of As(III) loss during chlorination and ozonation of real waters were accurately modeled using the rate constants determined in this investigation.     

Antioxidant Properties of Genistein in a Model Edible Oil System

ABSTRACT:  Antioxidant properties of genistein were tested during the low temperature oxidation of linseed oil. Four linseed oil solutions were prepared: linseed oil, linseed oil containing 2 μmol added genistein/g oil, linseed oil containing 4 μmol added genistein/g oil, and linseed oil containing 200 ppm butylated hydroxyanisole (BHA). Dimethyl sulfoxide (DMSO) (1.7%) was added to all solutions to allow for the solubilization of genistein. Antioxidant activities were analyzed using 2 techniques: (i) the oven stability test carried out at 60 °C with periodic determination of peroxide values (PV); and (ii) oxidation on a heated (60 °C) FTIR-ATR crystal with periodic scanning and collection of infrared spectra. Induction points (IP) for each solution were determined. A strong correlation ( r = 0.91) was noted between the 2 analytical methods used. Three significantly ( P < 0.10) different levels of IP were generally observed. The shortest IP (17 h for PV, 36.9 h for FTIR) was found for the linseed oil. Intermediate IP's were obtained for the 2 μmol added genistein/g oil (32.4 h for PV, 43.5 h for FTIR) and 4 μmol added genistein/g oil (33.9 h for PV, 44.2 h for FTIR) samples. The longest IP (39.9 h for PV, 54.2 h for FTIR) was obtained for the 200 ppm BHA containing solution. Although genestein was not as effective as BHT in retarding oxidation, the results clearly demonstrate that it is able to act as an antioxidant in a bulk oil system.     

Occurrence of phthalate metabolites in human urine from several Asian countries

The occurrence of 14 phthalate metabolites was found in human urine samples collected from seven Asian countries: China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam. Phthalate metabolites were found in all samples, indicating widespread exposure of humans to phthalates in these Asian countries. The highest total (the sum of 14 phthalates) phthalate metabolite concentrations were found in samples collected from Kuwait (median: 1050 ng/mL), followed in decreasing order by samples from India (389 ng/mL), China (234 ng/mL), Vietnam (133 ng/mL), Japan (120 ng/mL), Korea (117 ng/mL), and Malaysia (94.9 ng/mL). The creatinine-adjusted median concentrations of total phthalates for urine samples from Kuwait, India, China, Vietnam, Japan, Korea, and Malaysia were 692, 506, 289, 119, 103, 104, and 169 μg/g creatinine, respectively. Monomethyl phthalate (mMP), monoethyl phthalate (mEP), mono (2-isobutyl phthalate) (miBP), mono-n-butyl phthalate (mBP), and metabolites of di-(2-ethylhexyl) phthalate (DEHP) were the dominant compounds, collectively accounting for >95% of the total concentrations in the samples from the seven countries. The profiles of urinary phthalate metabolite concentrations varied among the samples collected from the seven countries. Urine samples from Kuwait contained the highest concentrations of mEP (median: 391 ng/mL), mBP (94.1 ng/mL), and the metabolites of DEHP (202 ng/mL), whereas samples from China and Japan contained the highest concentrations of miBP (50.8 ng/mL) and mMP (17.5 ng/mL), respectively. mEP was the predominant metabolite in urine samples from India and Kuwait (accounting for 49% of the total), mBP and miBP were the predominant compounds in samples from China (52%), and DEHP metabolites were the predominant compounds in samples from Korea (46%) and Vietnam (52%). Based on the urinary concentrations of mEP, mBP, miBP, and DEHP metabolites of the samples from the seven Asian countries, we estimated daily intake rates of diethyl phthalate (DEP), dibutyl phthalate (DBP), and DEHP. The results indicated that people in the seven Asian countries are exposed to DEP, DBP, and DEHP at levels well below the reference doses (RfD) suggested as unsafe by the U.S. Environmental Protection Agency (EPA). The estimated exposure doses to DEHP in Kuwait, however, were above the RfD recommended by the EPA.     

Open dumping site in Asian developing countries: a potential source of polychlorinated dibenz-p-dioxins and polychlorinated dibenzofurans

Open landfill dumping areas for municipal wastes in Asian developing countries have recently received particular attention with regard to environmental pollution problems. Because of the uncontrolled burning of solid wastes, elevated contamination by various toxic chemicals including dioxins and related compounds in these dumping sites has been anticipated. In this study, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (PCBs) were determined in soils from dumping sites in the Philippines, Cambodia, India, and Vietnam. Residue concentrations of PCDD/Fs and coplanar PCBs in dumping site soils were apparently greater than those in soils collected in agricultural or urban areas far from dumping sites, suggesting that dumping sites are potential sources of PCDD/Fs and related compounds. Observed PCDD/F concentrations in soils from dumping sites in the Philippines and Cambodia were comparable or higher than those reported for dioxin-contaminated locations in the world (e.g., near the municipal waste incinerators and open landfill dumping sites). Homologue profiles of PCDD/Fs in dumping site soils from the Philippines and, to a lesser extent, from Cambodia and India reflected patterns of samples representing typical emissions, while profiles of agricultural or urban soils were similar to those of typical environmental sinks. This result suggests recent formation of PCDD/Fs in dumping site areas and that open dumping sites are a potential source of dioxins in Asian developing countries. Uncontrolled combustions of solid wastes by waste pickers, generation of methane gas, and low-temperature burning can be major factors for the formation of dioxins in dumping sites. Elevated fluxes of PCDD/Fs to soils in dumping sites were encountered in the Philippines, Cambodia, India, and Vietnam-Hanoi, and these levels were higher than those reported for other countries. Considerable loading rates of PCDD/Fs in the dumping sites of these countries were observed, ranging from 20 to 3900 mg/yr (0.12-35 mg TEQ/yr). PCDD/F concentrations in some soil samples from the Philippines, Cambodia, India, and Vietnam-Hanoi exceeded environmental guideline values, suggesting potential health effects on humans and wildlife living near these dumping sites. The estimated intakes of dioxins via soil ingestion and dermal exposure for children were higher than those for adults, suggesting greater risk of dioxin exposure for children in dumping sites. To our knowledge, this is the first comprehensive study on PCDD/Fs contamination in open dumping sites of Asian developing countries. On the basis of the result of this study, we have addressed a new environmental issue that open dumping sites are potential sources of PCDD/Fs and related compounds, and dioxin contamination in dumping sites may become a key environmental problem in developing countries.     

The effects of salt concentration on conformational changes in cod (Gadus morhua) proteins during brine salting

The effects of different salt concentrations (6%, 15%, 18% and 24% NaCl (w/w)) on the conformational changes of cod muscle proteins during brine salting were examined in this study. Proteins were extracted from the brine salted samples with solutions of 1 M (5.9%) and 4 M (23.4%) NaCl and the quantity of salt soluble proteins (SSP), disulfide bond (S–S), total sulfhydryl (SH) and available SH content in the soluble fraction were determined. Increased salt concentration in cod muscle promoted protein denaturation and aggregation. The SSP and total SH content decreased, whereas the S–S bond and available SH content increased with increased salt concentration in cod muscle. Disulfide bond formation correlated (r = −0.6) with a decrease in total SH groups. Higher SSP and available SH groups of the samples at lower brine concentrations was explained by smaller concentration gradients and salt diffusion rates, resulting in stronger salting-in at early stages of the brining process. There was a significant difference in conformational changes in proteins extracted with a salt solution of 1 and 4 M, mainly due to a different degree of protein aggregation.     

Anti-melanoma, tyrosinase inhibitory and anti-microbial activities of gold nanoparticles synthesized from aqueous leaf extracts of Teraxacum officinale

There has been a tenacious search for pharmaceuticals of natural origin, as they are cost-effective and are noted for having little or no side effects. The rate at which diseases are developing resistance to synthetic drugs is quite alarming, and the side effects of these drugs remain an excruciating agony to the pharmaceutical industry. Gold nanoparticles (AuNPs) have wide applications in current technology. However, their use in medicine has not been adequately explored. Chemical methods for the synthesis are associated with environmental benignity and tissue toxicity on in vivo administration. For the first time, we have synthesized AuNPs from leaf extracts of Teraxacum officinale that were found to have significant anti-melanoma, tyrosinase inhibitory and anti-microbial effects, and hence stand as promising candidates for use in cosmetics medical and food industries.     

Red yeast barley reduces plasma glucose levels and activates AMPK phosphorylation in <Emphasis Type=Italic>db/db</Emphasis> mice

Red yeast (Monascus purpureus) fermented over rice has a limited hypoglycemic activity. To enhance its glucose-lowering effect, we fermented red yeast over waxy barley, a hypoglycemic grain with high levels of fibers and β-glucans, and investigated the metabolic effects of red yeast barley (RYB) in high-fat-fed hyperglycemic db/db mice for 6 weeks. The fasting glucose levels were significantly reduced in the RYB group at 6 weeks by 25% (p<0.05), as was the glucose tolerance (−27% of area under the curve in RYB vs. controls, p<0.05). Plasma insulin levels and the expression of PPAR-γ were unaltered, however, the phosphorylation activation of hepatic AMP-activated protein kinase (AMPK) was increased significantly in RYB group compared with controls suggesting that hypoglycemic effect of RYB may be achieved by AMPK-dependent mechanism. RYB may be used as a hypoglycemic functional food modulating cellular AMPK activity.     

Neurofuzzy control of a low‐temperature desulphurization plant

Low‐temperature desulphurization (LTD) is a low‐cost alternative to conventional wet scrubbing for removing sulphur dioxide from flue gas produced by power generating plants. A problem in the design of conventional controllers to achieve and maintain process conditions for optimal desulphurisation is the lack of mathematical models to characterise the complex desulphurization process and unexpected environ mental disturbances. The aim of the work reported in this paper was to replace a skilled human operator who could successfully regulate the LTD plant through manipulation of low‐level controllers with a competitive neurofuzzy system, which possesses both the learning ability of neural networks and the structural transparency of fuzzy logic systems. A hierarchical control structure was adopted whereby the competitive neurofuzzy method was used at the top level for co‐ordinating actions of low‐level conventional controllers. This approach would considerably simplify the task of designing the control system and has been shown to yield high‐level controllers with performances at least equalling that of expert operators, as demonstrated in this paper. Copyright © 2001 John Wiley & Sons, Ltd.