Remediation of methyl iodide in aqueous solution and soils amended with thiourea

Methyl iodide (MeI) is considered a very promising fumigant alternative to methyl bromide (MeBr) for controlling soil-borne pests. Because atmospheric emission of highly volatile fumigants contributes to air pollution, feasible strategies to reduce emissions are urgently needed. In this study, thiourea (a nitrification inhibitor) was shown to accelerate the degradation of MeI in soil and water. In aqueous solution, the reaction between MeI and thiourea was independent of pH, although the rate of MeI hydrolysis increased in alkaline solution. Substantial increases in the rate of MeI dissipation were observed in thiourea-amended soils. Transformation of MeI by thiourea in aqueous solution was by a single chemical reaction process, while MeI degradation in thiourea-amended soil apparently involved a catalytic mechanism. The electron delocalization between the thiourea molecule and the surfaces of soil particles is energetically favorable and would increase the nucleophilic reactivity of the thiono group toward MeI, resulting in an enhancement of the dissipation rate. The soil half-life for MeI was reduced from >300 h for unamended soils to only a few hours in soil or sand amended with thiourea at a 2:1 molar ratio (thiourea:MeI). The MeI transformation rate in thiourea-amended soil increased with increasing soil temperature and decreasing soil moisture. Therefore, spraying thiourea on the soil surface to form a "reactive surface barrier" may be an effective and innovative strategy for controlling fumigant emissions to the atmosphere and for improving environmental protection.     

Combined application of stable carbon isotope analysis and specific metabolites determination for assessing in situ degradation of aromatic hydrocarbons in a tar oil-contaminated aquifer

To evaluate the intrinsic bioremediation potential in an anoxic tar oil-contaminated aquifer at a former gasworks site, groundwater samples were qualitatively and quantitatively analyzed by compound-specific isotope analysis (CSIA) and signature metabolites analysis (SMA). 13C/12C fractionation data revealed conclusive evidence for in situ biodegradation of benzene, toluene, o-xylene, m/p-xylene, naphthalene, and 1-methylnaphthalene. In laboratory growth studies, 13C/12C isotope enrichment factors for anaerobic degradation of naphthalene (epsilon = -1.1 +/- 0.4) and 2-methylnaphthalene (epsilon = -0.9 +/- 0.1) were determined with the sulfate-reducing enrichment culture N47, which was isolated from the investigated test site. On the basis of these and other laboratory-derived enrichment factors from the literature, in situ biodegradation could be quantified for toluene, o-xylene, m/p-xylene, and naphthalene. Stable carbon isotope fractionation in the field was also observed for ethylbenzene, 2-methylnaphthalene, and benzothiophene but without providing conclusive results. Further evidence for the in situ turnover of individual BTEX compounds was provided by the presence of acetophenone, o-toluic acid, and p-toluic acid, three intermediates in the anaerobic degradation of ethylbenzene, o-xylene, and p-xylene, respectively. A number of groundwater samples also contained naphthyl-2-methylsuccinic acid, a metabolite that is highly specific for the anaerobic degradation of 2-methylnaphthalene. Additional metabolites that provided evidence on the anaerobic in situ degradation of naphthalenes were 1-naphthoic acid, 2-naphthoic acid, 1,2,3,4-tetrahydronaphthoic acid, and 5,6,7,8-tetrahydronaphthoic acid. 2-Carboxybenzothiophene, 5-carboxybenzothiophene, a putative further carboxybenzothiophene isomer, and the reduced derivative dihydrocarboxybenzothiophene indicated the anaerobic conversion of the heterocyclic aromatic hydrocarbon benzothiophene. The combined application of CSIA and SMA, as two reliable and independent tools to collect direct evidence on intrinsic bioremediation, leads to a substantially improved evaluation of natural attenuation in situ.     

Arsenic removal with iron(II) and iron(III) in waters with high silicate and phosphate concentrations

Arsenic removal by passive treatment, in which naturally present Fe(II) is oxidized by aeration and the forming iron(III) (hydr)oxides precipitate with adsorbed arsenic, is the simplest conceivable water treatment option. However, competing anions and low iron concentrations often require additional iron. Application of Fe(II) instead of the usually applied Fe(III) is shown to be advantageous, as oxidation of Fe(II) by dissolved oxygen causes partial oxidation of As(III) and iron(III) (hydr)oxides formed from Fe(II) have higher sorption capacities. In simulated groundwater (8.2 mM HCO3(-), 2.5 mM Ca2+, 1.6 mM Mg2+, 30 mg/L Si, 3 mg/L P, 500 ppb As(III), or As(V), pH 7.0 +/- 0.1), addition of Fe(II) clearly leads to better As removal than Fe(III). Multiple additions of Fe(II) further improved the removal of As(II). A competitive coprecipitation model that considers As(III) oxidation explains the observed results and allows the estimation of arsenic removal under different conditions. Lowering 500 microg/L As(III) to below 50 microg/L As(tot) in filtered water required > 80 mg/L Fe(III), 50-55 mg/L Fe(II) in one single addition, and 20-25 mg/L in multiple additions. With As(V), 10-12 mg/L Fe(II) and 15-18 mg/L Fe(III) was required. In the absence of Si and P, removal efficiencies for Fe(II) and Fe(III) were similar: 30-40 mg/L was required for As(II), and 2.0-2.5 mg/L was required for As(V). In a field study with 22 tubewells in Bangladesh, passive treatment efficiently removed phosphate, but iron contents were generally too low for efficient arsenic removal.     

Spatial distributions and profiles of atmospheric polycyclic aromatic hydrocarbons in two industrial cities in Japan

The spatial distribution and concentration profiles of 39 vapor and particulate polycyclic aromatic hydrocarbons (PAHs) have been investigated in two Japanese industrial cities (Fuji and Shimizu; a summer and winter season in each). The concentrations of particulate PAHs in winter tended to be higher than those in the summer, but for vapor PAHs, this was not the case. Significant correlations (p < 0.01) were found between most of the PAH concentrations monitored in winter, suggesting the presence of common emission sources. To identify PAH spatial distributions and emission sources in the area, we created contour maps for PAHs monitored; this indicates that the distinctive local distributions correspond to the emission sources. PAH profiles based on benzo[e]pyrene (BeP) concentration, especially for certain relatively heavy molecular weight PAHs, showed differential behaviors among divided areas related to potential regional emission sources such as paper-making plants, power plants, and traffic. We conclude that the origins of atmospheric PAHs in the surveyed areas were dominated by not only traffic but also by stationary emission sources such as paper-making plants and power plants and that local distributions were dependent on the local wind direction.     

Ribotyping and a study of transmission of Staphylococcus aureus collected from food preparation facilities

Food poisoning from Staphylococcus aureus is sometimes caused by improper handling of food items in food preparation facilities. Prevention of contamination by employees is particularly important in facilities where a significant amount of food preparation is performed by hand. Some experiments have been performed to describe bacterial cross-contamination in the food preparation process, but there have been few studies of cross-contamination in actual food preparation facilities. Aiming to shed light on the transmission of S. aureus in food preparation facilities, this study collected samples of 66 strains of this bacterium from the fingers of food preparation staff, foodstuffs, prepared foods, cooking utensils, and cooking equipment and typed them with the ribotyping method. S. aureus from the same ribogroup was detected on the hands of a study participant, a faucet, knife, frying pan, and a salad, indicating that bacteria found on the hands of the study participant was transmitted to cooking utensils and prepared foods. Transmission (from a faucet to a frying pan handle) of bacteria by another person, a third party, was also detected.     

Vulnerability of water distribution systems to pathogen intrusion: how effective is a disinfectant residual?

Can the spread of infectious disease through water distribution systems be halted by a disinfectant residual? This question is overdue for an answer. Regulatory agencies and water utilities have long been concerned about accidental intrusions of pathogens into distribution system pipelines (i.e., cross-connections) and are increasingly concerned about deliberate pathogen contamination. Here, a simulation framework is developed and used to assess the vulnerability of a water system to microbiological contamination. The risk of delivering contaminated water to consumers is quantified by a network water quality model that includes disinfectant decay and disinfection kinetics. The framework is applied to two example networks under a worst-case deliberate intrusion scenario. Results show that the risk of consumer exposure is affected by the residual maintenance strategy employed. The common regulation that demands a "detectable" disinfectant residual may not provide effective consumer protection against microbial contamination. A chloramine residual, instead of free chlorine, may significantly weaken this final barrier against pathogen intrusions. Moreover, the addition of a booster station at storage tanks may improve consumer protection without requiring excessive disinfectant.     

Toxicity increases in ice containing monochlorophenols upon photolysis: environmental consequences

The toxic effects of photoproducts formed upon the photolysis of 2- and 4-chlorophenol (CP) frozen solutions in polycrystalline ice phase were determined with a bacterial luminescence test (Vibrio fisheri), and in vitro biomarker assay for dioxin-like effects (inductions of AhR-dependent luciferase in H4IIE-luc cells) and compared to the toxic effects of products of the same photoreaction in aquatic phase. Coupling photoproducts formed in ice samples (3'-chlorobiphenyl-2,4'-diol and 3-chlorobiphenyl-2,2'-diol from 2-CP photolysis and 5-chlorobiphenyl-2,4'-diol from 4-CP photolysis) were found to be more toxic to V. fisheri than parent CPs and elicited significant inductions of dioxin-like effects (the effective concentrations EC50 approximately 3 x 10(-5) mol L(-1) corresponded to known weaker ligands of AhR, such as nonplanar polychlorinated biphenyls or polycyclic aromatic hydrocarbons). To complete the picture, a photoproduct formed from 4-CP (5-chlorobiphenyl-2,4'-diol) was synthesized, and a detailed toxicity assessment with purified compound confirmed the results obtained with irradiated samples. Our findings support a recently proposed model according to which solar radiation can trigger the formation of new types of organic pollutants in polar ice or tropospheric ice cloud particles, presenting possibly greater risk to the environment than the parent compounds.     

Changes in lipid fractions and sensory properties of Idiazabal cheese induced by lipase addition

This work studied the addition of an adequate lipase to enhance lipolysis reactions and the development of piquant flavour and sharp odour in Idiazabal cheese, as an alternative to the use of lamb rennet paste. Cheeses were manufactured from bulk raw ewes' milk in 50 l vats with commercial bovine rennet and 80 lipase units of pregastric or 180 lipase units of fungal lipase and ripened for 180 days. A higher lipolytic activity was induced by lipase addition promoting strong changes in odour and flavour attributes. Both fungal and pregastric lipases increased the content of total free fatty acids (FFA), but the fungal lipase released mainly medium- and long-chain FFA. In contrast, the pregastric lipase preferably released short-chain FFA. Diglyceride (DG) content was considerably higher in cheeses made with added pregastric lipase compared with those made with fungal lipase or with no lipase. Monoglycerides (MG) were detected only in cheeses made with either lipase added, reaching comparable concentrations after ripening for 180 days. The cheeses made with pregastric lipase had the highest scores for odour and flavour intensity, and sharp and rennet odours, desirable attributes for the Idiazabal cheese made with lamb rennet paste. None of the texture attributes were significantly influenced by the concentrations of MG and DG in the cheeses made with either lipase. Thus, the pregastric lipase was more appropriate than the fungal lipase to develop a more traditionally-flavoured Idiazabal cheese.     

Effect of lying behavior on uterine blood flow in cows during the third trimester of gestation

Seven Holstein cows (BW = 639.4 +/- 28.8 kg, age = 62.6 +/- 6.9 mo, parity = 3.1 +/- 0.4 yr) (mean +/- SE) were used to measure uterine blood flow using a transit time ultrasonic flow meter. Ultrasonic flow probes were implanted (d 218 +/- 4 of gestation) around both uterine arteries (n = 3) or the gravid uterine artery (n = 4) to measure variations in uterine blood flow through this vessel in response to postural change (standing and lying). Implantation of the ultrasonic blood flow probe was successful in all 7 cows. Uterine blood flow was measured for 22.9, 23.1, and 21.4 h/d on d 226, 248, and 269 of gestation, respectively. Cows exhibited normal durations of gestation (272.8 +/- 1.6 d), gave birth to normal healthy calves (birth weight = 41.5 +/- 3.0 kg), and did not retain their placenta. Uterine blood flow to the gravid horn during lying was greater than during standing on d 226 (standing vs. lying, 8.04 vs. 8.79 L/min, respectively), d 248 (9.87 vs. 11.06 L/min), and d 269 (8.15 vs. 9.74 L/min) of gestation. Cows spent nearly 50% of their time lying during our observations at all gestational ages. Greater blood supply to the gravid uterus was observed during lying than during standing in this study.     

Aflatoxins in pozol, a nixtamalized, maize-based food

To determine whether pozol, a nixtamalized maize-based food was contaminated with aflatoxins, samples of non-fermented pozol were collected during the period November 2002 to April 2003 from local markets at Comitan in Chiapas, Mexico. The samples were analyzed for the presence of aflatoxins. Nineteen out of one hundred and eleven samples were contaminated with aflatoxin B2 (AFB2) and traces of aflatoxin B1 (AFB1). The percentage of samples contaminated with AFB2 in pozol prepared with white maize was 5.4%. Pozol mixed with toasted cacao paste had a contamination rate of 41.5%. No aflatoxins were detected in pozol prepared with yellow maize. It was found that only 1 of 19 contaminated samples had aflatoxin concentrations above 20 ppb.