Metabolomics reveals target and off-target toxicities of a model organophosphate pesticide to roach (Rutilus rutilus): implications for biomonitoring

The ability of targeted and nontargeted metabolomics to discover chronic ecotoxicological effects is largely unexplored. Fenitrothion, an organophosphate pesticide, is categorized as a "red list" pollutant, being particularly hazardous to aquatic life. It acts primarily as a cholinesterase inhibitor, but evidence suggests it can also act as an androgen receptor antagonist. Whole-organism fenitrothion-induced toxicity is well-established, but information regarding target and off-target molecular toxicities is limited. Here we study the molecular responses of male roach ( Rutilus rutilus ) exposed to fenitrothion, including environmentally realistic concentrations, for 28 days. Acetylcholine was assessed in brain; steroid metabolism was measured in testes and plasma; and NMR and mass spectrometry-based metabolomics were conducted on testes and liver to discover off-target toxicity. O-demethylation was confirmed as a major route of pesticide degradation. Fenitrothion significantly depleted acetylcholine, confirming its primary mode of action, and 11-ketotestosterone in plasma and cortisone in testes, showing disruption of steroid metabolism. Metabolomics revealed significant perturbations to the hepatic phosphagen system and previously undocumented effects on phenylalanine metabolism in liver and testes. On the basis of several unexpected molecular responses that were opposite to the anticipated acute toxicity, we propose that chronic pesticide exposure induces an adapting phenotype in roach, which may have considerable implications for interpreting molecular biomarker responses in field-sampled fish.     

Tribromopyrrole,brominated acids,and other disinfection byproducts produced by disinfection of drinking water rich in bromide

Using gas chromatography/mass spectrometry (GC/MS), we investigated the formation of disinfection byproducts (DBPs) from high bromide waters (2 mg/L) treated with chlorine or chlorine dioxide used in combination with chlorine and chloramines. This study represents the first comprehensive investigation of DBPs formed by chlorine dioxide under high bromide conditions. Drinking water from full-scale treatment plants in Israel was studied, along with source water (Sea of Galilee) treated under carefully controlled laboratory conditions. Select DBPs (trihalomethanes, haloacetic acids, aldehydes, chlorite, chlorate, and bromate) were quantified. Many of the DBPs identified have not been previously reported, and several of the identifications were confirmed through the analysis of authentic standards. Elevated bromide levels in the source water caused a significant shift in speciation to bromine-containing DBPs; bromoform and dibromoacetic acid were the dominant DBPs observed, with very few chlorine-containing compounds found. Iodo-trihalomethanes were also identified, as well as a number of new brominated carboxylic acids and 2,3,5-tribromopyrrole, which represents the first time a halogenated pyrrole has been reported as a DBP. Most of the bromine-containing DBPs were formed during pre-chlorination at the initial reservoir, and were not formed by chlorine dioxide itself. An exception wasthe iodo-THMs, which appeared to be formed by a combination of chlorine dioxide with chloramines or chlorine (either added deliberately or as an impurity in the chlorine dioxide). A separate laboratory study was also conducted to quantitatively determine the contribution of fulvic acids and humic acids (from isolated natural organic matter in the Sea of Galilee) as precursor material to several of the DBPs identified. Results showed that fulvic acid plays a greater role in the formation of THMs, haloacetic acids, and aldehydes, but 2,3,5-tribromopyrrole was produced primarily from humic acid. Because this was the first time a halopyrrole has been identified as a DBP, 2,3,5-tribromopyrrole was tested for mammalian cell cytotoxicity and genotoxicity. In comparison to other DBPs, 2,3,5-tribromopyrrole was 8x, 4.5x, and 16x more cytotoxic than dibromoacetic acid, 3-chloro-4-(dichloromethyl)-5-hydroxy-2-[5H]-furanone [MX], and potassium bromate, respectively. 2,3,5-Tribromopyrrole also induced acute genomic damage, with a genotoxic potency (299 microM) similar to that of MX.     

Impact of γ-irradiation,CIPC treatment,and storage conditions on physicochemical and nutritional properties of potato starches

In the present study, three potato varieties were treated with chlorpropham (CIPC, 35 ppm), γ-irradiated (0.1 kGy) and stored for up to 5 months at 8 °C, and the physicochemical properties and in vitro starch digestibility of native and cooked starches were investigated. Sprouting was found to be satisfactorily suppressed by γ-irradiation and CIPC treatment. However, irradiation increased total free glucose content in two potato varieties, and decreased the thermal transition and pasting temperature of starch. The crystallinity of starch in irradiated potatoes decreased significantly (p ? 0.05) which may explain its decreased resistant starch content. Sprout inhibiting treatments and storage had no effect on in vitro starch digestibility in cooked starches, but cooling cooked starch significantly (p ? 0.05) increased its resistant starch content.     

Potentiometric titration for determination of amylose content of starch – A comparison with colorimetric method

Amylose, the amount of which varies significantly depending on the source, is one of the key components of starch. The proportion of the essentially linear amylose and the highly branched amylopectin greatly influences the physico-chemical properties of starch. In this study, potentiometric titration using an auto-titrator and colorimetric methods were compared for determining amylose contents of a variety of starch samples. Potentiometric titration results for starches from a variety of botanical sources were within the reported literature ranges while the colorimetric method seemed to overestimate amylose content.     

Effect of physical properties on the stability of Lactobacillus bulgaricus in a freeze-dried galacto-oligosaccharides matrix

The ability of galacto-oligosaccharides (GOS) to protect Lactobacillus delbrueckii subsp. bulgaricus upon freeze drying was analyzed on the basis of their capacity to form glassy structures. Glass transition temperatures (T(g)) of a GOS matrix at various relative humidities (RH) were determined by DSC. Survival of L. bulgaricus in a glassy GOS matrix was investigated after freezing, freeze drying, equilibration at different RHs and storage at different temperatures. At 32 °C, a drastic viability loss was observed. At 20 °C, the survival was affected by the water content, having the samples stored at lower RHs, the highest survival percentages. At 4°C, no decay in the cells count was observed after 45 days of storage. The correlation between molecular mobility [as measured by Proton nuclear magnetic resonance (1H NMR)] and loss of viability explained the efficiency of GOS as cryoprotectants. The preservation of microorganisms was improved at low molecular mobility and this condition was obtained at low water contents and low storage temperatures. These results are important in the developing of new functional foods containing pre and probiotics.     

Electrostatic spraying of food-grade organic and inorganic acids and plant extracts to decontaminate Escherichia coli O157:H7 on spinach and iceberg lettuce

The prevalence of foodborne illnesses is continually on rise. In the U.S.A., Escherichia coli O157:H7 (E. coli) has been associated with several outbreaks in minimally processed foods. Spinach and lettuce pose higher food safety risks and recurring food recalls suggest the insufficiency of current disinfection strategies. We aimed at offering a natural antimicrobial alternative using organic acids (malic, tartaric, and lactic acids [MA, TA, and LA, respectively]) and grape seed extract (GSE) and a novel application method using electrostatic spraying to evenly distribute the antimicrobials onto produce. Spinach and lettuce samples were washed, sanitized with sodium hypochlorite solution (6.25 mL/L), dip inoculated in water containing E. coli (7.0 log CFU/mL) for 24 h, and rewashed with sterile water to remove nonadhered pathogens. The samples were sprayed electrostatically with MA, LA, and GSE alone and in combinations and for comparison, with phosphoric acid (PA) and pH controls with deionized water adjusted to 1.5/2.3/3.6 and stored at 4 °C. When combined with LA (3%), MA (3%) showed 2.1 to 4.0 log CFU/g reduction of E. coli between the days 1 and 14 on spinach and 1.1 to 2.5 log CFU/g reduction on lettuce. Treatment with PA (1.5%) and PA (1.5%)-GSE (2%) exhibited 1.1 to 2.1 log CFU/g inhibition of E. coli on spinach during the 14-d storage. Our findings demonstrated the efficacy of electrostatic spraying of MA, LA, and GSE on fresh produce to improve the safety and lower the public health burden linked to produce contamination. PRACTICAL APPLICATION: Electrostatic spraying is an emerging technique that can be adopted to improve the distribution and application of antimicrobials during fresh produce sanitation. Relatively simple and quick, the process can access most/all parts of produce surface and offer protection from food pathogens. The use of malic and lactic acids with or without grape seed extract can serve as effective antimicrobials when sprayed electrostatically, lowering the risk from postcontamination issues with spinach and iceberg lettuce. This application technology can be extended to improve the commercial food safety of other produce, fruits, poultry, and meat.     

Fate of Zinc Oxide Nanoparticles during Anaerobic Digestion of Wastewater and Post-Treatment Processing of Sewage Sludge

The rapid development and commercialization of nanomaterials will inevitably result in the release of nanoparticles (NPs) to the environment. As NPs often exhibit physical and chemical properties significantly different from those of their molecular or macrosize analogs, concern has been growing regarding their fate and toxicity in environmental compartments. The wastewater-sewage sludge pathway has been identified as a key release pathway leading to environmental exposure to NPs. In this study, we investigated the chemical transformation of two ZnO-NPs and one hydrophobic ZnO-NP commercial formulation (used in personal care products), during anaerobic digestion of wastewater. Changes in Zn speciation as a result of postprocessing of the sewage sludge, mimicking composting/stockpiling, were also assessed. The results indicated that "native" Zn and Zn added either as a soluble salt or as NPs was rapidly converted to sulfides in all treatments. The hydrophobicity of the commercial formulation retarded the conversion of ZnO-NP. However, at the end of the anaerobic digestion process and after postprocessing of the sewage sludge (which caused a significant change in Zn speciation), the speciation of Zn was similar across all treatments. This indicates that, at least for the material tested, the risk assessment of ZnO-NP through this exposure pathway can rely on the significant knowledge already available in regard to other "conventional" forms of Zn present in sewage sludge.     

Recent Advance in Aromatic Volatile Research in Tomato Fruit: The Metabolisms and Regulations

Aroma, an essential characteristic of tomato fruit, plays an important role in determining the perception and acceptability of tomato products by consumers. During tomato fruit ripening, associated with color changes from green to red involving the conversion of chloroplasts to chromoplasts are changes of aromatic volatile profiles. Although the biosynthetic pathways for some aromatic volatiles have been established in tomato fruit recently, our knowledge of regulatory mechanisms is still rudimentary. On the other hand, many internal and external factors modify volatile metabolism in tomato fruit. This review first summarizes the current knowledge of expression patterns and biosynthetic pathways of aromatic volatiles in tomato fruit along with the role of ethylene in their biosynthesis. The impact of internal and pre- and postharvest external factors on volatile composition is then discussed. This review will provide critical information for research on tomato aromatic volatiles and their manipulation.