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Residues analysis of post-harvest imidazole fungicides in citrus fruit by HPLC and GLC.

The determination of imazalil and prochloraz fungicide residues has been carried out by HPLC with an UV detector at 204 nm and by GLC with an electron capture detector (ECD). In both cases fungicide residues were extracted with hexane/acetone (90:10, v/v) after pH adjustment and purified by a liquid-liquid partitioning process. When HPLC was used for prochloraz and imazalil analysis, it was necessary to eliminate the interfering substances with a further clean-up process. This was also required when samples with low residue levels were analyzed by GLC. Recovery was always higher than 70%. The detection limit was 0.04 ppm for the HPLC method and 0.02 for the GLC method. Imazalil and prochloraz residues in "Washington Navel" oranges and "Hernandina" clementine fruits, dipped in a 1000 ppm fungicide solution, are reported.

Chromatography, Gas↗

Study of heavy metal pollution and speciation in Buyak Menderes and Gediz river sediments.

In this study, two economically important rivers of Turkey, Gediz and Buyuk Menderes (BM) are studied to determine their environmental pollution levels. An old analytical procedure involving sequential chemical extraction is improved and used for the partitioning of particulate trace metals (Cu, Co, Cr, Mn, Fe, Zn, Pb and Ni). Cationic and anionic Mn and Cr species with different phases are also determined by using leaching, extraction and ion exchange speciation processes. The sediment samples are analysed using graphic-furnace atomic absorption spectroscopy and differential pulse anodic stripping voltameter. Experimental results obtained on five replicate samples of fluvial bottom surface sediments at the sampling points demonstrate that the relative standard deviation of the sequential extraction procedure is generally better than +/-10%. The accuracy, determined by comparing total metal concentrations with the sum of the five sequential chemical extractions, is proved to be satisfactory. The detection limits established for three standard deviations of blank for different metals are identical and found to be 0.1mg/kg for sediment samples and 1 ppb for water samples. The results show that the pollution levels are significant especially for Pb, Cr, Mn and Zn in the Gediz river and Co, Mn, and Zn in the BM river. Comparison between our results and the measurements outlined before industrialization and the beginning of the intensive pesticide applications in agricultural fields (In: Broekaert et al., editors, Metal speciation in the environment, vol. 23. 1989. p. 601-11; A research on the environmental pollution in the agricultural fields and watering in the Aegean region, Ege University Research Project, No. 127 1988 (in Turkish); DSI Water Analyses Report, Ankara, 1985 (in Turkish)) show that the pollution in these rivers is probably originated from industrial, agricultural and domestic waste discharges.

Environmental Monitoring↗

Application of a computer-based chromatograph for automated water pollution analyses.

A modified head-space analysis technique, coupling thermal extraction with subsequent adsorption of organics on a poly (para 2,6-diphenyl phenylene) oxide adsorbent (Tenax-GC), has been found to be an efficacious tool when combined with gas chromatography for the study and monitoring of low molecular weight organics present in drinking water supplies (1-4). This procedure has allowed for the analysis of volatile organics in the low parts-per-billion range from 1 liter or less of tap water. Because thermal extraction requires smaller sample sizes than required in carbon-chloroform extraction methods and liquid/liquid extractions, the EPA has recently adopted this type of methodology (5,6). Passage of the Safe Water Drinking Act in December of 1974 has mandated that each state assumes the primary responsibility for carrying out the purposes of the legislation (7). Because the Act says that any supplier of water serving 25 individuals or more must comply with these regulations, large-scale monitoring programs will have to be undertaken. It was thus our desire to try to simplify the sample collection and data acquistion and reduction processes as much as possible, in the effort to make the procedure more adaptable for incorporation into routine monitoring programs. Also, automation reduces the experience and number of personnel required to perform the analyses. In addition to analysis of drinking water samples, the automated procedure described hereinafter can also be applied to monitoring industrial plant effluents, waste water treatment processes, and general quality control monitoring of low molecular weight organic compounds.

Autoanalysis↗

Production of lactic acid and fungal biomass by Rhizopus fungi from food processing waste streams.

This study proposed a novel waste utilization bioprocess for production of lactic acid and fungal biomass from waste streams by fungal species of Rhizopus arrhizus 36017 and R. oryzae 2062. The lactic acid and fungal biomass were produced in a single-stage simultaneous saccharification and fermentation process using potato, corn, wheat and pineapple waste streams as production media. R. arrhizus 36017 gave a high lactic acid yield up to 0.94-0.97 g/g of starch or sugars associated with 4-5 g/l of fungal biomass produced, while 17-19 g/l fungal biomass with a lactic acid yield of 0.65-0.76 g/g was produced by the R. oryzae 2062 in 36-48 h fermentation. Supplementation of 2 g/l of ammonium sulfate, yeast extract and peptone stimulated an increase in 8-15% lactic acid yield and 10-20% fungal biomass.

Ananas↗

Petroleum hydrocarbons and polycyclic aromatic hydrocarbons in the surficial sediments of Xiamen Harbour and Yuan Dan Lake, China.

Surficial sediments were sampled from nine stations in Xiamen Harbour and two stations in Yuan Dan Lake during April 2002. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Selected ion monitoring was at M/Z=57 for petroleum hydrocarbons (PHCs) and individual M/Zs for each of the 15 typical polycyclic aromatic hydrocarbons (PAHs) and nine alkylated PAHs. The results showed that concentrations of PHCs and total PAHs in the sediments of Yuan Dan Lake were 1397 microg g(-1) (dry weight, dw) and 1377 ng g(-1) (dw), respectively. The ranges for PHCs and total PAHs in the sediments from Xiamen Harbour were 133-943 microg g(-1) (dw) and 98-309 ng g(-1) (dw), respectively. Shipping activities, industrial wastewater discharges, fuel oil spillage from ships and vehicles were the main sources of PHCs and PAHs in the Harbour. In addition, the widespread use of coal for industrial processes and domestic consumption accounted for the second largest source of PAHs in the sediments, while atmospheric transport and deposition of PAHs are also important.

China↗

Conversion of Dexon (p-dimethylaminobenzenediazo sodium sulfonate) to N, N-dimethyl-p-phenylenediamine by Pseudomonas fragi Bk9.

The metabolism of the fungicide Dexon (p-dimethylaminobenzenediazo sodium sulfonate) by a soil bacterium is reported for the first time. The organism which is capable of using Dexon only by a co-metabolic process was obtained by enrichment culture and was identified as Pseudomonas fragi. The first metabolic product of Dexon was identified as N,N-dimethyl-p-phenylenediamine. The presence of an enzyme, p-dimethylaminobenzenediazo sodium sulfonate reductase, capable of reducing Dexon to N,N-dimethyl-p-phenylenediamine has been demonstrated in the cell-free extracts of the organism. The enzyme is found to be in the soluble fraction and requires dithiothreitol as a reductant.

Azo Compounds↗

Occupational IgE sensitisation to phytase, a phosphatase derived from Aspergillus niger.

OBJECTIVE: Phytase is a phosphatase derived from Aspergillus niger that enhances phosphate bioavailability in the gut, and therefore has been increasingly used as an animal feed additive since the early 1990s. The aim of this study was to assess whether work related respiratory symptoms among workers in a so called premix factory producing animal feed additives, could be due to type I (mediated by immunoglobulin E (IgE) allergic sensitisation to phytase. METHODS: Preparations of specific IgE against phytase as used in the factory were assessed by enzyme immunoassay (EIA) in serum samples of 11 exposed workers who regularly handled the enzyme, in 11 office and laboratory workers of the same plant (non-exposed internal controls), and in 19 laboratory animal workers as external controls. The factory workers also completed a questionnaire on common and work related respiratory symptoms. RESULTS: Depending on the cut off level in the EIA for IgE, and the preparation used as coated allergen, antiphytase sensitisation was found in one to four of the 19 external controls, in one to five of the 11 internal controls, and in four to 10 of the 11 exposed workers. Strongest IgE reactions were found in four exposed workers who reported work related respiratory symptoms, particularly wheezing, and in one internal control who possibly had become sensitised because the structure of the factory building did not preclude airborne exposure in the offices and corridors of the plant. Experiments with inhibition EIA for IgE showed that (a) phytase of another commercial source was only partially cross reactive with phytase as used in the premix factory, and (b) phytase used as an animal feed additive did not cross react with common mould extracts, except for extracts from the species of origin, Aspergillus niger. The amount of IgE binding phytase in Aspergillus niger was estimated to be between 0.1% and 1% of the extractable mould proteins. CONCLUSIONS: Phytase is a potentially important new occupational allergen causing specific IgE immune responses among exposed workers. Such IgE sensitisation could probably be the cause of work related asthmatic and other respiratory symptoms if no effective measures are taken to prevent airborne occupational exposure at sites where phytase is handled, particularly during addition of enzyme preparations to animal feed.

6-Phytase↗

A sampling and analytical method for airborne m-phenylenediamine (MPDA) and 4,4'-methylenedianiline (MDA).

A method has been developed and validated for monitoring worker exposure to airborne m-phenylenediamine (MPDA) and 4,4'-methylenedianiline (MDA) in an epoxy resin manufacturing operation. Aerosol and vapor MPDA and MDA are collected on an acid-coated, glass-fiber filter to stabilize them as their amine salts. The amines are extracted from the filter with a mixture of acetonitrile in aqueous base and then treated with acetic anhydride to form the diacetamide derivatives. Studies were performed on the acetylation reaction to establish sample work-up conditions. The derivatives are analyzed by high performance liquid chromatography with UV detection. The method was tested for precision and accuracy using the National Institute for Occupational Safety and Health (NIOSH) criteria for a valid industrial hygiene method. The method may be used with confidence to measure from 0.90 to 755 micrograms of MPDA and/or 0.36 to 55 micrograms of MDA in a total air volume of 200 to 630 L, sampling at a rate of 1.5 to 2.0 L/min. Collected samples remain stable on filters for at least 1 week before analysis. The method will not suffer from interference from high relative humidity or other process volatiles, including diglycidyl ether of bisphenyl A and bis(2,3-epoxycyclopentyl) ether. Test atmospheres of the process materials were prepared in the laboratory for validation of the overall sampling and analytical method. This method can be applied to most aromatic amines and is recommended for monitoring both ambient and workplace air.

Acetylation↗

Photodegradation of organic waste coupling hydrogenase and titanium dioxide.

In this work the results of the study on the degradation of dairy waste and lactose with use of titanium dioxide (TiO2), as photocatalyst, are presented. The ability of TiO2 to degrade dairy waste is compared either in the presence of molecular oxygen or of a bacterial hydrogenase as electron acceptor. The enzyme-mediated H2 production rates or the O2 consumption rates are used to measure electron donor degradation. The results obtained clearly indicate that dairy waste can be degraded by the TiO2 photocatalyst. Proteins present in the dairy waste have a strong inhibitory effect on the degradation process. Indeed lactose alone can easily be degraded. When the protein extract obtained from the dairy waste was added to the lactose solution, the reaction for both electron acceptors, hydrogenase and oxygen, was inhibited. When the dairy waste solutions were diluted, there was a positive effect on the reaction rate. This was particularly true in the case of hydrogenase, and to a lesser extent in the case of oxygen acceptor. The reduction of the pH from 8 to 6 also increased H2 production when the enzyme was used.

Chromatography, Gas↗

The application of neuroimaging techniques to drug development.

Neuroimaging is a powerful and innovative tool for studying the pathology of psychiatric diseases and, more recently, for studying the drugs used in their treatment. Technological advances in imaging have made it possible to noninvasively extract information from the human brain regarding a drug's mechanism and site of action. Until now, our understanding of human brain pharmacology has depended primarily on indirect assessments or models derived from animal studies. However, the advent of multiple techniques for human brain imaging allows researchers to focus directly on human pharmacology and brain function. This review outlines available neuroimaging techniques and examines how these various methods have already been applied to the drug development process, as well as how they might be applied in the future.

Antipsychotic Agents↗

Waste water from citrus processing as a source of hesperidin by concentration on styrene-divinylbenzene resin.

This paper describes a procedure for recovering hesperidin from the waste water of orange juice processing, namely, yellow water, by concentration of diluted extracts on styrene-divinylbenzene resin. Turbid raw material flowing out from centrifuges of essential oil separation contains considerable amount of hesperidin ( approximately 1 g/L) mainly associated with solid particles. Yellow water was treated with calcium hydroxide until pH 12 to solubilize hesperidin, filtered, neutralized at pH 6, and loaded on resin up to saturation. Desorption with 10% ethanol aqueous solutions at different NaOH concentrations (0.23-0.92 M) assured high concentration of hesperidin in selected fractions (10-78 g/L), from which it precipitated in high yield and purity immediately after acidification at pH 5. Best results were obtained using 0.46 M NaOH as eluent: 71.5% of the adsorbed hesperidin was desorbed in 300 mL, with an overall 64% yield of isolated product at 95.4% purity (HPLC). These experiments can constitute a useful starting point for an industrial application.

Citrus↗

Polychlorinated biphenyls (PCBs) in mussels along the Chilean coast.

GOAL, SCOPE AND BACKGROUND: Chile signed the Stockholm Convention, which establishes measures to reduce or eliminate Persistent Organic Pollutants (POPs) release into the environment, including the prohibition of their use and reduction of secondary products release, as well as management related with waste treatment. Among POPs, PCBs are a family of 209 compounds that differ in chlorine level and position. These substances present a wide variability in their physicochemical properties such as vapor pressure, water solubility and partition coefficients that determine their behavior and mobility within the different environmental compartments. In Chile, as in other countries, the use of these compounds were and continue to occur in diverse industrial applications such as dielectric fluid in transformers and condensers, with a use in Chile of approximately 550,000 L. A sampling of bivalves was performed during the years 2000-2002 in order to obtain information on the spatial distribution of the PCB levels for the length of the long Chilean coast (18 degrees-54 degrees South latitude, 4,200 km), contributing in this way to a better understanding of the PCB trend and eventual fractionation along latitudinal gradients in Chile, using as the bivalve Perumytilus purpuratus ('Chorito Maico') bioindicator. METHODS: The marine bivalves Perumytilus purpuratus were collected in 16 localities in northern and southern Chile. All samples were lyophilized, and PCBs (51 congeners) were extracted in a Soxhlet system (24 h) with n-hexane. Samples were cleaned in florisil and analyzed by GC-ECD. Blanks, certified reference materials and standards were processed along with the samples. RESULTS AND DISCUSSION: The results obtained for P. purpuratus indicate a congeneric distribution profile associated to a latitudinal gradient, and the statistical analysis of the congeneric composition of the PCBs indicated five groups in relation to the molecular weight (number of chlorines), where the lighter congeners were observed in areas corresponding to high latitudes with total PCB values of 298 ng/g dry weight. CONCLUSION: P. purpuratus turns out to be a good bioindicator of PCB levels in the coastal areas of Chile due to its wide distribution. The highest concentrations and the more volatile congeners were found in southern Chile, which could be the result of processes of long-range transport or illegal discharge occurring in such remote areas. These results confirm previous data from the International Mussel Watch project ten years ago. RECOMMENDATION AND OUTLOOK: Future studies are needed to confirm our findings utilizing another environmental matrix such as soil/sediments and air samples.

Animals↗

The use of three dye-binding procedures for the assessment of heat damage to food proteins.

1. A study has been made of pure proteins heated either alone or in contact with sugars, so as to cause a severe fall in their reactive lysine contents, and also of commercial protein concentrations. 2. For unheated materials, and for bovine plasma albumin and fat-extracted, dried chicken muscle severely heated in the absence of sugar, Acid Orange 12 binding values (mmol bound dye/kg crude protein (nitrogen times 6-25)) were close to the sum of total histidine, total arginine and reactive lysine contents (mmol/kg crude protein (N times 6-25)), which we have termed HARL values. The dye-binding values and the HARL values were reduced similarly by heat treatment. 3. For materials in which protein and glucose had reacted under mild conditions (37 degrees), the dye-binding capacity with Acid Orange 12 was unchanged even though the HARL value of these materials was considerably reduced. When protein and glucose or sucrose were heated more severely, the dye-binding capacity was slightly lowered but not to the same extent as the reduction in the basic amino acids. 4. Animal feeding-stuffs, whether unheated, industrially processed or diliberately heated, appeared to react with Acid Orange 12 in the same way as the model systems (selected to represent three types of heat damage: 'advanced' and 'early' Maillard and protein-protein damage). 5. Remazol blue binding values and fluorodinitrobenzene (RDNB)-reactive lysine values were similarly reduced in materials that had been severely heated, either with or without added sugars; however, when protein and glucose had reacted under mild conditions the fall in Remazol blue binding was less than that in FDNB-reactive lysine. 6. For the model materials, binding with cresol red was, in general, higher for heated samples but the results showed no correlation with FDNB-reactive lysine values. For meat and groundnut meals, changes in values after heat treatment were smaller than those that have been reported for soya-bean meals.

Alkanesulfonates↗

Evaluation of a method based on liquid chromatography/electrospray tandem mass spectrometry for analyzing eight triazolic and pyrimidine fungicides in extracts of processed fruits and vegetables.

The feasibility of using liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) for determining 8 fungicides (triadimenol, penconazole, propiconazole, hexaconazole, cyproconazole, myclobutanil, fenarimol, and bitertanol) in extracts of tomato puree and lemon juice concentrate has been evaluated. A miniaturized extraction-partition procedure requiring small amounts of nonchlorinated solvents has been used. The extracts (5 microL) were analyzed by LC/ESI-MS/MS without any previous cleanup step. Chromatographic determination has been performed using a C18 column and isocratic elution. Seventeen MS/MS transitions of precursor ions were monitored simultaneously (2 or 3 for each pesticide). The excellent selectivity and good linearity of the LC/MS/MS method allowed quantitation and identification at low levels (limits of quantitation <0.010 mg/kg), even in difficult matrixes, with a run time of only 1.5 min.

Chromatography, Liquid↗

Evaluation of concrete incorporating bottom ash as a natural aggregates replacement.

A study on the incorporation of coal bottom ash from thermoelectric power stations as a substitute material for natural sand in the production of concrete is here presented. The normally coarse, fused, glassy texture of bottom ash makes it an ideal substitute for natural aggregates. The use of bottom ash in concrete presents several technical challenges: the physical and mineralogical characteristics of the bottom ash; the effect on water demand and the participation on cements hydratation. In the production of the concrete, substitutions in volume were used. Two different ways to employ bottom ash were used to make up the mix proportions: one considering the natural humidity present in the porous particles and the other not considering it, seeking to maintain the same strength. These considerations are fundamental given that the process of bottom ash extraction is carried out through moisture. Mechanical tests by compressive strength were performed and the elastic modulus was determined. An analysis of the influence of bottom ash in the formation of pores was carried out through tests for the water loss by air drying and water uptake by capillary absorption. The results show that the higher the bottom ash contents in the concrete, the worse the performance regarding moisture transport. However, for one bottom ash concrete type, the mechanical properties were maintained.

Adsorption↗

Development of a sandwich enzyme-linked immunosorbent assay for the detection of egg residues in processed foodst.

Chicken eggs are used extensively as an excellent source of dietary proteins. These proteins have many functional properties, making them valuable food ingredients. However, eggs are a frequent cause of food hypersensitivity, especially in children. Of major concern to food processors is the inadvertent cross-contact of food products with allergenic residues, which could result in potentially life-threatening reactions in those with a food allergy. The aim of the present study was to develop an enzyme-linked immunosorbent assay (ELISA) for the detection of undeclared egg residues in foods. Commercially purified ovalbumin (OVA) and dehydrated egg white solids were used as antigens to induce antibodies in rabbits and goats. Reference pasta standards and various food samples were extracted, then clarified by centrifugation. Goat anti-egg white antibodies were used as the capture reagent, nonspecific sites were blocked with gelatin, then standard and sample extracts were added. Rabbit anti-OVA antibodies were used as detector antibodies, followed by addition of commercial goat anti-rabbit IgG antibody labeled with alkaline phosphatase and subsequent substrate addition. Twenty brands of egg-free pasta (two lots each) were analyzed using the ELISA. Fourteen common pasta ingredients were also evaluated for cross-reactivity problems in the method. The detection limit of the assay was 1 ppm spray-dried whole egg. Fifty-five percent (22 samples) of the egg-free pasta samples tested positive for the presence of undeclared egg residues, with values ranging from 1 to >100,000 ppm. Minimal cross-reactivity was encountered in general, but portobello mushrooms and basil caused some minor matrix effects. This sandwich-type ELISA method can be used to detect undeclared egg residues in processed foods and to evaluate industrial clean-up operations.

Animals↗

A skeletal muscle troponin T specific ELISA based on the use of an antibody against the soluble troponin T (16-31) fragment.

Proteolytic degradation of muscle, which occurs post-mortem as part of the meat-ageing process, results in the production of protein fragments. In beef, degradation of skeletal muscle troponin T (TnT) results in the generation of a 16-residue long peptide (TnT (16-31)), identified in trichloroacetic acid (TCA) soluble extracts. We report the development of a competitive enzyme-linked immunosorbent assay (ELISA) for the quantification of TnT (16-31), using polyclonal antibodies raised against synthetic TnT (16-31). The ELISA procedure is based on inhibition of binding of the antibodies to immobilised TnT (16-31) by TnT (16-31) present in solution. Its useful range is 30 pmol to 2 nmol TnT (16-31)/ml. Quantification of TnT (16-31) in TCA muscle extracts showed that its concentration was enhanced with ageing. Moreover, a correlation between TnT (16-31) levels and meat tenderness was observed. The ELISA developed herein may prove advantageous for future use at the research and industrial level.

Animals↗

Process-induced changes on bioactive compounds in whole grain rye.

Manufacturing of healthy wholegrain foods demands knowledge of process-induced changes in macro-, micro- and non-nutrients. The high content of dietary fibre is a challenge in relation to good product texture and sensory quality. The stability and bioavailability of bioactive compounds have a marked influence on the health effects of cereal foods. It was confirmed that sterols, folates, tocopherols and tocotrienols, alkylresorcinols, lignans, phenolic acids and total phenolics are concentrated in the bran layers of the rye grain, and are only present at low levels in the flour endosperm. The levels of folate and easily-extractable phenolic compounds increase in germination and sourdough baking, but there are negligible changes in the levels of sterols, lignans and alk(en)ylresorcinols. The levels of tocopherols and tocotrienols are reduced during the sourdough fermentation. In conclusion, many of the bioactive compounds in wholegrain rye are stable during food processing, and their levels can even be increased with suitable processing.

Dietary Fiber↗