Use of small charcoal/alumina cleanup columns in determination of trichothecene mycotoxins in foods and feeds

Small charcoal/alumina cleanup columns have been effectively used to remove interfering materials from grain, feed, and food extracts prior to chromatographic determination of trichothecene mycotoxins. A thin layer chromatographic method has been developed that can simultaneously detect part per billion concentrations of deoxynivalenol, fusarenon X, nivalenol, T-2 toxin, HT-2 toxin, neosolaniol, and diacetoxyscirpenol in food and feed samples. Recoveries of 90-99% can be obtained. The use of charcoal/alumina cleanup columns in conjunction with liquid chromatography and gas chromatography of trichothecenes is also discussed.     

Ethanol/Water extraction combined with solid-phase extraction and solid-phase microextraction concentration for the determination of chlorophenols in cork stoppers

The appearance of 2,4,6-trichloroanisole (TCA) in cork stoppers is of great concern because it can cause off-flavors in bottled wine. To prevent this sensorial defect, there should not be any traces of 2,4,6-trichlorophenol (TCP), 2,3,4,6-tetrachlorophenol (TeCP), or pentachlorophenol (PCP) in the finished corks, because they are the direct precursors of TCA. In the course of this study two methodologies based upon an extraction with ethanol/water mixtures to determine the chlorophenolic content in cork matrices were developed. The cork extract is preconcentrated using both solid-phase extraction and solid-phase microextraction methodologies. The latter was optimized by applying a full two-level factorial design. Finally, spiked ground corks at nanogram per gram levels of each chlorophenol were analyzed under optimal conditions and by applying both procedures. The obtained results demonstrate that chlorophenols can be detected in corks contaminated at the nanogram per gram level and, thus, these approaches can be successfully applied as quality control measures in the cork industry.     

Use of ten gram samples of corn for determination of mycotoxins

Data were gathered, during a study on the development of an automated system for the extraction, cleanup, and quantitation of mycotoxins in corn, to determine if it was scientifically sound to reduce the analytical sample size. Five, 10, and 25 g test portions were analyzed and statistically compared with 50 g test portions of the same composites for aflatoxin concentration variance. Statistical tests used to determine whether the 10 and 50 g sample sizes differed significantly showed a satisfactory observed variance ratio (Fobs) of 2.03 for computations of pooled standard deviations; paired t-test values of 0.952, 1.43, and 0.224 were computed for each of the 3 study samples. The results meet acceptable limits, since each sample's t-test result is less than the published value of the /t/, which is 1.6909 for the test conditions. The null hypothesis is retained since the sample sizes do not give significantly different values for the mean analyte concentration. The percent coefficients of variation (CVs) for all samples tested were within the expected range. In addition, the variance due to sample mixing was evaluated using radioisotope-labeled materials, yielding an acceptable CV of 22.2%. The variance due to the assay procedure was also evaluated and showed an aflatoxin B, recovery of 78.9% and a CV of 11.4%. Results support the original premise that a sufficiently ground and blended sample would produce an analyte variance for a 10 g sample that was statistically comparable with that for a 50 g sample.     

Development of a solid-phase extraction method for phenoxy acids and bentazone in water and comparison to a liquid-liquid extraction method

A rapid solid-phase extraction (SPE) method was developed for the determination of bentazone and the phenoxy acids 2,4-D, dichlorprop, MCPA, and mecoprop in Norwegian environmental water samples. Cartridges with a high-capacity cross-linked polystyrene-based polymer were used for off-line preconcentration. The effects of elution solvent, elution volume, sample volume, sorbent mass, pH, and flow rate on the recoveries of the pesticides were investigated using HPLC. Average recovery of >90% was achieved with 500 mg sorbents using 2 mL of methanol with 5% NH3 as elution solvent. The recoveries were independent of sample pH in the tested range of pH 1-7. Using a sample volume of 200 mL, the limits of determination for the phenoxy acids and bentazone are 0.02 microg/L. Sample volumes up to 2000 mL at a flow rate of 60 mL/min could be handled without any loss of analytes, which makes it possible to lower the limits of determination. The SPE method was compared to a routinely used liquid-liquid extraction method. Three different water matrices spiked at 1.0 and 0.05 microg/L were extracted, and the quantification was performed by GC-MS. Both methods permitted the determination of phenoxy acids and bentazone in distilled water, creek water, and well water down to a level of 0.05 microg/L with recoveries >80% for 200 mL samples. Important advantages of the SPE method compared to the liquid-liquid extraction method were the short extraction times, lack of emulsions, use of disposable equipment, and reduced consumption of organic solvents.     

Comparison of solid-phase microextraction and stir bar sorptive extraction for the quantification of malodors in wastewater

Malodors in wastewater from animal-rearing facilities are due to the presence of characteristic polar compounds. The efficiency and reproducibility of three solid-phase microextraction (SPME) fibers (Carboxen-PDMS, polyacrylate, and PDMS) as well as PDMS-coated stir bars for the measurement of some of these compounds in the liquid phase were compared. In initial experiments, the SPME fibers and stir bars were exposed to a standard water solution containing a mixture of 18 compounds with a range of octanol-water partition coefficients. The polyacrylate SPME fibers and PDMS-coated stir bars, having been found to possess the best combination of extraction efficiency and reproducibility of measurement, were compared for the extraction of a high-strength swine wastewater. Ten compounds, which are known contributors to malodors in wastewater, were quantified by both methods of extraction. For most compounds, greater levels were estimated by the PDMS-coated stir bars than by SPME, and measurement reproducibility was also greater. For both methods of extraction, there was greater variation in the measurement of volatile fatty acids than there was for aromatics.     

Use of sequential extraction to evaluate the heavy metals in mining wastes

Lead-zinc mine tailings from the ‘old lead-belt’ in Missouri were chemically characterized using total chemical analysis and sequential extraction. These tailings have been considered as an inert and safe material for years. However, the levels of heavy metals in these tailings were found elevated with Pb values as high as 5000 ppm. The sequential extraction results indicated that the Pb was primarily found in the residual fraction and probably is in the PbS form. Some Pb was found in the oxide fraction. Cu, Zn, and Cd were found in several different fractions, but primarily in the residual fraction. Some Cu was found in the organic fraction. The Zn showed a wide variation between samples with high levels in the carbonate, oxide and residual fractions. Very little Pb, Cd, Cu, and Zn was leached by water. The heavy metals in these tailings do appear to be in the more inert forms and should not be readily available to the environment unless there is an interaction of the tailings with acids, microorganisms or chelating materials. The breathing and ingestion of this material may provide such an environment for such interactions and these materials should still be considered dangerous and managed properly.     

Conceptual model and sensitivity analysis for simulating the extraction kinetics of soil washing

Purpose  

Most previous studies focused on the metal extraction efficiency of chelant-enhanced soil washing under various operational conditions; however, one of the keys to cost-effective field application is to maintain a high throughput rate (i.e., short washing time) while achieving the treatment objectives. Therefore, this study presented a conceptual model for simulating the kinetic extraction of heavy metals and evaluated its sensitivity analysis to the predetermined parameter values in five soils with different initial metal distributions.     

Evaluation of some systems for classifying soil sensitivity to acid deposition in the South African highveld

Abstract. The Skokloster and Stockholm Environmental Institute (SEI) approaches were applied to the assessment of 145 soils of the South African highveld region in terms of sensitivity to acid deposition. The critical load class calculated by variants of these methods was compared with the acid neutralizing capacity (ANC) determined by pH measurement of soil suspended in a dilute acetate buffer solution. This rapid index of ANC correlates well both with ANC determined by an established but more laborious method which involves titration and equilibration of soil with HCl, and with a number of soil properties related to base status. The correlation between Skokloster or SEI critical load classes and ANC was weak. It was concluded that ANC determination would be a preferable basis for classifying these soils in terms of their sensitivity to acid deposition, since the method is direct and integrates the contribution of various soil properties to acid sensitivity instead of requiring the relative contribution to be calculated according to somewhat arbitrary weightings given to broadly defined classes of soil properties.     

Use of molecularly imprinted solid-phase extraction sorbent for the determination of four 5-nitroimidazoles and three of their metabolites from egg-based samples before tandem LC-ESIMS/MS analysis

A nitroimidazole, molecularly imprinted polymer (MIP) was tested to extract four 5-nitroimidazoles (i.e., dimetridazole (DMZ), ipronidazole (IPZ), metronidazole (MNZ), and ronidazole (RNZ)) and three of their metabolites (i.e., DMZOH, IPZOH, and MNZOH) from egg powder samples. Various MIP templates were produced, and their selectivity was assessed on nitroimidazole standard solutions using liquid chromatography coupled with ultraviolet detection. The optimal cleanup was then used for the extraction of nitroimidazole in egg powder samples, and their quantification was achieved by isotope dilution LC-ESIMS/MS. The sample preparation entails a solubilization of the samples with water and acetonitrile followed by a MISPE cleanup step before LC-ESIMS/MS analysis. Data acquisition was achieved using selected reaction monitoring, and quantification was done with five deuterated analogues (i.e., DMZ- d(3), RNZ- d(3), IPZ- d(3), DMZOH- d(3), and IPZOH- d(3)). DMZOH- d(3) was used to quantify MNZ and MNZOH since they do not have their corresponding internal standards. The method was validated according to the European Union criteria by spiking experiments at concentration levels of 1, 2, and 3 microg/kg. At these three levels and for compounds having their own internal standards, acceptable performance data were obtained, with internal standard corrected recoveries ranging from 91 to 111%, and decision limits (CCalpha) and detection capabilities (CCbeta) were below 0.34 and 0.39 microg/kg, respectively.     

Use of background correction to improve the accuracy of the selective reduction method for determining methyl mercury in fish

Background correction is used with a previously published flameless atomic absorption method for the concurrent determination of inorganic and methyl mercury. The use of background correction simplifies the procedure, but, more importantly, eliminates errors in mercury readings due to broad band absorption by other volatile compounds produced during the determination.     

Use of cyclodextrins as secondary antioxidants to improve the color of fresh pear juice

In this paper, the color of fresh pear juice was evaluated for the first time in the presence of some natural and modified cyclodextrins (CDs) and the effect of these compounds as browning inhibitors was determined using the color space CIELAB system. Furthermore, because contradictory claims have been published concerning the mechanism by which enzymatic browning is inhibited by CDs, a kinetic model in the presence of CDs is proposed and the corresponding apparent complexation constants between the mixtures of diphenols present in pear juice and alpha-, beta-, and maltosyl-beta-CD have been calculated. Moreover, pear juice color was studied in the presence of different polyphenoloxidase inhibitors. Finally, we show that maltosyl-beta-CD enhances the ability of ascorbic acid to prevent enzymatic browning because of the protection that maltosyl-beta-CD offers against ascorbic acid oxidation. In this respect, maltosyl-beta-CD seems to act as a "secondary antioxidant", reducing pear juice browning and enhancing the naturally occurring antioxidant capacity of pear juice.     

Optimization of a solid-phase extraction method using centrifugation for the determination of 16 polycyclic aromatic hydrocarbons in water

A fast and reliable method for the determination of polycyclic aromatic hydrocarbons (PAHs) in water samples by solid-phase extraction (SPE) using centrifugation has been developed and optimized. A silica-based C18 cartridge was used; parameters affecting the extraction procedure such as type and volume of the elution solvent, breakthrough volume of the percolated water sample, drying of the sorbent, and evaporation of the elute have been studied. The innovation of this work was the examination of the use of a centrifugation technique in both the drying and elution steps. When combined with centrifugation, the volume of the elution solvent was reduced to 1 mL and the time for sorbent drying decreased also to 10 min under vacuum. Under optimal conditions, recoveries for the 16 U.S. EPA PAHs were between 70 and 85% and the relative standard deviation varied between 1 and 14%. Surrogate standard recoveries were similarly between 61 and 94% with a relative standard deviation between 2 and 15%. The simplicity of the described method, use of less of organic solvent, short procedure time, and good recoveries demonstrate the advantages of this environmentally friendly approach for routine analysis of numerous samples.     

Use of dicarboxylic acids to improve and diversify the material properties of porous chitosan membranes

Several nontoxic dicarboxylic acid solutions (oxalic acid, succinic acid, malic acid, and adipic acid solutions) instead of an acetic acid solution were used as solvents for chitosan dissolution. The amount of free amino groups of the chitosan in the solution decreased due to the ionic cross-linking of the dicarboxylic acids with chitosan. These solutions were used to fabricate porous chitosan membranes. Replacing acetic acid with these dicarboxylic acids for membrane preparation improved the water uptake (by 35% at most), tensile strength (by 110% at most), and elongation capability (by 50% at most) of the membranes. These dicarboxylic acid solutions not only act as solvents but also improve the material properties of the chitosan membranes due to the ionic cross-linking and hydrogen bond formation. In brief, a nontoxic and straightforward cross-linking method has been developed for chitosan material; this method does not result in a brittle product, thus making it better than the use of toxic cross-linking reagents.     

Use of fungal phytase to improve breadmaking performance of whole wheat bread.

The possible use of phytase as a breadmaking improver has been tested in whole wheat breads by adding different amounts of fungal phytase. The effect of phytase addition on the fermentation stage and the final bread quality was analyzed. The phytase addition shortened the fermentation period, without affecting the bread dough pH. Regarding the whole wheat bread, a considerable increase of the specific bread volume, an improvement of the crumb texture, and the width/height ratio of the bread slice were obtained. An in vitro assay revealed that the improving effect of phytase on breadmaking might be associated with the activation of alpha-amylase, due to the release of calcium ions from calcium-phytate complexes promoted by phytase activity. As a conclusion, phytase offers excellent possibilities as a breadmaking improver, with two main advantages: first, the nutritional improvement produced by decreasing phytate content, and second, all the benefits produced by alpha-amylase addition can be obtained by adding phytase, which promotes the activation of endogenous alpha-amylase.     

Dummy molecularly imprinted solid-phase extraction for selective determination of five phthalate esters in plastic bottled functional beverages

In this paper, a highly selective sample cleanup procedure combing dummy molecular imprinting and solid-phase extraction (DMI-SPE) was developed for the simultaneous isolation and determination of five phthalate esters in plastic bottled beverages. The new imprinted microspheres were synthesized via precipitation polymerization using diisononyl phthalate as a dummy template that showed high selectivity and affinity to the five kinds of phthalate esters and were successfully applied as selective sorbents of DMI-SPE for the simultaneous determination of the phthalate esters from plastic bottled beverages. Good linearity was obtained in a range of 5.0-750.0 μg/L, and the average recoveries of the five phthalate esters at three spiked levels ranged from 84.3 to 96.2% with the relative standard deviations less than 5.49%. The developed extraction protocol eliminated the effect of template leakage on quantitative analysis and could be applied for the determination of phthalate esters in complicated functional beverages products.     

Rapid magnetic solid-phase extraction based on magnetic multiwalled carbon nanotubes for the determination of polycyclic aromatic hydrocarbons in edible oils

In this study, magnetic multiwalled carbon nanotubes were fabricated by a simple method and applied to magnetic solid-phase extraction (MSPE) of eight heavy molecular weight polycyclic aromatic hydrocarbons (PAHs) including chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene from edible oil samples. Several parameters affecting the extraction efficiency were investigated, including the type and volume of desorption solvent, extraction and desorption time, washing solution and the amount of sorbent. Under the optimized conditions, a simple and effective method for the determination of PAHs in edible oils was developed by coupling with gas chromatography-mass spectrometry (GC-MS). The whole pretreatment process was rapid, and it can be accomplished within 10 min. The limits of quantitation for the target PAHs were found to be 0.34-2.9 ng/g. The recoveries in oil sample were in the range 87.8-122.3% with the RSDs less than 6.8% (intraday) and 9.6% (interday). This method was successfully applied to the analysis of PAHs in seven kinds of edible oils from local markets.     

Development of a solid-phase extraction coupling chemiluminescent enzyme immunoassay for determination of organophosphorus pesticides in environmental water samples

Solid-phase extraction (SPE) and direct competitive chemiluminescence enzyme immunoassay (dcCL-EIA) were combined for the detection of organophosphorus pesticides (OPs) in environmental water samples. dcCL-EIA based on horseradish peroxidase labeled with a broad-specificity monoclonal antibody against OPs was developed, and the effects of several physicochemical parameters on dcCL-EIA performance were studied. SPE was used for the pretreatment of water samples to remove interfering substances and to concentrate the OP analytes. The coupling of SPE and dcCL-EIA can detect seven OPs (parathion, coumaphos, phoxim, quinalphos, triazophos, dichlofenthion, and azinphos-ethyl) with the limit of quantitation below 0.1 ng/mL. The recoveries of OPs from spiked water samples ranged from 62.5% to 131.7% by SPE-dcCL-EIA and 69.5% to 112.3% by SPE-HPLC-MS/MS. The screening of OP residues in real-world environmental water samples by the developed SPE-dcCL-EIA and their confirmatory analysis using SPE-HPLC-MS/MS demonstrated that the assay is ideally suited as a monitoring method for OP residues prior to chromatographic analysis.     

利用稻壳炭提高复合肥料在土壤中的磷素有效性

[目的]研究稻壳炭添加对复合肥料在土壤中磷素有效性的影响,旨在为养分高效、环境友好型复合肥料的开发提供科学依据.[方法]以磷酸一铵(MAP)、磷酸二铵(DAP)、硝酸磷肥(NP)和聚磷酸铵(APP)为磷源,设置0、5％、10％3个稻壳生物炭加入量,与尿素、氯化钾、石粉以及其他辅料制作N-P2O5-K2O比例为15-10...     

Novel procedure for the extraction and concentration of carotenoid-containing chromoplasts from selected plant systems

Natural sources of carotenoids for nutraceutical use are desired by the food industry as a result of the increased production of convenience and other highly processed foods. As new physiological roles are discovered for some of the minor carotenoids that are found in only small amounts in present sources, the need for discovery of new sources will amplify. Thus, a method is needed that will effectively and gently concentrate carotenoids from potential new sources for subsequent identification and analysis. A procedure is presented by which carotenoid-containing tissue chromoplasts can be extracted and subsequently concentrated by precipitation, all in an aqueous milieu. The chromoplasts are extracted and solubilized with 0.3% sodium dodecyl sulfate (SDS) in water. The addition of a nominally equal volume of acetonitrile to the chromoplasts in SDS immediately precipitates the chromoplasts out of solution with generally >90% recovery. Carotenoids contained in the concentrated, still-intact chromoplasts can then be solubilized by organic solvent extraction for subsequent analysis. This methodology offers a means to effectively and gently concentrate carotenoids from fruit tissues where yields are often low (e.g., yellow watermelon).     

Enzymatic treatment to improve extraction of capsaicinoids and carotenoids from chili (Capsicum annuum) fruits

Enzymatic treatments using noncommercial enzymes as a means to the improve the extraction of carotenoids and capsaicinoids from chili fruits are explored in this study. The results show that it is possible to obtain chili fruit powder with a higher concentration of both capsaicinoids and carotenoids than previously reported for similar processes. Furthermore, extraction yields above 96% for carotenoids and 85% for capsaicinoids as separate fractions can be achieved using a sequential and selective two-stage extraction. Evidence is presented demonstrating that the content and extraction yield depend directly on the extent of the enzymatic hydrolysis of chili cell walls, and higher yields are obtained when the sample is completely hydrolyzed. The enzymatic treatment described here is a promising alternative to current industrial practices, and it improves the extraction of carotenoids and capsaicinoids from chili fruits.