Determination of total gossypol in cottonseed and cottonseed meals by derivative UV spectrophotometry

A new method for the determination of total gossypol in cottonseed and cottonseed meals has been developed. The method involves oxalic acid hydrolysis of the bound gossypol in a methyl ethyl ketone-water azeotrope, partitioning the liberated gossypol into chloroform, and quantification by 2nd derivative UV spectrophotometry. The 2nd derivative transformation and measurement of the conventional analytical band around 300 nm permits direct quantification of all compounds containing naphthalene nuclei; chromogenic reaction is not required. The method was tested at concentration levels of total gossypol normally expected for cottonseed and cottonseed meal. Precision and accuracy data suggested an overall relative standard deviation of 4.0% and an overall recovery of 89.5%. Although results for cottonseed and solvent-extracted cottonseed meal analyses were comparable to those obtained by use of American Oil Chemists' Society methods, results were lower for screw-pressed meals. The lower results were attributed to the partial conversion of gossypol, during the cooking process of these meals, to compounds that differ in composition and structure from gossypol and which react with aniline to give false readings.     

Effect of gamma-sterilization and autoclaving on soil organic matter structure as studied by solid state NMR, UV and fluorescence spectroscopy

Sterilized soil is often used, for example in degradation studies, sorption experiments, microbiological tests and plant test systems, to distinguish between microbial processes and abiotic reactions. The most commonly used technique for sterilization is autoclaving of the soil. Another technique is irradiation with high‐level gamma radiation (γ‐radiation). One major drawback of sterilization procedures is the possible alteration of the structure of soil components, for example the organic matter. A change in the chemical structure of the soil organic matter can cause different reactions in the above‐mentioned experiments and hence interfere with the aim of clearly distinguishing between biotic and abiotic processes. Two soils (Gleyic Cambisol and Orthic Luvisol) were sterilized by two γ‐irradiation procedures (4 kGy hour^?1 for 9 hours and 1.3 kGy hour^?1 for 27 hours) and repeated autoclaving at 121°C. Gentle physical aggregate fractionation of the sterilized soils revealed a decrease in the aggregation of the soil, which was reflected in an increase of the clay fraction. Subsequent analysis of the aqueous phase revealed much more dissolved organic matter (DOM) in the γ‐sterilized and autoclaved soils than in the untreated soils. Ultraviolet (UV) and fluorescence spectra of the DOM showed a decrease in the aromaticity and polycondensation of the dissolved organic carbon (DOC). ¹³C cross‐polarization/magic‐angle spinning nuclear magnetic resonance (¹³C‐CP/MAS NMR) spectra of the unfractionated soils and their respective soil fractions before and after sterilization showed that the most important change occurred in the carbohydrate and N‐alkyl region, the main components of microorganisms. In general, the impact of the sterilization method was stronger for autoclaving. The γ‐sterilized soils and fractions displayed both fewer and smaller changes in the soil organic matter.     

Improved sample preparation to determine acrylamide in difficult matrixes such as chocolate powder, cocoa, and coffee by liquid chromatography tandem mass spectroscopy

An improved sample preparation (extraction and cleanup) is presented that enables the quantification of low levels of acrylamide in difficult matrixes, including soluble chocolate powder, cocoa, coffee, and coffee surrogate. Final analysis is done by isotope-dilution liquid chromatography-electrospray ionization tandem mass spectrometry (LC-MS/MS) using d3-acrylamide as internal standard. Sample pretreatment essentially encompasses (a) protein precipitation with Carrez I and II solutions, (b) extraction of the analyte into ethyl acetate, and (c) solid-phase extraction on a Multimode cartridge. The stability of acrylamide in final extracts and in certain commercial foods and beverages is also reported. This approach provided good performance in terms of linearity, accuracy and precision. Full validation was conducted in soluble chocolate powder, achieving a decision limit (CCalpha) and detection capability (CCbeta) of 9.2 and 12.5 microg/kg, respectively. The method was extended to the analysis of acrylamide in various foodstuffs such as mashed potatoes, crisp bread, and butter biscuit and cookies. Furthermore, the accuracy of the method is demonstrated by the results obtained in three inter-laboratory proficiency tests.     

Preparation of pentachlorophenol derivatives and development of a microparticle-based on-site immunoassay for the detection of PCP in soil samples

Pentachlorophenol (PCP) is used as a herbicide in agriculture and as an insecticide for termite control. Because of the apparent hazard associated with its usage, there is a need for an efficient and economic on-site screening method. A 5-min on-site test has been developed for the detection of PCP based on the OnTrak format, a successful Roche on-site test format for drugs of abuse, utilizing the principle of latex agglutination immunoassay. The test detects 1 ppm of PCP in soil samples.     

Rapid detection of kernel rots and mycotoxins in maize by near-infrared reflectance spectroscopy

Near-infrared (NIR) spectroscopy is a practical spectroscopic procedure for the detection of organic compounds in matter. It is particularly useful because of its nondestructiveness, accuracy, rapid response, and easy operation. This work assesses the applicability of NIR for the rapid identification of micotoxigenic fungi and their toxic metabolites produced in naturally and artificially contaminated products. Two hundred and eighty maize samples were collected both from naturally contaminated maize crops grown in 16 areas in north-central Italy and from ears artificially inoculated with Fusarium verticillioides. All samples were analyzed for fungi infection, ergosterol, and fumonisin B1 content. The results obtained indicated that NIR could accurately predict the incidence of kernels infected by fungi, and by F. verticillioides in particular, as well as the quantity of ergosterol and fumonisin B1 in the meal. The statistics of the calibration and of the cross-validation for mold infection and for ergosterol and fumonisin B1 contents were significant. The best predictive ability for the percentage of global fungal infection and F. verticillioides was obtained using a calibration model utilizing maize kernels (r2 = 0.75 and SECV = 7.43) and maize meals (r2 = 0.79 and SECV = 10.95), respectively. This predictive performance was confirmed by the scatter plot of measured F. verticillioides infection versus NIR-predicted values in maize kernel samples (r2 = 0.80). The NIR methodology can be applied for monitoring mold contamination in postharvest maize, in particular F. verticilliodes and fumonisin presence, to distinguish contaminated lots from clean ones, and to avoid cross-contamination with other material during storage and may become a powerful tool for monitoring the safety of the food supply.     

近红外光谱技术快速无损诊断黄瓜植株氮、镁元素亏缺

为了快速无损诊断黄瓜植株氮、镁元素亏缺,以K-最近邻域法（k-nearest neighbors, KNN）模型识别率作为遗传算法中染色体的适应度值,采用遗传算法（genetic algorithm, GA）优选近红外光谱特征子区间,交互验证优化主成分因子数和K值后建立了特征子区间对应的GA-KNN诊断模型。通过控制营养液中氮和镁的含量,在温室大棚内以无土栽培方式培育氮、镁元素亏缺植株,并用近红外光谱仪采集缺氮、缺镁植株老叶的光谱信息。结果表明：原始光谱经过标准正交变换预处理和子区间总数优化后,均匀划分为     

Single-sided and semisingle-sided NMR sensors for highly diffusive samples: application to bottled beverages

Single-sided NMR sensors such as the NMR-MOUSE have been very successfully implemented for quality control applications in the rubber and polymer industries. More recently, single-sided NMR was also applied in characterization of the fat components in foods. Both industrial polymers and the fat components in food exhibit relatively low self-diffusion coefficients on the order of 5x10(-11) m2/s or lower. The application of conventional single-sided NMR to highly mobile, watery phases in foods and beverages is hampered by the strong magnetic field gradient present in standard single-sided NMR devices. In this contribution, we present both a single-sided NMR sensor with a reduced magnetic field gradient and another ("semisingle-sided") sensor design with an open sample bay using a single-sided RF coil. The latter design allows much better sensitivity without sacrificing the necessary open access needed for measurements on entire food packages such as bottles. As a first application, the sensors were used for determining the oxygen content in bottles with superoxygenated table water.     

Quantitation of indomethacin, naproxen, and ibuprofen in pharmaceutical dosage forms by first and second derivative ultraviolet spectrometry

First and second derivative ultraviolet spectrometric methods are described for the estimation of indomethacin, naproxen, and ibuprofen in pharmaceutical dosage forms. The proposed methods permit the rapid, precise, and accurate determination of indomethacin capsules BP, naproxen capsules, and ibuprofen tablets BP. Matrix interference is successfully corrected. The results obtained by first and second derivative techniques are in accord with those obtained by the official assay method.     

Improved method for the analysis of organic acids and new derivatization of alcohols in complex natural aqueous matrixes: application to wine and apple vinegar.

An improvement in the procedure for investigation of organic acids and a new derivatization method, amenable to gas chromatographic-mass spectrometric detection of alcohols, are presented. The latter is based on the formation of phenacetyl esters. The simultaneous application of the two methods also allows data to be obtained on some volatile neutrals present in complex natural aqueous fluids. Application to wine and cider vinegars allowed detection of a number of previously unreported components, among which are interesting partially esterified polycarboxylic esters.     

新疆煤矿土地复垦为草地的适宜性评价方法与应用

土地复垦适宜性评价是土地复垦工作的基础,其评价结果直接决定将来土地复垦的方向和类型。该文以新疆15个煤矿为研究背景,选取了土地待复垦单元土地损毁后的地面坡度、损毁土地深度或压占区堆积物平整量、土地损毁后复垦土源保证率、土壤中黏粒含量、土壤有机质含量、覆土厚度和土地复垦单元可用于灌溉的地表径流量等7个因素作为土地复垦适宜性评价因子,构建了适合新疆煤矿土地复垦为草地的适宜性评价指标体系;以15个煤矿的76个待土地复垦单元作为学习样本,首先采用Q型聚类分析方法将76个样本划为4类,将分类结果与以往结合规范分类结果进行对比,其结果唯一,符合实际且更加精确;然后采用判别分析方法对76个样本进行训练,建立了相应的评价模型,采用回代估计方法对样本逐一进行检验,正确率达到98.7%。将该评价模型应用到新疆尼勒克科尔克煤矿和新疆皮里青煤矿,对2个煤矿的11个待土地复垦单元其复垦为草地的适宜性进行评价,评价分类结果与神经网络模型、因子和聚类联合分析的分类结果一致,分类结果符合规范分类结果范围且更加精确和符合实际。该评价指标体系和评价模型可为新疆煤矿土地复垦工作提供参考。     

Rapid determination of fumonisin B1 in food samples by enzyme-linked immunosorbent assay and colloidal gold immunoassay

A rapid enzyme-linked immunosorbent assay (ELISA) test (microwell plate) and a membrane-based colloidal gold immunoassay in flow-through and lateral-flow formats for the rapid detection of fumonisin B1 (FB1) were developed. The rapid microwell assay can be completed within 20 min with the detection limit of 0.5 +/- 0.2 microg/L. Membrane-based colloidal gold immunoassays had a visual detection limit of 1.0 microg/L for FB1 with the detection time of <10 min. Matrix interference was eliminated by 15-fold dilutions of methanol extracts with buffer. These immunoassays can be used as quantitative or qualitative tools for the rapid detection of FB1 residues in 10-20 min on-site.     

Rapid time-resolved immunofluorometric assay for the measurement of creatine kinase in serum and whole blood samples

A rapid and simple immunochemical method was developed for the assessment of the creatine kinase (MM) isoenzyme [CK(MM)], a protein marker linked with animal welfare and meat quality. The one-step time-resolved immunofluorometric assay produced quantitative results from serum or whole blood samples in 20 min. The analytical limit of detection (mean + 2s) for the immunoassay was 17 ng/mL (n = 6), and the functional limit of detection for the analysis of porcine whole blood samples was 426 ng/mL (n = 24). The working range of the method was linear up to 50 micro g/mL, and the within-assay precision varied between 2.1 and 10.9%. The analysis of porcine serum samples showed that the results from the immunoassay method and colorimetric CK enzyme activity determination were highly correlated (r(2) = 0.965, n = 17, p < 0.001). The practicability of the assay was demonstrated by the analysis of 300 porcine whole blood samples in a slaughterhouse environment.     

Detection of nutrient elements and contamination by pesticides in spinach and rice samples using laser-induced breakdown spectroscopy (LIBS)

The laser-induced breakdown spectroscopy (LIBS) technique was applied to quantify nutrients (Mg, Ca, Na, and K) in spinach and rice and to discriminate pesticide-contaminated products in a rapid manner. Standard reference materials (spinach leaves and unpolished rice flour) were used to establish a relationship between LIBS intensity and the concentration of each element (Mg, Ca, Na, and K) (i.e., calibration line). The limits of detection (LODs) for Mg, Ca, Na, and K were found to be 29.63, 102.65, 36.36, and 44.46 mg/kg in spinach and 7.54, 1.76, 4.19, and 6.70 mg/kg in unpolished rice, respectively. Concentrations of those nutrient elements present in spinach and unpolished rice from a local market were determined by using the calibration lines and compared with those measured with ICP-OES, showing good agreement. The data also suggested that the LIBS technique with the chemometric method (PLS-DA) could be a great tool to distinguish pesticide-contaminated samples from pesticide-free samples in a rapid manner even though they have similar elemental compositions. Misclassification rates were found to be 0 and 2% for clean spinach and pesticide-contaminated spinach, respectively, by applying the PLS-DA model established from the training set of data to predict the classes of test samples.     

Rapid shift from denitrification to nitrification in soil after biogas residue application as indicated by nitrous oxide isotopomers

Nitrous oxide (N₂O) is one of the major greenhouse gases emitted from soils, where it is mainly produced by nitrification and denitrification. It is well known that rates of N₂O release from soils are mainly determined by the availability of substrates and oxygen, but N₂O source apportioning, highly needed to advance N₂O mitigation strategies, still remains challenging. In this study, using an automated soil incubation system, the N₂O site preference, i.e. the intramolecular ¹⁵N distribution, was analyzed to evaluate the progression in N₂O source processes following organic soil amendment. Biogas fermentation residue (BGR; originating from food waste fermentation) was applied to repacked grassland soil cores and compared to ammonium sulfate (AS) application, both at rates equivalent to 160 kg NH₄⁺-N ha⁻¹, and to unamended soil (control). The soil cores were incubated in a helium-oxygen atmosphere with 20 kPa O₂ for 43 days at 80% water-filled pore space. 43-day cumulative N₂O emissions were highest with BGR treated soil accounting for about 1.68 kg N₂O-N ha⁻¹ while application of AS caused much lower fluxes of c. 0.23 kg N₂O-N ha⁻¹. Also, after BGR application, carbon dioxide (CO₂) fluxes showed a pronounced initial peak with steep decline until day 21 whereas with ammonium addition they remained at the background level. N₂O dual isotope and isotopomer analysis of gas samples collected from BGR treated soil indicated bacterial denitrification to be the main N₂O generating process during the first three weeks when high CO₂ fluxes signified high carbon availability. In contrast, in the second half after all added labile carbon substrates had been consumed, nitrification, i.e. the generation of N₂O via oxidation of hydroxylamine, gained in importance reaching roughly the same N₂O production rate compared to bacterial denitrification as indicated by N₂O SP. Overall in this study, bacterial denitrification seemed to be the main N₂O forming process after application of biogas residues and fluxes were mainly driven by available organic carbon.     

Method for analysis of tannic acid and its metabolites in biological samples: application to tannic acid metabolism in the rat

A new analytical method for measuring tannic acid (TA) using tannase was developed and applied to the investigation of TA metabolism in the rat following oral administration at a dose of 1.0 g/kg. The proposed method for TA determination was based on the enzymatic hydrolysis of TA to gallic acid (GA) and subsequent determination by HPLC. TA metabolites were determined by HPLC. 4-O-Methylgallic acid (4-OMGA), pyrogallol (PY), and resorcinol (RE) were detected in serum. TA was excreted into urine as GA (0.01%), 4-OMGA (0.10%), PY (0.24%), and RE (2.06%) and into feces as TA (62.74%), GA (0.19%), PY (0.02%), and RE (0.76%) within 54 h after oral administration. It was suggested that >60% of TA remained unchanged but that some was hydrolyzed to GA by tannase in the intestine and further metabolized to 4-OMGA, PY, and RE.     

Sulfuric acid cleanup and KOH-ethanol treatment for confirmation of organochlorine pesticides and polychlorinated biphenyls: application to wastewater samples

The efficacy of sulfuric acid cleanup and KOH-ethanol hydrolysis confirmation was studied for 22 organochlorine pesticides and 2 polychlorinated biphenyls (PCBs). Mean recoveries for different treatment times are given. The method was applied to analysis of several wastewater samples by gas chromatography with electron capture detection. Organochlorine compounds were extracted by using separatory funnels and 15% diethyl ether in hexane as extractant. All the compounds studied could be analyzed except trifluralin, dichloran, dieldrin, and endrin, which were destroyed after treatment with concentrated H2SO4. The pesticides found most commonly in the samples analyzed were fenson, tetradifon, lindane, methoxychlor, and dicofol.     

Application of near-infrared reflectance spectroscopy to the evaluation of rutin and D-chiro-Inositol contents in tartary buckwheat

Tartary buckwheat [Fagopyrum tataricum (L.) Gaench] is rich in rutin and D- chiro-inositol (DCI), which have beneficial effects in the treatment of hemorrhagic diseases and insulin-resistant diseases, respectively. The current methods of extraction and detection of rutin and DCI are complex and time-consuming; a simple way of analyzing these compounds in the native matrix would be desirable. In this work, near-infrared reflectance spectroscopy (NIRS) was applied to determine the contents of rutin and DCI in tartary buckwheat. The spectral data were compared with those determined from high-performance liquid chromatography (HPLC) methods. Models for predicting rutin and DCI contents in buckwheat were developed using a partial least-squares algorithm. Cross-validation procedures indicated good correlations between HPLC data and NIRS predictions (R2 = 0.76 for rutin and R2 = 0.86 for DCI). The rutin content ranged from 0.998 to 1.75%, while the DCI content covered 0.179-0.200%. The results showed that NIRS, a well-established and widely applied technique, could be applied to determine rutin and DCI in tartary buckwheat rapidly and nondestructively.