Sample homogenization procedure for determination of lead in canned foods.

To improve the homogeneity of canned foods before Pb determination, composited samples or single can contents (150--500 g) are treated with an equal weight of dilute nitric acid, and then thoroughly blended in a high efficiency, probe-type Polytron homogenizer; subsamples are then either dry-ashed or wet-ashed in preparation for analysis. Within-can variability is reduced from the 20--50% coefficient of variation range obtained with conventional blending procedures to a coefficient of variation of less than 5% by using the proceudre described. Precision data for Pb, using both the probe-type and conventional blade-type homogenizers, are compared. The procedure described for Pb determination was used to analyze a number of canned products. Data indicate that the Polytron plus dilute acid procedure improves overall Pb homogeneity for subtle as well as severe initial Pb heterogeneity.     

Sample oxidation procedures for the determination of chromium and nickel in biological material

Abstract

Sample preparation methods for atomic absorption spectrophotometric analysis of chromium and nickel in biological materials were examined. Radiotracer recovery, precision of analysis and analysis of NBS reference samples were the criteria used. Chromium and nickel in biological materials can be successfully prepared for atomic absorption spectrophotometry by dry ashing with nitric acid treatment of the partially oxidized sample. It was necessary to use at least 5% nitric acid to extract the chromium and nickel from the ash. Vet digestion with nitric acid alone was satisfactory for nickel but not for chromium. Wet digestion gave greater variance and required considerably more time. We found no evidence of loss of chromium by either volatilization or insolubility. Since this method is satisfactory for nickel determination it may be implied that it is also satisfactory for other nonvolatile first transition series elements.     

Protein-peptide interactions in mixtures of whey peptides and whey proteins

The effects of several conditions on the amounts and compositions of aggregates formed in mixtures of whey protein hydrolysate, made with Bacillus licheniformis protease, and whey protein isolate were investigated using response surface methodology. Next, the peptides present in the aggregates were separated from the intact protein and identified with liquid chromatography-mass spectrometry. Increasing both temperature and ionic strength increased the amounts of both intact protein and peptides in the aggregates. There was an optimal amount of added intact WPI that could aggregate with peptides, yielding a maximal amount of aggregated material in which the peptide/protein molar ratio was around 6. Under all conditions applied, the same peptides were observed in the protein-peptide aggregates formed. The dominant peptides were beta-lg AB [f1-45], beta-lg AB [f90-108], and alpha-la [f50-113]. It was hypothesized that peptides could form a kind of glue network that can include beta-lactoglobulin via hydrophobic interactions at the hydrophobic binding sites at the surface of the protein.     

磁致伸缩生物传感器尺寸对沙门氏菌检测灵敏度的影响

为了研究不同尺寸传感器的检测灵敏度,该文以磁致伸缩膜片为物理传感器,多克隆抗体为生物识别元件,采用Langmuir-Blodgett(LB)技术将多克隆抗体固定在磁致伸缩膜片表面,制备了用于检测沙门氏菌的磁致伸缩生物传感器。检测时,将不同尺寸的生物传感器浸在含有沙门氏菌的被测溶液里,由于生物传感器对沙门氏菌的吸附使传感器质量增加,从而使传感器共振频率发生改变。采用尺寸为2 mm×0.4 mm×15μm,5 mm×1 mm×15μm和25 mm×5 mm×15μm的传感器检测浓度为102~109 CFU/m L的沙门氏菌溶液,并利用扫描电子显微镜观察传感器表面。研究结果表明,由传感器共振频率变化计算获得的沙门氏菌浓度与扫描电子显微镜观察统计分析获得的直观浓度吻合得很好,两者最大相对差值小于10%。传感器尺寸越小,检测灵敏度越高。尺寸为2 mm×0.4 mm×15μm,5 mm×1 mm×15μm和25 mm×5 mm×15μm的检测极限分别为5×103 CFU/m L,105 CFU/m L和107 CFU/m L。研究结果可为磁致伸缩生物传感器实际应用时,根据预测的细菌浓度,在保证灵敏度的前提下选择合适尺寸的传感器提供参考。     

Sample size calculations for studies designed to evaluate diagnostic test accuracy

We developed a Bayesian approach to sample size calculations for cross-sectional studies designed to estimate sensitivity and specificity of one or more diagnostic tests. Sample size calculations can be made for common study designs such as one test in one population, two conditionally independent or dependent tests in ≤2 populations, and three tests in ≤2 populations. We determine a sample size combination that yields high predictive probability, with respect to the future study data, of accurate and precise estimates of sensitivity and specificity. We also consider hypothesis testing for demonstrating the superiority or equivalence of one diagnostic test relative to another. The predictive probability can also be computed when the sample size combination is fixed in advance, thereby providing a “power-like” measure for the future study. The method is straightforward to implement using the S-Plus/R library emBedBUGS together with WinBUGS.     

Statistical power for detecting trends with applications to seabird monitoring

Power analysis is helpful in defining goals for ecological monitoring and evaluating the performance of ongoing efforts. I examined detection standards proposed for population monitoring of seabirds using two programs (MONITOR and TRENDS) specially designed for power analysis of trend data. Neither program models within- and among-years components of variance explicitly and independently, thus an error term that incorporates both components is an essential input. Residual variation in seabird counts consisted of day-to-day variation within years and unexplained variation among years in approximately equal parts. The appropriate measure of error for power analysis is the standard error of estimation (S.E._est) from a regression of annual means against year. Replicate counts within years are helpful in minimizing S.E._est but should not be treated as independent samples for estimating power to detect trends. Other issues include a choice of assumptions about variance structure and selection of an exponential or linear model of population change. Seabird count data are characterized by strong correlations between S.D. and mean, thus a constant CV model is appropriate for power calculations. Time series were fit about equally well with exponential or linear models, but log transformation ensures equal variances over time, a basic assumption of regression analysis. Using sample data from seabird monitoring in Alaska, I computed the number of years required (with annual censusing) to detect trends of −1.4% per year (50% decline in 50 years) and −2.7% per year (50% decline in 25 years). At α=0.05 and a desired power of 0.9, estimated study intervals ranged from 11 to 69 years depending on species, trend, software, and study design. Power to detect a negative trend of 6.7% per year (50% decline in 10 years) is suggested as an alternative standard for seabird monitoring that achieves a reasonable match between statistical and biological significance.     

Sample volume effect on determination of soil salinity

Abstract

Five pedons from a 200 hectare area were sampled to study the effect of the soil sample volume on determination of salinity. Four sample sizes, 5, 50, 500 and 5000 g, were used, with five to ten replicates each, for the top 25 cm of the profiles. These samples were prepared and analyzed for soil salinity, soluble cations and anions in 1: 2 (soil: water) extracts. Data revealed that the variations due to the different sample sizes were highly significant. Highest values of EC, cations and anions were obtained when using 5‐g samples. The confidence intervals tended to be lowest for the 5000‐g samples in most of the EC, cation and anion determinations. The 500‐g sample size was awkward and apparently the 5‐g sample size was too small.     

基于贝叶斯理论的工程车辆载荷样本长度计算方法

确定载荷样本长度是载荷谱编制的一个关键步骤,直接影响着零部件疲劳寿命预测的准确性。为了找到一种有效地确定载荷样本长度的方法,该文以轮式装载机为例,结合其零部件的受载特点,假定载荷均值服从正态分布,均值的先验分布也服从正态分布,提出了用贝叶斯理论和加权平方损失函数来计算载荷样本长度的方法。该方法以加权平方损失函数的后验损失期望值取最小值为条件,得到了包含先验信息、样本信息以及总体信息的后验参数估计值;然后结合t分布得到了在满足一定置信度和误差要求时的载荷样本长度。     

Sample preparation and liquid chromatographic determination of vitamin D in food products

Vitamin D in different fortified foods is determined by using liquid chromatography (LC). Sample preparation is described for fortified skim milk, infant formulas, chocolate drink powder, and diet food. The procedure involves 2 main steps: saponification of the sample followed by extraction, and quantitation by LC analysis. Depending on the sample matrix, additional steps are necessary, i.e., enzymatic digestion for hydrolyzing the starch in the sample and cartridge purification before LC injection. An isocratic system consisting of 0.5% water in methanol (v/v) on two 5 microns ODS Hypersil, 12 X 0.4 cm id columns is used. Recovery of vitamin D added to unfortified skim milk is 98%. The results of vitamin D determination in homogenized skim milk, fortified milk powder, fortified milk powder with soybean, chocolate drink powder, and sports diet food are given.     

Sample extraction method combining micellar extraction-SPME and HPLC for the determination of organochlorine pesticides in agricultural soils

A method for the determination of organochlorine pesticides in soil samples combining microwave assisted micellar extraction (MAME) with solid-phase microextraction (SPME) and high-performance liquid chromatography-UV has been developed. A mixture of two nonionic surfactants (polyoxyethylene 10 lauryl ether and polyoxyethylene 10 stearyl ether) was used for the extraction of pesticides from agricultural soils, and different types of SPME fibers were compared. The different parameters which affect extraction efficiency in the SPME procedure were optimized such as extraction time and temperature. The method developed involves extraction and preconcentration for the target analytes in soil samples. The analytical parameters were also studied and good recoveries obtained, RSD being lower than 10% and detection limits ranging between 36 and 164 ng g(-1) for the pesticides studied. The proposed method was successfully applied to the determination of some organochlorine pesticides in several kinds of agricultural soil samples with different characteristics.     

Assessment of the interactions of metals and nitrilotriacetic acid in soil/sludge mixtures

The solution phase forms of Cu, Mn, Ni, and Zn in digested sewage sludge and a soil/sludge mixture were investigated. Gel filtration chromatographic analysis indicated that Cu and possibly Ni were maintained in solution by association with a soluble, high molecular weight organic fraction; Mn solubility was due to the presence of unbound inorganic species and soluble Zn was distributed equally between the two forms. Speciation of the metals in the solution phase of the soil/sludge mixture generally reflected that of the sludge. However, the total amount of soluble Mn in the soil/sludge mixture was approximately 25 times greater than in the sludge and was attributed to heavy metal induced release of indigenous soil Mn. Increases in the quantities of soluble Ni and Zn in both the sludge and the soil/sludge mixture following equilibration with 40 mg L^?1 NTA were due to conversion of solid phase forms to soluble metal-NTA complexes. The preferential complexation of NTA with Cu already present in soluble organic forms resulted in a change in speciation without a corresponding increase in solubility. The importance of changes in speciation with regard to potential metal mobility and bioavailability within sludge-amended soil is discussed.     

New methods for aerosol size distribution determination with a diffusion battery

The method of precipitation of granules on the walls of narrow flow tubes furnishes data that are dependent on both the grain size and the particle abundance. The objective desired is to determine both of these quantities from the observations. The paper presents an analytic method for doing so. It is tested on a uranine aerosol, and the results are found to compare favorably with electron microscope studies of the same aerosol.     

The oxidation of soil organic matter by KBrO for particle size determination

Abstract

The oxidation of soil humus by alkaline KBrO solution at boiling temperature has been shown to be successful even with samples as carbonaceous underwater soils. With these soils treatment with H₂O₂ produces a cohesive foam which prevents further oxidation.     

Sample size influences estimation of cotton dry matter,nitrogen accumulation,and lint yield

Abstract

Accurate estimates of cotton (Gossypium hirsutum) dry matter accumulation and nitrogen content are important for both production and environmental reasons. One of the important factors in estimate accuracy is sample size. The objective of this investigation was to determine the cotton sample size necessary for acceptable estimates of cotton dry matter, lint yield, and shoot N per 100 kg of lint ratio (NLR) values. Three cotton cultivars (DeltaPine 90, DeltaPine 5415, and Stoneville 474) were planted on 13 May 1997 in an Eunola loamy sand (fine‐loamy, siliceous, thermic Aquic Hapludult) in 9.3‐m² subplots of a split‐split plot design. Split plots were four sampling dates. Split‐split plots were four sampling techniques [a) four randomly selected plants (4RP), b) 0.3 meter of row (0.3‐m), c) one meter of row (1‐m), and d) two meters of row (2‐m)]. Each entire subplot was harvested on each sampling date after sampling by the four techniques. Shoot dry matter for the whole plot was 7.2 Mg ha^‐1, and lint yield was 1.46 Mg ha^‐1. Cotton shoot dry matter and NLRs were significantly overestimated by both the 4RP and 0.3‐m techniques, but not by the 1‐ and 2‐m techniques. The NLRs of cultivar subplots varied with cultivar from 9.1 to 11.4. The earliest maturing cultivar, DeltaPine 90, had the lowest NLR and the latest maturing cultivar, Stoneville 474, had the highest NLR. Accurate estimates of cotton dry matter accumulation and N content will likely require 1‐m samples, and 2‐m samples should further improve precision. The NLRs were similar to data (NLR <15) that suggest 1.6 Mg ha^‐1 (3‐bale/acre) cotton lint yields can be achieved with less than 250 kg ha^‐1 of shoot‐accumulated N.     

Sample preparation,extraction efficiency,and determination of six arsenic species present in food composites

Several sample preparation techniques were investigated to maximize the efficiency of arsenic species extraction from food composites. The optimized method includes lyophilization of food followed by prewashing with acetone and extraction by sonication with 50/50 methanol/water. Six arsenic species were separated and quantitated using an ammonium carbonate buffer system by ion exchange chromatography coupled to inductively coupled plasma mass spectrometry. The performance of the method for speciated arsenic components was evaluated using a matrix containing high fat food composite fortified with arsenic species. A certified reference material, dogfish muscle, was used to evaluate extraction methods for total arsenic content in food composites. More than 200 food composite samples were analyzed during an 18 month period, demonstrating the reliability of the analytical method over a long time period.     

One- and two-dimensional direct chiral liquid chromatographic determination of mixtures of diclofop-Acid and diclofop-methyl herbicides

Simple one- and two-dimensional high-performance liquid chromatography (HPLC) methods for the simultaneous enantiomeric determination of alkyloxyphenoxypropionic acid herbicides is presented. Compounds studied were ( R, S)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid (diclofop-acid) and ( R, S)-2-[4-(2,4-dichlorophenoxy)]methyl propionate (diclofop-methyl). Mobile phases necessary to separate their enantiomers on an alpha1-acid glycoprotein chiral stationary phase are different; therefore, the simultaneous separation by an isocratic mode is not possible. The chiral separation method proposed involves a one-step gradient allowing for the simultaneous determination of both racemic enantiomers. Detection limits of the method were 0.03 mg/L for both diclofop-acid enantiomers and 0.14 and 0.15 mg/L for diclofop-methyl enantiomers, respectively. The two-dimensional method involves the use of two chromatographs in one achiral-chiral coupling. The LC-LC method is more suitable for complex samples because it involves an online cleanup effect. Detection limits were 1.25 and 1.87 mg/L for diclofop-acid and 2.70 and 3.02 mg/L for diclofop-methyl enantiomers, respectively. Accuracy, repeatability, and reproducibility have been studied in standard samples and a technical product.     

Analysis of mixtures of drugs/chemicals along a fixed-ratio ray without single-chemical data to support an additivity model

This article presents and illustrates an approach to designing and analyzing studies involving mixtures/combinations of drugs or chemicals along fixed-ratio rays of the drugs or chemicals for generalized linear models. When interest can be restricted to a specific ray, we consider fixed-ratio ray designs to reduce the amount of experimental effort. When a ray design is used, we have shown that the hypothesis of additivity can be rejected when higher order polynomial terms are required in the total dose-response model. Thus, it is important that we have precise parameter estimates for these higher order polynomial terms in the linear predictor. We have developed methodology for finding a D _s -optimal design based on this subset of the terms in the linear predictor.     

Strategies for risk assessment of existing chemicals in soil

In the risk assessment of industrial chemicals, an assessment of the risk to soil should be performed whenever relevant inputs occur via the following pathways: application of sewage sludge, wet or dry deposition, application as a pesticide constituent (e.g. solvent or metabolite), irrigation. An evaluation of the results for 34 chemicals from the first EU priority list showed that only 35% of the risk assessments for the terrestrial compartment were performed on the basis of at least 2 valid tests with soil organisms. In the vast majority of cases, the equilibrium partitioning method was used to extrapolate from aquatic to soil toxicity. However, no indications exist for a correlation between aquatic and terrestrial toxicity. Moreover, the exposure routes for soil organisms (uptake via pore water, air included in soil pores, ingestion of soil particles) are much more complex than those for aquatic organisms. As a new approach, it is therefore suggested that, in cases of relevant exposure (e.g. estimated or measured concentrations of >10 μg/kg), an assessment should generally be performed on the basis of valid terrestrial tests rather than on an extrapolation from the aquatic toxicity. It is recommended that prolonged exposure tests should be used already for an initial assessment of substances that have a strong tendency to adsorb on soil particles and thus a long residence time in soil. A decision scheme for the risk assessment of industrial chemicals in soil is presented, trigger values, testing strategies as well as assessment factors for derivation of a Predicted No Effect Concentration (PNEC_soil) are discussed. An example of a terrestrial risk assessment for substances from the first EU priority list is given in order to illustrate current practice.     

Automatic spectrophotometric determination of copper in plant material,soil, and fertilizer mixtures by a kinetic method

Abstract

Knowledge of metal concentration in soils, plant material, and fertilizers is important both for plant nutrition as for environment contamination studies. In this paper, an automated spectrophotometric method using Flow Injection Analysis (FIA) for copper (Cu) determination was studied. That method was based on the catalytic effect of Cu²⁺ ions in the color fading of the red‐purplish complex formed when iron (Fe³⁺) and thiosulfate (S₂O₃ ^2‐) ions react. The principal feature of the studied method is its high selectivity, which allowed the Cu determination in a complex matrix as nitrogen (N):phosphorus (P):potassium (K) fertilizer mixtures without effect of interference. Soil and plant tissue samples were also analyzed with good precision and accuracy when compared with atomic absorption spectrophotometry.