Determination of total sulfite in shrimp, potatoes, dried pineapple, and white wine by flow injection analysis: collaborative study

A method for the determination of total sulfite in shrimp, potatoes, dried pineapple, and white wine by flow injection analysis (FIA) was collaboratively studied by 8 laboratories. In the method, the sample solution is reacted with sodium hydroxide to liberate aldehyde-bound sulfite. The sample stream is acidified to produce SO2 gas, which diffuses across a Teflon membrane in the gas diffusion cell into a flowing stream of malachite green. The degree of discoloration of the malachite green is proportional to the amount of sulfite in the sample solution. Red wine was included in the study but interlaboratory precision for these samples was not satisfactory and correlation with Monier-Williams results was poor. The present method is not recommended for use with these samples. For shrimp, potatoes, dried pineapple, and white wine, average reproducibility (RSDR) of results was 25% for samples at 10 ppm SO2 and 10% for samples at greater than 50 ppm. Overall average reproducibility was 14%. Recoveries of sulfite added to samples averaged 80%. Comparison of FIA with the Monier-Williams method indicated comparable results by the 2 methods. The FIA method has been adopted official first action for determination of greater than or equal to 5 ppm total sulfite in shrimp, potatoes, dried pineapple, and white wine.     

Comparison of three liquid chromatographic methods with FDA optimized Monier-Williams method for determination of total sulfite in foods

Three liquid chromatographic (LC) methods employing amperometric detection were compared with the collaboratively studied FDA optimized Monier-Williams distillation method for the determination of total sulfite in 5 food types. The foods included lemon juice, white wine, instant mashed potatoes, golden raisins, and onion flakes. Two of the LC methods (one employing headspace sampling and the other direct injection) used ion-exchange chromatography with a basic mobile phase (pH about 10.8) and a glassy carbon electrode; the third (employing direct injection) used ion-exclusion chromatography with an acidic mobile phase (pH about 2) and a platinum electrode. All 4 methods produced similar results for the wine, lemon juice, and raisins. Results were different for instant mashed potatoes and onion flakes. The headspace-LC method and direct ion-exclusion LC method, both of which employed an alkaline sample extraction, yielded significantly higher values for sulfite in instant potatoes than did the other 2 methods. A large interfering peak with both direct LC methods prevented quantitation of sulfite in the onion flakes. All methods can detect sulfite as low as about 1 microgram/g in 4 of 5 food types examined.     

Determination of sulfite in foods and beverages by ion exclusion chromatography with electrochemical detection: collaborative study

A liquid chromatographic (LC) method for determination of total sulfite in foods and beverages by alkali extraction followed by ion exclusion chromatographic separation and electrochemical detection (IEC-EC) was collaboratively studied by 9 laboratories. Blind duplicate samples of starch, diluted lemon juice, wine cooler, dehydrated seafood, and instant mashed potatoes were analyzed without spiking and with added sulfite at 2 levels. The initial sulfite levels varied from 0 to 384 ppm SO2, and the levels added varied from 10 to 400 ppm. The initial sulfite levels determined by the IEC-EC method and the Monier-Williams method were in good agreement. Recovery of added sulfite by the IEC-EC method was generally higher than that by the Monier-Williams method. Within-laboratory repeatability (RSDr) for the IEC-EC method varied from 4.4 to 26.0%, and overall reproducibility (RSDR) varied from 8.5 to 39.3%. The collaborators found the method to be fast, sensitive, and easy to use, which makes it a useful alternative to the Monier-Williams method. The method has been adopted official first action.     

Differential pulse polarographic determination of sulfites in foods: collaborative study

A differential pulse polarographic (DPP) method for the determination of "free" and "total" sulfite in foods was collaboratively studied by 8 laboratories. The collaborators analyzed blind duplicate samples of shrimp, orange juice, peas, dried apricots, and dehydrated potatoes. Collaborators also analyzed the same samples spiked with sulfites at 2 levels, which ranged from 10 to 1100 micrograms added SO2/g. The variability of free SO2 results was excessive for quantitative analysis, but the method can be used for qualitative detection of free SO2. The method for total SO2 determination was suitable for as low as approximately 10 micrograms/g. Recoveries are comparable to those for the official Monier-Williams method at high levels and are superior at low levels. The method has been adopted official first action for determination of total SO2 in the foods studied.     

Apple peels as a value-added food ingredient

There is some evidence that chronic diseases, such as cancer and cardiovascular disease, may occur as a result of oxidative stress. Apple peels have high concentrations of phenolic compounds and may assist in the prevention of chronic diseases. Millions of pounds of waste apple peels are generated in the production of applesauce and canned apples in New York State each year. We proposed that a valuable food ingredient could be made using the peels of these apples if they could be dried and ground to a powder without large losses of phytochemicals. Rome Beauty apple peels were treated with citric acid dips, ascorbic acid dips, and blanches before being oven-dried at 60 degrees C. Only blanching treatments greatly preserved the phenolic compounds, and peels blanched for 10 s had the highest total phenolic content. Rome Beauty apple peels were then blanched for 10 s and dried under various conditions (oven-dried at 40, 60, or 80 degrees C, air-dried, or freeze-dried). The air-dried and freeze-dried apple peels had the highest total phenolic, flavonoid, and anthocyanin contents. On a fresh weight basis, the total phenolic and flavonoid contents of these samples were similar to those of the fresh apple peels. Freeze-dried peels had a lower water activity than air-dried peels on a fresh weight basis. The optimal processing conditions for the ingredient were blanching for 10s and freeze-drying. The process was scaled up, and the apple peel powder ingredient was characterized. The total phenolic content was 3342 +/- 12 mg gallic acid equivalents/100 g dried peels, the flavonoid content was 2299 +/- 52 mg catechin equivalents/100 g dried peels, and the anthocyanin content was 169.7 +/- 1.6 mg cyanidin 3-glucoside equivalents/100 g dried peels. These phytochemical contents were a significantly higher than those of the fresh apple peels if calculated on a fresh weight basis (p < 0.05). The apple peel powder had a total antioxidant activity of 1251 +/- 56 micromol vitamin C equivalents/g, similar to fresh Rome Beauty peels on a fresh weight basis (p > 0.05). One gram of powder had an antioxidant activity equivalent to 220 mg of vitamin C. The freeze-dried apple peels also had a strong antiproliferative effect on HepG(2) liver cancer cells with a median effective dose (EC(50)) of 1.88 +/- 0.01 mg/mL. This was lower than the EC(50) exhibited by the fresh apple peels (p < 0.05). Apple peel powder may be used in a various food products to add phytochemicals and promote good health.     

High pressure liquid chromatographic determination of vitamin D3 in instant nonfat dried milk

Vitamin D3 was determined in commercially fortified instant nonfat dried milk by using normal phase high pressure liquid chromatography (HPLC). The sample was extracted with dichloromethane with sodium phosphate tribasic solution added. The sample was cleaned up by using a Sep-Pak silica cartridge and then a microparticulate column containing 10 micrometer Partisil-10 PAC packing material. The final analysis was performed by using a normal phase HPLC system with 10 micrometer LiChrosorb NH2 column. Recovery of vitamin D3 at levels as low as 10000 IU/kg was 97.7% with a standard deviation of 3.9%.     

离子色谱法测定福建南平地区植烟土壤中的全钾和有效钾含量

建立测定植烟土壤中全钾和有效钾含量的离子色谱法。采用Dionex RFIC CS12A阳离子交换色谱柱(4.0mm×250 mm)配Dionex CG12A保护柱(4 mm×50 mm),以20 mmol/L甲基磺酸为流动相,流速1.0 m L/min,检测器为电导检测器,柱温25℃,进样量25μL。结果表明:钾离子在1.5~15 mg/L内与峰面积的线性关系良好,线性方程为:y=5.634x-0.252 8,r=0.999 3;最低检出限为0.31 mg/kg;定量限为1.01 mg/kg。样品中全钾和有效钾在不同浓度水平范围内的平均回收率测定结果为98.31%~101.3%,RSD(n=6)为0.5%~3.9%,表明该方法具有良好的准确性和精密度,操作简便、快速,可以满足实际分析的需要。样品分析的结果表明,邵武地区的砂土含钾量(包括全钾和有效钾)最高,而浦城地区的壤土含钾量最高,为该地区烟草培植施用钾肥提供了参考。     

Purification of cyclopiazonic acid by liquid chromatography

A purification procedure for cyclopiazonic acid has been developed, using sequential preparative and semi-preparative liquid chromatography. Crude cyclopiazonic acid (324 mg) was extracted from a 1 L fermentation medium with chloroform-methanol (80 + 20), dried, dissolved in chloroform, and chromatographed on an oxalic acid/silica preparative column with chloroform-methanol (99 + 1) as the eluant. A semi-preparative oxalic acid/silica column and chloroform-methanol (99.5 + 0.5) were then used for rechromatography of the partially purified cyclopiazonic acid. This second chromatographic treatment yielded fractions from which cyclopiazonic acid was readily crystallized (106.7 mg; 33% recovery). Analytical chromatography was developed using an amino column in an ion-exchange mode, with a methanol-phosphate buffer eluant. Response was linear from 10 to 800 micrograms/injection of standard solutions. Cyclopiazonic acid chemically binds sodium from soda-lime vials.     

噻菌茂在烟叶和土壤中的残留消解动态及安全性评价

为明确噻菌茂在烟草上使用后的环境安全性,建立了烟叶和土壤中噻菌茂残留的检测方法,并在山东和湖南两地开展了为期两年的噻菌茂在烟叶及其土壤中的消解动态和最终残留研究。结果表明,采用甲醇/水（70：30,V：V）提取,石油醚、二氯甲烷萃取,弗罗里硅土净化,高效液相色谱（HPLC-UV）测定,在0.01～5.0mg.kg-1添加水平下,噻菌茂在鲜烟叶、干烟叶和土壤中的平均回收率分别为90.50%～93.84%、88.19%～91.90%和88.34%～93.04%,相对标准偏差（RSD）分别为1.72%～2.79%、1.83%～4.13%、2.00%～2.71%。噻菌茂的最小检出量为1.4×10-12g,最低检出浓度分别为：鲜烟叶0.01mg.L-1,干烟叶0.01mg.L-1,土壤0.005mg.L-1。田间试验结果表明,噻菌茂在烟叶和土壤中消解较快,半衰期分别为2.85～3.44d和2.77～3.26d。噻菌茂可湿性粉剂按有效成分250g.hm-2（推荐高剂量）和375g.hm-（21.5倍推荐高剂量）于烟草旺长期-成熟期兑水施药3～4次,烟叶中噻菌茂最终残留量随采收间隔时间的延长而呈递减趋势,距末次施药后间隔7d采收的烟叶中噻菌茂的残留量为1.102～4.230mg.kg-1,21d残留量降为0.082～1.813mg.kg-1;而土壤中噻菌茂最终残留量均未检出（≤0.005mg.kg-1）。     

酸化沸石对尿素氮淋失和玉米籽粒氮素利用的影响

在尿素减量施用条件下,探究添加酸化沸石(SF)对氮素淋失及籽粒氮肥利用率的影响。通过等温吸附试验,结合土柱淋溶和玉米盆栽试验,研究酸化沸石对NH_4⁺—N和NO_3^-—N的吸附性能,以及不同施氮梯度下,酸化沸石对氮素淋失和氮肥利用率的影响,试验分别设置农民习惯施肥(CN)、氮肥减量15%(CN1)、氮肥减量30%(CN2)3个施氮梯度并分别添加土重0.2%的酸化沸石(CN+SF、CN1+SF、CN2+SF)。结果表明,酸化沸石对NH_4⁺—N和NO_3^-—N的最大吸附量分别为25.44,31.59 mg/g,吸附过程可用Langmuir模型较好拟合。在减氮15%和30%时,添加酸化沸石,使NH_4⁺—N累计淋失量较CN1、CN2分别降低7.10%,8.76%。在减氮30%时,酸化沸石可有效降低NO_3^-—N累计淋失量,较CN2处理减少15.90%。酸化沸石可有效提高土壤氮素含量和玉米籽粒氮肥利用率,添加酸化沸石(CN+SF、CN1+SF、CN2+SF)较单施尿素(CN、CN1、CN2)籽粒氮肥利用率分别提高10.37%,20.79%,47.14%。综上,酸化沸石在减施尿素条件下可有效降低土壤氮素淋失,提高玉米籽粒氮肥利用率,具有一定的农艺价值。     

Rapid softening of acidified peppers: effect of oxygen and sulfite

Evidence was found for two previously unreported, nonenzymatic reactions that affected texture retention in acidified red bell peppers. First, oxygen was found to cause rapid softening of the pepper tissue such that it lost at least 40% of the initial tissue firmness within 2 weeks after acidification. Second, sulfite added to the acidified peppers prevented the softening caused by oxygen. Combined addition of sulfite and calcium chloride resulted in better retention of tissue firmness during extended storage than the addition of either component by itself.     

Liquid chromatographic determination of sulfite in grapes and selected grape products

A liquid chromatographic (LC) method is described for the determination of sulfite in grapes and certain grape products. Sulfite is extracted from grapes with aqueous formaldehyde solution buffered at pH 5; free sulfite is converted to hydroxymethylsulfonate (HMS), which is extremely stable at pH 3-7. Subsequent heating to 80 degrees C for 30 min converts reversibly bound forms of sulfite to HMS. The extract is then analyzed by reverse-phase ion-pairing liquid chromatography, using a C18 column and a mobile phase of aqueous 0.005 M tetrabutylammonium ion in 0.05 M acetate, pH 4.7, and a flow rate of 1 mL/min. Aqueous KOH is added to the eluate to convert HMS to free sulfite, which is then treated with 5,5'-dithiobis[2-nitrobenzoic acid]. This reaction produces the 3-carboxy-4-nitrothiophenolate anion, which is determined by measurement of electronic absorption at 450 nm. For grapes spiked with HMS at 5-20 ppm (as SO2), recoveries ranged from 92 to 112%, with a coefficient of variation of 4.6%. The method was also used to determine sulfite in various grape products. Results were comparable to those obtained by the AOAC official Monier-Williams method.     

Assessment of the stability of pesticides during cryogenic sample processing. 1. Apples.

An assessment of the stability of a large number (106) of pesticides and related compounds during the cryogenic sample processing of apples has been undertaken. For the first time the procedure included an assessment of the losses during the freezing of the fruits, prior to processing. The stability of each pesticide during processing was assessed by comparing the mean recovery for the laboratory-spiked samples with the mean "survival" of the pesticides in cryogenically processed samples. The results clearly demonstrate that the vast majority, 94 of 106, of pesticides were stable during cryogenic processing. Of particular importance was that losses of several pesticides [bitertanol (95%), heptenophos (50%), isofephos (40%), and tolylfluanid (48%)] reported to occur during ambient processing of apples did not occur during cryogenic processing. Losses of dichlofluanid (54%), chlozolinate (22%), and etridiazole (40%), previously reported to occur during ambient processing of apples, were reduced to barely significant levels (10, 17, and 14%, respectively) by cryogenic processing. Small apparent losses for a few of the compounds were attributable to analytical and sample handling difficulties, rather than to losses during processing, and need further investigation.     

热泵干燥槟榔中试工艺参数优化

为了探索新型节能、低碳排放的槟榔干燥技术,应用热泵干燥设备对槟榔进行干燥研究,获得槟榔热泵干燥中试工艺参数。单因素试验分析了煮沸时间对槟榔硬度的影响,干燥温度和装载量对槟榔水分的影响;采用正交试验,通过加权评分值计算方法评价干果品质,优化热泵干燥工艺参数;测定储藏30 d后的干果进行理化和微生物指标;比较热泵干燥、蒸汽干燥和传统干燥槟榔的成本及品质。结果表明,新鲜槟榔经过沸水煮沸15 min,前12 h内干燥温度为50℃、12 h后干燥温度为65℃、装料量为3.5 t、烘房空气相对湿度为25%时,槟榔含水率为16.8%,好果率为96.0%,均匀度为91%,单位质量干果耗电量为0.92(k W·h)/kg,所干燥的槟榔干果综合评分为90.1分,呈橄榄黄或褐色。25℃储藏30 d无霉腐现象,检测结果显示含水率为17.8%,未检测出汞和苯并芘,铅和砷质量分数分别为0.02和0.1 mg/kg,致病菌未检出,大肠菌群数30 cfu/g,霉菌计数为30 cfu/g。经比较,热泵干燥槟榔比蒸汽干燥成本低11%,比传统土炉干燥成本低50%,零排放、无污染、操作智能化。研究结果为槟榔热泵干燥的标准化生产提供技术参考。     

CALCIUM DEFICIENCY OF WHEAT GROWN IN ACIDIC SANDY SOIL FROM SOUTHWESTERN AUSTRALIA

Calcium (Ca) deficiency has been associated with acidic very sandy soils that are widespread in Southwestern Australia (WA). There are no documented reports of Ca deficiency of cereals grown in the field. However, there is a possibility that Ca deficiency could be observed on the acidic very sandy soils of WA, particular where fertilizers low in Ca concentration are used.

For previously unfertilized sandy soil collected from under indigenous remnant vegetation in WA, there was no effect on yield of dried shoots of wheat (Triticum aestivum L.) due to addition of fertilizer Ca (0 up to 480 mg Ca/pot) to either the topsoil (top 10 cm of soil, pH 4.6) (1:5 soil 0.01 M CaCl₂, w/v) or subsoil (10–20 cm soil, pH 5.1). However, application of fertilizer Ca increased grain yields, by about 12% for the topsoil and up to about tenfold for the subsoil. For the subsoil, no grain was produced on the nil Ca treatment; about 0.16 g of grain was produced per plant at the second level of applied Ca (60 mg Ca/pot), and about 1.6 g of grain produced per plant at the highest amount of Ca (480 mg Ca/pot), a ten-fold increase in grain production. For the topsoil, grain yield for the highest level of Ca (480 mg Ca/pot) applied was about 1.8 times the amount of grain produced for the nil Ca treatment. The Ca concentration (% Ca) in dried shoots and grain increased with the addition of Ca to both the surface and subsoil. The Ca concentration in the dried tops declined with age of the wheat for both soils. For example, % Ca declined from 0.3% at GS25 to 0.1% at maturity. The highest Ca concentration in dried shoots at harvest always produced the largest amount of grain. There was no grain yield plateau reached in our study so critical concentrations of Ca within the plant tops for grain yield could not be determined.     

Reevaluation of Monier-Williams method for determining sulfite in food

The Monier-Williams distillation procedure has a long history of successful use for determining sulfite in fruit products and wine; however, a systematic evaluation of its accuracy and precision with other food matrices has not been undertaken. We found that the Monier-Williams distillation yielded greater than 90% recovery of sulfite added to foods such as table grapes, hominy, dried mangoes, and lemon juice. Less than 85% recovery was obtained with broccoli, soda crackers, cheese-peanut butter crackers, mushrooms, and potato chips. These results may, in fact, accurately reflect the residual levels of sulfite if a portion of the sulfite undergoes irreversible reaction with some food components. Analysis of commercial food products gave sulfite levels ranging from 1400 ppm in dried apple slices to 25 ppm in cream sherry.     

High-performance liquid chromatographic determination of the glycoalkaloids alpha-solanine and alpha-chaconine in 12 commercial varieties of Mexican potato

The glycoalkaloid content in 12 commercial varieties of Mexican potatoes was measured by HPLC in both the peel and the flesh of the potato. The principal glycoalkaloids alpha-solanine and alpha-chaconine were present in higher concentration in the peel than in the flesh of all varieties. The main alkaloid in the peel of the potatoes was alpha-chaconine and comprised about 65-71% of the total glycoalkaloids. The high concentration of alpha-chaconine in peel, which is more toxic than alpha-solanine, gives more protection to the tuber against predators. The total alkaloids in the peel of Alpha, Juanita, Michoacan, Norte?a, Rosita, and Tollocan varieties were higher than the limit recommended for food safety. However, the peel represents less than 10% of the total tuber in most of the varieties. The total alkaloids contained in the peel of Atzimba, Lopez, Marciana, Montsama, Murca, and Puebla was lower than the limits recommended for food safety. The glycoalkaloid content in the boiled peeled potatoes was less than 9 mg/100 g but in Alpha, Montsama, and Puebla varieties, both glycoalkaloids were absent. According to the results, the consumption of the 12 commercial varieties of Mexican potatoes does not represent any danger to human health.     

An automatic flow procedure for the determination of 3-hydroxybutyrate in animal serum and plasma

An automatic flow procedure based on the multicommutation concept, comprising three-way solenoid valves, for the spectrophotometric determination of 3-hydroxybutyrate in animal serum and plasma is proposed. The 3-hydroxybutyrate was enzymatically converted to acetoacetate with the reduction of NAD+ to NADH monitored at 340 nm. It was possible to carry out up to 600 determinations without a significant decrease in the analytical signal, with 5 mg of 3-hydroxybutyrate dehydrogenase immobilized on porous silica beads and packed in a column. The system enabled 60 determinations/h of 3-hydroxybutyrate in the range of 10-150 mg L(-1), with a consumption of 0.9 mg of NAD+ and 200 microL of sample per determination. A detection limit of 2 mg L(-1) for both animal serum and plasma and coefficients of variation of 1.4% and 1.2% (n = 17), respectively, were determined. Animal serum and plasma samples were analyzed without previous treatment, the results of which agreed with those obtained using the conventional method (UV kit, Sigma).     

亚硫酸盐对三价砷在土壤中氧化固定作用机制研究

土壤中硫的氧化还原过程对砷的释放与固定具有重要的影响,但有关硫形态对三价砷(As(Ⅲ))的氧化过程的机制与贡献并不清楚.基于此,本研究以土壤中普遍存在的硫转化中间产物亚硫酸盐为研究对象,研究其对土壤中As(Ⅲ)的氧化固定机制.结果表明,亚硫酸盐显著促进了土壤中As(Ⅲ)的氧化,与对照组相比,10 h内土壤悬液中As(Ⅲ...     

Results of the international aqueous mercury speciation intercomparison exercise

Twenty-seven laboratories from around the world agreed to participate in an intercomparison exercise for total Hg (Hg_t) and methyl Hg (MMHg) in pristine lake water. Unfiltered samples from a remote brown water lake in northern Wisconsin (USA) were collected into acid cleaned Teflon^® bottles using ultra-clean sample handling techniques. The samples were acidified in the field with 0.4% by volume of pre-analyzed HCl (12N; <5 pg Hg/mL), and sent to the primary reference laboratory (PRL) by overnight mail. Within one week of receipt, the samples were randomized, and 10% analyzed for Hgt and MMHg at the PRL to verify the homogeneity of the set. Each participating laboratory was then sent 3 randomly selected 1 L bottles, while the PRL retained 30, and the secondary reference laboratory (SRL) retained 12 samples. The participating laboratories were asked to analyze each bottle in triplicate for both Hgt and MMHg, reporting all QA data including blanks, spike recoveries, and detection limits. The PRL analyzed samples in triplicate at both the beginning and the end of the analytical window, to provide a controlled estimate of any changes in concentration or speciation over that time. Of the 23 laboratories that returned results, 18 utilized BrCl oxidation, gold trapping, and cold vapor atomic fluorescence (CVAFS) detection for Hg_t. Four laboratories reported similar techniques, varying either in detector (cold vapor atomic absorption), or wet chemistry. Only 16 laboratories reported MMHg results, with 15 using a variation of the aqueous phase ethylation, GC separation, and CVAFS detection technique. The results show good convergence between the participating labs for both Hg_t and MMHg. For Hgt 18 of 23 labs reported means within 20% of the consensus value and PRL results (1.27±0.18 ng/L and 1.27±0.14 ng/L respectively). For MMHg, 13 of the 16 labs reported results within 20% of either the consensus value (0.420±0.055 ng/L) or the PRL value (0.446±0.041 ng/L).