Comparative analysis of tobacco-specific nitrosamines and total N-nitroso compounds in moldovan cigarette tobacco

While previous studies have evaluated levels of tobacco-specific nitrosamines (TSNA) and total N-nitroso compounds (NOC) in tobacco, there are no reports in the literature on TSNA and total NOC in the same tobacco products. We compared levels of TSNA, total NOC, and NOC precursors (NOCP) in tobacco of cigarettes purchased in Moldova and in some tobacco types commonly used for the manufacturing of Moldovan cigarettes. Cigarette tobaccos included those from non-Moldovan, traditional Moldovan, and blended Moldovan cigarettes. The results demonstrate that tobacco of non-Moldovan cigarettes contains higher TSNA and NOC levels (mean, 16 and 63 nmol/g tobacco, n = 6) than that of Moldovan cigarettes (mean, 5 and 23 nmol/g tobacco, n = 25). TSNA and NOC levels were also generally higher in tobacco of blended than in traditional Moldovan cigarettes. NOCP levels in Moldovan and non-Moldovan cigarette tobacco were similar as follows: 29000 +/- 30000 and 33000 +/- 28000 nmol/g tobacco (mean +/- SD). Total NOC were strongly correlated with total TSNA levels (r = 0.66; P < 0.0001). These findings demonstrate that current technologies involved in the manufacture of some blended cigarettes create conditions that favor N-nitrosation of alkaloids and other tobacco constituents.     

Determination of volatile N-nitrosamines in frankfurters containing minced fish and surimi

A method was developed to quantitatively measure volatile N-nitrosamines, particularly N-nitrosodimethylamine (NDMA), in cured minced fish or surimi-meat frankfurters. This method is free from artifact formation. First, 2 dry solid-phase extraction columns are prepared. Solvent is passed through the top column containing the fish-meat into a second column containing acid Celite. The eluate from the Celite column is then passed through a third column containing silica gel. Nitrosamines are eluted from the acid Celite column and then from the silica gel column into the same receiver. Recovery of the internal standard, N-nitrosoazetidine, added at the 10 ppb level, was 86.5%. In addition, a few samples of nitrite-treated salmon (lox) were also tested for N-nitrosamines. The results show that the method is applicable to samples containing nitrite-treated fish and fish-derived products.     

Determination of total lipid and lipid subclasses in meat and meat products

Current interest in physiological and nutritional activities of the sterol, polyunsaturated fatty acid, and polar lipid fractions of meats and other foods indicates that analytical methods for lipids should be evaluated on their ability to recover and quantitate these classes. Current methods of lipid isolation furnish an extract that is dependent on the solvent(s) used, the type of food material, the temperature of extraction, and the relative proportions of the lipid classes present. Extraction with ethers or other relatively nonpolar solvents removes principally the neutral fats and nonpolar lipids. For an approximation of the crude fat content, such extraction is often sufficient, because the nonpolar fraction generally constitutes over 90% of the total lipids present. The polar lipids include the biochemically important (omega-3) and (omega-6) polyunsaturated fatty acid classes; thus, the method of lipid extraction of food products becomes relevant for a more complete and valuable characterization of their nutritional value. The various methods of lipid determination for meat products are examined for their total recovery of these important lipid groups. A sequential extraction in conjunction with subsequent analytical methods is recommended.     

Determination of total content of phenolic compounds and their antioxidant activity in vegetables--evaluation of spectrophotometric methods

This research studies in detail the contents of phenolic compounds determined by the Folin-Ciocalteu reagent and the antioxidant activities determined by the TEAC (Trolox equivalent antioxidant capacity), DPPH (using diphenyl-p-picrylhydrazyl radical), and FRAP (ferric reducing antioxidant power) methods, and their correlations for used standards with these methods (catechine, gallic acid, caffeic acid, ferulic acid, Trolox, ascorbic acid, and ferrous sulfate) and extracts from several species of commonly consumed vegetables were studied in detail. The comparison of absolute values of absorption coefficients for used standards and for individual methods allows one to choose optimal common standards for methods to be compared. The procedures applied for the same sets of the extracts using identical calibration procedures and common standards allowed better comparison of the results obtained by the TEAC, DPPH, and FRAP methods. The values of content of phenolic substances and total antioxidant activity of the sets of samples correlate very well for all used methods. The very high values of antioxidant activity were found in intensely colored vegetables (red cabbage, red onion, etc.), and the values were very low in watery vegetables such as potato, marrow, and cucumber.     

Effects of cooking on concentrations of polychlorinated dibenzo-p-dioxins and related compounds in fish and meat

We investigated the cooking-induced changes in concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) (dioxins) using mackerel and beef. The concentrations of dioxins (29 congeners) were determined by isomer specific analyses and were compared between uncooked and cooked samples. The cooking procedures examined in this study included grilling as a fillet, boiling as a fillet, and boiling as tsumire (small, hand-rolled balls) for mackerel and boiling as a slice, broiling as a slice, and broiling as a hamburger for beef. Three trials were carried out for each cooking method. Generally, concentrations of dioxins were reduced in every cooking trial. When nondetected congener concentrations were assumed to be half the limit of detection for mackerel, the maximum percentage reductions of total concentrations given as 2,3,7,8-tetraCDD equivalents (TEQ) were 31% in grilling as a slice, 14% in boiling as a slice, and 21% in boiling as tsumire under the conditions of this study. In contrast, for beef, the reductions were 42% in boiling as a slice, 42% in broiling as a slice, and 44% in broiling as a hamburger. These results suggest that ordinary cooking processes with heating undoubtedly reduce the dioxin content in animal products, and the reductions estimated should be considered when dioxin intake is evaluated using contamination data for individual food items.     

Determination of chlorinated methylthiobenzenes and their sulfoxides and sulfones in fish

A procedure was developed to determine chlorinated methylthiobenzenes and their respective sulfur oxidation products in fish. Perch samples fortified at the 0.1 ppm level with 2,4,5-trichloromethylthiobenzene, pentachloromethylthiobenzene, and their sulfoxides and sulfones were extracted and cleaned up using an adaptation of the official AOAC method for multiple residues of organochlorine pesticides. The Florisil column cleanup was modified; 200 mL 6% petroleum etherethyl ether eluted the methylthiobenzenes, 200 mL 50% PE-EE eluted the sulfones, and 200 mL EE eluted the sulfoxides. Recoveries determined by electron capture (ECD) gas chromatography (GC) were 75-101% for the methylthiobenzenes and their sulfones and 63-93% for the sulfoxides. Co-extracted materials in the Florisil eluates that interfered with the ECD/GC quantitation were removed by partitioning the sulfoxides and sulfones into sulfuric acid and by thin layer chromatography on silica gel, using methylene chloride-hexane (50 + 50) as the developing solvent. Seven fish samples containing residues of chlorinated benzenes or polychlorinated biphenyls (PCBs) were examined for chlorinated methylthiobenzenes, methylthio-PCBs, and their oxidation products by matching GC retention times obtained with the EC detector and a flame photometric detector operated in the sulfur mode. These analytes were not found in the fish samples above a detection level equivalent to 0.02 ppm 2,4,5-trichloromethylthiobenzene.     

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.     

Colorimetric determination of boric acid in prawns, shrimp, and salted jelly fish by chelate extraction with 2-ethyl-1,3-hexanediol.

Borate was directly chelate-extracted from foods with 5% 2-ethyl-1,3-hexanediol (EHD) in n-hexane-n-butyl acetate mixture (8 + 2), from which borate was selectively transferred into 1% NaOH, since EHD-chelated boron did not react with curcumin to develop color. Finally, an aliquot of the alkaline solution was acidified with HCl and reacted with curcumin in a rotary evaporator. Color development was increased by heating for 8 min at 80 degrees C under reduced pressure of 16 mm Hg. Frozen shrimp and prawns (peeled and with shells) and salted jelly fish were analyzed by the proposed method. Results were compared with the contemporary official method of Japan based on curcumin reaction on an incinerated sample. Over 90% of the boric acid was recovered by the proposed method when samples were fortified with 20 ppm boric acid. Recoveries were superior to those of the official method especially for shrimp and prawns with shells and salted jelly fish. Detection limit of boric acid is 1 ppm. Moreover, the method requires only about 1 hr for analysis of one sample, making it suitable for routine analysis.     

Cholesterol content in meat of some poultry and fish species as influenced by live weight and total lipid content

Total cholesterol content in 24 fillets (F) of males and females of common carp, 35 samples of male chicken breast meat (BM) and thigh meat (TM), and 48 samples of male turkey BM and TM, respectively, was determined by high-performance liquid chromatography after total lipid (TL) extraction using n-hexane/2-propanol mixture. Cholesterol content in male carp fillets (77.6 mg/100 g) was higher (P < 0.001) in comparison with females (69.4 mg/100 g). Irrespective of the sex differences, cholesterol content increased (P < 0.01) in the sequence chicken BM (53.0 mg/100 g) = turkey BM (53.0) < turkey TM (61.5) < carp F (73.5) < chicken TM (82.9 mg/100 g). Cholesterol content in chicken TM decreased (P < 0.05) with increasing live weight reached at the age of 43 days, but did not change (P > 0.05) in other tested tissues. Cholesterol concentration in TL of all five tested tissues within three animal species decreased sharply (P < 0.001) with increasing TL content reached in a given tissue at the fixed age. It follows from the results of the study that a two hundred gram portion of carp F and chicken TM without skin represents 49 and 55% of the upper limit of daily cholesterol intake, respectively.     

Quantitative determination of beta-carotene stereoisomers in fresh, dried, and solar-dried mangoes (Mangifera indica L.)

A rapid method for quantitative determination of beta-carotene, including cis-isomers, in dried mango has been developed. Applicability of available methods to dried products was limited because of formation of artifacts caused by extraction and preparation. The analytical procedure was based on the extraction of carotenoids from dried mango mesocarp using a mixture of methanol and acetone/hexane, allowing the separation of disturbing fibers. No saponification was required. Furthermore, carotenoid determination by HPLC on a C30 stationary phase was achieved. This method was applied to determine beta-carotene and its stereoisomers in fresh, dried, and solar-dried mango slices of four cultivars. Drying resulted in a complete and partial degradation of xanthophylls and all-trans-beta-carotene, respectively. Isomerization was shown to depend on the drying process. Whereas conventionally dried mangoes were characterized by elevated amounts of 13-cis-beta-carotene, solar-dried mango slices contained additional amounts of the 9-cis-isomer. Calculation of vitamin A values was based on the real amount of the beta-carotene stereoisomers and ranged from 113 to 420 and from 425 to 1010 RE/100 g for fresh and dried mango slices, respectively.     

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。     

Determination of fluorene in fish, sediment, and plants

Methods and their applications are described for the determination of fluorene in fish, sediment, and plants. Sample extracts are enriched by using 2 or more of the following: gel permeation, silica gel, potassium silicate, sulfuric acid-impregnated silica gel, and activated carbon. Efficiency was improved by applying the adsorbents in combination or as tandem enrichment modules. Analyses by liquid chromatography (LC) with ultraviolet or fluorescence detection (LC/UV or LC/F) yielded limits of detection of 30, 3, and 30 ng/g and average recoveries of 80, 81, and 74% for fish, sediment, and plants, respectively.     

Comparison of the most odor-active compounds in fresh and dried hop cones (Humulus lupulus L. variety spalter select) based on GC-olfactometry and odor dilution techniques

Application of aroma extract dilution analysis on the volatiles obtained from dried cones of Spalter Select hops grown in the German hop-growing area of Hallertau revealed 23 odorants in the flavor dilution (FD) factor range of 16-4096, 20 of which could be identified. On the basis of high FD factors, trans-4, 5-epoxy-(E)-2-decenal, linalool, and myrcene were identified as the most potent odorants, followed by ethyl 2-methylpropanoate, methyl 2-methylbutanoate, (Z)-1,5-octadien-3-one, nonanal, (E,Z)-1,3, 5-undecatriene, 1,3(E),5(Z),9-undecatetraene, propyl 2-methylbutanoate, 4-ethenyl-2-methoxyphenol, and 1-octen-3-one. Ten of the high-impact hop aroma compounds had previously not been identified as hop constituents and, in particular, 1,3(E),5(Z), 9-undecatetraene has not yet been reported as a food odorant. In an extract obtained from fresh hops, in addition to the odorants found in dry hops, (Z)-3-hexenal was characterized as a further key odorant rendering an additional green aroma note to the fresh material.     

Determination of tri-n-butyltin and di-n-butyltin compounds in fish by gas chromatography with flame photometric detection

An analytical method is described for the simultaneous quantitative determination of tri-n-butyltin and di-n-butyltin compounds in fish. The sample was extracted with 0.5N HCl-methanol, and the methanol solution was extracted with hexane. The extract was purified by gel permeation chromatography and treated with Grignard reagent to yield the methyl derivatives, which were determined by gas chromatography with flame photometric detection operated in the tin mode (610 nm). Recoveries of tri-n-butyltin chloride (Bu3SnCl) and di-n-butyltin dichloride (Bu2SnCl2) spiked to fish at the levels of 0.2 and 1.0 ppm ranged from 80 to 105%. Detection limits were 0.02 micrograms/g for both compounds. Tri-n-butyltin compounds equivalent to Bu3SnCl levels of 0.07-2.0 ppm and di-n-butyltin compounds equivalent to Bu2SnCl2 levels of 0.02-0.11 ppm were found in reared yellowtails, and these values showed good agreement with the results from gas chromatographic-mass spectrometric analysis.     

Dietary exposure of Canadians to perfluorinated carboxylates and perfluorooctane sulfonate via consumption of meat, fish, fast foods, and food items prepared in their packaging

Human exposure to perfluorinated compounds is a worldwide phenomenon; however, routes of human exposure to these compounds have not been well-characterized. Fifty-four solid food composite samples collected as part of the Canadian Total Diet Study (TDS) were analyzed for perfluorocarboxylates and perfluorooctanesulfonate (PFOS) using a methanol extraction liquid chromatography tandem mass spectrometry method. Foods analyzed included fish and seafood, meat, poultry, frozen entrées, fast food, and microwave popcorn collected from 1992 to 2004 and prepared as for consumption. Nine composites contained detectable levels of perfluorinated compounds-four meat-containing, three fish and shellfish, one fast food, and one microwave popcorn. PFOS and perfluorooctanoate (PFOA) were detected the most frequently; concentrations ranged from 0.5 to 4.5 ng/g. The average dietary intake of total perfluorocarboxylates and PFOS for Canadians was estimated to be 250 ng/day, using results from the 2004 TDS composites. A comparison with intakes of perfluorocarboxylates and PFOS via other routes (air, water, dust, treated carpeting, and apparel) suggested that diet is an important source of these compounds. There was a substantial margin of exposure between the toxicological points of reference and the magnitude of dietary intake of perfluorinated compounds for Canadians >/= 12 years old.     

Natural variations of precursors in pig meat affect the yield of heterocyclic amines--effects of RN genotype, feeding regime, and sex

Pig meat shows natural variations in the concentrations of precursors of heterocyclic amines (HCAs), which may affect formation of HCAs in cooked pig meat. To study this, 26 pigs with an inherent genetic variation (carriers and noncarriers of the RN(-) allele) were subjected to different feeding regimes (conventional feed compared with feed composed according to organic standards). In addition, the effect of sex (castrated males or females) was considered when assessing chemical and technological meat quality parameters. Concentrations of precursors of HCAs, i.e., creatine, residual glycogen, dipeptides, and free amino acids, were analyzed in the raw meat, and the levels of some HCAs (4,8-DiMeIQx, MeIQx, PhIP, harman, and norharman) were then determined in fried meat patties prepared from these pigs. The RN genotype most affected technological meat quality parameters and the level of precursors of HCAs, especially the level of residual glycogen, where carriers of the RN(-) allele showed levels four times as high as those of noncarriers (75.3 +/- 2.6 compared with 17.2 +/- 2.4 micromol/g meat, least-squares means +/- SE). The increased level of residual glycogen resulted in about 50% lower amounts of total mutagenic HCAs in cooked meat compared with cooked meat from normal pigs. Fried meat from carriers of the RN(-) allele obtained darker crust color than meat from noncarriers. Feeding regime and sex did not significantly affect the chemical composition of the meat or the formation of HCAs.     

Formation of N-nitroso-N-methylurea in various samples of smoked/dried fish, fish sauce, seafoods, and ethnic fermented/pickled vegetables following incubation with nitrite under acidic conditions

In continuation of our previous studies on N-nitroso-N-methylurea (NMU) formation in cured meats following incubation with nitrite at gastric pH, we extended the investigation to other foods mentioned in the title of this paper. The main objective was to determine whether these foods have the potential to form NMU at pH's that can be found in the human stomach. This was done by nitrosating an aliquot (5 g for fish sauce, 10 g for the others) of each with 7.25 microM to 1.59 mM levels of sodium nitrite for 2 h at room temperature at pH 0.8--1.5 and measuring the amounts of NMU formed. Of the samples tested, fish sauce formed 2--712 ng of NMU, followed in decreasing order by herring (<0.3--688 ng); dried anchovy, shrimp, and other fishes (<0.3--134 ng); crab and lobster paté (<0.3--342 ng); sardines (6--59 ng); oysters and mussels (11--31 ng); dried squid (3--47 ng); kimchi (7--107 ng); and Japanese pickled radish (<0.3--72 ng). Incorporation of 200-2000 ppm of ascorbic acid in the fish sauce and other foods, prior to nitrosation, appreciably inhibited such NMU formation. Although previous researchers in China reported NMU formation in nitrosated samples of fish sauce, this is the first reported formation of NMU upon nitrosation of the other foods mentioned above, and the first reported inhibition of such formation by added ascorbic acid.     

Exposure assessment of prepubertal children to steroid endocrine disruptors. 2. Determination of steroid hormones in milk, egg, and meat samples

In the present study, the occurrence of the main sex steroid hormones in milk, egg, and meat was evaluated on the basis of a highly specific gas chromatography-tandem mass spectrometry measurement method. Globally, the results indicated that targeted estrogens and androgens occurred at similar levels (concentration levels in the 10-100 ng kg (-1) range) in the analyzed muscle and milk samples. The same compounds occurred at about 10-fold higher concentrations (i.e., in the 100-1000 ng kg (-1) range) in eggs and kidney samples. More precisely, egg and milk appeared as a non-negligible sources of estradiol (i.e., 2.2 +/- 0.8 and 3.1 +/- 2.0 ng day (-1), respectively), whereas testosterone exposure is caused by ingestion of meat and/or egg (i.e., 12.2 +/- 48.2 and 5.2 +/- 2.3 ng day (-1), respectively). The provided exposure data will be further exploited in the scope of a risk assessment study regarding endocrine disruption associated with these molecules.     

Composition and antioxidant activity of the essential oils of Xylopia aethiopica (Dun) A. Rich. (Annonaceae) leaves, stem bark, root bark, and fresh and dried fruits, growing in Ghana

The chemical composition of the essential oils obtained from the leaves, the barks of the stem and the root, as well as from the fresh and dried fruits of Xylopia aethiopica, growing in Ghana, was investigated by gas chromatography/mass spectrometry analyses. Kovats indices, mass spectra, and standard compounds were used to identify a total of 93 individual compounds. The monoterpene hydrocarbons formed the main portion in all studied samples. beta-Pinene was predominant in all cases, while trans-m-mentha-1(7),8-diene was the main compound in the essential oils of the leaves and the barks of roots and stems. Their potential antioxidant activity was also investigated and found to be significant in scavenging superoxide anion radical.