Detection of Adulterated Vegetable Oils Containing Waste Cooking Oils Based on the Contents and Ratios of Cholesterol, ß-Sitosterol, and Campesterol by Gas Chromatography/Mass Spectrometry.

A simple and accurate authentication method for the detection of adulterated vegetable oils that contain waste cooking oil (WCO) was developed. This method is based on the determination of cholesterol, ß-sitosterol, and campesterol in vegetable oils and WCO by GC/MS without any derivatization. A total of 148 samples involving 12 types of vegetable oil and WCO were analyzed. According to the results, the contents and ratios of cholesterol, ß-sitosterol, and campesterol were found to be criteria for detecting vegetable oils adulterated with WCO. This method could accurately detect adulterated vegetable oils containing 5% refined WCO. The developed method has been successfully applied to multilaboratory analysis of 81 oil samples. Seventy-five samples were analyzed correctly, and only six adulterated samples could not be detected. This method could not yet be used for detection of vegetable oils adulterated with WCO that are used for frying non-animal foods. It provides a quick method for detecting adulterated edible vegetable oils containing WCO.

[Identification of irradiated abalone by ESR spectroscopy].

OBJECTIVE: To establish an analytical method for the detection and identification of irradiated abalone by electron spin resonance spectroscopy. METHODS: Electron spin resonance (ESR) was used to study the spectral characteristics of abalone and the characteristic peak for quantitation. RESULTS: There were obvious different ESR spectra between unirradiated and irradiated abalone. The g factor for unirradiated abalone was 2.0055-2.0060, the g1 and g2 factor for irradiated abalone were (2.0027 +/- 0.0001) and (1.9994 +/- 0.0001), respectively. The ESR signal intensity of characteristic peak was positively correlated with absorbed dose in the range of 0.5 - 10 kGy, left peak was the characteristic peak for quantitation and the detection limit was < or = 0.5 kGy. It was difficult to quantitate when the absorbed dose was over 10 kGy. ESR characteristic peak and g factor were able to qualitatively determine the irradiation of abalone. CONCLUSION: ESR spectroscopy is an effective method to determine whether the abalone being irradiated or not.

[Rapid determination of 40 pesticide residues in fruits using gas chromatography-mass spectrometry coupled with analyte protectants to compensate for matrix effects].

A gas chromatography-mass spectrometry (GC-MS) method was developed for the determination of 40 pesticides in fruits. The effects of adding analyte protectants were evaluated for compensating matrix effects and the impacts on the quantitative results. A new combination of analyte protectants - Polyethylene Glycol 400 (PEG 400) and olive oil combination, which can be dissolved in acetone, was used for the quantitative analysis. The pesticides were extracted from fruit samples with acetonitrile and the extracts were cleaned up using micro-solid phase extraction. A GC-MS method in selective ion monitoring (SIM) mode coupled with large volume injection was finally developed. Using the newly developed analyte protectant combination of PEG 400 and olive oil, a good linearity was obtained in the range of 1 - 200 microg/L with coefficients better than 0.99, and the detection limits were between 0.1 - 3.0 microg/L. The mean recoveries of the pesticides were 75% - 119% with the relative standard deviation values less than 16.6% except for dimethoate. The performance of the analyte protectants was compared with matrix-matched standards calibration curves in terms of quantitative accuracy. The results showed that the method of adding analyte protectants can replace the matrix-matched standard calibration, and can also reduce the sample pretreatment. When the devel- oped method was used for the analysis of apple, peache, orange, banana, grape and other fruit samples, a good matrix compensation effect was achieved, and thus effectively reduced the bad effects of the water-soluble agents to the gas chromatographic column.

The behavior of tetracyclines and their degradation products during swine manure composting.

The purposes of this study were to investigate the behavior of three tetracyclines including chlortetracycline (CTC), oxytetracycline (OTC) and tetracycline (TC) and their degradation products in a pilot scale swine manure composting, and also to study the degradation kinetics of CTC, OTC and TC. During the pilot scale composting, CTC, OTC and TC were degraded by 74%, 92% and 70%, respectively. Several degradation products were found like 4-epitetracycline (ETC), 4-epioxytetracycline (EOTC), 4-epichlortetracycline (ECTC), demeclocycline (DMCTC) and anhydrotetracycline (ATC). Both the simple and the adjusted first-order kinetic models successfully fit the degradation process of CTC, OTC and TC during the composting, but the adjusted first-order kinetic model fit much better with the calculated half-lives of 8.2, 1.1 and 10.0 days, respectively.

[Determination of dioxin like polychlorinated biphenyl residues in milk using isotope dilution gas chromatography-ion trap tandem mass spectrometry].

A method for the determination of dioxin like polychlorinated biphenyl (DL-PCB) residues in milk has been developed using high resolution gas chromatography coupled with ion trap mass spectrometry (GC-MS/MS-IT). Analytical procedure consisted of accelerate solvent extraction (ASE), lipid removal with acidic silica and clean-up using anthropogenic isolation column packed with multilayer silica. The analytes were separated on a DB-5 capillary column, detected with multiple reaction monitor mode (MRM) and quantified using internal standard calibration curve of isotope dilution technique. The correlation coefficients of calibration standard solution were above 0. 999 9 for all the DL-PCBs. The recoveries and relative standard deviations of labeled compound solution were in the oranges from 39% to 129% and from 5% to 22%, respectively. The detection limits in the range from 3 to 11 pg/g (fat) were established for the 12 DL-PCBs.

[Rapid and simultaneous determination of thirteen organic phosphorous pesticide residues in spinach using gas chromatography-mass spectrometry coupled with stomach large volume injection and mini solid phase extraction].

A stomach large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) coupled with mini solid phase extraction (SPE) method for the rapid and simultaneous determination of 13 organic phosphorous pesticide residues in spinach samples is presented. The compounds were identified with their retention times and the abundance ratios of qualifier and target ions. Quantification was calculated based on the extraction of spiking standards in a blank sample. The limit of detection (LOD) was determined by the experimental value of the signal-to-noise ratio of 3:1, and the limit of quantification (LOQ) was defined at the experimental value of the signal-to-noise ratio of 10:1. The recoveries obtained ranged from 76.8% to 114.0% with the relative standard deviations between 1.5% and 17.6% except dimethoate. The LODs ranged from 0.5 to 25 microg/kg. This simple, rapid and reliable method has wide applications for the simultaneous determination of multiple pesticide residues in spinach and possibly other species.

Multiwalled carbon nanotubes as a solid-phase extraction adsorbent for the determination of three barbiturates in pork by ion trap gas chromatography-tandem mass spectrometry (GC/MS/MS) following microwave assisted derivatization.

A new method was developed for the rapid screening and confirmation analysis of barbital, amobarbital and phenobarbital residues in pork by gas chromatography-tandem mass spectrometry (GC/MS/MS) with ion trap MSD. The residual barbiturates in pork were extracted by ultrasonic extraction, cleaned up on a multiwalled carbon nanotubes (MWCNTs) packed solid phase extraction (SPE) cartridge and applied acetone-ethyl acetate (3:7, v/v) mixture as eluting solvent and derivatized with CH3I under microwave irradiation. The methylated barbiturates were separated on a TR-5MS capillary column and detected with an ion trap mass detector. Electron impact ion source (EI) operating MS/MS mode was adopted for identification and external standard method was employed for quantification. One precursor ion m/z 169 was selected for analysis of barbital and amobarbital and m/z 232 was selected for phenobarbital. The product ions were obtained under 1.0 V excitation voltage. Good linearities (linear coefficient R > 0.99) were obtained at the range of 0.5-50 microg kg(-1). Limit of detection (LOD) of barbital was 0.2 microg kg(-1) and that of amobarbital and phenobarbital were both 0.1 microg kg(-1) (S/N > or = 3). Limit of quantification (LOQ) was 0.5 microg kg(-1) for three barbiturates (S/N > or = 10). Satisfying recoveries ranging from 75% to 96% of the three barbiturates spiked in pork were obtained, with relative standard deviations (R.S.D.) in the range of 2.1-7.8%.

[Determination of polychlorinated dibenzo-p-dioxins and dibenzo-furans in sediment by accelerated solvent extraction, fluid management systems and high resolution gas chromatography/high resolution mass spectrometry].

A rapid, sensitive and accurate method has been developed for the determination of seventeen 2, 3, 7, 8-substituted congeners of polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in sediment using isotope dilution high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). Dibenzo-p-dioxins and dibenzo-furans were extracted from samples by accelerated solvent extraction (ASE) and then purified by fluid management systems (FMS) with silica column, alumina column and carbon column. Confirmation and quantitative analysis at pg/g level of PCDD/Fs were performed by HRGC/HRMS using voltage selective ion record (VSIR) mode. Recoveries of fifteen isotopically labeled compound solutions (LCS) and the precision and recovery standards (PAR) were found to be in the range of 49.8% -85.3% and 93.2% - 113.8%, respectively. The detection limits of the method for both 2, 3, 7, 8-tetrachloro-dibenzo-furan (TCDF) and 2, 3, 7, 8-tetrachloro-dibenzo-p-dioxin (TCDD) were determined to be 0.1 pg/g. This method not only meets the requirements of international standards, but also shortens analysis time from 2 weeks to 2 days.

Simultaneous determination of three residual barbiturates in pork using accelerated solvent extraction and gas chromatography-mass spectrometry.

A new method was developed for the rapid extraction and unequivocal determination of barbital, amobarbital and phenobarbital residues in pork. The isolation of the analytes from pork samples was accomplished by utilizing an accelerated solvent extractor ASE 300. The procedure was automatically carried out in series for fat removing and extraction, respectively with n-hexane and acetonitrile pressurized constantly at 10.3 MPa for 30 min. After evaporation, the extracts were cleaned up on a C(18) solid phase extraction (SPE) cartridge and the barbiturates were eluted with hexane-ethyl acetate (7:3), evaporated on a rotary evaporator and derivatized with CH(3)I. The methylated barbiturates were separated on a HP-5MS capillary column and detected with a mass detector. Electron impact ion source (EI) operating in time program-selected ion monitoring mode (SIM) was used for identification and external standard method was used for quantification. Good linearity was obtained in the range from 0.5 microg/kg to 25 microg/kg. Average recoveries of the three barbiturates spiked in pork ranged from 84.0% to 103.0%, with relative standard deviations from 1.6% to 12%. The limit of detection (LOD) was 0.5 microg/kg for the three barbiturates (S/N>or=3). The quantification limit (LOQ) was 1 microg/kg for the three barbiturates (S/N>or=10).

[Simultaneous determination of 25 persistent organic pollutants in rice by gas chromatography-mass spectrometry with selected ion monitoring mode].

A multi-residue analytical method for the simultaneous determination of persistent organic pollutants (POPs) in rice samples was developed. POPs were extracted from rice with ethyl acetate/n-hexane (80:20, v/v) by sonication, and determined by gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode. A fused silica capillary column DB-35MS (30 m x 0.25 mm i.d. x 0.25 microm) was employed. Operating conditions were as follows: injector port temperature, 300 degrees C; column temperature, programming; carrier gas, helium; flow rate, 1.0 mL/min; sample size, 1 microL with splitless injection. The mass spectrometric detector (MSD) was operated in electron impact ionization mode with an ionizing energy of 70 eV. Analysis was performed with selected ion monitoring (SIM) using one target and one or two qualifier ion. POPs were confirmed by their retention times, their qualifier and target ions, and their qualifier/target abundance ratios. Recovery studies were performed at 0.05, 0.1, and 0.5 mg/L spiked levels of each POPs, and the recoveries obtained ranged from 81.99% to 100.60% with relative standard deviations between 2.37% and 18.48%. The detection limits of the method ranged from 0.1 to 5 ng/g for the different POPs except endrin, trans-chlordane and cis-chlordane. The results show that the method developed is sensitive and reliable.

[Determination of acrylamide in fried starchy foods by gas chromatography-mass spectrometry].

A method was developed for the determination of acrylamide in fried starchy foods using isotope dilution gas chromatograpy-selected mass spectrometry (GC-MS). The acrylamide was extracted from samples by water, then centrifuged and cleaned up by a column of graphitized carbon black. Acrylamide was derivatized through bromination at low pH and low temperature and determined by GC-MS. With the aid of the 13C-substituted acrylamide internal standard, the mass spectrum in GC-MS was interpreted, and the content of acrylamide was measured. The limit of quantitative detection (S/N > 10) was 5 microg/kg and the recovery was in the range of 90%-105% and relative standard deviation is 6.3%. The levels of acrylamide in some fried foodstuffs such as French fries was surveyed using the method. French fries were found to contain 278-4518 microg/kg acrylamide. It means that the content of acrylamide in French fries is 10,000 times higher than the drinking water guideline of World Health Organization for acrylamide.

[Simultaneous determination of the residues of pyrethriods, organochlorines and polychlorinated biphenyl congeners in unpolished rice by gas chromatography with gel permeation chromatography purification].

The separation behaviors of organochlorine pesticides, pyrethriod pesticides, polychlorinated biphenyl congeners (PCBs) and unpolished rice matrixes were systematically investigated with gel permeation chromatography (GPC) because of its outstanding capability in removing lipid and pigments from sample solutions. A separation method was proposed for the quantitative determination of 35 pesticides and PCBs in unpolished rice by GPC and gas chromatography simultaneously. Samples were extracted with ethyl acetate, purified by GPC, and then determined by gas chromatography and electron capture detection (GC-ECD). With external standard method, the recoveries of 3 standard addition levels of low, medium, high concentrations were 70.1% - 107.4%, 70.3% - 109.9%, 70.8% - 109.5%, respectively with relative standard deviations from 2.3% to 13.3%. The detection limits were 0.07 microg/kg for organochlorines and PCBs, and 0.44 microg/kg for pyrethriods.

Regional distribution of organochlorinated pesticides in pine needles and its indication for socioeconomic development.

The regional distribution of 10 potentially harmful organochlorinated pesticides (OCPs) was investigated in pine needles from 18 sites in six Chinese regions. The OCPs concentrations in six regions were as follows: sigmaHCH (sigmaHCH=alpha-+beta-+gamma-+delta-HCH), 4.7-51.5 ng/g; sigmaDDT (p,p'-DDT+p,p'-DDE+p,p'-DDD), 0.9-30.9 ng/g; hexachlorobenzene (HCB), 1.1-5.3 ng/g; sigmachlordane (cis-chlordane+trans-chlordane), no detected-4.3 ng/g, on dry weight basis. Samples from southeast Chinese area contained the highest concentrations of sigmaHCH, sigmaDDT and sigmachlordane, while the contamination levels of most OCPs in southwest Chinese area were the lowest. The ratios of alpha/gamma-HCH (ranged from 1.7 to 5) were observed to be noticeable increase from north to south China, and the ratio of 1.7 revealed the presence of the recent use of lindane in north Chinese area. The significant decrease of the sum concentrations of alpha-+gamma-HCH from mid-1980s to the present and the strong correlation between alpha-, beta-, gamma-, delta-HCH (r=0.87-0.98, n=18, p<0.05) indicated the main usage of the technical HCH in history in China. The p,p'-DDE/p,p'-DDT ratios of <1 revealed the new input of p,p'-DDT in south, southeast and southwest Chinese areas, which could be partly contributed to the new use of impure dicofol. Economic development will leave its mark in the environment, however, its impact on the input and distribution of OCPs on a regional scale is unknown. We attempted to use the socioeconomic index (gross domestic product (GDP) per capita) to explain the distribution and input of OCPs and found that HCB and sigmaDDT seemed to be linked to the economic development, while no relationship of HCH was observed. DDE% of sigmaDDT also showed a negative correlation with the GDP per capita.

2001 survey of organochlorine pesticides in retail milk from Beijing, P R China.

A monitoring study was conducted in 2001 to determine the organochlorine pesticides and their metabolite residues in milk taken from supermarkets in Beijing, P. R. China. The average concentrations of total HCH and DDT were 0.038 and 0.046 mg x kg(-1), respectively, expressed on a fat basis. The aldrin residue was detected in nine milk samples, with a mean concentration of 0.035 mg x kg(-1). Heptachlor and its epoxides were not found in any milk samples. Of 72 milk samples analysed, three from South China contained the higher levels of DDT and HCH residues that exceeded the FAO/WHO accepted tolerance level. Although organochlorine pesticides such as DDT and HCH have been banned in China since 1983, the residues of such compounds still exist in the environment and cause food contamination, a fact likely attributed to the short prohibition period and illegal use for agricultural purposes at present.

Levels of extractable organohalogens in pine needles in China.

Pine needles can accumulate organohalogens from the ambient air, which are, hence, able to serve as a biomonitor to evaluate the levels of organochlorinated contaminants in the atmospheric environment. Extractable organochlorine (EOCl), the most abundant of the extractable organohalogens (EOX) in environmental samples, has received much attention as a parameter for evaluation of total contamination levels of organochlorinated compounds (OCs). However, few data concerning EOCl in vegetation are available. In this study, we selected pine needles from 17 different areas in China as a sampling matrix to reflectthe regional distribution of OCs. EOX (EOX = EOCl + EOBr + EOI) were measured by instrument neutron activation analysis for their concentrations and distribution in pine needles. The concentrations of EOX were on the order of EOCl >> EOBr > EOI. About 5-38% of EOCl remained as sulfuric acid-resistant organochlorine (EPOCl). The relatively high concentrations of EPOCl in pine needles from remote areas suggested that EPOCl mainly originated from long-range atmospheric transport and contaminated soil. The relative proportions of the known organochlorines (such as HCHs, DDTs, aldrin, heptachlor, and chlordanes) to total EOCl and EPOCl were 0.3-5.2% and 1.4-19.8%, respectively, which implied that a major portion of the EPOCl measured in pine needles was unknown. The EPOX accumulation rates were preliminarily estimated under the natural condition, which suggested that the "young" needle accumulated EPOX more quickly than the "old" and more than 94% of EPOX was accumulated at the first year of pine needles.

Some polycyclic aromatic hydrocarbons in vegetables from northern China.

Nine important vegetables were collected from northern Chinese wholesale markets and analyzed for polycyclic aromatic hydrocarbon (PAH) contents. Anthracene, flupranthene, benzo(a)anthracene and benzo(a)pyrene were determined. The contents of the four PAH congeners were at the same level with the mean concentrations 6.46, 4.05, 3.33, 4.51 microg kg(-1) for fresh weight for anthracene, flupranthene, benzo(a)anthracene and benzo(a)pyrene, respectively. However, leafy and stem vegetables had higher PAH content than root and fruit vegetables. Peels of the root and fruit vegetables had higher PAH concentrations than their cores. Human exposure to PAHs by consumption of these vegetables is estimated, by using typical northern Chinese intake rates, although the study was not designed to be statistically representative for the China as a whole.

Nitrate and nitrite in vegetables from north China: content and intake.

The contents of nitrate and nitrite in potato, cabbage, Chinese cabbage, scallion (shallot), celery, cucumber, tomato, eggplant and wax gourd taken from the north China market from 1998 to 1999 were determined. These vegetables provide the major contribution to the nitrate intake from the diet. The highest content of nitrate was found in celery followed by Chinese cabbage, cabbage, scallion, wax gourd and eggplant. For all the products, a great variation in the content of nitrate was found. Generally, the nitrite content was low. The average intake of nitrate and nitrite from these vegetables was estimated as approximately 422.8 and 0.68 mg day(-1), respectively.