Pesticide residues in apples grown under a conventional and integrated pest management system

This paper describes method validation for determination of more than 40 pesticides in apples using a GC technique. Target compounds belonged to the organochlorine, organophosphorus, carbamates, pyrethroids, triazoles, dicarboximides and strobilurins groups, among others. Sample preparation consisted of acetone extraction and subsequent cleanup/concentration by SPE with a polymer-based sorbent. Single quadrupole GC–MS operating in SIM mode and electron impact ionization was used for identification and quantification of the pesticides. Average recoveries for analytes ranged between 70 and 110% at three fortification levels – 0.01, 0.1 and 0.2 mg kg^?1. Relative standard deviations were lower than 20% for all tested compounds. Calculated limits of detection and limits of quantification were below 0.01 mg kg^?1, which were sufficiently low compared to the maximum residue levels (MRLs) established by European legislation. The proposed method was applied for determination of pesticide residue in four selected apple varieties after harvesting. Whole and processed fruits (peel and peeled fruits) were analyzed from different treatment systems: two conventional, one based on integrated pest management (IPM) and two variants based on organic production (controls). Higher levels of pesticide residues were found in apple fruits under conventional conditions. Fenitrothion and chlorpyrifos residues were detected frequently in apple peel at concentrations up to 0.45 and 0.77 mg kg^?1, respectively. The levels found in the whole fruits of the same samples were much lower than in peel and below the respective MRLs (0.5 mg kg^?1 for both pesticides). Measurable residues of triadimenol only, up to 0.05 mg kg^?1, concentrated in the peel, were found in the apples from IPM.     

Headspace solid-phase microextraction for the evaluation of pesticide residue contents in cucumber and strawberry after washing treatment

The headspace solid-phase microextraction was developed to examine the organophosphorus (diazinon, malathion, chloropyrifos, quinalphos, profenofos) and organochlorine (chlorothalonil, α-endosulfan and β-endosulfan) pesticide residues in vegetable (cucumber) and fruit (strawberry) samples. The effects of washing by different solutions were evaluated for the reduction of organophosphorus and organochlorine pesticide residues contents. Gas chromatography with electron capture detection was used to analysis the investigated pesticides. The results showed that washing by a non-toxic solution can decrease the concentration of pesticide residues in the fruit and vegetable samples. The data further indicated that acetic acid was the most effective solution in removing the residues of the investigated pesticides from the fruit and vegetable samples when compared to sodium carbonate, sodium chloride and tap water. The amount of pesticides removed by solution washing is related to their water solubility and vapour pressure properties.     

Assessment of average exposure to organochlorine pesticides in southern Togo from water,maize (Zea mays) and cowpea (Vigna unguiculata)

Drinking water, cowpea and maize grains were sampled in some potentially exposed agro-ecological areas in Togo and analysed for their contamination by some common organochlorine pesticides. A total of 19 organochlorine pesticides were investigated in ten subsamples of maize, ten subsamples of cowpea and nine subsamples of drinking water. Analytical methods included solvent extraction of the pesticide residues and their subsequent quantification using gas chromatography-mass spectrometry (GC/MS). Estimated daily intakes (EDIs) of pesticides were also determined. Pesticides residues in drinking water (0.04–0.40 µg l^?1) were higher than the maximum residue limit (MRL) (0.03 µg l^?1) set by the World Health Organization (WHO). Dieldrin, endrin, heptachlor epoxide and endosulfan levels (13.16–98.79 µg kg^?1) in cowpea grains exceeded MRLs applied in France (10–50 µg kg^?1). Contaminants’ levels in maize grains (0.53–65.70 µg kg^?1) were below the MRLs (20–100 µg kg^?1) set by the Food and Agriculture Organization (FAO) and the WHO. EDIs of the tested pesticides ranged from 0.02% to 162.07% of the acceptable daily intakes (ADIs). Population exposure levels of dieldrin and heptachlor epoxide were higher than the FAO/WHO standards. A comprehensive national monitoring programme on organochlorine pesticides should be undertaken to include such other relevant sources like meat, fish, eggs and milk.     

Multi-residual Pesticide Monitoring in Commercial Chinese Herbal Medicines by Gas Chromatography–Triple Quadrupole Tandem Mass Spectrometry

To investigate multi-residual pesticide monitoring data in commercial Chinese herbal medicines on major markets, an easy, rapid, and selective gas chromatography with mass spectrometry (GC/MS/MS) method was established for simultaneously determining multi-residual pesticides including organochlorine, pyrethroid, carbamate, and organophosphorus pesticides in Chinese herbal medicines. The analytical method was based on an efficient extraction procedure and further cleanup steps by solid-phase extraction columns, yielding recovery rates in the range of 70.0–120.0 % for the majority of pesticides, except for hexachlorobenze, diazinon, β-HCH, δ-HCH, and omethoate, with precision values expressed as relative standard deviation of 0.1–14.7 %. The limits of detection of the established GC/MS/MS method for all investigated pesticides ranged from 0.01 to 3.6 μg kg^?1 and limits of quantification from 0.03 to 11.88 μg kg^?1. With this validated method, multi-residual pesticides of 132 Chinese herbal medicine samples were analyzed. The monitoring results indicated that pesticide residue was found in 74 samples. In total, 51 pesticides were found with detection rate ranging from 0.76 to 18.94 %. An 82.3 % of positive pesticides were found in less than 6 % of samples. Hexachlorobenzene was found in 25 samples, quintozene in 15 samples, and acephate and simazine in 13 samples. Concentrations of pesticide residue from monitoring data obtained ranged from 0.5 to 203.5 μg kg^?1. The simple and rapid method can be used as routine analysis method in multi-residual pesticide monitoring of Chinese herbal medicines.     

气相色谱法测定粮食中4种有机磷农药残留量的不确定度评定

目的 对气相色谱法测定粮食中乐果、杀螟硫磷、对硫磷、马拉硫磷农药残留量的方法进行不确定度评估。方法 依据JJF 1059.1-2012《测量不确定度评定与表示》和JJF 1135-2005《化学分析测量不确定度评定》中有关规定, 建立了用气相色谱法测定粮食中4种有机磷农药残留量的不确定度评估数学模型, 对测定中的不确定度来源进行分析和评估。结果 当粮食中乐果、杀螟硫磷、对硫磷、马拉硫磷的残留量分别为0.10、0.19、0.095、0.093 mg/kg时, 扩展不确定度分别为: 0.01、0.01、0.010、0.006 mg/kg, 4种有机磷残留量分别表示为: (0.10±0.01) mg/kg (k=2)、(0.19±0.02) (k=2)、(0.095±0.006) mg/kg (k=2)、(0.093±0.007) mg/kg (k=2)。 结论 实验过程中的不确定度主要来源于标准物质配制和样品稀释过程, 本评估方法可为气相色谱法检测多组分农药残留量的不确定度评估提供依据。     

Occurrence of the C-series fumonisins in maize from the former Transkei region of South Africa

Fumonisins are a group of structurally related mycotoxins produced mainly in maize by Fusarium verticillioides and F. proliferatum. The most abundant naturally occurring analogue is fumonisin B₁ (FB₁), with lesser amounts of fumonisin B₂ (FB₂) and fumonisin B₃ (FB₃) occurring. The C-series fumonisins (FCs) are structurally analogous to the B-series but lack the C-1 methyl group. Good and mouldy subsistence-grown maize samples were collected from the Centane and Bizana districts in the former Transkei region of South Africa. After extraction with methanol/water and clean-up on strong anion exchange solid phase extraction cartridges, FB₁, FB₂, FB₃, FC₁, FC₃ and FC₄ were determined by reversed-phase LC–MS/MS using positive ion electrospray ionisation. FB₁ levels in both good and mouldy maize from Centane (means (±SD) 2.75?±?2.24 and 23.4?±?12.5?mg?kg^?1, respectively) were higher than the corresponding levels in maize samples from Bizana (means 0.056?±?0.157 and 3.71?±?5.01?mg?kg^?1, respectively). Similarly, FC₁ levels in both good and mouldy maize from Centane (means 0.107?±?0.099 and 0.814?±?0.391?mg?kg^?1, respectively) were higher than in Bizana, where FC₁ was detected in only one (0.018?mg?kg^?1) of 19 good maize samples and occurred in mouldy maize with a mean of 0.102?±?0.135?mg?kg^?1. A significant correlation (r?=?0.982, p?<?0.01) was observed between FB₁ and FC₁ levels in all samples, with FC₁ levels at 3.3% of the corresponding FB₁ levels. FC₄ levels were similar to FC₁, whereas only low amounts of FC₃ were detected.     

Relative severity of fumonisin contamination of cereal crops in West Africa

Traditional and improved varieties of maize, pearl millet and sorghum were planted by small-scale farmers under the direction of the International Institute for Tropical Agriculture in two Nigerian agro-ecological zones: the Sudan Savanna and the Northern Guinea Savanna. Samples were collected for the determination of Fusarium infection and fumonisin (B₁, B₂ and B₃) contamination. A previous paper reported Aspergillus infection and aflatoxin contamination of these samples. Fusarium infection levels, measured by per cent kernels infected, were modest with mean levels for the above cereals of 16% ± 11% (SD), 12% ± 7% and 13% ± 16%, respectively. However, the Fusarium species recovered from maize were predominantly the fumonisin producers F. verticillioides and F. proliferatum, together making an infection rate of 15% ± 10%, whereas these species were present to a limited extent only in the other two cereals, 1% ± 1% for pearl millet and 2% ± 6% for sorghum. Fumonisin contamination was variable but reflected the diversity of Fusarium producers in these three cereals. Mean levels were 228 ± 579 µg kg^–1 (range < 5–2860 µg kg^–1) for maize, 18 ± 7 µg kg^–1 (range = 6–29 µg kg^–1) for pearl millet and 131 ± 270 µg kg^–1 (range < 5–1340 µg kg^–1) for sorghum. Together with previous results on aflatoxin, this study confirmed the co-occurrence of aflatoxins and fumonisins in maize as well as in the traditional African cereals, millet and sorghum (89% co-occurrence across all three cereals). The low fumonisin levels may be ascribed to the use of good agricultural practices. Of the Fusarium species present, those in maize consisted mainly of fumonisin producers, the opposite of what was observed in pearl millet and sorghum. It is concluded that replacement of maize by pearl millet and sorghum could improve food safety with regards to aflatoxin B and fumonisin B exposure.     

Determination of Chromium Species in Various Medicinal Plants Consumed in Hatay Region in Turkey

In this study, 22 species of medicinal plants (anise, centaury, chamomile, fennel, flax, green tea, indian hemp, laurel, licorice, linden, marestail, melissa, nettle, oat, red clover, riesenfenchel, rosehip, rosemary, sage, senna tea, yam, yarrow) were taken from five different local herbalists in Hatay. Chromium concentrations were determined by inductively coupled plasma-atomic emission spectroscopy. The highest chromium concentrations were detected in chamomile (4.21 ± 0.18 mg kg^?1), licorice (2.80 ± 0.12 mg kg^?1), melissa (2.71 ± 0.10 mg kg^?1), marestail (2.66 ± 0.10 mg kg^?1), and anise (1.98 ± 0.06 mg kg^?1). Minimal concentrations of chromium were found in riesenfenchel (0.33 ± 0.01 mg kg^?1), red clover (0.37 ± 0.01 mg kg^?1), centaury (0.43 ± 0.01 mg kg^?1), senna tea (0.49 ± 0.01 mg kg^?1), and linden (0.50 ± 0.01 mg kg^?1). Cr(III) and Cr(VI) concentrations in medicinal herbs were found in the range of 0.26–3.12 mg kg^?1 and 0.07–1.09 mg kg^?1, respectively.     

Dietary risk assessment of organophosphorus and dithiocarbamate pesticides in a total diet study at a Brazilian university restaurant

In this study ready-to-eat food samples were collected in the production line of the university restaurant of the University of Brasilia, Brazil, which serves non-vegetarian and vegetarian meals daily. Samples were analysed for the presence of ten organophosphorus insecticides (OPs) by GC/FPD, after extraction with ethyl acetate and anhydrous sodium sulfate (LOQ?=?0.002?mg?kg^–1), and for dithiocarbamate fungicides, as CS₂, using the spectrophotometric method (LOQ?=?0.05?mg?kg^?1). About 43% of the 175 samples analysed contained at least one OP compound at levels up to 1.83?mg?kg^?1. Methamidophos was the compound most detected (37.7%), present in most of the soup, soybean and salad samples. No OP residues were found in fruit juice, beans and bran rice samples. The cumulative acute intake of OPs was estimated using methamidophos and acephate as index compounds (IC). The total cumulative intake represented 9.1% and 47.7% of the methamidophos ARfD for the non-vegetarian and vegetarian diets, respectively. When acephate was used as IC, the total intakes represented 20.7% and 116% of the ARfD for the non-vegetarian and vegetarian diets, respectively. Dithiocarbamates were detected in 70% of the 177 samples analysed, at levels up to 0.51?mg?kg^?1 CS₂; all salad samples were positive and no residues were found in fruit juice. The chronic intake of dithiocarbamates represented 8.6 and 8.9% of the ADI (mancozeb) for the vegetarian and non vegetarian diets, respectively.     

Characterization and prediction by near-infrared reflectance of mineral composition of rocket (Eruca vesicaria subsp. sativa and Eruca vesicaria subsp. vesicaria)

BACKGROUND: Minerals are essential for human nutrition and must be obtained from our diet. Crucifer vegetables are a good source of these nutrients. Our objectives were to determine the genetic variability for mineral content and to evaluate the use of near‐infrared reflectance spectroscopy (NIRS) for prediction of ashes and minerals among and within the rocket species Eruca vesicaria subsp. sativa and vesicaria. The minerals studied were iron (Fe), copper (Cu), sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), manganese (Mn) and zinc (Zn). RESULTS: The maximum mean values obtained for all the accessions (mean ± SE) were 235.5 ± 1.5 mg ashes kg^?1, 273.3 ± 4.2 mg Fe kg^?1, 18.1 ± 0.4 mg Cu kg^?1, 2.8 ± 0.1 g Na kg^?1, 71.6 ± 1.0 g K kg^?1, 64.6 ± 1.2 g Ca kg^?1, 6.8 ± 0.1 g mg kg^?1, 101.6 ± 1.2 mg Mn kg^?1, and 67.1 ± 0.4 mg Zn kg^?1 of dry weight. CONCLUSION: The statistical analysis showed significant differences for all the minerals, except Ca, for each accession studied individually and for accessions grouped within countries. The results indicate that NIRS can be used as a rapid screening method for determining total mineral, Fe, Na, K, and Zn in rocket. Copyright © 2011 Society of Chemical Industry     

Analysing organochlorine pesticides in strawberry jams using GC-ECD,GC-MS/MS and QuEChERS sample preparation

This paper describes a comparison of adaptations of the QuEChERS (quick, easy, cheap, effective, rugged and safe) approach for the determination of 14 organochlorine pesticide (OCP) residues in strawberry jam by concurrent use of gas chromatography (GC) coupled to electron capture detector (ECD) and GC tandem mass spectrometry (GC-MS/MS). Three versions were tested based on the original QuEChERS method. The results were good (overall average of 89% recoveries with 15% RSD) using the ultrasonic bath at five spiked levels. Performance characteristics, such as accuracy, precision, linear range, limits of detection (LOD) and quantification (LOQ), were determined for each pesticide. LOD ranged from 0.8 to 8.9?µg?kg^?1; LOQ was in the range of 2.5–29.8?µg?kg^?1; and calibration curves were linear (r ^2?>?0.9970) in the whole range of the explored concentrations (5–100?µg?kg^?1). The LODs of these pesticides were much lower than the maximum residue levels (MRLs) allowed in Europe for strawberries. The method was successfully applied to the quantification of OCP in commercially available jams. The OCPs were detected lower than the LOD.     

Organochlorine pesticides in canned tuna and sardines on the Serbian market

The aim of this study was to determine the level of organochlorine (OC) pesticides in 57 samples of canned tuna and 31 samples of canned sardines in vegetable oil, collected from supermarkets in Serbia. OC pesticides α-HCH, β-HCH, δ-HCH, dichlorodiphenyltrichloroethane (DDT), DDE, DDD, dielderin, endosulfane I, endosulfane II, endosulan sulfate, endrin, endrin ketone, heptachlor, heptachlor epoxide, lindane, aldrin, metoxichlor, cis-chlordane and trans-chlordane were determined using a GS-MS method. The highest concentrations (µg kg^?1, arithmetic means) in canned tuna were for δ-HCH (60.6 ± 97.0) and p, p´-DDT (55.0 ± 25.1), while the corresponding values in canned sardines were for δ-HCH (90.7 ± 102.7) and endosulfane II (78.0 ± 145.9). Mean level for the sum of endosulfans was above the maximum limit in canned sardines (85.0 µg kg^?1). Also, dieldrin (39.7 µg kg^?1) was measured above the ML.     

Validation of the procedure for the determination of maduramicin in concentrates,premixes, and feeds by liquid chromatography

A single laboratory validation was carried out for the determination of maduramicin in concentrates, premixes, and feed. The method comprised sample extraction of maduramicin, derivatization with dansylhydrazine and liquid chromatography with ultraviolet light detection. The limit of detection (LOD) and limit of quantification (LOQ) were 0.4 and 1.0 mg kg^?1, respectively. The repeatability expressed as the average difference between the results of duplicate measurements was 5.9% at the concentration level of 1% (concentrate), 7.1% at the concentration level of 1 g kg^?1 (premix), and 11% with the feed containing maduramicin with the nominal concentration of 5 mg kg^?1 and feed spiked at the concentration level of 1 mg kg^?1. The relative standard deviations for the within-laboratory reproducibility (RSD_W) were 9.2%, 16%, 18%, and 17% at the concentration levels of 1%, 1 g kg^?1, 5 mg kg^?1, and 1 mg kg^?1, respectively. The measurement uncertainties were ±0.2%, ±0.3 g kg^?1, ±1.9 mg kg^?1, and ±0.3 mg kg^?1 at the same concentration levels, respectively.     

Development of lipid oxidation during manufacturing of horse mackerel surimi

When fatty fish are transformed into surimi, lipid oxidation takes place, decreasing the quality of the product. This study was aimed to identify the critical stages of the process in terms of the development of lipid oxidation. Horse mackerels were transformed into surimi on a pilot line and samples taken (hand‐skinned fillets = minced fillets, mince, washed and refined minces, paste, surimi and washing water). Most of the lipids were removed during the process and neutral lipids were lost in higher proportion than polar lipids. As a consequence, total lipids of surimi contained more polyunsaturated fatty acids (338 ± 19 g kg^?1) than total lipids of the minced fillets (220 ± 8 g kg^?1). Thiobarbituric acid reactive substances (TBARS) was higher in the minced fillets than in the mince because less subcutaneous fat and dark muscle were removed during hand‐mincing, indicating that the settings of the skinning–deboning machine can strongly influence the final quality of the product. Concentrations of lipid oxidation products increased significantly during the next stages of surimi processing. The increase was more pronounced for TBARS than hydroperoxides. Concentrations in hydroperoxides were similar in mince and washed mince (15.3 ± 2.8 and 16.6 ± 2.8 mmoles kg^?1 lipid) and increased in refined mince (29.6 ± 2.8 mmoles kg^?1 lipid). TBARS accounted for 2.7 ± 1.0 mg kg^?1 lipid in mince, 40.4 ± 2.3 mg kg^?1 lipid in washed mince and 237 ± 7 mg kg^?1 lipid in refined mince. Hydroperoxides and TBARS were found in appreciable amounts in washing water (76.9 ± 4.7 mmoles kg^?1 lipid and 479 ± 8 mg kg^?1 lipid respectively), when they decreased in surimi (27.3 ± 3.8 mmoles kg^?1 lipid and 44.2 ± 0.8 mg kg^?1 lipid respectively) compared with refined mince. This shows that the last dewatering stage is crucial to ensure surimi quality. Copyright © 2005 Society of Chemical Industry     

Optimization of the QuEChERS Method for Determination of Pesticide Residues in Chicken Liver Samples by Gas Chromatography-Mass Spectrometry

The goal of this research was to evaluate the application of Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method for the determination of organochlorine, organophosphate, and carbamate pesticides in fatty animal matrices such as liver of chicken obtained from National Research Institute of Animal Production in Balice (Poland). Pesticides extraction effectiveness was evaluated at two different spiking levels (0.010 and 0.020 mg kg^?1) and efficiency of the dispersive solid-phase extraction (d-SPE) clean-up step was evaluated by comparison adding different d-SPE sorbent combinations (PSA?+?GCB, PSA?+?C₁₈, PSA?+?SAX, and PSA?+?NH₂). The analysis of pesticide residues was performed by gas chromatography ion trap mass spectrometry (GC/IT-MS). The linear relation was observed from 0 to 400 ng mL^?1 and the determination coefficient R ²?>?0.997 in all instances for all target analytes. Better recoveries were obtained in samples at 0.020 mg kg^?1 spiking level. The recoveries were in the range 70–120 %, with relative standard deviation (RSD) values lower than 15 % at 0.020 mg kg^?1 spiking level for most pesticides. Similar recovery ratios were obtained with the four different combinations of sorbents tested in the clean-up step, with better precision when the (PSA?+?SAX) combination was tested. Limits of detection (LODs) ranged from 0.001 to 0.005 mg kg^?1 and limits of quantification (LOQs) ranged from 0.003 to 0.015 mg kg^?1. The proposed method was successfully applied analyzing pesticide residues in real chicken liver samples; detectable pesticide residues were observed, but in all of the cases, the contamination level was lower than the default maximum residue levels (MRLs) set by European Union (EU), Regulation (EC) N 396/2005.     

Evaluation of table olive by‐product as a source of natural antioxidants

The main by‐product from the table olive canning industry is the stone with some residual olive flesh. The purpose of this study was to evaluate the composition – phenolic compounds (hydroxytyrosol, tyrosol and oleuropein) and tocopherol – and the antioxidant activity in different fractions (flesh, stone and seed) from the table olive by‐product and the whole by‐product. The highest amounts of phenolic compounds (1710.0 ± 33.8 mg kg^?1) as well as the highest antioxidant activity (8226.9 ± 9.9 hydroxytyrosol equivalents mg kg^?1) were obtained in the seed. The highest amounts of hydroxytyrosol (854.8 ± 66.0 mg kg^?1) and tyrosol (423.6 ± 56.9 mg kg^?1) were found in the whole by‐product from the pepper stuffed olives, while the stone without seed had the maximum oleuropein content (750.2 ± 85.3 mg kg^?1). α‐Tocopherol values were between 79.8 ± 20.8 mg kg^?1 in the seed of the olive stone and 6.2 ± 1.2 mg kg^?1 in the whole by‐product from the anchovy‐stuffed olives. In light of the results obtained, it would seem possible to use table olive by‐product as a source of natural antioxidants in foods, cosmetics or pharmaceutical products, thus contributing to diminishing the environmental impact of table olive by‐product and to its revalorisation.     

Survey of organophosphorus pesticide residues in virgin olive oils produced in Chile

Dimethoate, diazinon, parathion methyl, pirimiphos methyl, malathion, fenthion, chlorpyriphos, methidathion and azinphos methyl were determined in 71 olive oil samples produced in Chile from different varieties of olives (arbequina, frantoio, picual, lechino and blend) at three different harvest periods (2007, 2008 and 2009). The target pesticides were determined using a validated analytical method based on microwave-assisted liquid–liquid and solid-phase extraction with subsequent GC–FPD detection and GC–MS/MS for confirmation purposes. In 79% of the samples, five of the nine pesticides tested were detected with a frequency of one pesticide per sample. The highest detection rates were observed for the residues of chlorpyriphos and diazinon. The average concentration of chlorpyriphos, diazinon, azinphos methyl and methidathion were 0.084, 0.057, 0.024 and 0.010 µg g^?1, respectively. Higher contents of organophosphorus pesticides (OPPs) were found in regions where intensive agriculture is practiced. However, the levels of OPPs were reassuringly low and indicate that olive oil produced and exported from Chile does not currently represent any risk for consumers.     

Determination of pesticides and their metabolites in processed cereal samples

Fifteen pesticides including some of their metabolites (disulfoton sulfoxide, ethoprophos, cadusafos, dimethoate, terbufos, disulfoton, chlorpyrifos-methyl, malaoxon, fenitrothion, pirimiphos-methyl, malathion, chlorpyrifos, terbufos sulfone, disulfoton sulfone and fensulfothion) were analysed in milled toasted wheat and maize as well as in wheat flour and baby cereals. The QuEChERS (quick, easy, cheap, effective, rugged and safe) methodology was used and its dispersive solid-phase extraction procedure was optimised by means of an experimental design with the aim of reducing the amount of co-extracted lipids and obtaining a clean extract. Gas chromatography with nitrogen phosphorus detection were used as the separation and detection techniques, respectively. The method was validated in terms of selectivity, recoveries, calibration, precision and accuracy as well as matrix effects. Limits of detection were between 0.07 and 34.8?µg?kg^?1 with recoveries in the range of 71–110% (relative standard deviations were below 9%). A total of 40 samples of different origin were analysed. Residues of pirimiphos-methyl were found in six of the samples at concentrations in the range 0.08–0.47?mg?kg^?1, which were below the MRLs established for this pesticide in cereal grains. Tandem mass spectrometry confirmation was also carried out in order to identify unequivocally the presence of this pesticide.     

Determination of volatile compounds of precooked prawn (Penaeus vannamei) and cultured gilthead sea bream (Sparus aurata) stored in ice as possible spoilage markers using solid phase microextraction and gas chromatography/mass spectrometry

BACKGROUND: Solid phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) have been reported as useful techniques for analysing volatile compounds to monitor fish freshness. In this study, SPME/GC/MS was applied to cultured gilthead sea bream and precooked prawn stored in ice for 6 days in order to find possible markers of spoilage. Total volatile basic nitrogen (TVB‐N) was also determined as a common index of spoilage. RESULTS: The TVB‐N value at the end of the storage period for cultured gilthead sea bream (302.40 ± 8.50 mg kg^?1) was within the range of acceptability for edible fish (300–400 mg kg^?1) but could be considered at the beginning of spoilage. For precooked prawn the TVB‐N value at day 6 (863.04 ± 7.84 mg kg^?1) was not acceptable for human consumption. SPME/GC/MS identified 30 compounds in cultured gilthead sea bream and 49 compounds in precooked prawn. In particular, 3‐methyl‐1‐butanol, 2‐methylbutanal, 3‐methylbutanal and 3‐hydroxy‐2‐butanone increased during refrigerated storage both in the two species investigated here and in other species reported elsewhere and could be considered as markers of spoilage. CONCLUSION: This study confirmed that SPME/GC/MS can be considered an efficient method suitable for analysing the volatile compounds of both raw fish and fishery products in order to monitor loss of freshness. Copyright © 2008 Society of Chemical Industry     

Household dietary exposure to aflatoxins from maize and maize products in Kenya

Aflatoxicosis has repeatedly affected Kenyans, particularly in the eastern region, due to consumption of contaminated maize. However, save for the cases of acute toxicity, the levels of sub-lethal exposure have not been adequately assessed. It is believed that this type of exposure does exist even during the seasons when acute toxicity does not occur. This study, therefore, was designed to assess the exposure of households to aflatoxins through consumption of maize and maize products. Twenty samples each of maize kernels, muthokoi and maize meal were randomly sampled from households in Kibwezi District of Makueni County in Eastern Kenya and analysed for aflatoxin contamination. The samples were quantitatively analysed for aflatoxin contamination using HPLC. The uncertainty and variability in dietary exposure was quantitatively modelled in Ms Excel using Monte Carlo simulation in @Risk software. Aflatoxins were found in 45% of maize kernels at between 18 and 480 μg kg^–1, 20% of muthokoi at between 12 and 123 μg kg^–1, and 35% of maize meal at between 6 and 30 μg kg^–1. The mean dietary exposure to aflatoxin in maize kernels was 292 ± 1567 ng kg^?1 body weight day^?1, while the mean dietary exposure to aflatoxin in maize meal and muthokoi were 59 ± 62 and 27 ± 154 ng kg^?1 body weight day^?1 respectively. The results showed that the amount and frequency of consumption of the three foods is the more important contributing factor than the mean aflatoxin concentration levels, to the risk of dietary exposure to aflatoxins.