Contamination of Italian citrus essential oils: presence of chloroparaffin

In this study, the contamination by chloroparaffin of Sicilian and Calabrian citrus essential oils, produced in the crop years 1994-1996, was investigated. The analyses were carried out on 102 lemon oils, 98 orange oils, and 96 mandarin oils, using a dual-channel GC-ECD. It was found that 53% of lemon oil, 33% of orange oil, and 38% of mandarin oil samples were contaminated. The mean contamination levels were 7.1 ppm (lemon), 2.5 ppm (orange), and 5.3 ppm (mandarin). The highest concentration of chloroparaffin found was 60 ppm in a lemon oil sample.     

Contamination of Italian citrus essential oils: presence of phthalate esters.

Contamination by phthalate esters of Sicilian and Calabrian citrus essential oils, produced in the crop years 1994-1996, was investigated using a GC-MS system with direct injection of the samples. A total of 35 lemon oils, 31 orange oils, and 21 mandarin oils were analyzed. Diisobutyl phthalate and/or bis(2-ethylhexyl) phthalate were found in almost all samples, while di-n-butyl phthalate was present in 8. Concentrations up to a maximum of 62 ppm were found for diisobutyl phthalate and up to a maximum of 29.9 ppm for bis(2-ethylhexyl) phthalate.     

Tyrosinase inhibitory activity of citrus essential oils

Thirteen kinds of citrus essential oils and their volatile flavor constituents were investigated for tyrosinase inhibitory activity. Eureka lemon, Lisbon lemon, Keraji, and Kiyookadaidai significantly inhibited the oxidation of L-dihydroxy phenylalanine (L-DOPA) by mushroom tyrosinase. Citral and myrcene among volatile flavor constituents of citrus essential oils exhibited tyrosinase inhibitory activities with Ki values of 0.318 and 2.38 mM, respectively. The inhibition kinetics analyzed by a Lineweaver-Burk plot indicated that citral is a noncompetitive inhibitor and myrcene is a competitive inhibitor. These results indicated that citral and myrcene are responsible for the tyrosinase inhibitory activity of citrus essential oils.     

Organochlorine pesticide residues in different Indian cereals, pulses, spices, vegetables, fruits, milk, butter, Deshi ghee, and edible oils.

A total of 244 samples of cereals (wheat flour, rice, and maize), pulses (arhar, moong, gram, lentil, and black gram), spices (turmeric, chili, coriander, and black pepper), vegetables (potato, onion, spinach, cabbage, brinjal, and tomato), fruits (mango, guava, apple, and grape), milk, butter, Deshi ghee, and edible oils (vegetable, mustard, groundnut, and sesame) collected from different cities of Northern Province (Utter Pradesh) were analyzed by gas liquid chromatography for the presence of organochlorine pesticide residues. Residues of hexachlorocyclohexane (HCH) and 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane (DDT) were detected in about 85% of the total samples of cereals, spices, milk, butter, Deshi ghee, and edible oils analyzed in the present study. However, the residue levels were either very small (less than 0.06 ppm) or not detected at all in pulses, vegetables, and fruits as compared with very high concentrations in wheat flour (4.42 and 0.12 ppm), butter (1.19 and 4.85 ppm), mustard oil (1.26 and 2.42 ppm), Deshi ghee (1.10 and 3.84 ppm), vegetable oil (1.02 and 0.59 ppm), groundnut oil (0.51 and 1.49 ppm), and chili (0.48 and 1.92 ppm). The levels of HCH and DDT residues detected in rice, maize, turmeric, corlander, black pepper, and all the vegetables and fruits were also lower than those found in wheat flour, oil, and fat samples analyzed in the present study. These findings suggest that a restricted and controlled use of such persistent pesticides may be useful for decreasing their contamination levels in different food items.     

Organochlorine pesticide residues in strawberries from integrated pest management and organic farming

A rapid, specific, and sensitive method based on the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) method and a cleanup using dispersive solid-phase extraction with MgSO(4), PSA, and C18 sorbents has been developed for the routine analysis of 14 pesticides in strawberries. The analyses were performed by three different analytical methodologies: gas chromatography (GC) with electron capture detection (ECD), mass spectrometry (MS), and tandem mass spectrometry (MS/MS). The recoveries for all the pesticides studied were from 46 to 128%, with relative standard deviation of <15% in the concentration range of 0.005-0.250 mg/kg. The limit of detection (LOD) for all compounds met maximum residue limits (MRL) accepted in Portugal for organochlorine pesticides (OCP). A survey study of strawberries produced in Portugal in the years 2009-2010 obtained from organic farming (OF) and integrated pest management (IPM) was developed. Lindane and β-endosulfan were detected above the MRL in OF and IPM. Other OCP (aldrin, o,p'-DDT and their metabolites, and methoxychlor) were found below the MRL. The OCP residues detected decreased from 2009 to 2010. The QuEChERS method was successfully applied to the analysis of strawberry samples.     

Production process contamination of citrus essential oils by plastic materials

Twelve samples of plastic materials employed in the industrial extraction of citrus essential oils were analyzed for the presence of phosphorated plasticizers, chloroparaffins, and phthalate esters. The samples tested were found to release these contaminants into the essential oils during the production process. Contamination tests were carried out using dichloromethane and uncontaminated samples of citrus essential oils as extractants. The extracts were analyzed by HRGC/FPD, ECD, and MS. Only one sample of plastic material was found to release triaryl phosphates, 5 samples released chloroparaffins, 6 released diisobutyl phthalate, and 8 released bis(2-ethylhexyl) phthalate. Significantly larger quantities of contaminants were released by new plastic parts than by used plastic parts.     

Comparison of fast and conventional GC analysis for citrus essential oils

This investigation concerns the application of fast GC in the analysis of essential oils. These are complex matrixes that usually undergo GC separation with conventional methods involving long columns, slow programmed temperature rates, and consequently, a high cost in terms of time. Fast GC techniques are based on the use of narrow bore capillary columns that allow the achievement of high-speed separations on complex samples while maintaining excellent resolution. This work saw the application of two methods on five different citrus essential oils and the comparison of all the results obtained.     

Survey of polychlorinated dibenzo-p-dioxins (PCDDs), Polychlorinated Dibenzo-p-furans (PCDFs), polychlorinated biphenyls (PCBs), and mineral components in Italian citrus cold-pressed essential oils

Investigation of PCDDs, PCDFs, PCBs, Al, As, Pb, Ba, Co, Cu, Cr, Fe, Mn, Cd, Ag, Sn, Zn, and Hg contents in 60 samples of cold-pressed essential oils produced in Calabria and Sicily in 2003-2005 was carried out. PCDDs, PCDFs, and PCBs were analyzed by HRGC-HRMS techniques using U.S. EPA 1613/94 and U.S. EPA 1668/A (1999) analytical methods. Mineral components were determined through GFAAS techniques; Hg content was determined by FI-M/H-AAS. The results of this study showed that essential oil contamination was due to a widespread pollution, typical background of rural areas, with relatively higher concentrations of PCDDs compared to PCDFs and little presence of PeCDF. Congeners OCDD, HpCDF, and OCDF were found at high concentrations. Regarding mineral components, mean values of Cr, Fe, and Ni were in agreement with data reported in the literature. Concentrations of As and Pb were below the maximum limits accepted by the current legislation. Finally, none of the samples analyzed were contaminated with Hg.     

Fast HPLC for the analysis of oxygen heterocyclic compounds of citrus essential oils.

A fast HPLC method for the determination of the oxygen heterocyclic compounds of citrus essential oils was developed. Five different oils were analyzed under identical conditions, by reversed-phase HPLC with photodiode array detector, for a direct comparison of the composition of their oxygen heterocyclic fraction. Analysis time was 7 min. The oils analyzed were lemon, bergamot, mandarin, sweet orange, and bitter orange. The method developed is good for rapid screening or fingerprinting of these essential oils; a slightly slower method is recommended for higher resolution and better quantitative results.     

Inhibitory effects of citrus essential oils and their components on the formation of N-nitrosodimethylamine

Twenty-eight kinds of citrus essential oils and their components were studied for inhibitory effects on the formation of N-nitrosodimethylamine (NDMA). The reaction mixture consisted of dimethylamine and sodium nitrite adjusted at pH 3.6, in addition to essential oils and an emulsifying agent. The quantification was determined by high-performance liquid chromatography monitored at 220 nm. All of the essential oils inhibited the formation of NDMA in the range of 20-85%. The oils of ujukitsu (Citrus ujukitsu Hort. ex Shirai), yuzu (C. junos Tanaka), mochiyu (C. inflata Hort. ex Tanaka), and ponkan (C. reticulata Blanco cv. F-2426) inhibited the formation of NDMA much more effectively than other citrus oils. The inhibitory proportions of components of citrus essential oils such as myrcene, alpha-terpinene, and terpinolene were as high as 80%.     

Organochlorine pesticide contents of tributaries into Blanca Bay,Argentina

Thirteen 1-L replicate water samples from streams emptying into Blanca Bay, Argentina, were taken to study the environmental quality of the surface waters. Out of tests for eleven chlorinated pesticides, five were detected in all the sampling places as both dissolved and adsorbed species: alpha-HCH, gamma-HCH (lindane), heptachlor, delta-HCH, and aldrin. The concentrations were in the following ranges: alpha-HCH = 3 to 68 ng L^?1 and 9 to 239 ng g^?1, lindane = 2 to 42 ng L^?1 and 10 to 542 ng g^?1, heptachlor = 5 to 32 ng L^?1 and 9 to 390 ng g^?1, delta-HCH = 1 to 10 ng L^?1 and n.d. to 87 ng g^?1, and aldrin = 1 to 7 ng L^?1 and n.d. to 33 ng g^?1 for filtered water and suspended matter samples, respectively. Heptachlor epoxide, dieldrin, o-p′ DDD, and p-p′ DDT were found to be present in solution at only one sampling site whereas p-p′ DDD and o-p′DDT were not detected. The analyses revealed a non-uniform distribution of these compounds over the studied area. The higher concentrations of organochlorines were detected downstream urban areas.     

Organochlorine pesticide residues in leek (Allium porrum) crops grown on untreated soils from an agricultural environment

Leek (Allium porrum) plants from organic farming were harvested at 15, 59, and 210 days after seed germination. Organochlorine pesticide (OCP) levels were quantified by GC-ECD in vegetative tissues (roots and aerial), bulk soil and rhizosphere. Leek plant bioaccumulate OCPs efficiently in their aerial and root tissues and alter the concentration of the soil where they are grown. OCPs distribution pattern of bulk soil was endosulfans > DDTs > dieldrin, while it was endosulfans > HCHs > DDTs in leek tissues. There were statistically significant declines in DDTs, chlordane, dieldrin, and heptachlor in the rhizosphere, indicating that recalcitrant residues of OCPs may be removed from contaminated soil using leek crops under normal growing conditions. The DDE/DDT and alpha-/gamma-HCH ratios of < 1 would indicate recent inputs of DDT and lindane in the environment. The occurrence of OCPs in this farm could be the result of atmospheric deposition and/or surface runoff of these pesticides.     

Organochlorine insecticide residues in the rain water in Delhi,India

Rain water samples were regularly collected from three sites, namely, Netaji Nagar, Moti Nagar and Town Hall within the Delhi city area from July, 1980 to June, 1982. The pesticide residues were adsorbed on polyurethane foam coated with 0.5 % DC-200 and subsequently extracted and analyzed for DDT, HCH and their metabolites/isomers. The concentration of total DDT ranged from 0.22 to 108 μg L^?1 with a mean value of 12.5 μg L^?1. The samples of rain water contained varying levels of 4,4-DDT, 2,4-DDT, 4,4-DDE, and 4,4-DDD. The 4,4-DDT, 4,4-DDE and 2,4-DDT were the main components of total DDT. The range of HCH residues in rain water was from 0.08 to 43 μg L^?1 with a mean of 5.3 μg L^?1. The residues of HCH consisted mainly of α- and γ-isomers with traces of β and δ-isomers. The α- and γ-isomers accounted for 76 and 24% of total HCH, respectively. The concentrations of DDT and HCH in rain water were generally less than 10 μg L^?1 and exceeded 10 in only 4 and 3 cases, respectively. The residues of these insecticides were generally higher during October to December. Residues of DDT were higher at Moti Nagar which is near a DDT factory. Residues of HCH were maximum at Town Hall, a commercial area of the city.     

Radical-scavenging activities of citrus essential oils and their components: detection using 1,1-diphenyl-2-picrylhydrazyl

Thirty-four kinds of citrus essential oils and their components were investigated for radical-scavenging activities by the HPLC method using 1,1-diphenyl-2-picrylhydrazyl (DPPH). To examine the oils' relative radical-scavenging activities compared with that of a standard antioxidant, Trolox was employed. All of the essential oils were found to have scavenging effects on DPPH in the range of 17. 7-64.0%. The radical-scavenging activities of 31 kinds of citrus essential oils were comparable with or stronger than that of Trolox (p < 0.05). The oils of Ichang lemon (64.0%, 172.2 mg of Trolox equiv/mL), Tahiti lime (63.2%, 170.2 mg of Trolox equiv/mL), and Eureka lemon (61.8%, 166.2 mg of Trolox equiv/mL) were stronger radical scavengers than other citrus oils. Citrus volatile components such as geraniol (87.7%, 235.9 mg of Trolox equiv/mL), terpinolene (87.4%, 235.2 mg of Trolox equiv/mL), and gamma-terpinene (84.7%, 227.9 mg of Trolox equiv/mL) showed marked scavenging activities on DPPH (p < 0.05).     

Determination of some heavy metals and selenium in Sicilian and Calabrian citrus essential oils using derivative stripping chronopotentiometry

This paper aims to bring some novelty about the concentration of some heavy metals and selenium in biological citrus essential oils (CEO) produced in Sicily and Calabria in different crop years. Derivative stripping chronopotentiometry has been used as an accurate, sensitive, and rapid technique for the determination of Cd, Cu, Mn, Ni, Pb, Zn, and Se in hydrochloric acid extracts of CEO; in the optimized electrochemical conditions, detection limits of <1 microg kg(-1) were obtained for all of the studied metals. In particular, the concentrations of metals were determined in biological bergamot essential oils produced in Calabria in 1999 and 2000 and in biological CEO produced in Sicily in 2003 and 2004. The obtained results provided evidence that Mn was the most abundant metal in all of the studied CEO followed by Zn, Ni, Cu, Pb, and Se; Cd concentrations were always lower than the limit of detection (0.6 microg kg(-1)).     

植物精油与环糊精包合物的制备及对柑橘绿霉病的抑制作用

植物精油及其活性组分能降低柑橘采后病害且不影响果实品质,是一种潜在的生物杀菌剂,但存在易挥发和不稳定等问题,限制了其实际应用。将植物精油与环糊精包合能有效克服上述缺陷,提高植物精油的应用效果。为了提升植物精油组分反式-2-己烯醛对柑橘绿霉病菌的控制效果,该研究拟采用饱和水溶液法制备反式-2-己烯醛与α-环糊精（α-CD）、β-环糊精（β-CD）、γ-环糊精（γ-CD）和羟丙基-β-环糊精（HP-β-CD）包合物,并考察包合物对指状青霉的离体和活体控制效果,在此基础上解析效果较优包合物的结构特点和包合模式。结果显示,通过饱和水溶液法成功制备了反式-2-己烯醛与α-CD、β-CD、γ-CD和HP-β-CD的4种包合物（α-CDTH、β-CDTH、γ-CDTH和HP-β-CDTH）。外观形态结果显示,α-CDTH、β-CDTH和γ-CDTH粉末细腻绵密,HP-β-CDTH粉末粗糙,颗粒分明。4种环糊精包合物均能有效抑制P.digitatum菌丝体的生长且具有浓度依赖性,β-CDTH和γ-CDTH抑制P.digitatum菌丝体生长的最小杀菌浓度（Minimum Fugicide Concen...     

State programs for pesticide residues in foods

Two U.S. data collection and dissemination programs, FEEDCON and FOODCONTAM, are described. FEEDCON provides information on contamination levels in animal feeds of toxic chemical residues (pesticides, industrial chemicals, heavy metals, mycotoxins, natural plant toxins, salmonella, and therapeutic drug cross-contaminations). FEEDCON data are collected from approximately 40 state feed regulatory agencies, feed manufacturers, and related groups who subscribe ($100-$200 per year) to the program, which is sponsored by the Association of American Feed Control Officials. FOODCONTAM provides similar information, but is limited to pesticides, heavy metals and industrial chemicals (polychlorinated and polybrominated biphenyls, etc.) in human foods. Both programs have been developed and initiated under U.S. Food and Drug Administration contracts with the Mississippi State Chemical Laboratory. Program structures of both are outlined conceptually, and FOODCONTAM is described in detail. FOODCONTAM data-sharing program development is essentially complete, but expansion by incorporating FDA data with State Laboratory data is nearing reality.