Determination of Dicofol in Tea Using Surface-Enhanced Raman Spectroscopy Coupled Chemometrics.

Dicofol is a highly toxic residual pesticide in tea, which seriously endangers human health. A method for detecting dicofol in tea by combining stoichiometry with surface-enhanced Raman spectroscopy (SERS) technology was proposed in this study. AuNPs were prepared, and silver shells were grown on the surface of AuNPs to obtain core-shell Au@AgNPs. Then, the core-shell Au@AgNPs were attached to the surface of a PDMS membrane by physical deposition to obtain a Au@AgNPs/PDMS substrate. The limit of detection (LOD) of this substrate for 4-ATP is as low as 0.28 × 10-11 mol/L, and the LOD of dicofol in tea is 0.32 ng/kg, showing high sensitivity. By comparing the modeling effects of preprocessing and variable selection algorithms, it is concluded that the modeling effect of Savitzky-Golay combined with competitive adaptive reweighted sampling-partial least squares regression is the best (Rp = 0.9964, RPD = 10.6145). SERS technology combined with stoichiometry is expected to rapidly detect dicofol in tea without labels.

Vortex-assisted magnetic dispersive solid-phase microextraction for rapid screening and recognition of dicofol residues in tea products.

A simple and rapid vortex-assisted magnetic dispersive solid-phase microextraction (VAMDSME) method coupled with gas chromatography-electronic capture detection was developed for rapid screening and selective recognition of dicofol in tea products. The magnetic molecularly imprinted microspheres (mag-MIMs) synthesised by aqueous suspension polymerisation using dichlorodiphenyltrichloroethane (DDT) as a dummy template showed high selectivity and affinity to dicofol in aqueous solution and were successfully applied as special adsorbents of VAMDSME for rapid isolation of dicofol from complex tea matrix. Good linearity was obtained in a range of 0.2-160 ng g(-1) and the limit of detection based on a signal to noise ratio of 3 was 0.05 ng g(-1). The recoveries at three spiked levels ranged from 83.6% to 94.5% with the related standard deviations (RSD) ⩽ 5.0%. The VAMDSME-GC protocol, which took advantages of the selective adsorption of molecularly imprinted microspheres and rapid magnetic phase separation, as well as the short equilibrium time by vortex-assisted, could avoid the time-consuming procedures related to other traditional extraction methods.

Synthesis of multi-core-shell magnetic molecularly imprinted microspheres for rapid recognition of dicofol in tea.

Magnetic multi-core-shell molecularly imprinted microspheres (Fe3O4@MIMs) based on multi-Fe3O4 nanoparticles as core structures and dummy imprinted materials as shell structures have been synthesized by a surface-imprinted technique using dichlorodiphenyltrichloroethane as the dummy template and were successfully used as a specific adsorbent for rapid isolation of trace levels of dicofol from teas. The resulting Fe3O4@MIMs were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, vibrating sample magnetometer, and thermogravimetric analysis. In comparison to the imprinted polymers prepared by the traditional polymerizations, the obtained Fe3O4@MIMs showed regularly spherical shape, porous morphologies, high saturation magnetization [56.8 electromagnetic units (emu)/g], and rapid response time (15 s). The as-synthesized Fe3O4@MIMs, which incorporated the excellent molecular recognition and magnetic separation properties, were successfully used as special adsorbents for rapid isolation and extraction of trace levels of dicofol and its analogues from a complicated tea matrix.

Survey on the pesticide residues in tea in south India.

Tea is considered as a 'health beverage' due its antioxidant properties and resultant beneficial effects on human health. Such a beverage should be free from toxic elements such as pesticide residues and heavy metals. A large scale survey of teas produced in the tea factories of south India had been carried out for a period of three years from 2006 to 2008 and 912 tea samples were analysed for the residues of certain pesticides such as dicofol, ethion, quinalphos, hexaconazole, fenpropathrin, fenvalerate and propargite which are used for pest and disease control in tea in this part of the country. The analytical data proved that only less than 0.5 percentage of tea samples had residues of these pesticides. However, residues of pesticides were below their maximum limits in tea, stipulated by the European Union, Codex Alimentarius Commission of FAO/WHO and Prevention of Food Adulteration Act of Govt. of India.

Pesticide and plasticizer residues in bergamot essential oils from Calabria (Italy).

Organophosphorus and organochlorine pesticides, phosphorated plasticizers, chloroparaffins and phthalate esters contamination in bergamot essential oils produced in Calabria in the crop years 1999-2000 was studied by HRGC in connection with detectors FPD, ECD, MS. Residues of dicofol and tetradifon were found in oils from both crop years. The mean dicofol concentration was 0.26 mg/l in samples from 1999 and 0.20 mg/l in those from 2000; the mean tetradifon content was 0.06 mg/l for both the crop years. Among plasticizers, residues of diisobutyl phthalate, di-n-butyl phthalate, and bis(2-ethylhexyl) phthalate were found in samples from crop years 1999 and 2000, the mean content were 1.22 and 1.23 mg/l, 1.51 and 1.65 mg/l, 1.38 and 1.42 mg/l respectively.

[Determination of dicofol residue in tea by wide-bore capillary gas chromatographic column].

Dicofol residue is harmful to health. More and more countries have established the limitation of dicofol in foods. This paper describes an efficient method of determination for the dicofol residue in tea. The dicofol was extracted from the tea sample with 20% acetone-hexane, cleaned up on a column of Florisil and acidic siliceous earth (sulfuric acid 0.3 mL/g) in series. Then the column was washed with 10 mL, 20% dichloromethane-hexane, the flow rate was 1 mL/min. At last dicofol was hydrolyzed with potassium hydroxide solution, forming p,p'-dichlorobenzophenone(DBP), which was separated from other ingredients through wide-bore capillary(LZ-II, 25 m x 0.53 mm i.d.) and determinated by gas chromatography with electron capture detector(ECD), using Aldrin as internal standard. When the mass ratio of dicofol was in the range of 0.05-3.0 mg/kg, the recoveries were 78%-104% and the limit of determination was 0.5 microgram/kg. This method is simple, sensitive and suitable for pesticide residue analysis. It can also be applied to the determination of dicofol residues in other plant samples such as vegetables, fruits and so on.

Reproductive potential: its influence on the susceptibility of a species to pesticides.

Acute lethal concentration estimates (72-hr LC50) and population growth rates (7-day instantaneous rate of increase) of two mite species, an herbivore, the two-spotted spider mite Tetranychus urticae Koch, and the generalist predator mite Iphiseius degenerans Berlese, were developed after exposure to two pesticides, dicofol and Neemix. For each pesticide, LC50 estimates for both species were similar, yet the two species exhibited completely different susceptibility when population growth rate was the endpoint evaluated; I. degenerans was much more susceptible than T. urticae to either pesticide. For example, populations of I. degenerans became extinct after exposure to 250-ppm azadirachtin, the active ingredient in Neemix, while T. urticae populations became extinct after exposure to 1000 ppm. A similar relationship was found for dicofol. The no observable effect concentration (NOEC) for population growth rates after Neemix exposure was 4 ppm for I. degenerans and 125 ppm for T. urticae. These NOEC values were equivalent to the acute LC2 for the immature stage of I. degenerans and the acute LC65 for the immature stage of T. urticae. Consequently, populations of T. urticae were able to compensate for high losses of individuals while I. degenerans populations could not compensate for losses. An analysis of reproduction data indicated that unexposed T. urticae produced four to five times more offspring than I. degenerans. This in itself was important because it indicated that I. degenerans was intrinsically more susceptible than T. urticae because similar effects on reproduction would be more devastating to the species with a lower reproductive rate. Results indicate that a species' reproductive potential can greatly influence its susceptibility to toxicants.

[The structure, growth and formation of bones in toxic exposure of the body to pesticides and antioxidant therapy]. / Stroenie, rost i formirovanie kostei pri toksicheskom vozdeistvii na organizm pestitsidov i antioksidantnoi terapii.

In the experiment performed on 175 white male rats by means of a complex of morphological, biochemical and biomechanical methods peculiarities of structure, growth, outline formation and mineralization of the skeletal bones have been investigated under a toxic lesion of the organism with pesticides (chlorophose and keltan) and at a simultaneous administration of antioxidants of various groups (tocopherol, ionol, sodium selenit). Osteotoxic effect of the pesticides, manifested as an inhibition of bone growth, as a disbalance of mineral saturation and their composition, as a decrease in indices of firmness is leveled by means of therapeutic doses of the antioxidants. The stabilizing effect of the antioxidant applied correlates to the manifestation of the pesticides osteotoxic effect, to the ability of their cumulation in the organism and is directly connected with the supposed mechanism of damaging effect to the organism and/or cell. The expressiveness of the toxic effect of the chemical poison, in its turn, is defined not only by the dose, mechanism and duration of the effect, but by age peculiarities of the organism and by functional state of its reactivity. When the poisons are applied for a long time, in order to level their osteotoxic effect, a multiple increase of therapeutic doses of the antioxidants and a combined potentiation of their effect are necessary.