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On-column trace enrichment by sequential frontal and elution electrochromatography II. Enhancement of sensitivity by segmented capillaries with z-cell configuration--application to the detection of dilute samples of moderately polar and nonpolar pesticides.

An on-column trace enrichment method for capillary electrochromatography of dilute samples is described. It involves the sequential use of frontal and elution electrochromatography on a segmented capillary column comprising of two contiguous segments each packed with a different sorbent. While the entering segment is for preconcentration by frontal electrochromatography the second segment is much longer and is meant for separation of the enriched analytes in the subsequent elution electrochromatography step. The preconcentration segment is usually packed with a sorbent that affords the highest affinity towards the solutes of interest while the separation segment is packed with a stationary phase that exhibits the highest selectivity and separation efficiency for the analytes. The detection is performed in the UV using a z-cell configuration for achieving an increased path length for detection. The effectiveness of this on-column trace enrichment is demonstrated on dilute samples of moderately polar solutes (e.g., carbamate insecticides) and nonpolar solutes (e.g., pyrethroid insecticides). Under optimal frontal and elution electrochromatography conditions. 817- and 1100-fold sensitivity increase are achieved for permethrin (a pyrethroid insecticide) and methiocarb (a carbamate insecticide), respectively, with a UV detector. The method is demonstrated with real water samples (e.g., tap and lake water samples) spiked with carbamate and pyrethroid insecticides. The limits of detection for the pesticides achieved in tap and lake waters reached 10(-8) to 10(-9) M.

Chromatography, Micellar Electrokinetic Capillary↗

Selective extraction of pyrethroid pesticide residues from milk by solid-matrix dispersion.

A rapid procedure has been developed that allows a single-step, selective extraction and clean-up of pyrethroid (PYR) pesticide residues from milk dispersed on solid-matrix diatomaceous material filled into disposable cartridges and eluted by means of light petroleum saturated with acetonitrile and ethanol. The extract was cleaned up by high-performance size-exclusion chromatography. Determinations were carried out by gas chromatography with electron-capture detection. Recovery experiments were carried out on homogenized commercial milk (3.6% fat content) that was spiked with solutions of 14 PYR pesticides, viz., tefluthrin, tetramethrin, cyphenothrin, cyfluthrin, flucythrinate, fluvalinate, deltamethrin, bioallethrin, fenpropathrin, lambda-cyhalothrin, permethrin, alpha-cypermethrin, esfenvalerate and tralomethrin, at levels ranging from 0.04 to 0.41 mg/kg for the different PYR pesticides. Average recoveries were in the range 60-119% for the different PYR pesticides, with relative standard deviations from ca. 2.5 to 14.4%. Coextracted fatty material amounted to an average of ca. 5 mg/ml of milk. The sole extraction step requires about 30 min. The main advantages of the procedure are that extraction of PYR pesticides (with a minimum carry over of fat) is performed in a single step, emulsions do not occur, several samples can be run in parallel by a single operator, reusable glassware is not needed and simple operations are required.

Animals↗

Clean-up of aqueous acetone vegetable extracts by solid-matrix partition for pyrethroid residue determination by gas chromatography-electron-capture detection.

Disposable, ready-to-use cartridges filled with macroporous diatomaceous material are used to carry out a partition clean-up that, in a single step, is capable of transferring pesticide residues from aqueous acetone extracts into light petroleum-dichloromethane (75:25, v/v). This procedure takes the place of some functions (such as separatory-funnel partition, drying over anhydrous sodium sulphate and partial adsorption clean-up) usually performed by separate steps in classical schemes. Fourteen pyrethroid pesticides, including tefluthrin, tetramethrin, cyphenothrin, cyfluthrin, flucythrinate, tau-fluvalinate, deltamethrin, bioallethrin, fenpropathrin, lambda-cyhalothrin, permethrin, alpha-cypermethrin, esfenvalerate and tralomethrin were determined using the described procedure with satisfactory recoveries for most of them, at spiking levels ranging from 0.08 to 0.82 mg/kg for the different compounds. Crops subjected to the described procedure included strawberry, apple, and orange gave extracts containing a mass of co-extractives that was between 5 and 30 mg. Compared with classical schemes, the described procedure is simple, less labour intensive, allows parallel handling of several extracts and does not require the preparation and maintenance of equipment. Troublesome emulsions such as those frequently observed in separation funnel partitioning do not occur.

Acetone↗

Determination of pyrethroid pesticide residues in fatty materials by solid-matrix dispersion partition, followed by mini-column size-exclusion chromatography.

The method studied uses a combination of a solid-matrix dispersion partition (SMDP) followed by high-performance size-exclusion chromatography on a minicolumn (HPmSEC) of 7.8 mm I.D. for the separation of pyrethroid (PYR) residues from fatty material. The solid-matrix dispersion extraction is carried out by absorbing a fat solution onto an Extrelut-3 cartridge (filled with a macroporous diatomaceous material) and extracting the PYR residues with acetonitrile. Up to 1 g of fatty material can be extracted with 15 ml acetonitrile. The small amount (mean +/- S.D. = 12.4 +/- 5.9 mg) of fatty material which is eluted into the acetonitrile is further removed by HPmSEC. PYR pesticide residues are collected in a 2-ml fraction between 7 and 9 ml, the column being washed up to 24 ml. The two techniques used in series allow a better removal of fat, a greater input of sample and a lower consumption of solvent compared to the sole SEC on macrocolumns, and a lower limit of determination compared to the sole SEC on minicolumns. Recoveries of 9 PYR out of the 14 investigated residues from soya oil were in the range 66-83% at spiking levels ranging 0.49-2.57 mg/kg, while for 6 PYR residues tested at spiking levels in the range 0.13-0.53 mg/kg the recoveries were in the range 80-111%. Recovery of fluvalinate and permethrin could not be calculated due to interferences from soya oil, while lambda-cyhalothrin, esfenvalerate and tralomethrin gave low recovery. The final extract contains small amount (mean +/- S.D. = 2.4 +/- 0.9 mg) of lipid residue and is not completely free from interferences.

Chromatography, Gas↗

Developmental expression and stress induction of glutathione S-transferase in the spruce budworm, Choristoneura fumiferana.

Developmental and stress-induced expression of Choristoneura fumiferana glutathione S-transferase (CfGST) mRNA and protein were examined using Northern blots and Western blots. High levels of CfGST mRNA and protein were detected in 1st instar larvae and diapausing 2nd instar larvae. Expression of CfGST gradually decreased during larval development from 3rd to 5th instar, after which the expression increased once again, reaching peak levels in 6th instar larvae. CfGST mRNA and protein were undetectable in the pupal stage. Exposure to low temperature did not induce an increase in CfGST expression. Feeding on balsam fir foliage resulted in an increase in the expression of CfGST as compared to larvae that fed on artificial diet. The bacterial insecticide, Bacillus thuringiensis delta-endotoxin (Bt), the non-steroidal ecdysone analog, tebufenozide, and the synthetic pyrethroid, permethrin, induced the expression of CfGST mRNA in 5th instar larvae, whereas the chitin synthesis inhibitor, diflubenzuron, did not have any such effect. These results suggest that CfGST plays an important role in detoxifying various allelochemicals and insecticides in the spruce budworm. The developmental expression pattern strongly suggests that in addition to detoxification, CfGST might be involved in other functions.

Journal Article↗

Stability of organophosphate and pyrethroid pesticides on wheat in storage.

The pesticides chlorpyriphos-methyl, pirimiphos-methyl and permethrin were applied to wheat and stored for 52 weeks at 25, 30, 35 and 40 degrees C, and at 10 and 13% m.c. Rates of loss were calculated from the residue analyses of pesticides in treated wheat at monthly intervals during the storage period. Calculated half-lives and pseudo first-order rate constants of these pesticides are discussed with reference to temperature and moisture.

Journal Article↗

Epidemic typhus in a prison in Burundi.

The International Committee of the Red Cross investigated an outbreak of fever of unknown origin in Ngozi prison, Burundi, which resulted in a crude mortality rate of 2.61% in January 1996. A definite diagnosis of epidemic typhus caused by Rickettsia prowazekii was established by enzyme-linked immunosorbent assay using specific antigens. Control measures included complete cleansing of the prison with cyfluthrine, shaving and dusting all prisoners with permethrin 0.5% dusting powder, and replacement of all mattresses and clothes. All prisoners and guards received a single dose of doxycyline (100 mg) simultaneously. The crude mortality rate dropped abruptly to 1.27% in February 1996 and remained at or below 0.5% from March onwards. Health authorities and medical agencies working in Burundi need to consider epidemic typhus in the differential diagnosis of fever of unknown origin in order to be able to take appropriate control measures in time.

Anti-Bacterial Agents↗

Comparison of nutrient and contaminant fluxes in two areas with different hydrological regimes (Empordà Wetlands, NE Spain).

Nutrient (N and P), heavy metal (Ni, Cd, Cr, Cu and Pb) and pesticide (DDT, DDD, DDE, lindane, aldrin, endrin, dieldrin, permethrin, atrazine and simazine) concentrations in water and sediment were analysed in the Empordà Wetlands, a Mediterranean wetland area in NE Spain. Mean nutrient and contaminant concentrations and input and output loads via tributaries were compared in two marshes with different water turnover: a freshwater marsh (FWM), with a high water turnover rate due to continuous surface water inputs and outputs, and a brackish water marsh (BWM), with lower turnover and no continuous surface output, where water remains confined during dry periods. Mean concentrations of most heavy metals exceeded the maximum permissible concentration (MPC) in BWM, whilst only some pesticides reached MPC in FWM. The confined waters of BWM showed higher sensitivity to contaminant input loadings than FWM due to the lack of continuous water outputs. Non-point source pollution inputs during runoff (mainly in FWM) and concentration during confinement (mainly in BWM) showed as the main environmental problems related to nutrients and contaminants in these ecosystems. Thus, the importance of confinement and its effect on pollutant concentrations must be borne in mind to achieve correct management of Mediterranean wetlands.

Ecosystem↗

Evaluation of pesticide uptake by Lupinus seeds.

Pesticide uptake by seeds depends on the properties of the chemical, such as structure, stability, log k(ow) and diffusion rate, type of water, pH, temperature, content of organic matter and composition, and on seed characteristics such as permeability of the seed coat. The efficiency with which Lupinus angustifolius seeds retain different herbicides (simazine, atrazine, isoproturon, linuron,) and insecticides (carbaryl, fenamiphos, permethrin) was evaluated using both a batch and a continuous system. Factors which affect pesticide uptake by seeds, such as flow rate, seed biomass, pesticide concentration, contact time, pH, seed saturation and also the speed of the retention process for 17 days, were tested. L. angustifolius showed a high retention capacity for the above mentioned pesticides. The extraction of pesticides from seeds using different organic solvents, such as methanol, acetonitrile, ethyl acetate and n-hexane was evaluated and no pesticide residues were detected in any of the solvents tested. This could be attributed to the capacity of the seed to degrade the pesticides. From the results obtained, L. angustifolius seems to be a promising seed to be applied for phytoremediation of industrial effluents or contaminated water.

Biodegradation, Environmental↗

System-level responses of lake ecosystems to chemical stresses using exergy and structural exergy as ecological indicators.

This paper presents the system-level responses of experimental lake ecosystems to three chemical stresses (acidification, copper and pesticide contamination) using exergy and structural exergy as ecological indicators. The results indicate that the doses or toxicity of the three chemical stressors contributed to changes in both exergy and structural exergy. Remarkable changes in exergy and structural exergy occurred under acidic conditions and in the presence of Dursban, 24D-DMA, permethrin, bifenthrin, Carbaryl, TCP, PCP, trichlorethylene, benzene, and high doses of Cu, oil, and hexazinone. This seemed to indicate that the subject ecosystems were seriously contaminated by these chemical stressors. For low doses of Cu, oil, atrazine, HCBP, and hexazinone, exergy and structural exergy were either unchanged or only slightly changed, suggesting that the lake ecosystems were not significantly impacted by these chemical stressors. Discussion of the relationships between ecosystem-level changes and structural and functional changes in stressed lake ecosystems indicates that the above-mentioned ecosystem-level changes were in accordance with the changes in structure and function. The observed changes in exergy and structural exergy were also consistent with Odum's predictions of shortened food chains, reduced resource use efficiency, poor stability, low information, and high entropy in stressed aquatic ecosystems. The findings lead the authors to conclude that it is feasible for exergy and structural exergy to serve as ecological indicators when characterizing the system-level responses of experimental lake ecosystems to chemical stress. These results for experimental lake ecosystems would be extrapolated to actual lakes.

Animals↗

Malaria eradication on islands.

BACKGROUND: To be successful, a malaria control programme needs to be tailored to the local epidemiological characteristics. Vanuatu consists of 80 inhabited islands in the Southwest Pacific, with hypoendemic and mesoendemic malaria and suitable conditions for sustained parasite elimination. We aimed to assess whether malaria can be eliminated on isolated islands. METHODS: Weekly mass drug administration of chloroquine, pyrimethamine/sulfadoxine (Fansidar), and primaquine was carried out on the entire population of 718 inhabitants of Aneityum island for 9 weeks in 1991 before the onset of the rainy season. Simultaneously with the administration of drugs, permethrin-impregnated bednets were distributed to the entire population. Larvivorous fish were also introduced into several identified breeding sites of Anopheles farauti. Periodic malariometric monitoring has continued for the past 9 years. Two additional islands of Vanuatu, one with and one without malaria transmission, have been monitored for comparison. FINDINGS: High community involvement as measured by drug compliance (88.3%) and bednet provision (0.94 nets per villager) has resulted in sustained interruption of malaria transmission in Aneityum. The surveys showed complete absence of Plasmodium falciparum after mass drug administration, and P. vivax disappeared from 1996 onwards, with the exception of two instances of imported infections (one mixed infection in 1993 and one P. vivax infection in 1999). INTERPRETATION: Malaria can be eliminated on isolated islands with well-adapted short-term mass drug administration and sustained vector control if there is a high degree of community participation.

Adolescent↗

Scabies.

Scabies is a neglected parasitic disease that is a major public health problem in many resource-poor regions. It causes substantial morbidity from secondary infections and post-infective complications such as acute post-streptococcal glomerulonephritis. Disease control requires treatment of the affected individual and all people they have been in contact with, but is often hampered by inappropriate or delayed diagnosis, poor treatment compliance, and improper use of topical compounds such as permethrin, lindane, or benzyl benzoate. In addition to concerns over toxicity with such compounds, parasite resistance seems to be increasing. Oral ivermectin is an alternative that has been used successfully in community control programmes. Plant derivatives such as turmeric, neem, and tea tree oil are also promising future treatments. The disease is strongly associated with poverty and overcrowding, and the associated stigma can ostracise affected individuals. Treatment of scabies in poor countries needs to integrate drug treatment programmes with efforts to improve the socioeconomic conditions and education programmes to reduce stigma. We expect the future to bring more sensitive and specific clinical and laboratory-based diagnostic methods, as well as new therapeutic strategies.

Adult↗

Bed-nets (mosquito-nets) and morbidity from malaria.

A study was undertaken in the Farafenni area of The Gambia to determine the relation between morbidity from malaria in children and the use of bed-nets (mosquito-nets). From comparisons of parasite and spleen rates in bed-net users and in non-users it seemed that bed-nets had a strong protective effect. However, the prevalence of malaria in the study population was also influenced by ethnic group and place of residence, and the association of bed-net use with these two confounding factors accounted for some of the differences observed between bed-net users and non-users. Nevertheless, a significant inverse correlation between splenomegaly and the use of bed-nets remained. This suggests that bed-nets give Gambian children some protection against malaria and that the use of bed-nets, either untreated or treated with an insecticide such as permethrin, should be investigated further as a means of malaria control in Africa.

Adolescent↗

Carbon-based quantitation of pyrethrins by supercritical-fluid chromatography.

All six insecticide active ingredients in pyrethrum extract were quantified by supercritical fluid chromatography and carbon calibration. Allethrin is a suitable reference compound for carbon calibration and pyrethrins calibrations. Carbon quantification in SFC is also applied to pyrethroids (phenothrin, permethrin, cypermethrin, fenvalerate and deltamethrin) and alkanes. Halogen substitution on pyrethroids requires halogens on the reference calibration compound. The method was applied to commercial extracts.

Alkanes↗

Demodex abscesses: clinical and therapeutic challenges.

A 53-year-old man had a 6-week history of confluent erythematous papules, pustules, and abscesses of the face initially limited to the right nasolabial fold. Histologic investigation revealed a perifollicular infiltrate with lymphocytes, histiocytes, and many Demodex folliculorum mites. A large number of mites were seen in skin scrapings. The skin manifestations progressed and persisted for the following 5 years and were unresponsive to numerous antiparasitic treatments, including repeated oral administration of ivermectin and external application of lindane, permethrin, and benzoyl benzoate. Therapy with oral administration of 250 mg metronidazole 3 times a day for 2 weeks resulted in rapid and lasting recovery. Demodex folliculitis remains a diagnostic and therapeutic challenge. Antiparasitic therapies used against lice or scabies may fail in control of D folliculorum mites. In the presence of clinical and microscopic findings typical of Demodex folliculitis or abscesses, treatment failure with acaricidal agents does not exclude the diagnosis. Oral metronidazole seems to work in the management of this chronic mite infestation.

Administration, Oral↗

Papulonodular demodicidosis associated with acquired immunodeficiency syndrome.

We describe a papulonodular variant of demodicidosis seen in two patients with acquired immunodeficiency syndrome and its successful treatment with 1% gamma benzene hexachloride and 1% permethrin cream rinse. Alterations in T cell function may allow otherwise commensal organisms to proliferate to the point of causing disease.

Acquired Immunodeficiency Syndrome↗

Pityriasis folliculorum revisited.

Six cases of facial erythema with follicular plugging are described. These cases correspond with characteristics of the disorder pityriasis folliculorum, a presumed demodicidosis. Treatment modalities included topical tretinoin, gamma benzene hexachloride (lindane) lotion, and 1% permethrin cream rinse.

Adult↗

Binding capacity of various fibre to pesticide residues under simulated gastrointestinal conditions.

The purpose of this study was to compare the effect of the nature and quantity of various dietary fibre (cellulose, hemicellulose, pectin, lignin) in diets on the binding capacity to pesticides azinphos-methyl (AZM), chlorpropham (CLP), chlorothalonil (CKL), permethrin (PER) as estimated by solubility under conditions of pH and temperature simulating those in the gastrointestinal tract (incubated at pH 2 for 30 min at 37 degrees C, then at pH 7 for 60 min). The ratios of fibre to pesticides were determined in omnivorous diets. In this model, the binding capacity of lignin was equal to hemicellulose for PER, AZM and CLP, but it was significantly higher for CKL. Hemicellulose bound more CKL, AZM and CLP than did cellulose. Although pectin appreciably decreased all pesticides, its effect was lower than other fibres with one exception--cellulose-CKL. In the presence of equal amounts of fibre, lignin exerted the most significant effect on pesticide solubility. Hemicellulose and cellulose bind to the same extent PER and AZM. The effect of pectin was significant only on CKL and AZM when compared to the control.

Adult↗