Endrin Aldehyde Research Articles

Polycyclic aromatic hydrocarbons and pesticides in soil of Vojvodina

The paper deals with several groups of compounds that represent the most frequent pollutants of soil in the world. The paper also reviews results of long-term studies conducted at the Institute of Field and Vegetable Crops in Novi Sad on the residues of pesticides and polycyclic aromatic hydrocarbons (PAHs) in the soil of the Vojvodina Province. The analyzed samples have been found to contain residues of persistent pesticides and their metabolites lindane and its metabolites 6,20 ?g/kg, alachlor 3,56 ?g/kg, aldrin 2,3 ?g/kg, heptachlor epoxide 0,99 ?g/kg, chlordane 3,82 ?g/kg, DDT and its metabolites 10,77 ?g/kg, dieldrin 2,04 ?g/kg, endrin 3,57 ?g/kg and endrin aldehyde 1,36 ?g/kg. Soil samples from Novi Sad municipality contained 53,69 ?g/kg of DDT and its metabolites. The values of atrazine ranged from 0,0005 to 0,8 mg/kg. The values of PAHs were 6,64 mg/kg in industrial soil, 4,93 mg/kg in agricultural soil, and 4,55 mg/kg and 5,48 mg/kg in the Novi Sad municipality. The lowest value, 0.83 mg/kg, was found for nonagricultural/nonindustrial soils.

Sample Purification for Analysis of Organochlorine Pesticides in Sediment and Fish Muscle

The methods of sample purification for determinations of organochlorine pesticides (OCPs) in sediment and fish muscle were investigated in this study. A two-step procedure with preliminary cleanup and florisil column fraction was adopted. The working conditions of florisil column were firstly optimized. As to preliminary cleanup, liquid–liquid extraction by mixture of dimethyl formamide (DMF) and hexane and sulphonation by concentrated sulfuric acid were applied respectively and compared for the studied samples. The results indicated that liquid–liquid distribution could effectively separate lipids from fish muscle extracts, while failed in elimination of chlorophyll extracted from the relicts of hydrophytes in the sediment sample. In view of the sample appearance and clarity of gas chromatogram, sulphonation was more suitable to purify the sediment sample, however, the recoveries of the spiked standards were poor. The use of eluting solvent with stronger polarity could improve the corresponding recoveries significantly. Due to complete loss of Dieldrin, Endrin, and Endrin aldehyde after sulphonation, this pretreatment was improper to the three components. Sulfur, as the particular disturbing element in sediment, could be removed sufficiently by addition of activated copper powder. The relevant detection limits of the selected methods for OCPs in the studied substrates were also provided.

Determination of organochlorine pesticides in seawater using liquid-phase hollow fibre membrane microextraction and gas chromatography–mass spectrometry

The use of hollow fibre membrane microextraction in analytical chemistry has been increasing as the technique is a simple and efficient method for the extraction of trace organic compounds from environmental matrices. A simple liquid-phase microextraction technique using a hollow fibre membrane in conjunction with gas chromatography–mass spectrometry has been developed for the extraction and analysis of organochlorine pesticides (OCPs), i.e. α-hexachlorocyclohexane (BHC), lindane, β-BHC, heptachlor, aldrin, dieldrin, endrin, endosulfan, p, p′-DDD, p, p′-DDT, endrin aldehyde and methoxychlor, from seawater. The technique requires minimal sample preparation time and solvent consumption, and represents a significant advantage over conventional analytical methods. Optimum extraction conditions have been evaluated with respect to sample pH, salt content and stirring rate, as well as solvent type and extraction time. A high level of detection linearity (coefficient of >0.9995, less than 14% RSD) was obtained for OCPs over a range of analyte concentrations between 5 and 100 μg l −1, with detection limits in the parts per trillion (ppt) to sub-parts per billion range. Comparison between liquid-phase microextraction with hollow fibre membrane and US Environmental Protection Agency Method 508 showed that the novel method has comparable detection limits of between 0.013 and 0.059 μg l −1 in seawater.

Dimensionless volatilization rate for two pesticides in a lake

AbstractIn recent years, toxic pollution has become a relevant topic in lake management, especially in developed countries. Consequently, great effort has been made to increase our knowledge of contaminant transport and transformation phenomena, and their effects on lake water quality.The present paper reports on the characterization of input parameters for a dimensionless steady‐state model that simulates fate processes of volatile environmental contaminants. Dimensionless volatilization rates for two pesticides, 2,3,7,8‐ tetrachlorodibenzo‐p‐dioxin (TCDD) and endrin aldehyde, in particular, are estimated using field data from almost 80 Italian lakes. Careful analyses of the results allow us to define the variation range of input parameters and introduce some simplifications into the complete solutions of the model.

Solid-phase microextraction for organochlorine pesticide residues analysis in Chinese herbal formulations

Solid-phase microextraction (SPME) coupled with gas chromatography–mass spectrometry (GC–MS) was used to determine pesticide residues in Chinese herbal formulations. Fibers coated with a 100-μm film thickness of poly(dimethylsiloxane) was used to extract 19 organochlorine pesticides (OCPs). The pesticides in the study consisted of α-, β-, γ- and δ-hexachlorocyclohexane, p, p′-DDD, p, p′-DDE, p, p′-DDT, o, p′-DDT, aldrin, dieldrin, endrin, endrin aldehyde, endrin ketone, endosulfan (I, II and sulfate), heptachlor, heptachlor epoxide, and methoxychlor. The optimal experimental procedures for the adsorption and desorption of pesticides were evaluated. The linearity was obtained with a precision below 11% RSD for the studied pesticides expect endosulfan sulfate (21%) in a wide range from 1 to 200 ng/g. Detection limits were reached at below ng/g levels. Heptachlor epoxide was determined at a calculated limit of 0.03 ng/g. Comparison between SPME and Soxhlet extraction showed that SPME has a less than one order detection limit for residue pesticide determination. The proposed method was tested by analyzing herbal formulations from a local market for OCP multi-residues. Some residues studied were detected in the analyzed samples. The results demonstrate the suitability of the SPME–GC–MS approach for the analysis of multi-residue OCPs in Chinese herbal formulations.

Organochlorine contaminants in Morelet’s crocodile ( Crocodylus moreletii) eggs from Belize

Non-viable eggs of Morelet’s crocodile ( Crocodylus moreletii) were collected from Gold Button (GBL) and New River lagoons (NRL) in northern Belize and screened for organochlorine (OC) compounds using gas chromatography (GC) with electron capture detection (ECD). All egg samples from both lagoons ( n=24) tested positive for one or more OCs. Primary contaminants were p, p-DDE and methoxychlor, detected in 100% and 29% of the eggs examined, respectively. Concentrations of individual OC contaminants ranged from 1 ppb (ng chemical/g egg) to >0.5 ppm (μg chemical/g egg). Total concentrations of OCs (sum of all OCs) for one egg collected from a nest at GBL reached as high as 0.7 ppm. Sediment samples from both lagoons also tested positive for OCs (lindane, aldrin, methoxychlor, heptachlor epoxide, p, p-DDT, among others). Nest media (soil and plant material) collected from crocodile nests at GBL were positive for p, p-DDT, methoxychlor, aldrin, endosulfan II, and endrin aldehyde. Based on the 24 egg samples analyzed to date, crocodiles from both lagoons are being exposed to OCs. Such exposure may present a health threat to populations of crocodiles in Central America.

Supercritical fluid extraction and clean-up of organochlorine pesticides in Chinese herbal medicine

A method involving the simultaneous extraction and clean-up of 13 organochlorine pesticides (OCPs) from Chinese herbal medicines (CHMs) was developed using supercritical fluid extraction (SFE) followed by gas chromatography–electron capture detection and mass spectrometric confirmation. The pesticides in the study consisted of α-, β-, γ-, and δ-benzene hexachloride, heptachlor, aldrin, heptachlor epoxide, endosulfan I, 4,4′-DDE (1,1-dichloro-2,2-bis( p-chlorophenyl)ethene), dieldrin, endrin, 4,4′-DDD (1,1-dichloro-2,2-bis( p-chlorophenyl)ethane), endosulfan II, 4,4′-DDT (2,2-bis( p-chlorophenyl)1,1,1-trichloroethane), endrin aldehyde, and endosulfan sulfate. A series of experiments was conducted to optimize the final extraction conditions [pure CO 2, 250 atm extraction pressure (1 atm=101 325 Pa), 50°C extraction temperature, 5 min static extraction time, 20 min dynamic extraction time, 2.0-g Florisil sorbent on top of 0.1-g samples, 12-ml n-hexane eluting at 1 ml/min, and a 10-ml extraction vessel]. Florisil sorbent was placed with the sample in the SFE vessel to provide a facile and effective clean-up approach. Mean recoveries of 78–121% with reproducibilities of 5–31% were obtained for the pesticides except for endosulfan II, endosulfan sulfate and endrin aldehyde. The simple and rapid method may be used to determine OCPs in CHMs routinely, and in fact, was used to analyze CHMs sold in Taiwan.

Organochlorine insecticide residues in Egyptian mothers’ milk

Two hundred ninety‐two mother's milk samples were collected during 1994 from ten Egyptian governorates representing rural, metropolitan, and newly reclaimed desert areas. The samples were analyzed for 14 organochlorine insecticides and metabolites using electron capture gas chromatography and confirmed by gas chromatography/mass spectrometry (GC/MS). The overall samples average showed that the most abundant organochlorine insecticide residues were p,p'‐DDE, α‐endosulfan, β‐HCH and, p,p’‐DDT. Residues in the range of not detectable to less than 14μg/l whole milk were recorded for α‐HCH, heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin endrin aldehyde and p,p'‐DDD. The percentage of samples exceeding the acceptable daily intake for children (ADIs) set by the FAO/WHO ranged from 19% to 44% in all governorates included in the study except the governorate of Minia in which only 2.6% of the samples exceeded the ADI values. The insecticides exceeding ADI values are mostly heptachlor and heptaclor epoxide (ADI = 3.12 μg/1 whole milk).

Supercritical fluid extraction of organochlorine pesticides in eggs.

The efficacy of supercritical fluid extraction (SFE) for the recovery of 16 common organochlorine pesticides (OCPs) from liquid whole eggs was investigated by employing supercritical carbon dioxide (SC-CO(2)) without the use of a solvent modifier to minimize interfering coextractives. The OCPs tested included aldrin; alpha-, beta-, delta-, and gamma-BHCs; p,p'-DDD, -DDE, and -DDT; dieldrin; endosulfans I, II, and sulfate; endrin; endrin aldehyde; heptachlor; and heptachlor epoxide. The SFE conditions were as follows: 10000 psi (680 bar), 40 degrees C, SC-CO(2) flow rate of 3.0 L/min with an extraction time of 40 min for a total of 120 L of CO(2). The OCPs were trapped off-line in an SPE cartridge containing Florisil and then eluted by an acetone/hexane mixture and analyzed by gas chromatography-electron capture detection (GC-ECD). Recovery studies were carried out on homogenized eggs fortified at the 0.05, 0.10, and 0.20 ppm levels. At the lowest level, 0.05 ppm, recoveries ranged from 81.8 to 108.3%, with CVs < 9.8%. All recoveries were significantly higher than those obtained by an AOAC/FDA solvent extraction method. Eggs containing incurred endosulfan I were also effectively extracted by SFE. This study suggests that the application of SFE for the extraction of OCPs from eggs will result in significant savings in analysis time and lower solvent use and disposal costs compared to conventional solvent extraction procedures.

The assessment of teratogenic petential of sulfadiazine

The distribution of organochlorine pesticides in the aquatic ecosystem from the Densu river revealed varying levels of concentration in water and the sediment samples. Three locations were sampled along the river to evaluate the levels of organochlorine pesticide residue in the river. Sediment and surface water samples were extracted by soxhlet and liquid–liquid extraction respectively and analyzed using Gas Chromatograph coupled with electron capture detector. The detectable organochlorine pesticides were gamma-hexachlorocyclohexane (HCH), delta-hexachlorocyclohexane, heptachlor, aldrin and dieldrin. The other pesticides that were investigated are gamma-chlordane, alpha endosulfan, endosulfan sulfate, p,p′-DDT and its metabolite p,p′-DDE, methoxychlor, endrin and its metabolite endrin aldehyde and endrin ketone. The order of increasing frequency of detection of samples was higher in sediment than water. In sediment, the mean concentration ranged from 0.030 μg kg−1 dry weight (endrin) to 10.98 μg kg−1 dry weight (aldrin). The highest detected concentration of organochlorine in water was endosulfan sulfate with mean concentration of 0.185 μg L−1. Analysis of variance indicated significant differences for most organochlorine pesticide residue in the sediment sampled from the various locations. Some of the levels of organochlorine pesticides detected in water were relatively high compared to guideline values set by World Health Organization and Australia and thus could be harmful if the trend is not checked.

Organochlorine Pesticides in Stream Mayflies and Terrestrial Vegetation of Undisturbed Tropical Catchments Exposed to Long-Range Atmospheric Transport

We investigated whether biota and sediments in river catchments consisting of primary forest in northwestern Costa Rica are contaminated by atmospheric transport of organochlorine pesticides from nearby regions where their use is intense. We measured organochlorine residues in stream mayflies, as well as in the bark and leaves of trees in catchments of an undisturbed dry tropical forest west of Volcán Orosí and Cerro Cacao (i.e., western catchments), and in tree leaves and bark in partially disturbed rain forest catchments east of Cerro Orosí (i.e., eastern catchments) in a region where agricultural activity is intense. Samples were solvent extracted, purified by silica gel clean-up, and concentrated before analysis by gas chromatography/mass spectrometry. Twelve organochlorine pesticides were detected in samples, including hexachlorocyclohexanes, heptachlor epoxide, endosulfans, DDT, DDE, dieldrin, endrin, endrin aldehyde, and aldrin. Endosulfans dominated the organochlorine signature of mayflies collected in the western catchments and of leaves and bark collected from eastern catchments. Leaves and bark collected in the undisturbed western catchments contained ten-fold lower concentrations of the endosulfans than those collected from the eastern catchments. Hexachlorocyclohexane isomers were dominated by the gamma isomer and were present at comparable levels in samples of leaves and bark collected from both sides of the volcanic ridge. An exception was high residues in bark collected from one eastern catchment, suggesting a local source. Stream mayflies and terrestrial vegetation in the undisturbed dry tropical forest contained substantial quantities of organochlorine pesticides, the most likely source being long- and short-range atmospheric transport.

Extraction and Gas Chromatographic Screening of 14 Chlorinated Pesticides in Crayfish (Procambarus clarkii) Hepatopancreas

A multiresidue isolation technique using matrix solid-phase dispersion (MSPD) and gas chromatography/electron capture detection is applied to crayfish (Procambarus clarkii) hepatopancreas for the extraction and determination of 14 chlorinated pesticides (alpha-BHC, beta-BHC, lindane, heptachlor, aldrin, heptachlor epoxide, p,p'-DDE, dieldrin, endrin, 4,4'-DDD, endrin aldehyde, p,p'-DDT, endosulfan sulfate, and methoxychlor). Pureed crayfish hepatopancreata (0.5 g aliquot) are fortified with the 14 pesticides and with delta-BHC as an internal standard before blending with 2 g C18 (octadecylsilyl)-derivatized silica. The C18-hepatopancreas matrix blend and 2 g activated Florisil comprise an extraction column from which the pesticides are eluted by adding 8 mL acetonitrile. Two microliters of the eluate is directly analyzed by gas chromatography with electron capture detection. Unfortified blank controls are treated similarly. The eluate contained all the pesticide analytes and was free of interfering coextractants at most fortification levels. Correlation coefficients for the 14 extracted pesticide standard curves (linear regression analysis) ranged from 0.9685 to 0.9985. Average relative percent recoveries (recoveries for all pesticides ranged from 55 +/- 10.4% to 118 +/- 45.2%, n = 15 for each pesticide) over the range of concentrations examined, interassay variability (7.1 +/- 5.7% to 16.0 +/- 5.6%, n = 15 for each pesticide), and intra-assay variability (0.0-26.2%, n = 5 for each pesticide) indicated that the MSPD methodology allowed for the successful extraction and determination of the 14 chlorinated pesticides at 125-2000 ng/g levels in crayfish hepatopancreas.

Matrix Solid-Phase Dispersion Extraction and Gas Chromatographic Screening of 14 Chlorinated Pesticides in Oysters (Crassostrea virginica)

A multiresidue isolation technique known as matrix solid-phase dispersion (MSPD) is presented for the extraction and subsequent gas chromatographic/electron capture detection (GC/ECD) determination of 14 chlorinated pesticides (alpha-BHC, beta-BHC, lindane, heptachlor, aldrin, heptachlor epoxide, p,p'-DDE, dieldrin, endrin, 4,4'-DDD, endrin aldehyde, p,p'-DDT, endosulfan sulfate, and methoxychlor) from oysters (Crassostrea virginica). Pureed whole oysters (0.5 g aliquots) are fortified with the 14 pesticides and delta-BHC, as an internal standard, and blended with 2 g C18 (octadecylsilyl)-derivatized silica. Pesticides are eluted from an extraction column composed of C18/oyster matrix blend and 2 g activated Florisil by addition of 8 mL acetonitrile-methanol (90 + 10). Then, 2 microL of the eluate is analyzed by GC/ECD. Unfortified blank controls are treated similarly. The eluate contained all the pesticide analytes and was free of interfering coextractants. Correlation coefficients for the standard curves of the 14 extracted pesticides (linear regression analysis) ranged from 0.9849 to 0.9980. Average relative percent recoveries over the range of concentrations examined (66 +/- 12.7% to 84 +/- 25.3%, n = 25 for each pesticide), interassay variability (13.6 +/- 8.8% to 30.2 +/- 9.1%, n = 25 for each pesticide), and intra-assay variability (5.8-11.8%, n = 5 for each pesticide) indicated that the MSPD methodology successfully extracted and determined the 14 chlorinated pesticides in oyster at levels of 31.3-500 ng/g.

Effect of endrin and endrin derivatives on hepatobiliary function and carbon tetrachloride-induced hepatotoxicity in male and female rats

The effects of the cyclodiene pesticide, endrin, and its aldehyde and ketone metabolites on hepatobiliary function and CCl 4-induced hepatotoxicity were investigated in Sprague-Dawley rats. The rats were given control diet or diets containing 5 or 10 ppm endrin, 10 ppm endrin aldehyde or 5 ppm endrin ketone for 15 days. Three to six rats from each treatment group were given a single ip dose (100 μl/kg body weight) of CCl 4 in corn oil (1 ml/kg) on day 15. Levels of serum glutamic-oxalacetic transaminase (SGOT), glutamic-pyruvic transaminase (SGPT), isocitrate dehydrogenase and ornithinecarbamyl transferase, bile flow and biliary excretion of an anionic model compound, phenolphthalein glucuronide (PG), were measured on day 16. Dietary treatment with endrin at either dose level did not significantly elevate serum enzyme levels, while endrin aldehyde produced a slight increase in SGOT and SGPT and endrin ketone produced a small elevation in SGPT levels. Treatment with endrin aldehyde or endrin ketone did not result in significant alterations of bile flow or biliary PG excretion. Treatment with 5 ppm endrin produced a significant reduction in bile flow and a corresponding reduction in PG excretion by male rats, whereas treatment with 10 ppm endrin reduced only the PG excretion by male rats. Female rats treated with 5 or 10 ppm endrin showed a dose-dependent choleretic effect with a commensurate increase in PG excretion. With the exception of a further slight reduction in PG excretion by male rats, treatment with the endrin or endrin derivative did not potentiate CCl 4-induced alterations in hepatobiliary functions. Although the levels of some serum enzymes of rats given endrin or endrin derivatives plus CCl 4 were elevated over those of rats given CCl 4 alone, the increases were not of the magnitude of those that have been reported previously for chlordecone. Generally, female rats challenged with CCl 4 or endrin/CCl 4 exhibited greater increases in serum enzyme levels than did male rats given corresponding treatments.

A microbial assay for determining the influence of physicochemical environmental factors on the toxicity of organics: phenol.

The toxicity of phenol to filamentous fungi was unaffected by pH or water hardness, but it was potentiated by salinity at levels comparable to those occurring in estuarine and off-shore marine waters. The effect of temperature on the response of the fungi to phenol was highly variable: depending on the fungus, the toxicity of phenol was either not affected, increased, or decreased as the temperature was raised from 22 to 32°C. The toxicity of phenol was not affected by heavy metals. The mediating influences of these abiotic environmental factors on the toxicity of phenol to filamentous fungi were similar to those reported for aquatic macrobiota. This similarity, which has also been noted with the effects of environmental factors on the toxicity of heavy metals, strengthens the concept of using microbial assays to evaluate initially the potential mediating influence of physicochemical factors of natural environments on the toxicity of organic pollutants. An antagonistic interaction in toxicity occurred between phenol and endrin aldehyde orp-chloro-m-cresol, and an additive interaction occurred between phenol and toxaphene, but no interactions were apparent between phenol and other phenolic compounds and pesticides.

Isolation and characterization of some methanonaphthalene photoproducts

The photodecomposition products of aldrin, dieldrin and endrin were investigated by means of gas chromatography mass spectrometry, nuclear magnetic resonance and infrared spectrophotometry. An alternate isomeric product of aldrin and four endrin analogs were encountered. The mass spectra of eight photoproducts are presented with direct inlet spectra of endrin aldehyde and endrin alcohol.

Chlorinated Hydrocarbon Insecticide Residues in Crops and Soil

AbstractA series of small Congaree sandy loam field plots at Beltsville, Maryland, were treated with 0, 56 or 112, and 224 kg/ha of aldrin, dieldrin, isodrin, endrin, heptachlor, chlordane, BHC, toxaphene, or Dilan in 1951. Sixteen years later the parent compounds were still detectable with mean total residues of 29 (pure aldrin), 35 (technical aldrin), 23, 16, 39, 10, 9, 7, 49, and 15%, respectively, remaining. Aldrin, isodrin, and heptachlor had oxidized primarily to their epoxide.Soybeans (Glycine max L., Merr.), corn (Zea mays L.), oats (Avena sativa L.), and wheat (Triticum aestivum L.) were grown consecutively in the plots beginning 15 years after treatment. Soybean seeds contained dieldrin, endrin, heptachlor epoxide, and alpha and gamma BHC; endrin transformation products, which include endrin aldehyde, endrin alcohol, and endrin ketone; and a gamma BHC degradation product, pentachlorocyclohexene. Only BHC and dieldrin were found in crop seeds other than soybeans, and no aldrin, isodrin, heptachlor, chlordane, toxaphene, or Dilan were detected in the seeds of any crop.

Endrin Transformations in Soil

AbstractA Lakeland sandy loam was treated at three depths with 14Cendrin insecticide in which one crop of soybeans (Glycine max L., Merr.) was grown. After harvesting the soybeans, the soil was sectioned and assayed for endrin residues. At least three and possibly five transformation products of endrin occurred. Two products were identified as 1,8,9,9,10,11‐hexachloropentacyclo [6.3.0.12,5 .03,7.06,10] dodecan‐12‐one (endrin delta ketone) and 1,8,9,9,10, 11‐hexachlorohexacyclo [6.3.0.12,5.03,7.06,10.011,12] dodecan‐12‐ol (endrin alcohol). A third product may have been 1,8,9,9,10,11‐hexachloropentacyclo [6.3.0.02,11.03,7.06,10] undecan‐12‐carboxaldehyde (endrin aldehyde). Endrin transformation appeared to increase with soil depth. In an extremely acid soil (pH 4.2) endrin transformed to some endrin ketone and probably endrin aldehyde during treatment of the dry soil, but not of moist soil. Acid or base treatment of endrin and several endrin isomers indicated that endrin was stable under basic conditions and that endrin alcohol and endrin aldehyde (presumably) were stable in all treatments tested, except the base treatment at 100C for endrin aldehyde.