Monitoring of some organochlorine residues in raw bovine milk in the west Delta area, Egypt.

Background: For decades, the use of organochlorine (OC) pesticides has had a detrimental effect on the environment and human health. Contamination of soil, water, and air has also resulted in contaminated milk. Aim: The purpose of this study was to investigate if any OC residues dichlorodiphenyltrichloroethane (DDT, Dieldrin, Endrin, and Lindane) were present in raw bovine milk from West Delta, Egypt. Methods: 200 fresh raw cow milk samples (500 ml of each sample) collected from three different governorates, west Delta, Egypt, for determination of OC pesticides residues using gas chromatography with an Agilent 6890A model gas chromatograph equipped with a 63Ni microelectron capture detector. Results: The obtained results revealed that åDDT, dieldrin, endrin, and lindane were detected in Alexandria, Behera, and Matrouh at incidence levels (22.7%, 30.7%, and 10%), (20%, 20%, and 16%), (9.33%, 13.3%, and 16%), and (12%, 10.7%, and 14%) with mean values of 232.2 ± 163.6, 156.4 ± 134.6 and 100.4 ± 85.9; 91.3 ± 61.2, 95.3 ± 59.8 and 57.6 ± 3.33; 15.7± 3.86, 15.1 ± 3.96 and 20.1 ± 7.33; 33.7 ± 10.6, 36.9 ± 5.51 and 52.2 ± 21.8 ng/g fat, respectively. El-Behera was the most contaminated province with an incidence level of 53.3% with a mean value of 136.8 ± 128.0 ng/g fat, followed by Alexandria at 44% with a mean value of 173.7 ± 155.5 ng/g fat, and finally, Matrouh 40% with a mean value of 74.5 ± 56.5 ng/g fat. Conclusion: This research demonstrated that milk samples contain varying levels of OC pesticide residues, which can be hazardous to consumer health. Therefore, to safeguard consumers, especially children, and the elderly, OC pesticide residues in milk must be closely monitored.

Application of hollow fiber-protected liquid-phase microextraction combined with GC-MS in determining Endrin, Chlordane, and Dieldrin in rice samples.

This paper introduces a novel and minimized sample preparation technique based on hollow fiber-protected liquid-phase microextraction that can be used in joint with gas chromatography-mass spectrometry (GC-MS) detection to extract three organochlorine pesticides-Endrin, Chlordane, and Dieldrin-from rice samples. To that end, a single-walled carbon nanotube (SWCNT) and a proper ionic liquid (IL) were ultrasonically dispersed and injected into the lumen of hollow fiber as the extraction phase for preconcentrating and extracting the target analytes from the rice samples. The effects of the type of nanoparticles, ILs, and desorption solvent on the efficiency of extracting the analytes were investigated based on the one-factor-at-a-time (OFAT) approach. In addition, other parameters influencing the extraction procedure were optimized using an experimental design that decreased the number of experiments, reagent consumption, and costs. Under optimized conditions, the limits of detection and quantification in determining mentioned pesticides varied between 0.019-0.029 and 0.064-0.098 ng mL-1, respectively. The calibration graphs to measure Endrin, Chlordane, and Dieldrin were linear over the concentration range of 0.064-13.2, 0.098-16.7, and 0.092-11.4 ng mL-1, respectively. The relative standard deviations for inter-day and intra-day analysis were below 7.06 and 4.75% for the triplicate determination of three organochlorine pesticides. Besides, the relative recoveries and standard deviations of Endrin, Chlordane, and Dieldrin for analyzing several Iranian rice samples were between 86.0-92.9% and 4.5-5.8%, respectively. The results were compared with other similar works in literature, proving that the proposed method is efficient and useful for routine monitoring of organochlorine compounds in food samples.

Accumulation of organochlorine pesticide (OCP) residues in surface water and sediment from the Iznik Lake in Turkey.

This study was carried out to evaluate organochlorinated pesticide (OCPs) concentrations in the water column and sediments of Iznik Lake. Water samples and sediment were collected in different regions (six sampling sites) of the lake between January and December 2019 and tested for OCPs by gas chromatography-mass spectrometry (GC-MS). The results revealed that OCP residues throughout the sites varied depending on the anthropogenic activities of the region. OCPs detected in surface waters ranged from 0.01 to 60.80 µg/L and sediments from 0.06 to 14.21 ng/g dw. Endrin ketone, endrin aldehyde, endosulfan II, endrin, heptachlor epoxy, beta-BHC, gamma-BHC, ppDDD, and ppDDT concentrations exceeded the maximum residue limits indicated by the World Health Organization (WHO) for surface waters. Of the 18 analyzed OCP components, 17 were detected in sediment samples, and it was noted that they reached the highest concentration in summer. The presence of relatively high OCP levels according to WHO regulations in the waters of Iznik Lake, around which agricultural activities have been increasing rapidly in recent years, is a serious concern, and therefore, appropriate actions should be taken into consideration by the regulatory authorities.

Determination of endrin and δ-keto endrin in five food products of animal origin using GC-µECD: A modified QuEChERS approach to traditional detection.

A simple quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based method was developed for the analysis of endrin and its metabolite, δ-keto endrin, in five animal-derived food products (chicken, pork, beef, egg, and milk) using a gas chromatography-micro electron capture detector (GC-µECD). Samples were extracted with acidified acetonitrile, salted out with magnesium sulfate and sodium acetate, and finally purified with a dual layer solid-phase extraction cartridge (SPE) that contains both Supelclean ENVI-Carb (upper layer) and primary secondary amine (lower layer) SPE sorbents. A seven-point external calibration curve was constructed both for the solvent and matrix for both compounds. Good linearity was achieved for both analytes, with coefficients of determination (R2) ≥ 0.9960. The limits of detection (LODs) were 0.003 mg/kg, whereas the limits of quantification (LOQ) were 0.01 mg/kg, which were 10 times lower than the extraneous maximum residue limit (EMRL) designated by CODEX Alimentarius for the specified matrices. The method was validated via recovery performances in triplicates, with three fortification levels equivalent to LOQ, 2 × LOQ, and 10 × LOQ. The method provided excellent recoveries, ranging between 75.63 and 117.92%, with relative standard deviations (RSD) ≤ 8.52% for both analytes in various matrices. The developed method was successfully applied to monitor market samples collected from 20 different places throughout the Republic of Korea, and none of the tested analytes were found in the analyzed samples. Conclusively, we could propose that the current method can be used for routine analysis of endrin and δ-keto endrin in any type of fatty food matrix.

Residues, distributions, sources, and ecological risks of OCPs in the water from Lake Chaohu, China.

The levels of 18 organochlorine pesticides (OCPs) in the water from Lake Chaohu were measured by a solid phase extraction-gas chromatography-mass spectrometer detector. The spatial and temporal distribution, possible sources, and potential ecological risks of the OCPs were analyzed. The annual mean concentration for the OCPs in Lake Chaohu was 6.99 ng/L. Aldrin, HCHs, and DDTs accounted for large proportions of the OCPs. The spatial pollution followed the order of Central Lakes > Western Lakes > Eastern Lakes and water area. The sources of the HCHs were mainly from the historical usage of lindane. DDTs were degraded under aerobic conditions, and the main sources were from the use of technical DDTs. The ecological risks of 5 OCPs were assessed by the species sensitivity distribution (SSD) method in the order of heptachlor > γ-HCH > p,p'-DDT > aldrin > endrin. The combining risks of all sampling sites were MS > JC > ZM > TX, and those of different species were crustaceans > fish > insects and spiders. Overall, the ecological risks of OCP contaminants on aquatic animals were very low.

Obsolete pesticide storage sites and their POP release into the environment--an Armenian case study.

Organochlorinated pesticides were widely applied in Armenia until the 1980s, like in all former Soviet Union republics. Subsequently, the problem of areas contaminated by organochlorinated pesticides emerged. Environmental, waste and food samples at one pesticide burial site (Nubarashen) and three former pesticide storage sites (Jrarat, Echmiadzin and Masis) were taken and analysed on the content of organochlorinated pesticides, polychlorinated dibenzo-p-dioxins and furans and dioxin-like polychlorinated biphenyls. Gradient sampling and diffusivity-based calculations provided information on the contamination release from the hot spots on a local scale. A risk analysis based on samples of locally produced food items characterised the impact of storage sites on the health of nearby residents. All four sites were found to be seriously contaminated. High pesticide levels and soil and air contamination gradients of several orders of magnitude were confirmed outside the fence of the Nubarashen burial site, confirming pesticide release. A storage in Jrarat, which was completely demolished in 1996 and contained numerous damaged bags with pure pesticides until 2011, was found to have polluted surrounding soils by wind dispersion of pesticide powders and air by significant evaporation of lindane and ß-endosulfan during this period. Dichlorodiphenyltrichloroethane-contaminated eggs, sampled from hens roaming freely in the immediate surroundings of the Echmiadzin storage site, revealed a significant health risk for egg consumers above 1E-5. Although small in size and previously almost unknown to the public, storage sites like Echmiadzin, Masis and Jrarat were found to stock considerable amounts of obsolete pesticides and have a significant negative influence on the environment and human health. Multi-stakeholder cooperation proved to be successful in identifying such sites suspected to be significant sources of persistent organic pollutants.

Evaluation of risk associated with organchlorine pesticide contaminated sediment of the Lake Lianhuan watershed.

Characteristics and risk evaluation of organchlorine pesticides (OCPs) in the sediments of four lakes located in the Lake Lianhuan area were conducted to observe the risks on ecological system and identify the sources of pollutants. Measurement of eleven OCPs, four hexachlorocyclohexane (HCH) isomers (α-HCH, ß-HCH, γ-HCH, δ-HCH), three dichlorodiphenyltrichloroethane (DDT) homologues (p,p'-DDT, p,p'-DDD, p,p'-DDE), and four cyclodienes (Aldrin, Dieldrin, Endrin and Heptachlor), indicated that concentrations of OCPs, HCHs and DDTs ranged from 0.04 to 9.95, 0 to 7.40 and 0 to 2.44 ng/g, respectively. The most dominant pollutants were the HCHs, high proportions of γ-HCH isomer indicating the recent input of lindane. The ratios of α-HCH/γ-HCH of four lakes are all lower than that in technical HCH mixtures indicated that there was input of lindane in the past several years, or that significant α-HCH evaporation into the atmosphere occurred. The ratios of (p,p'-DDE + p,p'-DDD)/p,p'-DDT in four sediments are all <1, and the mean ratios of (DDE + DDD)/∑DDT are all <0.5, suggesting recent DDT compounds input. The risk assessment was based on ERL and ERM values obtained by the approach used for assessment of ocean risk. The results suggest that OCPs in sediments of the Lake Lianhuan system poses a potential hazard to human health and environment.

Bioremediation of the organochlorine pesticides, dieldrin and endrin, and their occurrence in the environment.

Dieldrin and endrin are persistent organic pollutants that cause serious environmental problems. Although these compounds have been prohibited over the past decades in most countries around the world, they are still routinely found in the environment, especially in the soil in agricultural fields. Bioremediation, including phytoremediation and rhizoremediation, is expected to be a useful cleanup method for this soil contamination. This review provides an overview of the environmental contamination by dieldrin and endrin, along with a summary of our current understanding and recent advances in bioremediation and phytoremediation of these pollutants. In particular, this review focuses on the types and abilities of plants and microorganisms available for accumulating and degrading dieldrin and endrin.

[Preparation and characterization of a novel adsorbent made by cellulose acetate].

A novel adsorbent made by cellulose acetate was developed. Preparation method, structure, and adsorbing characterization of the adsorbent were discussed. SEM results showed that the surface of round adsorbent was stable membrane of cellulose acetate, free from obvious cracks, holes, or other defects; while the cross section of the adsorbent was meshy and a lot of cavities were found. The adsorption results of 4 organochlorinated pesticides, such as Dieldrin, Aldrin, Endrin and Heptachlor, show that the adsorbent has higher efficient for organic pollutants, the adsorption rate is about 85% after 12 h. The adsorption rate is faster with the higher lgKow, and the removal efficiency of Heptachlor and Aldrin is up to 99% after 0.5h. The adsorbent can be used to remove persistent organic pollutants effectively.

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.

Persistent organochlorine pesticides detected in blood and tissue samples of vultures from different localities in South Africa.

Gas chromatography was used to establish the presence of quantifiable residues of 14 persistent chlorinated hydrocarbon pollutants in whole blood, clotted blood, heart, kidney, liver and muscle samples obtained from individual African whitebacked (Pseudogyps africanus), Cape griffon (Gyps coprotheres) and Lappetfaced (Torgos tracheliotos) vultures from different localities in South Africa. The levels of pesticides measured in whole blood samples of live specimens were compared between nestlings from two natural breeding colonies, adults from a wildlife area and birds held in captivity. Statistically significant (P<0.05) differences between populations were detected in geometric means calculated for gamma-BHC (lindane), alpha(cis)-chlordane and alpha-endosulfan. Five of the organochlorine contaminants displayed significant variations between concentrations detected in the clotted blood, organs and muscles excised from vulture carcasses. This includes residues of gamma-BHC, alpha-chlordane, dieldrin, beta-endosulfan and heptachlor epoxide. Values of the respective biocides measured in vulture samples were generally low in comparison to results documented for a number of avian species. Although no threat is posed by any of the organochloride pesticides, continual monitoring of especially breeding colonies is recommended. Furthermore, the suitability of African whitebacked vulture nestlings as basic bioindicators is highly advocated.

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 (microgram 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.

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

Non-viable eggs of Morelet's crocodile (Crocodylus moreletti) were collected from Gold Botton (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 percent and 29 percent of the eggs examined, respectively. Concentrations of individual OC contaminants ranged from 1 ppb (ng 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. (AU)

Screening of nonfatty fish for organochlorine pesticide residues by solid-phase extraction cleanup: interlaboratory study.

Six U.S. Food and Drug Administration laboratories participated in an Interlaboratory trial of a solid-phase extraction cleanup method for determination of pesticides in nonfatty seafood products. The participants analyzed control and fortified (about 0.050 ppm lindane, heptachlor epoxide, p,p'-DDE, and endrin) croaker and flounder samples and a sea trout sample containing incurred p,p'-DDE residues. Mean recoveries of the fortified residues from the fish ranged from 89.1 to 107.8%. The within-laboratory coefficients of variation (CVs) ranged from 4.2 to 8.5%, and the among-laboratory CVs ranged from 10.9 to 26.5%. The 6 laboratories reported a mean value of 0.040 ppm p,p'-DDE in a fish sample which contained incurred residues. The same value (0.040 ppm) was obtained by using official methodology. The within-laboratory CVs ranged from 3.5 to 18.3%, and the among-laboratory CV was 17.3%.

Seizures after eating a snack food contaminated with the pesticide endrin. The tale of the toxic taquitos.

In September 1988 we investigated reports of seizures in persons who had eaten taquitos, a commercially prepared snack food. We identified and interviewed 5 persons with new-onset seizures within 12 hours of eating taquitos, all purchased during a 1-week period from a single store. Leftover taquitos were found to contain endrin, a highly toxic chlorinated hydrocarbon pesticide. Although tissue confirmation of exposure to endrin was not possible and the level of contamination in the tested taquitos was below that previously thought to be capable of inducing seizures, the pattern of symptoms and the common time and place of purchase strongly suggested that the seizures were due to endrin-contaminated taquitos. The source of endrin contamination could not be determined. This episode is the first report of illness associated with endrin-contaminated food products in the United States.

A high endrin concentration in a fatal case.

Gas chromatography coupled to mass spectrometry was employed to quantify endrin in biological fluids in a death attributed to endrin overdose. The blood concentration of endrin was 544.9 mg/l. Results are discussed in the light of the existing literature.