Persistent organochlorine pesticide residues in milk and dairy products in India

Monitoring of milk and dairy product samples of various brands from different cities in Maharashtra, India, was carried out to determine if there is any contamination due to organochlorine pesticide residues. The measurements were made using a gas chromatograph-electron capture detector system. Trace levels of DDT and HCH were detected in the samples. Total HCH levels in milk and milk product samples were lower than total DDT levels, which could be attributed to earlier extensive antimalaria sanitary activities. Butter had higher levels of DDT than cheese and milk powder. All levels of organochlorine pesticide residues in milk and milk products were well below the maximum permissible limits given by the FAO/WHO. More importantly, as compared with an earlier report, present levels of the contaminants are substantially lower, which indicate the gradual phase out of these compounds.     

Pesticide residues in foodstuffs in Great Britain. II. Persistent organochlorine pesticide residues in selected foods

Residue measurements for persistent organochlorine pesticides in milk, butter, corned beef, beef fat and mutton fat, produced in or imported into Britain in 1963 and 1964 are reported. The levels in mutton fat are compared with levels found earlier; only very low residues are found in most other produce examined though some butter samples contain up to 0·1 ppm of DDT and 0·4 ppm of total DDT equivalent. Levels in the fat of grass and store-fed animals were indistinguishable; results for milk suggest that the diet of cows in Britain contains very little γ-BHC or dieldrin.     

Emission of chiral organochlorine pesticides from agricultural soils in the cornbelt region of the U.S

Several organochlorine pesticides are chiral molecules manufactured as racemic mixtures. Past research has shown that selective degradation of pesticide enantiomers by microorganisms occurs resulting in nonracemic signatures in soils. In this work, volatilization of chiral pesticides from soil was investigated to determine if enantioselective breakdown in soils could be used as a source signature to track releases of chiral pesticides to the atmosphere. Air samples were taken directly above agricultural soils at several sites, and enantiomeric signatures were found to be nonracemic following patterns found in the soil. A follow up study at one site showed that for most compounds concentration decreased with increasing height above the soil, while enantiomer fractions for chiral pesticides were similar to that found in the soil, signifying the soil as a source to the air. The enantiomer fractions of ambient air samples from rural nonagricultural areas in the region were also found to be nonracemic.     

Determination of residues of organochlorine insecticides and polychlorinated biphenyls in cereals, feeds and water

A semimicro method for the quantitative determination of chloro-organic insecticides (COI) and polychlorinated biphenyls (PCB) in cereals, feed-pellets and water is presented. The extraction of the active compounds is carried out with n-hexane or dichloromethane. The extracts of cereals and pellets are purified by column chromatography with aluminum oxide. A silicagel column is used for the separation of the compounds into COI as well as PCB and hexachlorobenzene. The determination of the active compounds is carried out by gas chromatography using an electron capture detector. Recoveries range between 70 and 108%, except for beta-endosulphan.     

Persistent organochlorine pesticide levels in bovine fat from Mexico.

Organochlorine pesticides have been used in Mexico in agriculture as a seed dresser, in sanitation, in malaria control programmes and in livestock to combat ectoparasites. The pesticides applied drift to areas where cattle graze and plants grow. Because of their chemical stability, they accumulate in the lipid-rich tissues of the body. In the body, they circulate throughout all compartments and accumulate in adipose fat. The aim was to monitor the organochlorine pesticide levels in bovine muscle fat and kidney fat from cows living in an endemic malaria zone, where the environmental contamination can be suspected as being higher. Two hundred samples (100 muscle fat, 100 kidney fat) were analysed by gas chromatography. From the pesticides, only hexachlorobenzene (HCB), beta-hexachlorocyclohexane (HCH), gamma-HCH, pp'-1.1.1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT), op'-DDT and pp'-DDE, were detected frequently and at levels above the detection limits. The HCB mean level was low at 0.009 mg kg(-1) on a fat basis. From the HCH isomers, beta-HCH mean concentration was 0.039 mg kg(-1) and gamma-HCH was 0.025 mg kg(-1) on a fat basis. Among DDTs, pp'-DDT was the major constituent (0.032 mg kg(-1) on a fat basis) followed by pp'-DDE (0.025 mg kg(-1) on a fat basis) and op'-DDT (0.023 mg kg(-1) on a fat basis). The DDT total (sigma DDT) level was 0.067 mg kg(-1) on a fat basis. Comparing the previous study (1994) and the present one (2002-03), organochlorine pesticide levels were decreased. HCB decreased 3.7 times from 0.033 to 0.009 mg kg(-1) on a fat basis; beta-HCH decreased 3.8 times from 0.149 to 0.039 mg kg(-1) on a fat basis; pp'-DDE did not reveal a significant difference at 0.026 versus 0.025 mg kg(-1) on a fat basis. However, pp'-DDT decreased substantially, 6.7 times from 0.215 to 0.032 mg kg(-1) on a fat basis. The DDT total decreased 3.5 times from 0.236 to 0.067 mg kg(-1) on a fat basis. The tendency for reduced concentrations in organochlorine pesticide levels in Mexican cows is caused by their substitution with pyrethroids used in agriculture and by the Mexican Ministry of Health in sanitary programmes.     

The roles of food and water in the bioaccumulation of organochlorine compounds in high mountain lake fish

An integrated study encompassing the distribution of organochlorine compounds (OC) in water, food web (chironomids, terrestrial insects, cladocerans, mollusks, and cyanobacteria), and fish (brown trout) from a high mountain lake (Redon, Pyrenees) is reported. OC distributions in these compartments have been determined to assess theirtransport routes into fish. Food diets have been estimated by analysis of fish stomach content and food web stable isotopes (delta13C and delta15N). OCs with octanol--water partition coefficient (Kow) higher than 10(6) showed lower concentrations in food than expected from theoretical octanol--water partition, indicating thatthe distribution of these compounds does not reach equilibrium within the life span of the food web organisms (ca. 1 year). On the other hand, the degree of biomagnification in fish increased with Kow, except in the case of the largest compound analyzed (seven chlorine substituents, PCB #180). OC exchange at fish gill and gut has been evaluated using a fugacity model based on the water, food, and fish concentrations. All compounds exhibited a net gill loss and a net gut uptake. A pseudostationary state was only achieved for compounds with log(Kow) < 6. Calculation of fish average residence times for the compounds in apparent steady state gave values of days to a few weeks for HCHs, 1 year for HCB and 4,4'-DDE, and 2-3 years for 4,4'-DDT and PCB#28 and PCB#52. Residence times longer than one decade were found for the more chlorinated PCB.     

Low-temperature, mineral-catalyzed air oxidation: a possible new pathway for PAH stabilization in sediments and soils

Reactivity of polycyclic aromatic hydrocarbons (PAHs) in the subsurface is of importance to environmental assessment, as they constitute a highly toxic hazard. Understanding their reactivity in the long term in natural recovering systems is thus a key issue. This article describes an experimental investigation on the air oxidation of fluoranthene (a PAH abundant in natural systems polluted by industrial coal use) at 100°C on different mineral substrates commonly found in soils and sediments (quartz sand, limestone, and clay). Results demonstrate that fluoranthene is readily oxidized in the presence of limestone and clay, leading to the formation of high molecular weight compounds and a carbonaceous residue as end product especially for clay experiments. As demonstrated elsewhere, the experimental conditions used permitted the reproduction of the geochemical pathway of organic matter observed under natural conditions. It is therefore suggested that low-temperature, mineral-catalyzed air oxidation is a mechanism relevant to the stabilization of PAHs in sediments and soils.     

Seasonal variation of persistent organochlorine accumulation in birds from Lake Baikal, Russia, and the role of the south Asian region as a source of pollution for wintering migrants

Concentrations of persistent organochlorines (OCs) such as polychlorinated biphenyls (PCBs), DDT and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), and chlordane compounds (CHLs) were determined in whole body soft tissue homogenates and in muscles of resident and migratory birds collected from Lake Baikal, Russia. The residue pattern in both resident and migratory birds was in the following order: PCBs > DDTs > HCHs > CHLs. OC concentrations in migratory birds varied, depending on the feeding habit. The maximum levels of OCs were found in piscivores, followed by insectivores, omnivores, and herbivores. OC residue levels in Lake Baikal birds were lower than those in the Great Lakes region as well as in other lakes in Europe and Japan. Concentrations of HCHs and DDTs in most of the migratory birds collected in the spring were higher than for those collected in the autumn, indicating a notable accumulation in wintering grounds. Compilation and analysis of the available data in fish and birds from Asia suggested that the tropical and subtropical regions in south Asian countries may be a source of pollution for the wintering accumulation of migratory birds from Lake Baikal. Relatively higher compositions of alpha- and gamma-HCH in total HCHs, p,p'-DDT in total DOTs were observed in some migratory species, indicating recent exposure to HCHs and DDTs in Lake Baikal or wintering areas. PCB isomer patterns were different between residents and migrants, with the predominance of lower chlorinated congeners in migratory species, suggesting recent PCB accumulation in stopover sites during wintering. TEQ concentrations of toxic non- and mono-ortho coplanar PCBs in common terns from Lake Baikal were comparable to those reported in some species from Japan, the United States, and Europe. Relative contributions of non-ortho coplanar congeners to toxic equivalents (TEQs) were predominant, in which CB-126 accounted for the highest toxicity contribution. Estimated TEQ concentrations in the common tern from Lake Baikal exceeded the levels associated with enzyme induction in bald eagles. To our knowledge, this is the first comprehensive study showing the seasonal variations of OC accumulation in the birds from Lake Baikal.     

Lead,cadmium and organochlorine pesticide residues in hunted red deer and wild boar from northern Italy

The objectives of the present study were to assess heavy metal cadmium (Cd), lead (Pb) and organochlorine pesticide concentrations in tissues of red deer (Cervus elaphus) and wild boar (Sus scrofa) from nine hunting areas and to evaluate related risk factors for the host animal. Over a period of 2 years, a total of 1055 and 210 masseters, 424 and 201 livers, 642 and 152 kidneys were collected from wild boar and red deer, respectively, and concentrations of Cd, Pb and organochlorine pesticides were determined. Comparing the two species, Cd concentration in the kidney (3.72 mg/kg), liver (0.67 mg/kg) and muscle (0.02 mg/kg) of wild boar was found to be significantly higher than in the organs of red deer (1.02 mg/kg in the kidneys, 0.07 mg/kg in the liver and 0.006 mg/kg in muscle). Mean Pb concentrations were found to be similar in both animals, with 0.39, 0.52 and 2.60 mg/kg detected in the wild boar kidney, liver and muscle, respectively, and 0.24, 0.21 and 2.04 mg/kg in the respective organs of the red deer. No difference in concentrations were found based on age class, location of tissue sample or contaminant in the case of wild boar. By contrast, a significantly lower Cd concentration was found in the kidney of the young red deer. The search for organochlorine pesticides in both red deer and wild boar produced negative results with values below the limits of detection. Due to the high levels of renal Cd and muscle Pb detected in wild boar and red deer, further research needs to be carried out in an effort to identify the source of contamination and preserve the health of animals and humans.     

Organochlorine insecticide residues in earthworms from arable soils

Six species of earthworms from an arable soil were analysed for residues of aldrin, dieldrin, DDT and γ-BHC. The ratios between the concentrations of γ-BHC, aldrin + dieldrin and p,p′-DDT + p,p′-DDE in the earthworms and in the soil (concentration factors) were similar but the residue concentrations were consistently higher in the smaller more shallow-living species Allolobophora caliginosa, A. chlorotica and A. rosea than in the larger deeper-living species Lumbricus terrestris, A. longa and Octolasion cyaneum. In arable field plots, dieldrin residues in A. longa and A. chlorotica increased with increasing concentrations in the soil but the concentration factors decreased. The concentrations of residues in earthworms (W) appear to be related to those in the soil (S) by an equation of the form W = aS^b where a and b are constants, the latter being about 0.79 for a wide range of residue data embracing the uptake of aldrin-dieldrin, DDT components, and γ-BHC by earthworms.     

Persistent organochlorine pesticide levels in cow's milk samples from tropical regions of Mexico.

Organochlorine pesticides have been used in agriculture as a seed dresser, in sanitation, in malaria control programmes and in livestock to combat ectoparasites. Their residues accumulate in lipid-rich tissues due to their chemical stability and persistence. In the body they circulate throughout all compartments, deposit themselves in adipose fat and can be excreted during lactation. These pesticides are applied in tropical zones and drift to areas where cattle graze. Therefore, analyses of cow's milk samples can serve as an indicator of environmental and cows' exposure to them. One hundred and fifty milk samples were taken each year in 1998 and 2001 and analysed to determine concentrations of HCB, beta-HCH, pp"-DDE, op'-DDT and pp'-DDT. Results obtained indicate that beta-HCH is one of the main contaminants (0.106 and 0.087 mg x kg(-1) on fat basis) followed by pp'-DDT (0.078 and 0.037 mg x kg(-1) on fat basis) and pp'-DDE (0.051 and 0.033 mg x kg(-1) on fat basis). The HCB and op'-DDT were detected in lower quantities respectively (0.008 and 0.006 mg x kg(-1), and 0.031 and 0.010 mg x kg(-1) on fat basis). When comparing the results obtained with those from the previous study, it was noted that DDT levels decreased significantly in 2001 as a result of the substitution of the organochlorine insecticides with pyrethroids sprayed by the Mexican Ministry of Health to combat malaria since 1999.     

A millennium of metallurgy recorded by lake sediments from Morococha, Peruvian Andes

To date, information concerning pre-Colonial metallurgy in South America has largely been limited to the archaeological record of artifacts. Here, we reconstruct a millennium of smelting activity in the Peruvian Andes using the lake-sediment stratigraphy of atmospherically derived metals (Pb, Zn, Cu, Ag, Sb, Bi, and Ti) and lead isotopic ratios (206Pb/ 207Pb) associated with smelting from the Morococha mining region in the central Peruvian Andes. The earliest evidence for metallurgy occurs ca. 1000 A.D., coinciding with the fall of the Wari Empire and decentralization of local populations. Smelting during this interval appears to have been aimed at copper and copper alloys, because of large increases in Zn and Cu relative to Pb. A subsequent switch to silver metallurgy under Inca control (ca. 1450 to conquest, 1533 A.D.) is indicated by increases in Pb, Sb, and Bi, a conclusion supported by further increases of these metals during Colonial mining, which targeted silver extraction. Rapid development of the central Andes during the 20th century raised metal burdens by an order of magnitude above previous levels. Our results represent the first evidence for pre-Colonial smelting in the central Peruvian Andes, and corroborate the sensitivity of lake sediments to pre-Colonial metallurgical activity suggested by earlier findings from Bolivia.     

Separation, identification and determination of fluoroacetamide residues in water, biological materials and soils. I. Analytical technique

An improved analytical technique for fluoroacetamide residues below 0.2 ppm in water is described, together with a dialysis procedure that enables residues to be extracted from soils and foliage and to be estimated by the same procedure.     

Passive air sampling of PCBs, PBDEs, and organochlorine pesticides across Europe

This study presents concurrently sampled ambient air data for a range of persistent organic pollutants at the continental scale. This was achieved using a passive air sampling system, deploying polyurethane foam disks, which was prepared in one laboratory, sealed to prevent contamination, sent out by courier to volunteers participating in different countries, exposed for 6 weeks, collected, resealed, and returned to the laboratory for analysis. Europe was the study area--a region with a history of extensive POPs usage and emission and with marked national differences in population density, the degree of urbanization and industrial/agricultural development. Samplers were deployed at remote/rural/urban locations in 22 countries and analyzed for PCBs, a range of organochlorine pesticides (HCB, alpha-HCH, gamma-HCH, ppDDT, ppDDE), and PBDEs. Calculated air concentrations were in line with those obtained by conventional active air sampling techniques. The geographical pattern of all compounds reflected suspected regional emission patterns and highlighted localized hotspots. PCB and PBDE levels varied by over 2 orders of magnitude; the highest values were detected in areas of high usage and were linked to urbanized areas. HCB was relatively uniformly distributed, reflecting its persistence and high degree of mixing in air. Higher gamma-HCH, ppDDT, and ppDDE levels generally occurred in South and East Europe.     

Polychlorinated biphenyls, hexachlorobenzene, hexachlorocyclohexane isomers, and pesticide organochlorine residues in cod-liver oil dietary supplements

Levels of polychlorinated biphenyls (PCBs), hexachlorobenzene, hexachlorocyclohexane isomers (alpha, beta, gamma), and chlorinated pesticides (DDTs) in cod-liver oil used as a dietary supplement were determined. Total PCB and DDT concentrations varied from 25 to 201 ng g(-1) lipid weight basis and from 25 to 133 ng g(-1) lipid weight basis, respectively. Hexachlorobenzene contributed very little to the overall contaminant burden of dietary supplement oils, whereas hexachlorocyclohexane isomers were below the instrumental detection limits in all samples. The daily intake of PCBs and DDTs derived by the consumption of cod-liver oil at manufacturer-recommended doses varied from 0.004 to 2.01 microg/day and from 0.004 to 1.24 microg/day, respectively. Relative to some dioxin-like PCB congeners (mono-ortho PCB 105, 118, and 156; non-ortho PCB 77, 126, and 169), the intakes calculated varied from less than 0.001 to 0.74 pg of toxic equivalency values (TEQ) per kg of body weight per day. These values, although below the range of 1 to 4 pg of TEQ per kg of body weight per day set by the World Health Organization, emphasize the need for strict and continuous monitoring of fish oil contamination to reduce, as much as possible, the risks to human health.     

Pesticide residues in foodstuffs in Great Britain. IX. Aldrin, dieldrin and other organochlorine pesticide residues in potatoes and carrots

Potatoes from 186 commercial crops from fields treated with aldrin or dieldrin in the year of cropping contained mean residues of aldrin plus dieldrin of 0.01 ppm in the flesh and 0.1 ppm in the skin. Seventy crops from fields that had been treated with aldrin or dieldrin in years previous to the year of cropping and forty-four crops from reputedly untreated fields contained mean residues of aldrin/dieldrin of less than 0.01 ppm in the flesh and 0.02 ppm in the skin. Alpha- and/or gamma-BHC were detected in trace or greater amounts in 73% and pp' DDE in 10% of the samples. Carrots from 97 commercial crops from fields treated with aldrin or dieldrin in the year of cropping contained mean residues of aldrin plus dieldrin of less than 0.01 ppm in the flesh and 0.21 ppm in the skin. Fifty crops from fields that had been treated with aldrin or dieldrin in years previous to the year of cropping contained mean residues of aldrin/dieldrin of less than 0.01 ppm in the flesh and 0.07 ppm in the skin. Six crops from reputedly untreated fields contained a mean residue of less than 0.01 ppm dieldrin in the skin only. Alpha- and gamma-BHC were found in the majority of the samples (mean total residue of less than 0.01 ppm in the flesh and 0.03 ppm in the skin) but pp' DDE and/or pp' DDT were detected in only 12% of the samples.     

Time trends of selected persistent organic pollutants in lake sediments from Greenland

Sediments from seven lakes in West Greenland were used as natural archives to study past and present levels of PCBs (polychlorinated biphenyls, tri- to decachlorinated), tetra-BDE #47 (2,2',4,4'-bromodiphenyl ether), chlordane (cis- and trans-octachlordane) and HxCBz (hexachlorobenzene). The concentrations found are lower than or comparable to concentrations found in sediments from other Arctic regions and one to 2 orders of magnitude lower than concentrations typically found in sediments at lower latitudes. The observed temporal trends (direct and indirect dating) show a decreasing total PCB concentration. Even though local contamination sources exist, the POP deposition in the studied area is most likely a result from long-range transport. The hypothesis about "cold condensation" suggests a latitudinal fractionation to occur between different volatile compounds during the transport toward the pole. In this study a time delay in the deposition for the low-chlorinated PCBs (tri- and tetrachlorinated), compared to their emission histories and compared to higher chlorinated PCBs, was indicated. Although very low tetra-BDE #47 concentrations are observed in this study, there are indications for an increasing concentration in recent sediment layers that may reflect increasing environmental concentrations at lower latitudes. The investigated pesticides are still in use at lower latitudes, however neither chlordane nor HxCBz show any distinct temporal trend of increasing or decreasing concentration toward the sediment surface.     

气相色谱法快速测定食品中有机氯、拟除虫菊酯、有机磷农药残留量

本文通过气相色谱法检测食品中有机氯、拟除虫菊酯、有机磷农药残留量。本文采用乙腈作为提取溶剂,超声波提取目标农残,溶液用气相色谱(ECD检测器)检测有机氯和拟除虫菊酯,同样的溶液用气相色谱(FPD检测器)检测有机磷农残。该方法在国标基础上简化了前处理方法,实现了有机氯、拟除虫菊酯、有机磷农药残留量检测前处理的统一,大大缩短了前处理时间,减少了溶剂的消耗。16种有机氯、拟除虫菊酯以及11种有机磷的分离度好,相关系数0.9986～0.99998,定量限0.001～0.06mg/kg,相对标准偏差RSD小于5.0,加标回收率90.8%～108.3%。