Kegg Pathway: 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) degradation

J Toxicol Environ Health A. 2009; 72(13): 842-51
Sereda B, Bouwman H, Kylin H

The presence of pollutants in human breast milk is of major concern, especially in malaria control areas where 1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane (DDT) is currently used as indoor residual spray (IRS). The levels of DDT and pyrethroids (PYR) were determined in breast milk, bovine milk, and drinking water from northern KwaZulu-Natal, South Africa. Both reference and exposed mothers used the same market food, but the DDT levels in the exposed mothers (mean SigmaDDT 10 microg/g milk fat [mf]) were much higher than for the reference mothers (mean SigmaDDT 1.3 microg/g milk fat). This difference in residue levels indicates uptake from IRS-applied DDT, most likely via air and skin contact, and excludes food as the main source of pollutants. DDT levels in bovine milk (mean SigmaDDT 0.15 microg/g mf) from the exposed area were less than levels in breast milk from the reference area, and lower than the 20 microg/L maximum residue limit (MRL) set by the Food and Agriculture Organization (FAO). Mean SigmaDDT in water was 0.0065 microg/L, much lower then the WHO limit of the sum of all metabolites in drinking water of 1 microg/L, and therefore highly unlikely to have contributed to any extent toward levels in breast milk. Permethrin in breast milk (mean 1.1-1.6 microg/g milk fat) was probably derived from home garden and indoor use, while the other PYR (cypermethrin and cyfluthrin) at lower concentrations were probably derived from food and agricultural exposure. It is postulated that a better understanding of the indoor dynamics of DDT and other insecticides, through a concept of Total Homestead Environment Approach (THEA), is crucial for investigating options of reducing human exposure and uptake under malaria control conditions.

Hum Exp Toxicol. 2008 Dec; 27(12): 933-40
Tsatsakis AM, Tzatzarakis MN, Tutudaki M, Babatsikou F, Alegakis AK, Koutis C

We present the assessment of chronic exposure of the rural population of Helia Peloponnesus, Greece to banned organochlorine pesticides, hexachlorocyclohexane (HCH), and 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane (DDT), using hair analysis. A total of 222 head hair samples were collected and analyzed for the presence of those organochlorine pesticides and their metabolites or isomers. Gas chromatography coupled to mass spectrometry was used to measure the levels of the pollutants. The median concentrations of alpha-HCH, hexachlorobenzene, lindane, ortho para 1,1-dichloro-2,2-bis-(4-chlorophenyl)ethylene (opDDE), para para 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (ppDDE), ortho para 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (opDDD), para para 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (ppDDD) + ortho para 1,1,1-trichloro-2,2-bis(4-chlorophenyl)-ethane, and para para 1,1,1-trichloro-2,2-bis(4-chlorophenyl)-ethane were determined at 40.4, 19.7, 124.2, 6.2, 7.8, 73.1, 8.0, and 5.7 pg/mg. The median concentration of total HCHs and DDTs were 117.8 pg/mg and 9.4 pg/mg, respectively. The levels of total HCHs were much higher than the levels of DDTs in the hair samples of the studied population. This may be attributed to the presence of lindane, a pesticide officially banned in 2002. It is interesting to see that DDTs are still traced in samples despite their use being banned for more than three decades. There was no difference in the levels of the detected pesticides in hair sampled from men or women. The concentration of HCHs remains high and relatively stable across the age groups, suggesting constant exposure until very recently. The concentration of the total DDTs and the parent compound, pp-DDT presents a statistically significant decreasing trend across the age groups.

Environ Health Perspect. 2008 Oct; 116(10): 1407-10
Sunyer J, Alvarez-Pedrerol M, To-Figueras J, Ribas-Fitó N, Grimalt JO, Herrero C

BACKGROUND: Hexachlorobenzene (HCB) and other organochlorines induce porphyria cutanea tarda (PCT) in animal studies. Evidence in humans, however, is contradictory. In neonates and adults from a population historically highly exposed to HCB (Flix, Catalonia, Spain), no relation with PCT or with porphyrin excretion was found. OBJECTIVES: We aimed to analyze the association between urinary porphyrin excretion and exposure to HCB and other organochlorinated compounds in children 4 years of age. METHODS: Our birth cohort included all newborns from Flix and the five surrounding towns (where no airborne pollution occurred). Among the 68 children with porphyrins we measured in cord blood, 52 children 4 years of age provided blood to measure organochlorine compounds, hair for methylmercury, and urine for porphyrin excretion pattern. RESULTS: Quantitative porphyrin excretion was within the normal values. However, total porphyrins, coproporphyrin I (CPI), and coproporphyrin III (CPIII) adjusted to creatinine excretion increased with increasing levels of HCB, 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (p,p'-DDE), 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDT), and polychlorinated biphenyl congener 153 (PCB-153). We found no association with methylmercury. When we fitted multiple pollutant models, p,p'-DDE had the strongest association. We found these associations in children from both Flix and other towns, and they were independent of breast-feeding and of organochlorine and porphyrin levels at birth. CONCLUSION: HCB at current levels did not induce porphyria or increase uroporphyrins. However, the increase of urinary coproporphyrins suggests an incipient toxic effect of the organochlorines, especially for p,p'-DDE, on the hepatic heme-synthesis pathway that differs from the major effects seen in PCT.

J Biosci Bioeng. 2008 Jun; 105(6): 614-21
Purnomo AS, Kamei I, Kondo R

Twelve species of brown-rot fungi (BRF) have been investigated for their ability to degrade 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (DDT). In potato dextrose broth (PDB) medium, Gloeophyllum trabeum, Fomitopsis pinicola and Daedalea dickinsii showed a high ability to degrade DDT. 1,1-Dichloro-2,2-bis (4-chlorophenyl) ethane (DDD), 1,1-dichloro-2,2-bis (4-chlorophenyl) ethylene (DDE) and 4,4-dichlorobenzophenone (DBP) were detected as metabolic products of DDT degradation by G. trabeum in PDB medium. The DDT degradation pathway in G. trabeum is proposed, which differs from the proposed pathways in bacteria and other fungi, particularly in the transformation of DDE to DDD. On the other hand, DBP was not detected as a metabolic product of DDT degradation in FeSO(4)-deficient cultures of G. trabeum, whereas DDE and DDD were detected, indicating the involvement of an iron-dependent reaction. Only DBP was detected from DDT, DDE and DDD degradation via a chemical Fenton reaction under conditions similar to those in G. trabeum cultures. These compounds may be directly transformed to DBP via a Fenton reaction.

Sci Total Environ. 2008 Jun 15; 396(1): 34-41
Wang YR, Zhang M, Wang Q, Yang DY, Li CL, Liu J, Li JG, Li H, Yang XY

1,1,1-trichloro-2,2'-bis(4-chlorophenyl)ethane (DDT) exhibits its long persistence in the environment, unusual bioaccumulation, effects on wildlife, and the possibility of long-term adverse effects on human health, especially reproductive toxicity. Despite the prohibition of most persistent organochlorine pesticides in China, the presence of organochlorine residue, including DDT, has been widely indicated in environmental substance. However, scarce information is available about accumulative levels of DDT in human tissues in China. To evaluate levels of DDT and its potential effects on women and children's health in a Chinese pesticide-exposed area, we recruited 50 pairs of mother-child and 50 postpartum women, and determined the levels of total DDT and its four main metabolites (p,p'-DDE, p,p'-DDT, p,p'-DDD, o,p'-DDT) in venous blood, breast milk and umbilical blood cord by gas chromatography. Accordingly, data on reproductive outcomes of mothers and postpartum women and healthy status of children and infants were gathered through a questionnaire and medical examinations. Furthermore, we also assayed the DDT levels of some environmental samples (soil, food, milk, et al.). The levels of DDT in children's blood were higher than that in the women's. As compared to breast milk, the umbilical blood cord and the ventral fat individually demonstrated a significantly lower and higher level of DDT in the postpartum women. DDT was lower in milk and crucian carp than in the soil near the chemical plant. p,p'-DDT and p,p'-DDE were the main metabolites of DDT. Our findings suggested the cumulative effect of DDT in human body in Tianjin, China.

Environ Microbiol. 2008 Jun; 10(6): 1591-600
Blasco R, Ramos JL, Wittich RM

Pseudomonas aeruginosa RW41 is the first bacterial strain, which could be isolated by virtue of its capability to mineralize 4-chlorobenzenesulfonic acid (4CBSA), the major polar by-product of the chemical synthesis of 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT). This capability makes the isolate a promising candidate for the development of bioremediation technologies. The bacterial mineralization of 4CBSA proceeds under oxygenolytic desulfonation and transient accumulation of sulfite which then is oxidized to sulfate. High enzyme activities for the turnover of 4-chlorocatechol were measured. The further catabolism proceeded through 3-chloromuconate and, probably, the instable 4-chloromuconolactone, which is directly hydrolyzed to maleylacetate. Detectable levels of maleylacetate reductase were only present when cells were grown with 4CBSA. When the ordinary catechol pathway was induced during growth on benzenesulfonate, catechol was ortho-cleaved to cis,cis-muconate and a partially purified muconate cycloisomerase transformed it to muconolactone in vitro. The same enzyme transformed 3-chloro-cis,cis-muconate into cis-dienelactone (76%) and the antibiotically active protoanemonin (24%). These observations are indicative for a not yet highly evolved catabolism for halogenated substrates by bacterial isolates from environmental samples which, on the other hand, are able to productively recycle sulfur and chloride ions from synthetic haloorganosulfonates.

Environ Health Perspect. 2008 Feb; 116(2): 179-83
Cupul-Uicab LA, Gladen BC, Hernández-Avila M, Weber JP, Longnecker MP

BACKGROUND: Higher levels of 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE), the major degradation product of 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane (DDT), have been related to shorter duration of breast-feeding in previous studies. If DDE truly shortens lactation, this has public health importance regarding infant mortality and the use of DDT for malaria control. OBJECTIVE: Our aim was to assess the relationship of maternal DDE concentrations with length of subsequent lactation. METHODS: We conducted a relatively large study in a highly exposed area of Mexico. We followed 784 mother-son pairs to determine length of lactation. DDE and DDT were measured in maternal serum obtained within a day of delivery. We fit proportional hazard models with and without stratifying by previous breast-feeding, because an association of DDE with duration of lactation among those who breast-fed previously could be attributed to a noncausal mechanism. RESULTS: Compared with those with DDE concentrations < or = 3.00 microg/g, the adjusted hazard ratios of weaning according to DDE category were, for concentrations 3.01-6.00 microg/g, 1.27 [95% confidence interval (CI), 1.04-1.55]; for concentrations 6.01-9.00 microg/g, 1.23 (95% CI, 0.92-1.63); and for concentrations > 9.00 microg/g, 1.17 (95% CI, 0.92-1.49). The corresponding ratios for women who previously breast-fed were 1.40 (95% CI, 1.06-1.87); 1.91 (95% CI, 1.24-2.93); and 1.76 (95% CI, 1.22-2.53). Those for women who had not breast-fed previously were 1.14 (95% CI, 0.86-1.52); 0.90 (95% CI, 0.61-1.31); and 0.91 (95% CI, 0.66-1.26). CONCLUSIONS: Data from our relatively large study in a highly exposed area of Mexico did not support the hypothesis that exposure to DDE shortens length of lactation. The association seen in women who previously breast-fed was likely attributed to a noncausal mechanism. Nonetheless, whether DDT has other important adverse effects on humans is still an open question.

Sci Total Environ. 2007 Oct 15; 385(1-3): 235-41
Huang Y, Zhao X, Luan S

This research deals with biodegradation of 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane (DDT) by 4 selected ectomycorrhizal fungi (ECMF) species, Boletus edulis, Gomphidius viscidus, Laccaria bicolor, and Leccinum scabrum. The pure culture of the four ECMF species in a DDT environment (5 mg/l) showed that DDT almost completely disappeared from the media after 15 days, but only 40-50% was found being accumulated in mycelia. Further gas chromatography mass spectrometry (GC-MS) test of the hexane extractable metabolites identified that the remaining DDT degraded to 1,1-dichloro-2,2-bis (4-chlorophenyl) ethane (DDD) (retention time 17.39 min) and 4,4'-dihlorobenzophenone (DBP) (retention time 14.89 min). Therefore, these results, for the first time, demonstrated that ECMF can degrade DDT through a similar pathway found in white rot fungi.

Physiol Genomics. 2007 Aug 20; 30(3): 223-31
Yang J, McCart C, Woods DJ, Terhzaz S, Greenwood KG, ffrench-Constant RH, Dow JA

Insecticide resistance is a major problem for both medicine and agriculture and is frequently associated with overexpression of metabolic enzymes that catalyze the breakdown of pesticides, leading to broad-spectrum resistance. However, the insect tissues within which these metabolic enzymes normally reside remain unclear. Microarray analysis of nine adult tissues from Drosophila melanogaster reveals that cytochrome P-450s and glutathione-S-transferases show highly tissue-specific expression patterns; most were confined to one or more epithelial tissues, and half showed dominant expression in a single tissue. The particular detoxifying enzymes encountered by a xenobiotic thus depend critically on the route of administration. In particular, known insecticide metabolism genes are highly enriched in insect Malpighian (renal) tubules, implicating them in xenobiotic metabolism. The tubules thus display, with the fat body, roles analogous to the vertebrate liver and immune system, as well as its acknowledged renal function. To illustrate this, when levels of a single gene, Cyp6g1, were manipulated in just the Malpighian tubules of adult Drosophila, the survival of the whole insect after 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) challenge was altered, whereas corresponding manipulations in the nervous system or the fat body were without effect. This shows that, although detoxification enzymes are widely distributed, baseline protection against DDT resides primarily in the insect excretory system, corresponding to less than 0.1% of the mass of the organism.

J Environ Sci Health B. 2006; 41(8): 1291-303
Satapanajaru T, Anurakpongsatorn P, Pengthamkeerati P

The objective of this study was to quantify the effectiveness of different pretreated iron byproducts from the automotive industry to degrade DDT [(1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane] in aqueous solutions and soil slurry. Iron byproducts from automotive manufacturing were pretreated by three different methods (heating, solvent and 0.5N HCl acid washing) prior to experimentation. All pretreated irons were used at 5% (wt v-1) to treat 0.014 mM (5 mgL-1) of DDT in aqueous solution. Among the pretreated irons, acid pretreated iron results in the fastest destruction rates, with a pseudo first-order degradation rate of 0.364 d-1. By lowering the pH of the DDT aqueous solution from 9 to 3, destruction kinetic rates increase more than 20%. In addition, when DDT-contaminated soil slurry (3.54 mg kg-1) was incubated with 5% (wt v-1) acid-pretreated iron, more than 90% destruction of DDT was observed within 8 weeks. Moreover, DDT destruction kinetics were enhanced when Fe(II), Fe(III) or Al(III) sulfate salts were added to the soil slurry, with the following order of destruction kinetics: Al(III) sulfate > Fe(III) sulfate > Fe(II) sulfate. These results provide proof-of concept that inexpensive iron byproducts of the automotive industry can be used to remediate DDT-contaminated water and soil.

Environ Sci Technol. 2006 Oct 1; 40(19): 5882-90
Kronimus A, Schwarzbauer J, Ricking M

Eighteen pre-extracted samples derived from a subaquatic riverine sediment core taken from the Teltow Canal, Berlin (Germany), were treated by off-line TMAH-thermochemolysis and subsequently analyzed by GC-MS to investigate release and thermodegradation of non-extractable anthropogenic organic compounds (bound residues). Furthermore, six selected samples from the lower core section were additionally treated by off-line pyrolysis. Due to former investigations of the extractable fraction of Teltow Canal sediments, high amounts of compounds structurally related to the pesticide DDT (1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane) were anticipated within the nonextractable fraction. It has been shown that DDT-related bound residues can be gathered by pyrolysis and TMAH-thermochemolysis. Among other compounds, the experiments revealed two DDT-related degradation products (DDPU (3,3-bis(4-chlorphenyl)-1-propene) and DDPS (1,1-bis(4-chlorophenyl)propane)) which were detected for the first time in the environment. The latter compounds may represent formerly unknown metabolites or hints for the existence of carbon-carbon incorporated DDT-metabolites. Both methods tend to produce artifacts which complicate the interpretation of the results. With more knowledge on mechanisms occurring during application of pyrolysis and thermochemolysis, both methods can serve as valuable tools for analyzing bound residues in sediments.

Toxicol Sci. 2006 Nov; 94(1): 57-70
Sakai H, Iwata H, Kim EY, Tsydenova O, Miyazaki N, Petrov EA, Batoev VB, Tanabe S

To characterize the function of constitutive active/androstane receptor (CAR) in aquatic mammals, CAR complementary DNA (cDNA) was cloned from the liver of Baikal seal (Pusa sibirica) from Lake Baikal, Russia, and the messenger RNA (mRNA) expression levels in various tissues/organs of the wild population and the CAR ligand profiles were investigated. The seal CAR cDNA had an open reading frame of 1047 bp encoding 348 amino acids that revealed 74-84% amino acid identities with CARs from rodents and human. The mRNA expression profile of tissues/organs represented that Baikal seal CAR was predominantly expressed in the liver followed by heart and intestine. The expression analysis of hepatic CAR mRNA showed no correlation with expression of cytochrome P450 (CYP) 1A, 1B, 2B, 2C, and 3A-like proteins, indicating that the CAR expression level may not be the sole determinant of the regulation of these CYP expressions in the seal liver. There was no significant correlation between CAR expression and any of the persistent organic pollutants (POPs) levels. Furthermore, we performed an in vitro CAR transactivation assay using MCF-7 cells transfected with Baikal seal CAR expression plasmid and (NR1)(3)-luciferase reporter gene plasmid. In the transactivation analysis of Baikal seal CAR, neither repression by androstanol and androstenol, nor activation by estrone and estradiol, which are recognized as endogenous ligands for mouse and human CARs, was detected. On the other hand, bile acids such as chenodeoxycholic acid, deoxycholic acid, and lithocholic acid activated the seal CAR as well as mouse CAR. As for exogenous chemicals, the seal CAR was transactivated by a human CAR agonist, 6-(4-chlorophenyl)imidazo[2,1-b][1,3]thiazole-5-carbaldehyde O-(3,4-dichlorobenzyl)oxime), but not by a mouse CAR agonist, (1,4-bis[2-(3,5-dichloropyridyloxy)]benzene). In addition, the seal CAR was also activated by polychlorinated biphenyls (PCBs) (Kanechlor-500, International Union of Pure and Applied Chemistry No. PCB153; 2,2',4,4',5,5'-hexachlorobiphenyl and PCB180; 2,2',3,4,4',5,5'-heptachlorobiphenyl), and 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p'-DDT) and its metabolite, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p'-DDE). The seal CAR responded more sensitively to PCBs than the mouse CAR. Based on the results of CAR transactivation assay, the lowest observable effect levels of Kanechlor-500, PCB153, PCB180, p,p'-DDT, and p,p'-DDE in Baikal seal were estimated to be 10, 20, 20, 10, and 10 ppm on wet weight basis, respectively. These results suggest that CAR is conserved in diverse mammalian species including seals. Whereas the seal CAR-mediated gene transcription may potentially be a sensitive response to the exposure of certain POPs, the ligand profile of seal CAR may be different from those of other mammalian CARs. This study indicates that CAR-mediated responses may be useful information to assess the ecotoxicological risk of xenobiotics such as POPs in wildlife but the previous results derived from rodent and human CAR may not be applicable to the risk assessment in wild species.

J Hazard Mater. 2007 Jan 2; 139(1): 146-53
Gautam SK, Suresh S

The aim of our investigation was to compare the rates of dechlorination of DDT using Mg0/Pd4+ system in two different reaction phases, namely, water-acetone and 0.05% biosurfactant in water. Since palladium is expensive and its toxicity effects are not well known we also examined the reuse efficiency of Pd0 immobilized on alumina for dechlorinating DDT. Studies on the dechlorination of DDT in water-acetone (1:1, v/v) and 0.05% biosurfactant phases revealed that the reaction followed second order kinetics and rate of reaction is dependent upon both initial concentrations of the target compound and Mg0/Pd4+. The presence of acid enhanced the rate of reaction by providing protons and preventing passivation of metal that occurs due to deposition of magnesium hydroxide. GC-MS analyses revealed the formation of completely dechlorinated hydrocarbon skeleton of DDT namely, diphenylethane (DPE), as the end product in both reaction phases (water-acetone and 0.05% biosurfactant in water) thereby implying the removal of all five chlorine atoms (three alkyl and two aryl) of DDT. The optimum ratio of water and acetone to facilitate successful dechlorination reaction was found to be 9:1. Results suggested that salt form (K2PdCl6) of palladium had higher potential to dechlorinate DDT as compared to pellet (Pd0-alumina) form (efficiencies of 95 and 36%, respectively, for 100 ppm initial concentration of DDT). We noted that Pd0-alumina pellets could be reused at least four times for successful dechlorination of DDT provided Mg0 granules are present in sufficient quantity. Technical grade DDT (50 ppm) containing significant amounts of DDD was dechlorinated almost completely by the Mg0/Pd4+ (10mg/0.2mg/ml) within 1h in water-biosurfactant phase. Our studies reveal that Mg/Pd system is a promising option due to its high reactivity and its ability to achieve complete dechlorination of DDT. This bimetallic system may be useful for designing indigenous permeable barriers or reactors for the treatment of DDT contaminated water.

J Environ Sci Health B. 2006; 41(5): 647-69
Wan MT, Kuo JN, McPherson B, Pasternak J

Transient and permanent farm ditches flowing to the Lower Fraser River tributary fish streams of British Columbia, Canada, were sampled at several locations in 2003-2004 to determine the occurrence and concentration of residues of selected pesticides, their transformation products, and soluble/extractable Cu++ ions. Of the 43 compounds analyzed, 28 and 22 pesticides were detected in transient farm ditch water and sediments, respectively. About 34% fewer pesticides, however, were found in both matrices of permanent farm ditches. Average concentrations (microg L(-1)) of those most frequently detected in permanent farm ditch water were atrazine (0.20), alpha -chlordane (0.06), desethylatrazine (0.13), diazinon (0.55), dieldrin (0.28), endosulfan sulfate (0.16), glyphosate (6), metalaxyl (0.27); and soluble Cu++ ions (25). Those most often found in ditch sediments (microg kg(-1)) were aminomethylphosphonic acid (AMPA) (2,300), 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)ethane (DDT) (250), endosulfan sulfate (500), glyphosate (1,225); and extractable Cu++ ions (58,000). The risk potential of these pesticide residues to non-target aquatic organisms inhabiting Fraser River tributary fish streams contiguous to permanent farm ditches is evaluated and discussed.

Arch Environ Contam Toxicol. 2006 Aug; 51(2): 296-313
Minh TB, Watanabe M, Kajiwara N, Iwata H, Takahashi S, Subramanian A, Tanabe S, Watanabe S, Yamada T, Hata J

Concentrations of persistent organochlorines (OCs)-such as polychlorinated biphenyls (PCBs), 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), chlordane compounds (CHLs), hexachlorobenzene, and tris(4-chlorophenyl)methane [TCPMe]-were determined in plasma samples from residents of three sub-metropolitan locations in Japan (Miyako, Saku, and Tottori) for the purpose of studying the geographic variation and specific accumulation of OCs. Residue concentrations of PCBs and DDTs were the highest in samples collected in Saku (400 and 370 ng/g lipid wt, respectively) whereas samples from Miyako contained greater CHL residues (70 ng/g lipid wt) than those from the other two locations. This contamination pattern reflects the historic use of OCs in each area. For the first time, tris (4-chlorophenyl) methane (TCPMe) concentrations were detected in most of the plasma sample analyzed. Concentrations of TCPMe which ranged from <0.1 to 8.1 ng/g lipid wt eight, were lower than those previouly reported in other human tissue. Larger geographic differences in OC accumulation were observed for PCBs and CHLs, whereas DDTs and HCHs exhibited little variability. PCB concentrations in samples from Saku residents were higher than those from residents of countries in the circumpolar Arctic region but lower than those reported for some populations in the United States and Western European countries. Interestingly, CHL residue concentrations in human blood from Japan are among the highest values reported for the countries examined, suggesting continued increased exposure to CHLs of the Japanese population. Time-trend analysis of CHLs in human blood samples from Miyako (Okinawa prefecture) showed that CHL residues have decreased substantially during the last decade, indicating the effect of the official ban of CHLs in 1986 in Japan. Isomer-specific analysis of PCBs revealed lower proportions of higher chlorinated congeners such as hepta- and octachlorobiphenyls in women than in men, suggesting the possibility of preferential elimination of higher chlorinated biphenyls in women. The difference in sex-dependent accumulation of OC compounds in healthy and ill persons was suggested. To our knowledge, this is the first report on the specific accumulation of persistent QCs, including TCPMe, in human blood samples from Japan.

Congenit Anom (Kyoto). 2006 Jun; 46(2): 105-14
Hojo H, Aoyama H, Takahashi KL, Shimizu N, Araki M, Takizawa Y, Sakasai K, Kuwahara M, Saka M, Teramoto S

DDT, an organochlorine pesticide, has been cited as a representative chemical suspected of having endocrine disrupting effects. In this study, the potential endocrine disrupting activities of p,p'-DDT, a major component of DDT, were investigated in rats in a 2-generation reproduction toxicity study in accordance with the most current test guidelines of the Ministry of Agriculture, Forestry and Fisheries in Japan, Organization for Economic Cooperation and Development (OECD) and United States Environmental Protection Agency (USEPA) with some modifications and additions. p,p'-DDT was given to parental rats at dietary levels of 0, 5, 50 or 350 ppm. Systemic toxicities in the parental animals consisted of tremors and subsequent deaths (females only) and/or pathological alterations of the liver (both sexes of animals) of the 2 higher dose groups. Reproductive and postnatal developmental toxicities were not evident up to the highest dose level except for the decreased pup viability index on postnatal day 21 in the 350 ppm group. Changes in serum estradiol and progesterone levels and/or a delay in male sexual maturation were noted in the 2 higher dose groups in a dose-dependent fashion, suggesting alterations of endogenous endocrine functions. However, these changes never resulted in substantial reproductive disorders.

Chemosphere. 2006 Nov; 65(9): 1576-82
Pirnie EF, Talley JW, Hundal LS

Significant concentrations of chlorinated pesticides such as 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) and its two main transformation products, 1,1-dichloro-2,2-bis(4-chlorophenyl)ethane (DDD) and 1,1-dichloro-2,2-bis(4-chlorophenyl)ethylene (DDE) are still present in soil and sediment systems more than 30 years after DDT use was banned in the United States. DDT enters waterways via the runoff from industrial point sources, agricultural lands and atmospheric deposition. We evaluated zero-valent iron (Fe(0)), ferrous sulfide (FeS), as well as combining them with hydrogen peroxide (H(2)O(2)) as viable treatment technologies for degrading DDT in an aqueous solution. Treatment of DDT with Fe(0) and FeS resulted in approximately 88% and 56% transformation of DDT within 150h, respectively. DDE production was insignificant in all systems. The DDT removal was slower with FeS than with Fe(0), but the amounts of DDD and DDE produced did not exceed baseline. Treatment with a 1:1 mixture of Fe(0)-FeS removed about 95% of the added mass of DDT within 4days and generated significant amounts of DDD and minor amounts of DDMU. When small amounts of H(2)O(2) were introduced halfway through the Fe(0) and FeS treatment times, the mass of DDT decreased by 87% and 96%, respectively, within 2days. Our results demonstrate that mixtures of Fe(0)-FeS in combination with H(2)O(2) can be used for rapid and efficient removal of DDT from aqueous solutions.

Arch Environ Health. 2004 Sep; 59(9): 441-8
Waliszewski SM, Carvajal O, Infanzón RM, Gómez-Arroyo S, Villalobos-Pietrini R, Trujillo P, Hart MM

Samples of human blood sera (N = 118) for the determination of organochlorine pesticide levels were obtained at autopsy from auto accident victims in Veracruz, Mexico, during the years 2000 and 2001. The presence of hexachlorobenzene (HCH), beta-hexachlorocyclohexane (beta-HCH), 2,2-bis(p-chlorophenyl)-1,1-dichloroethylene (p,p'-DDE), 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDT), and o,p'-DDT was confirmed by gas-liquid-electron-capture detection chromatography. During the years 2000 and 2001, the respective mean levels of (a) HCB, (b) beta-HCH, (c) p,p'-DDE, (d) o,p'-DDT, (e) p,p'-DDT, and (f) total DDT were (a) 2.1 ng/ml and 1.4 ng/ml, (b) 3.0 ng/ml and 3.6 ng/ml, (c) 21.1 ng/ml and 23.8 ng/ml, (d) 1.2 ng/ml and 0.8 ng/ml, (e) 3.3 ng/ml and 2.5 ng/ml, and, finally, (f) 25.4 ng/ml and 27.1 ng/ml, respectively. High levels of persistent organochlorine pesticides were--and continue to be--present in the blood of individuals who live in Mexico. Levels of insecticide metabolites (e.g., beta-HCH, p,p'-DDE) in blood have increased during recent years (1997-2001), but levels of p,p'-DDT decreased in 2001 because the use of DDT for the control of malaria in Mexico was restricted.

Arch Environ Health. 2004 Jan; 59(1): 42-9
Barraza-Villarreal A, Farías P, Díaz Sánchez V, Bailey JL, De Jager T, Ayotte P, Hernández-Avila M, Dewailly E

A cross-sectional study was conducted to evaluate nonoccupational biological exposure to 1,1,1-Trichloro-2,2-bis(4-chlorophenyl)ethane (DDT) compounds and to identify the main factors associated with such exposure in a malaria endemic region in Mexico. Capillary gas column chromatography was used to determine levels of p,p'-DDT and its metabolites in plasma. The mean age of the 144 male participants was 28 yr. Mean p,p'-DDE (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene) and p,p'-DDT levels were 203.5 microg/l and 67.4 microg/l, respectively. Those whose houses had been sprayed for malaria control had much higher p,p'-DDE levels (p < 0.001). High levels of chlorinated pesticides were found despite being banned in Mexico for agricultural and public health use. Findings demonstrate the role of antimalarial campaigns as a major contributing factor for high DDT plasma levels.

Chemosphere. 2005 Dec; 61(10): 1427-38
Heim S, Ricking M, Schwarzbauer J, Littke R

To study the recent contamination history of DDT (1,1,1-trichloro-2,2-bis(chlorophenyl)ethane) and its metabolites, as well as methoxychlor (1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane), chlorfenson (4-chlorophenyl-p-chlorobenzenesulfonate), and further halogenated aromatics, a sediment core was collected from the Teltow Canal in Berlin (Germany). The sampling site is located nearby a former industrial point source, where recently analyses on pre-samples have indicated high concentrations of halogenated organic compounds. The deposition time of the investigated sediments was determined by gamma-spectrometrical dating. Pollution trends of selected contaminants were attributed to a time period between 5 and 10 years. Concentration profiles reflect not only the recent pollution history of these compounds, but also the time-depending effects of the ban, restriction and termination of DDT-production in the German Democratic Republic (GDR). DDT and other chlorinated aromatic compounds were produced onsite until the late 1980s. Maximum values of 133 mg kg(-1) (dry weight) for p,p'-DDD (1,1-dichloro-2,2-bis(chlorophenyl)ethane) and approximately 100 mg kg(-1) (dry weight) for p,p'-DDMS (1-chloro-2,2-bis(chlorophenyl)ethane), main metabolites of the anaerobic degradation of DDT, were determined. The occurrence of all selected contaminants, most of which have been banned more than 10 years ago, demonstrate recent contamination pathways, and the necessity of a continuous long-term monitoring of the affected environment.