Synthesis of chlorinated dibenzofurans and chlorinated amino-dibenzofurans from the corresponding diphenyl ethers and nitro-diphenylethers

The synthesis of five chlorinated dibenzofurans and three chlorinated animodibenzofurans from easily available diphenyl ethers is described. Also reported is the preparation of the diphenyl ethers. The ¹H-NMR and mass spectra data for the compounds are also reported.     

Synthesis of the DDT metabolite 2,4-dichloro-1-[2-chloro-1-(4-chlorophenyl)ethenyl]benzene (o-Cl-DDMU) and its detection in abiotic and biotic samples

Environmental Science and Pollution Research - Technical dichlorodiphenyltrichloroethane (DDT) has been used worldwide as a pesticide since the beginning of the 1940s. Due to its persistence, DDT...     

Isomer-specific analysis of chlorinated biphenyls,naphthalenes and dibenzofurans in Delor: polychlorinated biphenyl preparations from the former Czechoslovakia

Technical polychlorinated byphenyl (PCB) preparations--Delors 103, 104, 105, and 106--produced in the former Czechoslovakia were analyzed for their chlorobiphenyl (CB), chloronaphthalene (PCN) and chlorinated dibenzofuran (PCDF) composition and content using high resolution gas chromatography-mass spectrometry techniques. The congener patterns of Delors 103, 104, 105, and 106 resembled Aroclors 1242, 1248, 1254, and 1260. Delors contained PCNs and PCDFs, as impurities, at microgram per gram concentrations. Concentrations of PCNs and PCDFs in Delors were greater than those found in the corresponding Aroclors. The potential for the emissions of PCNs and PCDFs from Delor was estimated to be 3680 and 860 kg, respectively. Non- and mono-ortho PCBs were the major contributors to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents in Delor mixtures.     

Synthesis of [13C]- and [14C]-labeled phenolic humus and lignin monomers

Natural phenolic monomers are ubiquitous in the environment and are involved in the stabilization of atmospheric carbon and the transformation of xenobiotics. Investigations on the stabilization of phenolic carbons and their environmental fate are hampered by the unavailability of commercial [13C]- and [14C]-labeled phenols. Here we report the complete chemical synthesis of the lignin and humus structural monomers p-coumaric, ferulic, and caffeic acids, p-hydroxybenzaldehyde, protocatechualdehyde, vanillin, catechol, and guaiacol, uniformly [13C]- or [14C]-labeled in the aromatic ring, starting from commercially available [U-ring-13C]- or [U-ring-14C]-labeled phenol. The synthesis of these compounds involved selective ortho-hydroxylation of the aromatic ring, Friedel-Crafts alkylation, and Knoevenagel condensation. [U-ring-13C]- or [U-ring-14C]-p-coumaric acid was synthesized via p-hydroxybenzaldehyde with a 75% yield with respect to phenol. Synthesis of [U-ring-13C]- or [U-ring-14C]-ferulic acid, consisting of six single steps via guaiacol and vanillin, had an overall yield of up to 45%. Uniformly ring-labeled caffeic acid was synthesized either via catechol and protocatechualdehyde in five single steps, yielding [U-ring-14C]-caffeic acid with a 37% yield, or via guaiacol, vanillin, and ferulic acid in seven steps, yielding [U-ring-13C]-caffeic acid with an 18% yield. Ferulic acid, [14C]-labeled at beta-C of the propenoic side chain, was synthesized from [2-14C]-malonic acid under Knoevenagel conditions with a 67% yield with respect to malonic acid. Demethylation of the [beta-14C]-ferulic acid with BBr3 in CH3CN resulted in [beta-14C]-caffeic acid with a 62% yield. All [U-ring-13C]-labeled phenolic products were analyzed by 13C nuclear magnetic resonance (13C-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).     

Impact of repeated application on the binding and persistence of [14C]-DDT and [14C]-HCH in a tropical soil

An Indian sandy loam soil was initially treated with 1 kg a.i. ha(-1) of either [(14)C]-p,p'-DDT or [(14)C]-gamma-HCH during winter. DDT concentration after 30 days declined to 75.3%, which included 2.1% soil-bound residues. After 150 days, DDT levels further decreased to 42.4% with a concomitant increase in bound residues amounting to 5.9%. Identical treatment with HCH caused the residue levels to be reduced to 67.4 and 23.6%, after 30 and 150 days, respectively. During this period, the soil-bound residues of HCH increased from 5.2 to 12.8%. Repeat application to pre-treated soils in summer and subsequent field exposure for 30 days reduced the concentration of DDT to 52.1% and that of HCH to 42.4% of the total concentration following the second treatment. In parallel control experiments, which received only a single treatment, DDT levels declined to 61.3%, while HCH slumped to 45.3%, indicating a slower dissipation rate than in the corresponding repeated treatments. In repeat experiments, the soil-bound residues of DDT and HCH showed only a 1.07 to 1.08-fold increase in 30 days, as compared to three to ten-times increase in the control experiments. The results amply demonstrate that pre-treatment of tropical soils with DDT or HCH enhances their rate of dissipation and significantly reduce the formation of their soil-bound residues.     

Degradation of [14C]isofenphos in soil in the laboratory under different soil pH's, temperatures, and moistures

The effects of three soil pH's, three soil temperatures, and three soil moistures on [14C]isofenphos degradation were investigated. All three factors interacted strongly and significantly affected the persistence of isofenphos as well as the formation of the degradation products (p less than 1%). Isofenphos degradation was greatest at the higher temperatures 35 degrees C greater than 25 degrees C greater than 15 degrees C (except under alkaline pH's), medium moisture 25% greater than 30% greater than 15%, and in both alkaline (pH = 8) and acidic soils (pH = 6) compared with neutral soil (pH = 7). Isofenphos oxon formation was greatest at higher temperatures 35 degrees C compared with 25 degrees C and 15 degrees C, in acidic soil greater than neutral soil greater than alkaline soil, and under high moisture (30%) compared with the 15% and 22.5% moistures. The formation of soil-bound residues was greatest at higher temperatures 35 degrees C greater than 25 degrees C greater than 15 degrees C, higher moisture 30% compared with 15% and 22.5%, and in alkaline soil compared with neutral and acidic soils.     

Formation, characterization and release of non-extractable residues of [14C] -labeled organic xenobiotics in soils

The amount of non-extractable residues (NER) of organic xenobiotics in the soil can considerably exceed the amount of extractable residues which are accessible to normal residue analysis. The NER therefore present a burden to the soil, the toxicological and ecotoxicological potential of which is largely unknown. For the characterization of bound residues and their binding type, special solubilization methods such as supercritical fluid extraction are applied and experiments with radiolabeled model polymers are performed. Mineralization experiments with [¹⁴C] labeled xenobiotics in natural soil show that a total degradation is still also possible in the environment when in a bound form. Ecotoxicological effects of non-extractable residues may be recorded when their concentration is high, when the parent compound exhibits a high ecotoxicity and the applied detection method is sufficiently sensitive.     

The effect of temperature and solar radiations on volatilisation, mineralisation and degradation of [14C]-DDT in soil

The influence of temperature and solar radiations on the rapid dissipation of DDT from tropical soils was studied by quantifying volatilisation, mineralisation, binding and degradation of ((14)C)-p,p'-DDT in a sandy loam soil. The bulk of the DDT loss occurred by volatilisation, which increased fivefold when the temperature changed from 15 to 45 degrees C. Degradation of DDT to DDE was also faster at higher temperatures. Mineralisation of DDT, though minimal, increased with temperature and time. Higher temperatures also enhanced binding of DDT to soil. Flooding the treated soil further increased volatilisation and degradation, although mineralisation was greatly reduced. Exposure of flooded and unflooded soils treated with DDT to sunlight in quartz, glass and dark tubes for 42 days during summer resulted in significant volatile losses. Volatilisation in the quartz tubes was nearly twice as great as that in the dark tubes The volatilised organics from the quartz tubes contained larger amounts of p,p'-DDE than the glass and dark tubes. Higher rates of volatilisation and degradation were found in flooded soils. Also significant quantities of p,p'-DDD were detected in addition to DDE. The data clearly show that volatilisation is the major mechanism for the rapid dissipation of DDT from Indian soils.     

Metabolism of the nonylphenol isomer [ring-U-14C]-4-(3',5'-dimethyl-3'-heptyl)-phenol by cell suspension cultures of Agrostemma githago and soybean

The biotransformation of the nonylphenol isomer [ring-U-14C]-4-(3',5'-dimethyl-3'-heptyl)-phenol (4-353-NP, consisting of two diastereomers) was studied in soybean and Agrostemma githago cell suspension cultures. With the A. githago cells, a batch two-liquid-phase system (medium/n-hexadecane 200:1, v/v) was used, in order to produce higher concentrations and amounts of 4-353-NP metabolites for their identification; 4-353-NP was applied via the n-hexadecane phase. Initial concentrations of [14C]-4-353-NP were 1 mg L(-1) (soybean), and 5 and 10 mg L(-1) (A. githago). After 2 (soybean) and 7 days (A. githago) of incubation, the applied 4-353-NP was transformed almost completely by both plant species to four types of products: glycosides of parent 4-353-NP, glycosides of primary 4-353-NP metabolites, nonextractable residues and unknown, possibly polymeric materials detected in the media. The latter two products emerged especially in soybean cultures. Portions of primary metabolites amounted to 19-22% (soybean) and 21-42% of applied 14C (A. githago). After liberation from their glycosides, the primary 4-353-NP metabolites formed by A. githago were isolated by HPLC and examined by GC-EIMS as trimethylsilyl derivatives. In the chromatograms, eight peaks were detected which due to their mass spectra, could be traced back to 4-353-NP. Seven of the compounds were side-chain monohydroxylated 4-353-NP metabolites, while the remaining was a (side-chain) carboxylic acid derivative. Unequivocal identification of the sites of hydroxylation/oxidation of all transformation products was not possible. The main primary metabolites produced by A. githago were supposed to be four diastereomers of 6'-hydroxy-4-353-NP (about 80% of all products identified). It was concluded that plants contribute to the environmental degradation of the xenoestrogen nonylphenol; the toxicological properties of side-chain hydroxylated nonylphenols remain to be examined.     

Influence of a heavy rainfall event on the leaching of [14C]isoproturon and its degradation products in outdoor lysimeters

In four different agricultural soils the long-term leaching behaviour of [14C]isoproturon was studied in outdoor lysimeters (2 m length, 1 m2 surface area). The herbicide was applied in spring 1997 and spring 2001. At the end of the first 4-year-investigation period between 0.13% and 0.31% of the applied radioactivity was leached. Isoproturon or known metabolites could not be detected in the leachate. However, shortly after the second application isoproturon and its degradation products 2-hydroxy-isoproturon and monodemethyl-isoproturon were leached via preferential flow in one of the lysimeters (Mollic gleysol) in concentrations of 4.5 microg L-1, 3.1 microg L-1 and 0.9 microg L-1, respectively, thus considerably exceeding the EU threshold limit of 0.1 microg L-1 for ground and drinking water. The results indicate that in soils where mass flow transfer dominates, leaching of isoproturon to groundwater is of low probability whereas in highly structured soils which have the tendency to form macropores, isoproturon can be transported via preferential flow to the groundwater.     

Characterization of mass-labeled [13C14]-decabromodiphenylethane and its use as a surrogate standard in the analysis of sewage sludge samples

Very little data is available about the presence of the brominated flame retardant, DBDPE, in the environment. This study reports the characterization of [(13)C(14)]-decabromodiphenylethane and the use of this surrogate standard to positively identify and quantify the presence of DBDPE in sewage sludge samples. The large difference in response factors between BDE-209 and DBDPE predicates the use of [(13)C(14)]-decabromodiphenylethane as a surrogate standard to improve the accuracy when determining the levels of DBDPE in environmental samples.     

Tissue-specific accumulation and lactational transfer of polychlorinated biphenyls, chlorinated pesticides, and brominated flame retardants in hooded seals (Cistophora cristata) from the Gulf of St. Lawrence: applications for monitoring

Accumulation and mother-pup transfer of halogenated organic contaminants was studied in hooded seal tissues from eastern Canada. Blubber polychlorinated biphenyl (PCB) and total pesticide concentrations were relatively high, possibly due to their high trophic level and demersal feeding habits. Blood plasma showed the lowest contaminant concentrations compared to blubber and liver, possibly due to a lower affinity of these compounds to lipoproteins in blood plasma. Total contaminant body burden correlated well with blubber, liver, and milk contaminants, but not with blood plasma contaminants, indicating that blood plasma might be less suitable to monitor contaminants in hooded seals. Lactational transfer favored less lipophilic contaminants and was associated with relatively high blood plasma PCB and polybrominated diphenyl ether concentrations in females. Despite lactational transfer, females did not show significantly lower blubber contaminant concentrations or burdens than males. This might be caused by their low blubber, and thus contaminant, loss during lactation compared to other species.     

Degradation of RPA 202248 [U-14C-phenyl]alpha(-(cyclopropylcarbonyl)-2-(methylsulfonyl)-beta-oxo-4-(trifluromethyl)benzenepropanenitrile), the primary degradation product of isoxaflutole, in an outdoor aquatic microcosm system

Isoxaflutole, the active ingredient in BALANCE WDG and BALANCE PRO corn herbicides and a co-formulant with the herbicide flufenacet in the product EPIC, is readily degraded in soil and water to RPA 202248 alpha(-(cyclopropylcarbonyl)-2-(methyvlsulfonyl)-beta-oxo-4-(trifluromethyl)benzenepropanenitrile). Because RPA 202248 is responsible at the molecular level for isoxaflutole's herbicidal activity it is important to understand the environmental behavior of the degradation product. Laboratory studies suggest that RPA 202248 is stable to hydrolysis and photolysis in aqueous systems and hence poses a possible environmental concern. As part of a program of work towards understanding the actual field situation, an outdoor microcosm study was carried out. Over the course of the 29-day study, residues remained predominantly in the aqueous phase. A slow but steady degradation of RPA 202248 was observed leading to the formation of RPA 203328 (2-methylsulfonyl-4-trifluoromethylbenzoic acid), which has no herbicidal activity. The half-life of RPA 202248 was calculated to be 103 days. These findings indicate that aqueous degradation should be considered as a potential route of dissipation when assessing the fate of RPA 202248 in large scale impounded water bodies, such as ponds, lakes, or reservoirs in the Mid-West Corn Belt.     

New cytochrome P450 1B1, 1C1, 2Aa, 2Y3, and 2K genes from Chinese rare minnow (Gobiocypris rarus): Molecular characterization,basal expression and response of rare minnow CYP1s and CYP2s mRNA exposed to the AHR agonist benzo[a]pyrene

Cytochrome P450 (CYP450) genes play an important role in catalyzing oxidative metabolism of toxicants. Recently, CYP1 subfamily were discovered and reported in fish, however, little is known regarding the CYP2 isoforms in fish. In the present study, the cDNA fragments of CYP 1B1 and 1C1 and CYP2Aa, 2Y3, and 2K of rare minnow were cloned and exhibited a high amino acid sequence identity compared with their zebrafish orthologs. Basal expression showed CYP1C1 and CYP 2Aa expression were observed in all eight tissues analyzed (liver, gill, intestine, kidney, spleen, brain, skin, and muscle). CYP 1A, and 1B1 expression was found in all tissues except for muscle and skin. However, CYP 2Y3 was expressed in liver, spleen, intestine and muscle whereas CYP 2 K in liver, kidney and intestine. 4 and 100 μg L⁻¹ Benzo[a]pyrene (BaP) induced patterns showed that CYP 1A, 1B1 and 1C1 expression in liver, gill, and intestine was strongly up-regulated (p < 0.05). Furthermore, CYP 2Y3 was strongly induced in liver from BaP treatments (p < 0.05). The high induction on mRNA level of CYP1s and CYP 2Y3 by BaP could be associated with catalyzing detoxification and indicated that CYP2s may also be potential biomarker to screen AHR agonist. The high responsiveness of CYP1 and 2 genes suggested Chinese rare minnow is feasible to screen and assess pollution with AHR agonist.