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Hydrophilic and hydrophobic sorption of organic acids by variable charge soils: effect of chemical acidity and acidic functional group.

Sorption of organic acids by variable-charge soil occurs through both hydrophilic and hydrophobic sorption. In this study, the effect of chemical acidity and the type of acidic functional group on the relative contribution of hydrophilic and hydrophobic processes to sorption by a gibbsite-dominated and a kaolinite-dominated variable-charge soils was quantified by measuring sorption isotherms from different electrolytes (CaCl2, Ca(H2PO4)2, and KCl). The A1 soil is dominated by gibbsite whereas the DRC soil is primarily kaolinite. The organic acids investigated include five chlorinated phenols (pentachlorophenol, 2,3,4,6-tetrachlorophenol, 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, and 2,4-dichlorophenol) with pKa values ranging from 4.69 to 7.85 and two acidic herbicides (2,4-D (pKa = 2.8) and prosulfuron (pKa = 3.76)) that contain carboxyl and urea functional groups, respectively. Anion exchange of chlorinated phenols and prosulfuron on both variable-charge soils as well as 2,4-D sorption on the A1 soil was linearly correlated to chemical acidity. The effective positive surface charge [AEC/(AEC + CEC)] and the anionic fraction of the organic acid in solution, which are both pH-dependent, were sufficient to estimate the contribution of anion exchange to organic acid sorption except for 2,4-D sorption by DRC soil. The latter was much greater than would be predicted from the pKa of 2,4-D. Calcium bridging between silanol edge group and 2,4-D was hypothesized and corroborated by differences in sorption measured from KCl and CaCl2 solutions. For predicting contributions from hydrophobic processes, a log-log linear relationship between pH-dependent octanol-water (Kow(pH)) and organic carbon-normalized sorption coefficients (Koc(pH)) appeared adequate.

2,4-Dichlorophenoxyacetic Acid↗

Preliminary assessment of imidazolium-based room-temperature ionic liquids for extraction of organic contaminants from soils.

Alternative solvents known as room-temperature ionic liquids (RTILs) were considered for extraction of organic soil contaminants. A hydrophobic RTIL, 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim]PF6), and a hydrophilic RTIL, 1-butyl-3-methyl imidazolium chloride ([bmim]Cl), were selected as representative imidazolium-based RTILs to assess the extraction of several organic contaminants (OCs) from two model soils. The two soils were montmorillonite (clay minerals, high surface area, and no organic matter) and glacial till (organic matter). The soils were spiked separately with DDT, dieldrin, hexachlorobenzene, and pentachlorophenol. With the exception of DDT, extractions of OCs from montmorillonite using [bmim]PF6 (79-92%) were nearly as effective as extractions with acetone and ethanol (85-100%). The extraction of OCs from glacial till with RTILs (15-61%) was less effective than extraction with organic solvents (59-100%). The [bmim]Cl was as efficient as [bmim]PF6 for extraction of OCs from glacial till, while [bmim]PF6 was more efficient than [bmim]Cl for extraction of OCs from montmorillonite. The two RTILs were most effective for the extraction of dieldrin (the heaviest OC) from both soils. The extraction results for glacial till showed dependence of OC extraction on the viscosity and melting point of RTILs.

Imidazoles↗

Chlorinated dibenzo-p-dioxin and dibenzofuran concentrations in beef animals from a feeding study.

Four calves were fed polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans for 120 days at levels somewhat higher than what may be found in forage near some waste incinerators and manufacturing plants. Four calves were fed identical diets but without the chemicals. Using bioelectrical impedance measurements of total body fat, 30-50% of the dosed 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, and 2,3,4,7,8-PeCDF was estimated to be retained by the animals. Although these same congeners were bioconcentrated in adipose tissue (BCF approximately 10), consumer products such as ribeye showed concentrations less than what were found in the animal feed (BCF approximately 0.1). Distribution of the dioxins and furans into various lipid compartments appeared to be rather uniform in back fat, perirenal fat, and ribeye for tetra to hexa congeners. Ribeye, serum, and liver lipids had higher concentrations of the higher chlorinated congeners, due in part to not reaching a steady state. An unexpected source of dioxin and furan contamination was discovered during the experiment, resulting in the control animals having concentrations of some congeners that were equal to or in some cases greater than those of the dosed animals. Pentachlorophenol-treated wood components in the pole barn where the feeding experiment was conducted were found to have contributed to the animals' exposure.

Adipose Tissue↗

Analytical procedure for quantifying five compounds suspected as possible contaminants in recycled paper/paperboard for food packaging.

Because contaminants in recycled paper intended for food packaging could be a risk to public health, analytical methods are needed to identify and quantify residues of concern in paper/paperboard. The U. S. Food and Drug Administration is considering development of a guidance document for testing levels of contaminants that might be retained through paper recycling processes. An analytical procedure was developed using paper spiked with suspected contaminants at concentrations of 1-50 ppm in the paper. Benzophenone, dimethyl phthalate, anthracene, methyl stearate, and pentachlorophenol were introduced by soaking the paper in a solution in acetone at 25 degrees C for 24 h; the paper was removed and dried by evaporating the solvent with nitrogen. The model contaminant residues were extracted from the paper using ultrasonication and quantified by GC with flame ionization and electron capture detectors. Recoveries from the spiked paper were 80-109% with a repeatability of +/-4%. The method was also used to analyze commercial recycled paperboard to validate its applicability.

Chromatography, Gas↗

Ethanol/Water extraction combined with solid-phase extraction and solid-phase microextraction concentration for the determination of chlorophenols in cork stoppers.

The appearance of 2,4,6-trichloroanisole (TCA) in cork stoppers is of great concern because it can cause off-flavors in bottled wine. To prevent this sensorial defect, there should not be any traces of 2,4,6-trichlorophenol (TCP), 2,3,4,6-tetrachlorophenol (TeCP), or pentachlorophenol (PCP) in the finished corks, because they are the direct precursors of TCA. In the course of this study two methodologies based upon an extraction with ethanol/water mixtures to determine the chlorophenolic content in cork matrices were developed. The cork extract is preconcentrated using both solid-phase extraction and solid-phase microextraction methodologies. The latter was optimized by applying a full two-level factorial design. Finally, spiked ground corks at nanogram per gram levels of each chlorophenol were analyzed under optimal conditions and by applying both procedures. The obtained results demonstrate that chlorophenols can be detected in corks contaminated at the nanogram per gram level and, thus, these approaches can be successfully applied as quality control measures in the cork industry.

Chlorophenols↗

Determination of haloanisols in white wine by immunosorbent solid-phase extraction followed by enzyme-linked immunosorbent assay.

A high through-put screening immunochemical method to control the presence of 2,4,6-trichloroanisol (TCA) and 2,4,6-tribromoanisol (TBA), the main agents responsible for the musty odor in wine samples, has been developed. The method involves a selective (antibody-antigen) solid-phase extraction (SPE), followed by enzyme-linked immunosorbent assay (ELISA) analysis. The sample preparation method established uses for immunosorbents (ISs) prepared by covalently coupling antibodies developed for TCA on a sepharose support. At present, about 200-400 ng L-1 of TBA and TCA can be detected in white wine samples by the IS-SPE-ELISA method described here without any preconcentration step. Simultaneous analyses of many samples are possible with this method. Related chloroanisoles (2,3- and 2,6-dichloroanisols and 2,3,4,5-tetrachloroanisol) and chlorophenols (2,3,4,6-tetrachlorophenol and pentachlorophenol) usually present in contaminated wine samples are also effectively retained by the IS, although only 2,4,6-TCA and 2,4,6-TBA are detected by the ELISA used. The immunopurification procedure developed could also be useful as a selective cleanup method prior to chromatographic analysis.

Anisoles↗

Radiolytic transformations of chlorinated phenols and chlorinated phenoxyacetic acids.

Hydroxyl radical reactions of selected chlorinated aromatic phenols (2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol) and chlorinated phenoxyacetic acids [2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-D methyl ester, 2-(2,4-dichlorophenoxy)propionic acid (2,4-DP)] were studied using the radiolysis techniques of pulse radiolysis and gamma radiolysis. Hydroxyl radical addition was the prominent reaction pathway for the chlorinated phenoxyacetic acids and also for the chlorinated phenols at pH values below the pK(a) of the compounds. A very prominent change in (*)OH reactivity was observed with the chlorinated phenoxide ions in high pH solutions. Two different reaction pathways were clearly present between the hydroxyl radical and the chlorinated phenoxide ions. One of the reaction pathways was suppressed when the concentration of chlorinated phenoxide ions was increased 10-fold. Amid a greater electron-withdrawing presence on the aromatic ring (higher chlorinated phenoxide ions), the hydroxyl radical reacted preferably by way of addition to the aromatic ring. Steady-state experiments utilizing gamma radiolysis also showed a substantial decrease in oxidation with an increase in pH of substrate.

Journal Article↗

Metabolism of ochratoxin A: absence of formation of genotoxic derivatives by human and rat enzymes.

Ochratoxin A (OTA) is a potent renal carcinogen in male rats, although its mode of carcinogenicity is not known. The metabolism and covalent binding of OTA to DNA were investigated in vitro with cytochromes P450, glutathione S-transferases, prostaglandin H-synthase, and horseradish peroxidase. Incubation of OTA with rat or human liver microsomes fortified with NADPH resulted in formation of 4-(R)-hydroxyochratoxin A at low rates [10-25 pmol min(-1) (mg of protein)(-1)]. There was no evidence of OTA metabolism and glutathione conjugate formation with rat, mouse, or human kidney microsomes or postmitochondrial supernatants (S-9) [<5 pmol min(-1) (mg of protein)(-1)]. Recombinant human cytochromes P450 (P450) 1A1 and 3A4 formed 4-(R)-hydroxyochratoxin A at low rates [0.08 and 0.06 pmol min(-1) (pmol of P450)(-1), respectively]; no oxidation products of OTA were detected with recombinant human P450 1A2 or 2E1 or rat P450 1A2 or 2C11 [<0.02 pmol min(-1) (pmol of P450)(-1)]. Prostaglandin H-synthase produced small amounts of an apolar product [33 pmol min(-1) (mg of protein)(-1)], and OTA products were not formed with horseradish peroxidase. There was no evidence of DNA adduct formation when [(3)H]OTA was incubated with these enzyme systems in the presence of calf thymus DNA (<20 adducts/10(9) DNA bases); however, these enzymes catalyzed DNA adduct formation with the genotoxins aflatoxin B(1), 2-amino-3-methylimidazo[4,5-f]quinoline, benzo[a]pyrene, and pentachlorophenol. There was also no detectable [(3)H]OTA bound in vivo to kidney DNA of male Fischer-344 rats treated orally with [(3)H]OTA (1 mg/kg, 100 mCi/mmol, 24 h exposure, <2.7 adducts/10(9) DNA bases), based upon liquid scintillation counting. However, (32)P-postlabeling experiments did show evidence of DNA lesions with total adduct levels ranging from 31 to 71 adducts/10(9) DNA bases, while adducts in untreated rat kidney ranged from 6 to 24 adducts/10(9) DNA bases. These results do not support the premise that OTA or metabolically activated species covalently bind to DNA and suggest that the (32)P-postlabeled lesions are due to products derived from OTA-mediated cytotoxicity.

Animals↗

The contribution of N-oxidation to the metabolism of the food-borne carcinogen 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline in rat hepatocytes.

The metabolism of 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline, a potent bacterial mutagen and rodent carcinogen formed in low quantities in cooked meat and fish, was studied in freshly isolated rat hepatocytes. Ten metabolites were characterized by various spectroscopic methods. Sulfamate formation was the major route of metabolism in hepatocytes of untreated rats whereas ring-hydroxylated sulfuric and glucuronic acid conjugates were major metabolites in animals pretreated with the enzyme inducers Aroclor-1254, beta-naphthoflavone, or isosafrole. The formation of a mutagenic metabolite through N-oxidation, 2-(hydroxyamino)-3,8- dimethylimidazo[4,5-f]quinoxaline (HNOH-MeIQx), was an important route of metabolism in hepatocytes of pretreated animals. Its metastable derivative, the N-hydroxy-N-glucuronide, also was detected. The nitro derivative of MeIQx, a direct-acting bacterial mutagen, was readily detoxified by glutathione transferase, forming a conjugate where the thiol group of glutathione displaced the nitro moiety. Low but detectable levels of N-acetyltransferase activity were observed for MeIQx and sulfamethazine in hepatocytes. HNOH-MeIQx and 4-(hydroxyamino)biphenyl (HNOH-ABP), a recognized human carcinogen, displayed acetyl coenzyme A dependent DNA binding in hepatic cytosol assays. Sulfamethazine decreased the DNA binding of HNOH-MeIQx in hepatocytes, suggesting a competition for acetyltransferase. However, the binding of HNOH-MeIQx to DNA in hepatocytes was independent of sulfotransferase since inhibitors of this enzyme, 2,6-dichloro-4-nitrophenol (DCNP) and pentachlorophenol (PCP), did not diminish DNA binding. In contrast, binding of HNOH-ABP to DNA was not decreased by sulfamethazine, but binding was diminished by both sulfotransferase inhibitors. From these inhibition experiments it appears that a major route of binding of HNOH-MeIQx to DNA in hepatocytes is mediated through O-acetyltransferase while a significant portion of HNOH-ABP bound to DNA is catalyzed by sulfotransferase.

Acetyltransferases↗

Measurement of hemoglobin and albumin adducts of tetrachlorobenzoquinone.

Tetrachloro-1,4-benzoquinone (Cl4BQ), a metabolite of pentachlorophenol (PCP), is believed to play a role in the genotoxicity of PCP. We have developed a method to measure the adducts of Cl4BQ with cysteine residues of hemoglobin (Hb) and albumin (Alb). This method employs the use of Raney nickel to selectively cleave the sulfur-bound adducts. Adducts of Hb and Alb with Cl4BQ were measured following modification of rat blood with Cl4BQ (0-90 microM) in vitro. The formation of both Hb and Alb adducts was linear over the entire range with second-order rate constants of 6.89 and 167 L mol-1 h-1, respectively. The proportions of the concentrations of these Hb and Alb adducts to those of all covalently-bound products were estimated to be 0.053 and 0.178, respectively, at initial Cl4BQ concentrations between 3 and 90 microM. The overall rate of reaction of Cl4BQ in rat blood (in vitro) was pseudo-first-order with an estimated half-time of 4.35 h. Hb and Alb adducts of Cl4BQ were also measured in vivo following oral administration of PCP to rats (0-20 mg/kg body wt). Linear production of Hb and Alb adducts was observed over the entire range of dosages, with slopes of 0.09 and 8.22 pmol of adduct (g of protein)-1 [(mg of PCP)/(kg body wt)]-1, respectively. On the basis of production of Hb adducts in vitro and in vivo, it is estimated that 2.7 x 10(-7) mol of Cl4BQ was released to the blood of rats per mole of PCP administered.(ABSTRACT TRUNCATED AT 250 WORDS)

Albumins↗

Conversion of pentahalogenated phenols by microperoxidase-8/H2O2 to benzoquinone-type products.

This study reports the microperoxidase-8 (MP8)/H2O2-catalyzed dehalogenation of pentafluorophenol and pentachlorophenol, compounds whose toxic effects and persistence in the environment are well documented. The primary products of this dehalogenation reaction appear to be the corresponding tetrahalo-p-benzoquinones. Under the conditions used, the fluorinated phenol and its intermediate products are more susceptible to degradation than the corresponding chlorinated analogue and its products. The main degradation products of tetrachloro-p-benzoquinone and tetrafluoro-p-benzoquinone were identified as trichlorohydroxy-p-benzoquinone and trifluorohydroxy-p-benzoquinone, respectively. This secondary conversion of tetrafluoro-p-benzoquinone and tetrachloro-p-benzoquinone was not mediated by MP8, but was driven by H2O2. Evidence is presented for a mechanism where H2O2 molecules and not hydroxide anions are the reactive nucleophilic species attacking the tetrahalo-p-benzoquinones. In addition to the formation of the trihalohydroxy-p-benzoquinones, the formation of adducts of the tetrahalo-p-benzoquinone products with ethanol, present in the incubation medium, was observed. The adduct from the reaction of tetrachloro-p-benzoquinone with ethanol was isolated and identified as trichloroethoxyquinone. Thus, the present paper describes a system in which the formation of tetrahalo-p-benzoquinone-type products by an oxidative heme-based catalyst could be unequivocally demonstrated.

Ascorbic Acid↗

Transformation of 2,4,6-trichlorophenol by the white rot fungi Panus tigrinus and Coriolus versicolor.

The toxicity of thirteen isomers of mono-, di-, tri- and pentachlorophenols was tested in potato-dextrose agar cultures of the white rot fungi Panus tigrinus and Coriolus versicolor. 2,4,6-Trichlorophenol (2,4,6-TCP) was chosen for further study of its toxicity and transformation in liquid cultures of these fungi. Two schemes of 2,4,6-TCP addition were tested to minimize its toxic effect to fungal cultures: stepwise addition from the moment of inoculation and single addition after five days of growth. In both cases the ligninolytic enzyme systems of both fungi were found to be responsible for 2,4,6-TCP transformation. 2,6-Dichloro-1,4-hydroquinol and 2,6-dichloro-1,4-benzoquinone were found as products of primary oxidation of 2,4,6-TCP by intact fungal cultures and purified ligninolytic enzymes, Mn-peroxidases and laccases of both fungi. However, primary attack of 2,4,6-TCP in P. tigrinus culture was conducted mainly by Mn-peroxidase, while in C. versicolor it was catalyzed predominantly by laccase, suggesting a different mode of regulation of these enzymes in the two fungi.

Benzoquinones↗

The oxidation, fate and effects of iron during on-site bioremediation of groundwater contaminated by a mixture of polychlorophenols.

Kinetics of simultaneous iron and polychlorophenol (CP) oxidation by groundwater enriched cultures were studied in laboratory and during actual remediation in order to reveal the fate and effects of iron on aerobic on-site bioremediation of boreal groundwater. 2,4,6-tri- (TCP), 2,3,4,6-tetra- (TeCP) and pentachlorophenol (PCP) were degraded in fluidized-bed bioreactor (FBR) by over 99%, over 99%, and over 96%, respectively. The oxygen consumption rate for CP-biodegradation was 1.31 micromol DO L(-1) min(-1) and 0.29 micromol DO L(-1) min(-1) for iron oxidation, i.e. approximately 12% of the oxygen was consumed by iron oxidation during normal FBR operation. Mineralization of CPs was confirmed by DOC removal and chloride release of 158% and 78%, respectively. Excess DOC removal was due to partial degradation of the natural organic matter (NOM) (1.1 mg L(-1) or 24% DOC removal) in the groundwater. Removal of NOM consumed 0.91 micromol DO L(-1) min(-1). Iron oxidation in the FBR was over 94% of which chemical Fe(II) oxidation accounted for up to 10%. Fe(III) partially accumulated (58 to 69%) in the system. The TCP- and CP-biodegradation consumed DO at two times higher rates than the Fe(II)-oxidation in both, laboratory and full-scale, respectively. The batch assays at various TCP and Fe(II) ratios and DO concentrations showed simultaneous oxygen consumption by TCP and Fe-oxidizers and that increased Fe concentrations do not outcompete the bioremediation of CP's for available oxygen.

Aerobiosis↗

Biotreatability and kinetics of UASB reactor to mixtures of chlorophenol pollutants.

In most natural ecosystems heterotrophic microorganisms encounter complex mixtures of carbon sources, each of which is present at a concentration of few micrograms per litre. This study examined the biotreatability and kinetics of an upflow anaerobic sludge blanket (UASB) reactor to complex mixtures of chlorophenols encountered in environmental conditions using on-line and off-line experimental studies. Results indicate that (1) steady-state concentration was quite lower (98.3 mg L(-1)) with complex mixture of chlorophenols than steady-state concentration achieved when only 2.4 dichlorophenol (124 mg L(-1)) was studied alone on the same reactor; (2) that toxic effects of chlorophenols increase with increasing concentrations of toxicant. (Onset of the inhibitory effect occurred at a lower concentration in multi-substrate than in single substrate utilization): (3) addition of alternative utilizable substrate can mitigate toxic effects and enhance degradation; (4) the relative concentration of substrate was critical in determining utilization patterns. HPLC analysis of off-line experimental samples resulted in a steady-state treatment efficiency of 68% for COD, 36% for 2-chlorophenol, 40.5% for 4-chlorophenol, 70.7% for 2,4-dichlorophenol, 53.2% for 2,4,6-trichlorophenol and 42% for pentachlorophenol in presence of glucose. Kinetic constant in terms of Vmax and Ks were determined. Ks for the five chlorophenols ranged between 0.016 and 0.117 kg m(-3) day(-1) while Vmax range between 0.056 and 0.244 kg m(-3) day(-1).

Bacteria, Anaerobic↗

Phenol and lactone receptors in the distal sensilla of the Haller's organ in Ixodes ricinus ticks and their possible role in host perception.

Extract of steer wool odor was found to excite olfactory receptor(s) in a wall-pore olfactory sensillum on the distal knoll of the Haller's organ. Three active volatile compounds were revealed in this odor by gas chromatography. Electrophysiological experiments revealed two types of receptors (sensory neurons) within the sensilla examined. One type of receptor responded only to phenolic derivatives, such as o-chlorophenol, o-bromophenol, o-methylphenol, 2,6-dichlorophenol, 2,6-dibromophenol, 2,4,6-trichlorophenol, but not to o-nithrophenol, p-methylphenol, 2,5-dichlorophenol, 3,5-dichlorophenol, 2,6-dinithrophenol, 2,6-dimethylphenol, and pentachlorophenol. The other type of receptor responded only to gamma-valerolactone. It is assumed that these cells play an important role in perception of a host from long distances (10-15 m), which is typical of Ixodes ricinus ticks.

Animals↗

Cytotoxic effects of environmentally relevant chlorophenols on L929 cells and their mechanisms.

The chlorophenol chemicals (CPs) are a major class of widely distributed and frequently occurring persistent environmental pollutants. Pentachlorophenol (PCP) has been proposed to be procarcinogen in rodents and in possibly human beings. Human beings also easily expose to other chlorophenol chemicals, including 4-chlorophenol (CP), 2,4-dichlorophenol (DCP), 2,3,4-trichlorophenol (TCP), prompting this investigation of their comparative cytotoxic effects and cell death mechanisms, assayed in fibroblast L929 cells. The effective concentration for half-maximal response (EC50 values at 24 h for CP, DCP, TCP, and PCP are 2.18, 0.83, 0.46, and 0.11 mmol/L respectively and the EC50 values at 48 h are 1.18, 0.13, 0.08, and 0.06 mmol/L respectively by using 3-(4,5-dimethylthiazd-2-yl)-2,5-diphenyltentrazolium bromide (MTT) reduction assay. A clear structure-activity relationship was observed between toxicity of CPs and their octanol-water partition coefficients. The further studies indicate that CP, DCP, and TCP induce apoptosis in L929 cells in a concentration or time-dependent manner, but PCP mediates cell death more characteristic of necrosis than apoptosis. These results not only demonstrate that L929 cell growth inhibition bioassay may be useful to provide the comparative evaluation of toxicity of CPs in vitro, but also implicate that CP, DCP, TCP, in comparison with PCP, can induce L929 cell death by apoptosis, resulting in lower procarcinogensis, which may help to elucidate the molecular basis for the adverse health effects associated with CPs exposure.

Animals↗

Destruction of polychlorodibenzo-p-dioxins.

The release of 2,4,5-trichlorophenol (2,4,5-T) containing 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) at Sèveso highlighted the need for an efficient control procedure for the highly toxic dioxin. The concomitant formation of the dioxin and the trichlorophenol during hydrolysis of sym-tetrachlorobenzene has lead to demands for restrictions on the use of 2,4,5-T and related herbicides. An environmental hazard is also presented by pentachlorophenol which includes the more highly chlorinated dioxins, is particular octachlorodibenzo-p-dioxin (OCDD). The use of pholychlorophenol formulations has been banned in Sweden on the grounds that heat-stable chlorodioxins are formed during incineration; this also points to the need for degradation by chemical means. Dehalogenation of polychlorodibenzodioxins (PCDD) can be accomplished by photolysis in laboratory conditions, but material adsorbed on soil is little affected. Cleavage of the ether linkages with the formation of halophenols may be achieved by treatment with strong acids or quaternary ammonium salts. The dibenzodioxin nucleus, is however, rather resistant to chemical attack and in the absence of a suitable control procedure the use of 2,4,5-T has been restricted in the US by the Environmental Protection Agency. I now report the oxidative degeneration of TCDD and related compounds by ruthenium tetroxide.

Dioxins↗

Investigation of the relation between self-reported food consumption and household chemical exposures with urinary levels of selected nonpersistent pesticides.

Concerns about pesticide exposure through food consumption have increased during the past several years. The main objective of our study was to determine whether we could use data from the Third National Health and Nutrition Examination Survey (NHANES III) to detect a relation between self-reported food consumption--particularly consumption of fruits, vegetables, and bread products--and urinary levels of pesticides or their metabolites in a population of 978 adults living in the US. A secondary objective was to investigate whether these urine levels differed for people who reported exposure to selected common household chemicals including bug or insect spray, weed killer, and mothballs or crystals. We used monthly food frequency data from the NHANES III, 1988-1994. Urinary pesticide/metabolite levels and information about chemical exposures were taken from the Priority Toxicant Reference Range Study (a component of the NHANES III). Six pesticides or their metabolites were detected in at least 50% of the sample, three of which--1-naphthol (86.4%), pentachlorophenol (62.5%), and 3,5,6-trichloro-2-pyridinol (82.0%)--were possibly related to food consumption. We were unable to detect a relation between self-reported food consumption and their urinary levels. This may be due more to the limitations of the datasets than to a lack of a relation between food consumption and urine pesticide/metabolite levels. We did find that people who reported recently using selected common chemicals had higher geometric mean urine pesticide/metabolite levels than did people who reported not recently using these chemicals.

Adult↗