Surface sampling for a pesticide in dust and small spills of a solid dye.

The aim was to determine whether a published sampling technique for loose soil on hard surfaces achieved acceptable efficiency at surface dust/soil coverages of 10-20 mg/ 100 cm2. The sampler was a cordless personal sampling pump operated at 4.0 L/min connected to a cassette containing a filter, the cassette being also connected to a Tygon sampling probe that was moved manually on the surface to be sampled. Rhodamine 6G dye dust was evaluated at 10 mg/100 cm2 coverage at flow rates of 1.0-4.0 L/min. Two National Institute of Standards and Technology (NIST) standard reference materials (SRMs) were used for pesticide experiments: SRM 2711 Montana Soil, and SRM 1649a Urban Dust. The efficiencies for these SRMs were determined uncoated, and coated with 1300 microg chlorpyrifos/g as a Lorsban 4E emulsifiable concentrate formulation. The 3-pass technique sampled both the pesticide-coated and uncoated dust and soil at >79 percent efficiency and at better than 16 percent coefficient of variation (CV) above 15 mg collected mass. Sampling at 20 mg/100 cm2 coverage lowered the CV to < or = 7.1 percent. The dye was sampled with similar efficiency > or = 1.5 L/min, but the CV for the 3-pass technique was <10 percent at 1.5-2.0 L/min, and <20 percent at 1.5-4.0 L/min. The efficiency for a 5-pass technique for the dye exceeded 90 percent at > 1.5 L/min with CVs < 10 percent at 1.5, 2.0, 2.5, and 3.5 L/min. The weight change of the sampling probe and the cassette must be measured for accurate determination of low surface coverages rather than just the weight change of the filter alone. The method allows use of personal sampling equipment for aerosols to measure low coverages of loose dust, soil, and chemical solids on hard surfaces.

A comparison of techniques for preparing fish fillet for ICP-AES multielemental analysis and the microwave digestion of whole fish.

Four catfish fillet homogenate treatments before multielemental metal analysis by simultaneous inductively coupled plasma/atomic emission spectroscopy were compared in triplicate. These treatments were: nitric acid wet-ashing by Parr bomb digestion; nitric acid wet-ashing by microwave digestion; tetramethylammonium hydroxide/nitric acid wet digestion; and dry-ashing. The tetramethylammonium hydroxide/nitric acid method was imprecise (coefficients of variation > 20%). The dry-ashing method was fast and sensitive but had low recoveries of 50% for spiked Pb and Al and was not as precise as the Parr bomb or microwave treatments. The Parr bomb method was the most precise method but was less sensitive than the microwave method which had nearly the same precision. The microwave method was then adapted to homogenates of small whole fish < or = 3 cm in length. The whole fish homogenate required more vigorous digestion conditions, and addition of more acid after the evaporative step because of the presence of less oxidizable and acid-soluble components than fillet. The whole fish homogenate was also more heterogeneous than catfish fillet. A quality assurance protocol to demonstrate homogenate uniformity is essential. The use of a non-specialized microwave oven system allowed precise results for fillet and whole fish homogenates.

Synthesis of the O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine oximes of selected carbonyl compounds and their determination by liquid chromatography with ultraviolet detection.

The aims were to develop a liquid chromatographic (LC) method with ultraviolet detection (UVD) for O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) O-oximes of common aldehydes and ketones, and to define the steric limits of the synthetic reaction used to make the PFBHA O-oxime standards for gas chromatographic (GC) and LC methods. Ten new O-oximes were synthesized with the new optimized method, and their purities were demonstrated by GC/electron-capture detection (ECD), GC/mass spectrometry (MS), ultraviolet spectroscopy, infrared spectroscopy, and proton and 13C-nuclear magnetic resonance spectroscopy. Ketones substituted at both beta-carbons relative to the carbonyl carbon, like diisobutyl ketone and 2,4-hexanedione, showed lower synthetic yields by wet chemistry methods. A new C18 reverse-phase LC method with UVD at 200 nm and acetonitrile-water in both the isocratic and gradient-elution modes was then developed to sensitively resolve a mixture of 13 pure PFBHA O-oximes. The detection limit was near 100 ng O-oxime/mL or about 14-50 ng aldehyde/mL and the least quantifiable limits were near 500 ng/mL or about 70-250 ng aldehyde/mL, with lower limits for glyoxal, methylglyoxal, benzaldehyde, and acetophenone. Carbonyl compounds in 500 mL water samples were then determined in distilled water and tap water by gradient elution. Vapors of n-valeraldehyde and acrolein generated in gas bags at concentrations near occupational guidelines were also sampled, desorbed, and then determined by either isocratic or gradient elution at 200 or 254 nm within 30-45 min.

The environmental geochemistry and bioaccessibility of mercury in soils and sediments: a review.

There have been many studies of mercury geochemistry in the environment and its bioconcentration/bioaccumulation through the aquatic food chain. However, there is a dearth of information regarding the bioaccessibility of mercury in human receptors exposed primarily by soil ingestion. This paper reviews the current state of knowledge of mercury bioaccessibility and speciation in soils, and the utility of speciation methods to estimate mercury bioaccessibility. We conclude that additional research is necessary to determine: (1) whether analytical measurements can adequately determine the bioaccessibility of mercury in sediments and soils; (2) the accuracy of in vitro analyses in assessing mercury bioaccessibility; (3) the ability of mercury to cross tissue membranes of the mouth, esophagus, stomach, and the small and large intestines; (4) the speciation and distribution of mercury in biological fluids; and (5) mercury bioavailability using an in vivo animal model relevant to human gastrointestinal tract conditions.

Synthesis of 2-thiothiazolidine-4-carboxylic acid and its chromatography in rat and human urine.

2-Thiothiazolidine-4-carboxylic acid (TTCA), the urinary biological monitoring marker for carbon disulfide in humans was synthesized by reacting carbon disulfide with L-cystine. Validation of TTCA purity required elemental as well as mass spectral and chromatographic analyses. Two reversed-phase high-performance liquid chromatographic columns in series were necessary to resolve picomole amounts of TTCA from rat and human urine background peaks on detection at 272 nm even after prior diethyl ether extraction from acidified urines in the presence of saturated sodium chloride. The isolation procedure for TTCA from urine had a recovery of 94.0 +/- 8.1% in the linear 1.1-330 microM concentration range (0.0165-4.95 nmol injected mass) with a coefficient of variation of 8.6%. The detection limit was about 100 nM (1.5 pmol injected mass).

Urinary 2-thiothiazolidine-4-carboxylic acid (TTCA) as the major urinary marker of carbon disulfide vapor exposure in rats.

Male Sprague-Dawley rats (200-250 g; 60 per exposure group) were exposed to carbon disulfide (CS2) air concentrations of 0, 50, 150, and 500 ppm(v/v) for 6 hr/day, 5 days/week over six months. Following the exposures, nine rats from each exposure group had four sets of cumulated urines collected (between 0-8, 8-16, 16-24, and 24-48 hr). The urinary parameters measured were: 2-thiothiazolidine-4-carboxylic acid (TTCA), total thioethers (TE), and the compounds responsive to the iodine-azide (IA) test. Urinary TTCA elimination obeyed pseudo-first-order, one-compartment model kinetics of half-time (t0.5) 5.2 +/- 0.3 hr up to 16 hr of collection. The elimination of TE within 16 hr had a t0.5 of 8.5 +/- 0.6 hr. TTCA, IA, and TE were correlated highly in the first 16 hr. After 16 hr, the t0.5 for TE lengthened to 13.1 hr. At CS2 concentrations of 50, 150, and 500 ppm, the respective t0.5 for IA-responsive compounds were 12.6, 6.1, and 4.4 hr. TTCA had the highest correlation coefficient and p-value relative to CS2 exposure concentration, and also was the most sensitive, precise, and selective urinary marker.

In vitro micronucleus bioassay of human peripheral lymphocytes for adriamycin in the presence of cyclophosphamide and urines of patients administered anticancer drugs.

The aim of this study was to develop an in vitro human peripheral lymphocyte micronucleus bioassay involving phytohemagglutinin stimulant for urines containing adriamycin (ADR) and cyclophosphamide (CP). In vitro studies with defined concentrations of ADR, CP, and fresh urine showed that mitotic indices and micronuclei counts/1,000 cells had to be log (X + 1) transformed to be able to use parametric statistics and that a specific micronucleus assay for ADR in the presence of CP and urine for 5-15 ng ADR/mL had been developed. Whereas CP alone could be detected between 196-522 micrograms/mL, this effect was abolished in the presence of 15 ng ADR/mL. Interdonor variabilities relative to ADR sensitivity and CP linear dynamic range were marked, but intradonor variability was small. The MN bioassay tolerated < 10% urine. Results for urines from nine patients receiving antineoplastic drugs (CP, all; ADR, 3; 5-fluorouracil, 3; methotrexate, 3; vincristine, 4; procarbazine, 1; and megestrol acetate, 1) showed that only 1/3 patients given ADR were detected, and two others not given ADR were positive. All frozen urines from the 12 control subjects and the nine patients exhibited depressed mitotic index, with, however, no control patient urines inducing increased micronuclei. Two patients had urines of undefined genotoxic potential since undepressed mitotic indices were not attainable by dilution. The effects of combination chemotherapy in addition to freezing and storage influences were complex. More research is required to be able to interpret the results.

O-(2,3,4,5,6-pentafluorophenyl)methylhydroxylamine hydrochloride: a versatile reagent for the determination of carbonyl-containing compounds.

A review on the use of O-(2,3,4,5,6-pentafluorophenyl)methylhydroxylamine hydrochloride (PFBHA) for the determination of carbonyl-containing compounds is presented. PFBHA has been used in the determination of such diverse compounds as thromboxane B2, prostaglandins, amygdalin and a variety of other aldehydes, ketones and acids. PFBHA has been used for the determination of these compounds found in water, blood, urine, air and even clothing. The review covers literature referenced in Chemical Abstracts from 1975, when PFBHA was first synthesized, through March 1992.

Microtox EC50 values for drinking water by-products produced by ozonolysis.

The aim was to determine the Microtox EC50 values of some aliphatic aldehydes and carboxylic acids of normal chain length with 1-14 carbon atoms since these compounds have been detected as ozonolysis by-products in drinking water. The aqueous EC50 values decreased with increasing chain length except for formaldehyde and for the C1-C7 acids. At chain lengths above C7, where methanolic saline solutions were utilized to promote solubility, the aldehydes were more toxic than their corresponding carboxylic acids. Below a chain length of C7, the reverse situation applied. More precise and sensitive EC50 values were observed at 15 and 25 min than at 5 min. Both C14 aldehyde and acid as well as palmitoleic acid showed luminescence in methanolic saline solutions. The C14 compounds are known natural substrates for bacterial luciferase, and the present findings confirm this for Photobacterium phosphoreum. The concentrations of the aldehyde and/or carboxylic acid ozonolysis by-products reported in drinking water could not be detected by the Microtox test. This is the first report of Microtox EC50 values for these carboxylic acids and for aldehydes of chain lengths greater than C4.

Permeation of a 2,4-D isooctyl ester formulation through neoprene, nitrile, and Tyvek protection materials.

Tyvek (laminated saranax) and unsupported nitrile gloves gave protection from permeation against formulation concentrates and aqueous emulsions of Esteron 99 [isooctyl ester of (2,4-dichlorophenoxy)acetic acid] under conditions simulating extremes of field conditions. Neoprene gloves, whether unsupported or supported, lined or unlined, were permeated much more than unsupported nitrile gloves. An initial penetration was observed for all the materials. A cosolvent effect involving the "inert components" was observed, as implied by the appearance of inert components in the hexane collection medium of the ASTM cell before and with the 2,4-D ester. Degradation occurred in the neoprene and supported glove materials since nonformulation components also were detected on the collection side. The glove selection procedure involved the characteristics of single surrogate compounds in the brochure of a glove manufacturer, in addition to the characteristics of the carrier and inert ingredients. This procedure was sufficient to predict correctly that nitrile would protect better than neoprene; however, direct experimental confirmation was necessary to select the type of nitrile material which provided optimum protection.

Urinary thioether biological monitoring in the interaction between 1,2-dichloroethane and disulfiram in Sprague-Dawley rats.

The interaction between inhaled 1,2-dichloroethane (ethylene dichloride; EDC) and dietary Disulfiram (tetraethylthiuram disulfide; Antabuse; DSF) was investigated for male Sprague-Dawley rats in terms of urinary levels of thio-compounds extractable in ethyl acetate and then hydrolyzed in alkali (the classic urinary thioether assay). The assay was found to be an inadequate biological monitoring indicator for EDC or DSF exposure during the DSF/EDC interaction at exposures of 0, 153, 304 and 455 ppm EDC (7 hr/day, 5 days/week, 30 exposure days) for rats fed with AIN-76 diet fortified with 0.15% DSF. EDC inhibited the excretion of DSF-derived thio-compounds with increasing EDC concentration; the thioether content was dose-related in the absence of DSF. In situations where confounding agents generate neutral S-containing urinary metabolites without involvement of endogenous glutathione, the classic thioether assay requires supplementation by other biochemical monitoring strategies.

In vivo sister chromatid exchange induced by 1,2-dichloroethane on bone marrow cells of mice.

In vivo sister chromatid exchange induced by 1,2-dichloroethane (DCE) was studied in bone marrow cells of mice after acute treatment for 24 hr. With the exception of the lowest concentration (0.5 mg/kg), each treated series exhibited a statistically significant increase in SCEs when compared with the control.

Change in chromatogram patterns after volatilization of some aroclors, and the associated quantitation problems.

PCBs with the highest vapor pressures (fewest chlorines) in Aroclors 1016, 1242, 1254 and 1268 were enriched in the vapor phase relative to the original Aroclor during volatilization from a glass surface for up to 8 hr. PCBs with the lowest vapor pressures (most highly chlorinated) were enriched in the corresponding residue. Thus, visual matching of gas chromatograms with those of Aroclor standards may not be sufficient to identify a specific Aroclor since the past history of a sample is often unknown. The enrichment also was detected using isomeric classes, but not using total chlorine content. The perchlorination method and the Webb-McCall method using all chromatographic peaks agreed quantitatively; this was not always so for the NIOSH multiple peaks and the Webb-McCall methods.

Additivity of detector responses of a portable direct-reading 10.2 eV photoionization detector and a flame ionization gas chromatograph for atmospheres of multicomponent organics: use of PID/FID ratios.

The H-Nu PI-101 with a photoionization detector (PID) of 10.2 eV and the Century OVA-128 equipped with a flame ionization detector (FID) were evaluated for the additivity of their responses to a defined mixture of dissimilar organic vapors at a 0 and 90% relative humidity (RH). The responses of both instruments were additive as long as the effect of RH was accounted for with the PID. The PI-101 was not as precise as the Century OVA-128 for 90% RH atmospheres. PID/FID ratios did not change in the presence of 90% RH as long as the effect of RH also was accounted for in the PID reading.

Inhalation pharmacokinetics of 1,2-dichloroethane after different dietary pretreatments of male Sprague-Dawley rats.

The effect of the pretreatment of male Sprague-Dawley rats with phenobarbital (PB), butylated hydroxyanisole (BHA) and disulfiram (DSF) on the inhalation kinetics of 1,2-dichloroethane [ethylene dichloride (EDC)] was studied by the gas uptake method. A closed recirculating system was constructed and characterized. The rate curves in all the pretreatment regimens showed saturable dependence on EDC concentration. These saturable dependencies (Michaelis-Menten) appeared to be associated with enzymatic metabolism. In general, a two-compartment, steady-state pharmacokinetic model described the uptake data. Data were transformed by Hanes plots to calculate the inhalational Km, the ambient EDC concentration at which uptake proceeded at half maximum rate, and Vmax, the maximum rate of uptake (i.e., maximum rate of metabolism). Although PB and BHA pretreatments did not affect the Km of EDC, PB pretreatment increased the Vmax while DSF pretreatment decreased both the Km and Vmax.

Interaction between 1,2-dichloroethane and disulfiram. I. Toxicologic effects.

Inhalation and intraperitoneal (ip) studies with 1,2-dichloroethane (1,2-DCE) using Sprague-Dawley rats fed 0.15% disulfiram (tetraethylthiuram disulfide; Antabuse; DSF) in AIN-76 diet [approx. (79 +/- 11) mg DSF/kg body wt/day] resulted in the observation of a toxic interaction relative to either agent alone. The combination treatment caused testicular atrophy and histopathology in the liver and testes at 1,2-DCE inhalation concentrations greater than 300 ppm (an estimated dose of 194 mg/kg body wt/day) administered 5 days/week for 30 days or at ip doses of 150 mg 1,2-DCE/kg body wt/day over 30 days, 7 days/week. DSF lowered the 1,2-DCE dose at which liver enlargement, decreased liver/body weight ratios, and decreased body weight gains appeared relative to exposure to the 1,2-DCE alone. For the ip study, a decrease in spleen weight also occurred. Testicular atrophy and liver pathology had previously been observed in rats exposed to 20 ppm of ethylene dibromide (EDB) and fed 0.05% DSF in rat chow diet; EDB or DSF alone did not elicit testicular atrophy. These toxic effects indicate that 1,2-DCE may interact with DSF as does EDB, but at a much higher dose.

Simultaneous multi-instrumental monitoring of vapors in sewer headspaces by several direct-reading instruments.

Simultaneous monitoring of the vapors in several sewer headspaces by three direct-reading instruments, the Century OVA flame ionization detector, a 10.2 eV H-Nu Photoionization Detector, and a Hydrogen Sulfide Ecolyzer revealed that the majority of condensable organic vapors in areas of the Metropolitan Sewer District of Cincinnati appeared to be saturated aliphatic organics, except during short, unpredictable episodes. The monitoring was performed in the wet well of a sewage treatment plant, in sewers near two chemical plants, and in three other different sewers. The approach outlined in this paper does not require the use of gas chromatography-mass spectrometry (GC-MS) analysis.

Effect of disulfiram pretreatment on the tissue distribution, macromolecular binding, and excretion of [U-1,2-14C]dichloroethane in the rat.

The effect of disulfiram (DSF) pretreatment on the distribution of [14C]ethylene dichloride (EDC) in selected organs and/or tissues of control and EDC-pretreated rats was studied. The presence of EDC metabolites and their binding to an acid-insoluble extract of the tissues, as well as purified protein and DNA, were evaluated. Dietary DSF was found to modulate the distribution, excretion, and macromolecular binding of EDC and/or its metabolites at 4 and 24 hr following ip administration. The urinary excretion of [14C]EDC metabolites was not affected by subchronic inhalation exposure to nonradiolabeled EDC. However, DSF pretreatment increased the fat deposition of EDC and decreased the urinary excretion of its metabolites. DSF also increased the binding of EDC metabolites to DNA and decreased the binding to protein in the liver, kidneys, spleen, and testes. However, prior exposure to EDC alone increased the binding of its metabolites to DNA in the kidneys only.