High pressure liquid chromatographic determination of polynuclear aromatic hydrocarbons in oysters.

A high pressure liquid chromatographic (HPLC) procedure is described for determining 13 polynuclear aromatic hydrocarbon (PNA) compounds in oysters at the 2 ppb level. These compounds are extracted from shellfish with acetonitrile and partitioned into petroleum ether; the petroleum ether is removed and the residue is saponified. The aromatic compounds are isolated by passing the saponifeid residue through silica gel and further purified and fractionated by muStyragel gel permeation chromatography. The in-ividual PNAs are then quantitatively determined by using a reverse phase HPLC column coupled to fluorescence, spectrophotometric, and 254 nm absorbance detectors in series. Recoveries from spiked samples generally were greater than 80%.     

Rapid, low-cost cleanup procedure for determination of semivolatile organic compounds in human and bovine adipose tissues

A gas chromatographic/mass spectrometric (GC/MS) method is described for determination of organic environmental pollutants in human and bovine adipose tissues. Compounds such as organochlorine pesticides, polychlorinated biphenyls, polynuclear aromatic hydrocarbons, polychlorinated aromatics, and brominated aromatics are extracted with organic solvents and separated from coextracted lipids on a Florisil column. The eluate is concentrated and compounds are identified and quantitated by GC/MS analysis. The method was evaluated in a single laboratory for ability to recover compounds of environmental and regulatory importance. Except for a few more polar compounds, such as phthalates and phosphates, recoveries averaged about 85%. The elution system maximized recovery and allowed minimal coelution of lipid materials. Detection limits for most compounds studied were in the range of 5-50 ng/g (ppb).     

Volatile organic compounds in foods: a five year study

A purge and trap procedure was used with gas chromatography-mass spectrometry determination to analyze 70 foods for volatile organic compounds (VOCs). The results from analyses over a 5 year period (1996-2000) are reported. VOCs were found in at least one sample of all foods tested, although no single compound was found in each of the foods. The total amount of VOCs found in a single food item over the 5 year period ranged from 24 to 5328 ppb, with creamed corn (canned) the lowest and cheddar cheese the highest. Benzene was found in all foods except American cheese and vanilla ice cream. Benzene levels ranged from 1 to 190 ppb, with the highest level found in fully cooked ground beef. Benzene was found in 12 samples of cooked ground beef, with an average of 40 ppb. Benzene levels above 100 ppb were also seen in at least one sample each of a cola (138 ppb), raw bananas (132 ppb), and cole slaw (102 ppb). This compares to a maximum contaminant level of 5 ppb set by the U.S. EPA for drinking water.     

Liquid chromatographic monitoring of the depletion of carbadox and its metabolite desoxycarbadox in swine tissues

A liquid chromatographic method was used to monitor a depletion study of carbadox (and its most important metabolite, desoxycarbadox) in young pigs fed carbadox-treated rations for 1 week. Carbadox was found in blood (20 ppb), blood serum (26 ppb), and muscle tissue 24 h after withdrawal from treated ration; residues were reduced to a trace (less than 2 ppb) in 48 h, and eliminated by 72 h. Desoxycarbadox, although not detected in blood, was found in muscle (17 ppb) 24 h after withdrawal; it was reduced to 9 ppb at 48 h and to a trace by 72 h. Although no carbadox was detected in liver 24 h after withdrawal, appreciable desoxycarbadox (125 ppb) was found in liver 24 h after withdrawal; it was reduced to 17 ppb at 48 h and to a trace by 72 h. Whereas only a trace of carbadox was found in kidney 24 h after withdrawal, 186 ppb desoxycarbadox was found in kidney at 24 h, 34 ppb at 48 h, and a trace at 72 h. No metabolite of carbadox other than desoxycarbadox was found in extracts of swine tissues during this medicated feed trial, and no metabolite was found in blood extracts by using the established methodology. The effect of tissue storage (aging) at -20 degrees C on levels of the drug and its metabolite was a modest alteration of residue levels. The inadvertent use of feed adulterated with furazolidone and initially medicated with chlortetracycline, sulfamethazine, and penicillin G, did not affect the uptake of carbadox in this depletion study or interfere with the analytical methodology.     

Liquid chromatographic determination of basic nitrogen-containing polynuclear aromatic hydrocarbons in smoked foods

Several smoked foods were analyzed for basic nitrogen-containing polynuclear aromatic hydrocarbon (NPAH) content by a relatively rapid liquid chromatographic (LC) technique. The analyzed products included both domestic and imported market basket commodities. Nanogram quantities of NPAH standards were detected by UV and fluorescence detectors connected in series. The NPAHs were extracted from basic aqueous ethanolic solution into cyclohexane, extracted from cyclohexane into 6N HCl, and extracted back into cyclohexane after neutralization of the acid. The NPAHs were then purified by filtering the extract through deactivated basic alumina. The eluate from this step was concentrated to dryness, and the residue was dissolved in 95% ethanol and analyzed by LC, using a Vydac C-18 column and acetonitrile-water (9 + 1) as the mobile phase. Recoveries of 3 NPAHs, 5,7-dimethylbenz(a)acridine, dibenz(a,j)acridine, and dibenz(a,h)acridine, each added to salmon and sausage at the 5 ppb level, ranged from 62 to 101% by fluorescence measurement and from 64 to 106% by UV measurement. None of the NPAHs used as standards were found by either fluorescence or UV detection at levels greater than or equal to 5 ppb in any of the foods analyzed.     

Characterization and Degradation of Petroleum Hydrocarbons Following an Oil Spill into a Coastal Environment of South Texas, U.S.A.

Petroleum hydrocarbons were characterized at eleven sites withinthe sediments of a coastal stream in south Texas, U.S.A. following a medium sized crude oil spill. Bank and open-water(deep) sediments were collected at each site. Hydrocarbonstargeted for analysis included 22 aliphatic hydrocarbons (C-11to C-34) and 16 polynuclear aromatic hydrocarbons. Sedimentconcentrations were measured at intervals of 1, 2, 3, 4, 6, and12 months post-spill. Higher hydrocarbon concentrations were observed for a longerduration within the deep sediments than bank sediments. Initialhydrocarbon constituents in impacted sediments matched the crudeoil fingerprint accurately with the exception of the lighter-endhydrocarbons. The lighter-end aliphatic hydrocarbons areaffected immediately by evaporation and dissolution processesduring the spill event and were found below the detection levelsat most of the sites. Total hydrocarbon concentrations insediments within each hydrocarbon group returned to backgroundlevels by the end of the study period. Observed decreases inhigh molecular weight polycyclic aromatic hydrocarbons (PAH)concentrations exceeded known environmental degradation rateswhich suggests the influence of a sediment transport process. Overall, the fate of petroleum hydrocarbons within this type ofenvironment were likely related to both degradation and sedimenttransport processes. By the end of the study period, most individual PAH constituent concentrations were below thresholdconcentrations thought to produce toxic effects in marine andestuarine organisms. PAH constituents concentrations remainingabove threshold concentrations included benz(a)anthracene,chrysene, and benzo(a)pyrene.     

Current trends in levels of volatile N-nitrosamines in fried bacon and fried-out bacon fat

Commercially processed bacon samples purchased from the Washington, DC, retail market have been periodically analyzed since 1971 for the presence of volatile N-nitrosamines in the fried product. During that time, a downward trend in the concentration of N-nitrosopyrrolidine has been observed, and between 1978 and 1980 it plateaued at 4-30 ppb, with an average of 11 ppb. A recent survey, however, indicates a change in this downward trend, with N-nitrosopyrrolidine found at levels ranging from 1 to 65 ppb, average 21 ppb. Volatile N-nitrosamines were found at levels up to 110 ppb in the fried product and up to 85 ppb in the fried-out bacon fat.     

Determination of morantel-related residues in bovine milk by electron capture gas chromatography

A gas chromatographic assay was developed to determine major residues of morantel in bovine milk over a range that is suitable for monitoring residues of the drug. The method is based on hydrolysis of the N-methyl-tetrahydropyrimidine portion of morantel and its metabolites to N-methyl-1,3-propanediamine, and converting the diamine to an N,N-bis-(2-nitro-4-trifluoromethylphenyl) derivative. The addition of an internal standard, the N-desmethyl-N-ethyl homolog of pyrantel, to the milk sample circumvents any potential problem that could arise from variable reaction yields, and eliminates the true recovery as a factor affecting the accuracy and precision of the procedure. The concentrations of the derivatives are determined by pulsed electron capture gas chromatography over a linear dynamic range that is equivalent to 12.5-50 ppb morantel. The method was evaluated at the 0, 12.5, 25, and 50 ppb levels in fortified bovine milk, and in a withdrawal sample containing physiologically incurred morantel residues. Mean values of 14 +/- 1.7, 24 +/- 3.7, and 47 +/- 6.9 were found for the fortified samples, approximately 3 ppb for control milk, and 16 +/- 1.7 ppb for the withdrawal sample.     

Distribution of Polynuclear Aromatic Hydrocarbons (PAHs) in the Soil of Tokushima,Japan

The distribution of polynuclear aromatic hydrocarbons (PAHs) inthe soil samples of rural, suburban and urban areas of TokushimaCity was studied, HPMC with UV and fluorescence detection wasused for the determination of PAHs. The separation was acquiredby an ODS column and acetonitrile-water as the mobile phase.Results showed that the distribution of PAHs in the samplingsites were similar but differed from that in river sediment. Amodel test suggested that the burning of rice straw and otherplants was not the main source of PAHs in the soil of this citybut could be one of the important sources of PAHs in the river ecosystem.     

The Potential for Bioremediation of Soils Containing PAHs by Composting

? Environmental contamination by synthetic polynuclear aromatic hydrocarbons (PAHs) has become a major pollution problem. Plant tissues, lignin, soil humus constituents, some pesticides, and numerous commercial organic chemicals are also based upon aromatic building blocks. Many of these molecules are potentially toxic and carcinogenic. Some PAH compounds occur naturally at a low concentration in soils. Long exposure to naturally occurring hydrocarbons has enabled bacteria to evolve enzymes that degrade them.

Landfarming and incineration are the primary technologies used for removing PAH compounds from soils and groundwater. Recent data suggest that bioremediation by PAH composting can offer significant advantages to other treatment alternatives. Landfarming is a relatively uncontrolled method of reducing PAHs in residues. Composting is quicker, more controlled, and requires less space than landfarming. Although composting is slower and less complete than incineration, it is significantly more cost-effective.

This presentation deals with the feasibility of composting PAH contaminated soils and residues. Included will be methods for process evaluation and control, degradation potential of specific PAHs, and determining the application of composting to specific situations.     

Effect of cooking on levels of ethylene dibromide residues in rice

Two studies were conducted to determine the effect that cooking has on the level of residues of ethylene dibromide (EDB) in rice. In the first study, 4 samples of long and medium grain polished white rice containing 113, 295, 956, and 1568 ppb EDB were cooked according to typical label directions. Three batches of cooked rice were prepared from each sample of polished rice and frozen until analysis; each batch was analyzed in duplicate. EDB levels in all cooked rice samples were less than 10 ppb. In the second study, conducted jointly by the Food and Drug Administration (FDA) and the Environmental Protection Agency (EPA), a sample of medium grain polished white rice containing about 1600 ppb EDB was cooked by each laboratory. Overall average EDB levels in rice analyzed immediately after cooking were 16 and 37 ppb for FDA and EPA, respectively. The corresponding frozen samples contained 8 and 39 ppb EDB. The 2 laboratories exchanged these frozen samples and reanalyzed them to check variability in the analytical procedure. FDA found 49 ppb EDB in the sample cooked by EPA and EPA found 8 ppb EDB in the sample cooked by FDA, thus indicating that analytical methodology was not a major source of variability. The range of EDB levels was therefore attributed to minor differences in the way the rice was cooked or handled immediately after cooking.     

Solvent effects on response factors for polynuclear aromatic hydrocarbons determined by capillary gas chromatography using splitless injections

When standard solutions of polynuclear aromatic hydrocarbons (PAHs) were analyzed by capillary column gas chromatography using splitless injections, response factors were observed to be dependent on the solvent used to prepare the standard. This report presents the response factors for 16 individual PAHs in 5 commonly used solvents: acetonitrile, methanol, toluene, isooctane, and cyclohexane. To minimize quantitation errors due to differences in transfer efficiency, samples and standards of PAHs should be prepared in the same solvent.     

Improved method for determination of polynuclear aromatic hydrocarbons in pharmacopoeial paraffin and mineral oils.

An improved method has been developed for quantitative determination of polynuclear aromatic hydrocarbons (PAHs) in pharmacopoeial paraffin and medicinal white oil samples. This new method combines 2 liquid-liquid partition and adsorption chromatography procedures with a 2-step purification on Sephadex LH 20 and liquid chromatography with fluorometric determination. Selective elution of PAHs results in absence of background fluorescence. The minimum detectable level ranges from 0.2 ppt for benzofluoranthene isomers to 200 ppt for acenaphthene. Recoveries of PAHs added at 7 ppm varied from 92.1 to 111.4%. When a variety of medicinal white oil samples were analyzed by this improved method, 27 PAHs were identified, including 11 suspected carcinogens. Their identities were confirmed by capillary gas chromatography.     

洪水对河流底泥有机污染物分布的影响

文章结合我国１９９８ 年遭受特大洪水灾害的情况,介绍了美国密西西比河洪水对底泥有机污染物分布影响的研究成果。结果表明洪水前后所有底泥样品中都存在粪醇、多环芳烃（ 包括芘） 、直链烷基苯磺酸盐、多氯联苯和有机氯农药等污染物,浓度一般小于１ ｍｇ／ｋｇ ,其中上游浓度最高。洪水前后各种污染物浓度变化较大。洪水发生后,上游段底泥中芘和多氯联苯的浓度降低而粪醇浓度升高,这表明城市和农业水域中的污染底泥被洪水冲刷至河内并稀释或覆盖原来的底泥。并列举了这一成果给予我们的启示。     

Survey of baby bottle rubber nipples for volatile N-nitrosamines

A local market survey of 27 baby bottle rubber nipples for volatile N-nitrosamines was conducted. N-Nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosodibutylamine, and N-nitrosopiperidine were found at levels up to 387 ppb. All 4 nitrosamines migrated from the rubber nipples into water, milk, and infant formula when sterilized together in a manner typical of that used in the home. The source of the nitrosamines is the chemical accelerators and stabilizers added to raw rubber during the vulcanization process.     

Volatilisation of aromatic hydrocarbons from soil: Part I,fluxes from coal tar contaminated surface soils

The non-steady-state fluxes of aromatic hydrocarbons were measured in the laboratory from the surface of soils contaminated with coal tar. Four soil samples from a former gasworks site were used for the experiments. The fluxes were quantified for 11 selected compounds, 4 mono- and 7 polycyclic aromatic hydrocarbons, for a period of up to 8 or 16 days. The concentrations of the selected compounds in the soils were between 0.2 and 3,100 µg/g. The study included the experimental determination of the distribution coefficient of the aromatic hydrocarbons between the sorbed phase and the water under saturated conditions. The determined distribution coefficients showed that the aromatic hydrocarbons were more strongly sorbed to the total organic carbon including the coal tar pitch — by a factor of 8 to 25 — than expected for natural organic matter. The fluxes were also estimated using an analytical solution of the Fick's diffusion equation and assuming that the compounds diffused independently of each other and that instant equilibrium existed between the air, water and sorbed phases. A relatively good agreement was found between the predicted and the measured flux. The predicted fluxes were between 0.11 and 7.5 time the measured fluxes. The fluxes were overestimated for the monocyclic aromatic hydrocarbons and underestimated for 3-rings-PAHs.     

Aroma of Cooked Rice (Oryza sativa): Comparison Between Commercial Basmati and Italian Line B5-3

Selected lines of aromatic rice from American cv. A301 were cultivated in Italy, and the agronomic traits and chemical properties related to their aroma were studied. The most characteristic compound responsible for aromatic rice, 2-acetyl-1-pyrroline, was quantified in all lines. Line B5-3, characterized by high 2-acetyl-1-pyrroline content, was investigated in greater detail for its volatile components and was compared with a commercial Basmati rice. Volatiles were collected by steam-distillation. Several classes of compounds were identified and quantified in both samples, including hydrocarbons, aldehydes, alcohols, ketones, heterocyclic, terpenes, disulfides, and phenols. Hexanal was the most abundant compound in both samples, followed by pentanal, 2-acetyl-1-pyrroline, hexanol, benzaldehyde, oct-1-en-3-ol, 4-vinylguaiacol, indole, and trans-2- nonenal. 2-Acetyl-1-pyrroline was present at 570 and 2,350 ppb in Basmati and B5-3, respectively.     

Autoclave sterilization produces acrylamide in rodent diets: implications for toxicity testing

Acrylamide (AA) is a neurotoxic and carcinogenic contaminant that is formed during the cooking of starchy foods. Assessment of human risks from toxicants is routinely performed using laboratory rodents, and such testing requires careful control of unintended exposures, particularly through the diet. This study describes an analytical method based on liquid chromatography with electrospray tandem mass spectrometry that was used to measure endogenous AA in rodent diets and to survey a number of commercial products for contamination. Method sensitivity permitted accurate quantification of endogenous levels of AA in raw diets below 20 ppb. Autoclaving a standard rodent diet (NIH-31) increased the AA content 14-fold, from 17 to 240 ppb. A nutritionally equivalent diet that was sterilized by irradiation was found to contain approximately 10 ppb of AA (NIH-31IR). A toxicokinetic study of AA and its epoxide metabolite, glycidamide, was performed by switching mice from NIH-31IR to the autoclaved diet for a 30 min feeding period (average AA dose administered was 4.5 microg/kg of body weight). The concentrations of AA and glycidamide were measured in serum collected at various times. The elimination half-lives and the areas under the respective concentration-time curves were similar for AA and glycidamide. Mice maintained on autoclaved NIH-31 diet, but otherwise untreated, showed elevated steady state levels of a glycidamide-derived DNA adduct in liver relative to mice maintained on the irradiated diet. This study demonstrates that a heat sterilization procedure used in laboratory animal husbandry (i.e., autoclaving) can lead to the formation of significant levels of AA in basal diets used for toxicity testing. AA in rodent diets is bioavailable, is distributed to tissues, and is metabolically activated to a genotoxic metabolite, which produces quantifiable cumulative DNA damage. Although the contribution of endogenous AA to the incidence of tumors in multiple organs of rodents otherwise untreated in chronic carcinogenicity bioassays (i.e., control groups) is not known, the reduction of endogenous AA through the use of a suitable irradiated diet was deemed to be critical for ongoing studies of AA carcinogenicity and neurotoxicity.     

Polycyclic aromatic hydrocarbons in soils of Moscow

The contents of polycyclic aromatic hydrocarbons (PAHs) in the upper horizons of Moscow soils range up to 1400 mg/kg for individual compounds and up to 10000 mg/kg for their sum. The concentration coefficients of PAHs in the soil vary from 0.7 to 200 depending on individual polyarene properties and land use. The heavy polynuclear structures of technogenic origin have the highest concentration coefficients. The highest accumulation of PAHs is observed for the soils of dumping sites, residential-transport areas, and industrial zones. According to the state sanitary norms set in the Russian Federation for the content of benzo[a]pyrene in soils, more than one-third of the urban soils studied are classified as pure, and about half soils are classified as acceptable.     

Influence of organic matter on the sorption of aromatic hydrocarbons by peat and chernozem

The interaction of water-soluble monoaromatic hydrocarbons with an organic matrix of chernozem and peat was studied. As a result of high levels of soil pollution by monoaromatic hydrocarbons, soil organic matter with the high sorption capacity actively adsorbs aromatic hydrocarbons. The hydrophobic properties of aromatic compounds determine the strength of the interactions between themselves and the soil organic matrix. The presence of lipids in the organic matter of chernozem decreases the sorption of aromatic hydrocarbons because of the blocking of hydrophobic centers of the soil humic substances.