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Kovats and lee retention indices determined by gas chromatography/mass spectrometry for organic compounds of environmental interest

Retention indices of standard organic compounds of environmental interest were determined by gas chromatography/mass spectrometry, using a DB‐5 fused‐silica capillary column. Retention indices are useful references for tentative compound identification by gas chromatography, or confirmation by gas chromatography/mass spectrometry. They provide elution order for isomers that might be indistinguishable based on mass spectra. Modified Kovats and Lee retention indices are given for polycyclic aromatic hydrocarbons; sulfur heterocycles; nitrogen heterocycles; aromatic amines; oxygen heterocycles; phenols; alcohols; ketones; alkanes; nitriles; and methylesters of fatty, dicarboxylic, and aromatic acids for comparison and reference. Retention index values for heterocycles by gas chromatography/mass spectrometry are comparable with gas chromatography values previously reported.

Journal of Separation Science↗

Gas-liquid chromatographic and gas-liquid chromatographic-mass spectrometric determination of fenvalerate and permethrin residues in grasshoppers and duck tissue samples

A procedure is described for determining fenvalerate and permethrin residues in grasshoppers and duck tissues. Samples are Soxhlet-extracted with hexane and cleaned up by gel permeation chromatography with an in-line alumina column. Samples are analyzed by gas-liquid chromatography with electron capture detection, and confirmed by gas-liquid chromatography-mass spectrometry. The average recovery from fortified tissues was 97%.

Journal of the Association of Official Analytical ↗

GLC determination of quinaldine residue in fish

A procedure for the determination of quinaldine residue in various fish tissues is described. Homogenized tissues are extracted with hexane-ethyl ether, the extracts are concentrated by partitioning through 0.1N sulfuric acid, and the residues are measured by alkali flame ionization gas chromatography. Muscle tissues containing from 0.01 to 10.0 ppm quinaldine were successfully analyzed with recoveries from 75 to 100%.

Journal of the Association of Official Analytical ↗

Gas-liquid chromatographic determination of 3-trifluoromethyl-4-nitrophenol residues in fish

A procedure for the determination of 3-trifluormethyl-4-nitrophenol (TFM) in fish tissues is described. Homogenized tissues are extracted with hexane-ethyl ether; the extract is cleaned up by partitioning the TFM from the extracting solvent into 0.1 N NaOH, acidifying the aqueous solution, and partitioning again with hexaneethyl ether. The TFM is methylated with diazomethane and analyzed by gas-liquid chromatography, using electron capture detection. Recoveries ranged from 75 to 100% from fish muscles that were spiked with 0.01—2.00 μg TFM/g.

Journal of the Association of Official Analytical ↗

Radiochemical determination of very low concentrations of nickel in rocks and minerals

A radiochemical procedure has been developed for the determination of very low concentrations of nickel in rocks and minerals. Sensitivity is 0.01 μ g Ni. Accuracy and precision is estimated to be ±5 percent to levels as low as 0.1 μ g Ni a marked improvement over other analytical techniques. Samples are irradiated, combined with nickel carrier, and treated by a series of chemical procedures: (1) collection of nickel in a lead bead using a fire-assay technique, (2) refusion of the lead bead and precipitation of basic element hydroxides, (3) anion-exchange chromatography, and (4) precipitation of nickel dimethylglyoxime. The nickel precipitate is weighed to determine chemical yield and counted for β activity of Ni 65 along with a precipitate from irradiated nickel standard solution.

Journal of Research of the U.S. Geological Survey↗

Combined extraction-cleanup column chromatographic procedure for determination of dicofol in avian eggs

Dicofol in avian eggs was completely oxidized to dichlorobenzophenone (DCBP) when a hexane Soxhlet extraction procedure was used. This degradation did not occur with other avian tissues (muscle and liver). For this reason, a combined extraction-cleanup column chromatographic procedure, without added heat, was developed for the determination of dicofol in avian eggs. Homogenized subsamples of eggs were mixed with sodium sulfate, and the mixture was added as the top layer on a column prepacked with Florisil. The dicofol and other compounds of interest were then eluted with ethyl etherhexane. The extracts, relatively free from lipids, were quantitated on a gas chromatograph equipped with a 63Ni electron-capture detector and a methyl silicone capillary column. Recoveries from chicken eggs, fortified with dicofol and other DDT-related compounds, averaged 96%. Analysis of eggs of eastern screech-owls, fed a meat diet containing 10 ppm technical Kelthane, showed that both dicofol and DCBP were present. Results were confirmed by gas chromatography/ mass spectrometry. This method is rapid and reliable, involves a minimum of sample handling, and is well suited for high volume determination of dicofol in eggs and other avian tissues .

Journal of the Association of Official Analytical ↗

A laboratory and field evaluation of a portable immunoassay test for triazine herbicides in environmental water samples

The usefulness and sensitivity, of a portable immunoassay test for the semiquantitative field screening of water samples was evaluated by means of laboratory and field studies. Laboratory results indicated that the tests were useful for the determination of atrazine concentrations of 0.1 to 1.5 μg/L. At a concentration of 1 μg/L, the relative standard deviation in the difference between the regression line and the actual result was about 40 percent. The immunoassay was less sensitive and produced similar errors for other triazine herbicides. After standardization, the test results were relatively insensitive to ionic content and variations in pH (range, 4 to 10), mildly sensitive to temperature changes, and quite sensitive to the timing of the final incubation step, variances in timing can be a significant source of error. Almost all of the immunoassays predicted a higher atrazine concentration in water samples when compared to results of gas chromatography. If these tests are used as a semiquantitative screening tool, this tendency for overprediction does not diminish the tests' usefulness. Generally, the tests seem to be a valuable method for screening water samples for triazine herbicides.

International Journal of Environmental Analytical ↗

A bridging study for oxytetracycline in the edible fillet of rainbow trout: Analysis by a liquid chromatographic method and the official microbial inhibition assay

Oxytetracycline (OTC) is a drug approved by the U.S. Food and Drug Administration (FDA) to control certain diseases in salmonids and catfish. OTC is also a likely control agent for diseases of other fish species and for other diseases of salmonids and catfish not currently on the label. One requirement for FDA to extend and expand the approval of this antibacterial agent to other fish species is residue depletion studies. The current regulatory method for OTC in fish tissue, based on microbial inhibition, lacks sensitivity and specificity. To conduct residue depletion studies for OTC in fish with a liquid chromatographic method, a bridging study was required to determine its relationship with the official microbial inhibition assay. Triplicate samples of rainbow trout fillet tissue fortified with OTC at 0.3,0.6,1.2,2.4,4.8, and 9.6 ppm and fillet tissue with incurred OTC at approximately 0.75,1.5, and 3.75 ppm were analyzed by high-performance liquid chromatography (HPLC) and the microbial inhibition assay. The results indicated that the 2 methods are essentially identical in the tested range, with mean coefficients of variation of 1.05% for the HPLC method and 3.94% for the microbial inhibition assay.

Journal of AOAC International↗

Semiquantitative determination of polychlorinated biphenyls in tissue samples by thin layer chromatography

A method is described for the analysis of polychlorinated biphenyl (PCB) compounds in tissue samples. Cleanup by hexane-acetonitrile partitioning and Florisil column chromatography are performed on samples before oxidative treatment to convert DDE to DCBP. PCB components are then determined semi-quantitatively by TLC. No prior separation of PCB from chlorinated pesticides is required. The lower limit of sensitivity is 0.2 μ g.

Journal of the Association of Official Analytical ↗

Persistence of rotenone in ponds at different temperatures

Two ponds were treated with liquid rotenone (5% rotenone), one with 3 mg/L at 24°C and the other with 2 mg/L at 0°C (concentrations of active rotenone were 0.15 and 0.10 mg/L, respectively). Water samples were collected and analyzed by high-performance liquid chromatography. The concentration of rotenone declined to 0.02 mg/L in 48 h in warm water and in 11 d in cold water. The half-life of rotenone was calculated at 13.9 h in warm water and 83.9 h in cold water.

North American Journal of Fisheries Management↗

A study of the distribution of the polychlorinated biphenyls in the aquatic environment

Data gathered from monitoring activities and project studies indicate the ubiquitous occurrence and distribution of polychlorinated biphenyls in the aquatic environment. Residues have been detected in samples from 19 States, representing nearly every region of the country. Concentrations ranged from 0.1 to 4.0 ug/l in unfiltered water samples and 5.0 to 3,200 ug/kg in bottom sediments. PCB residues were also found in fish and aquatic plants. Samples were prepared by the same techniques used for general chlorinated insecticide detection, with special attention to cleanup and separation of PCB's from other compounds. Basic identification and quantification were made by dual-column electron-capture gas chromatography and confirmed by gas chromatography mass spectrometry whenever possible. The sampling program is expected to be broadened geographically in 1973 and increased in successive years in order to more adequately define the distribution of PCB residues in the major drainage basins of the United States.

Journal of Research of the U.S. Geological Survey↗

Characterization of coal-derived hydrocarbons and source-rock potential of coal beds, San Juan Basin, New Mexico and Colorado, U.S.A.

Coal beds are considered to be a major source of nonassociated gas in the Rocky Mountain basins of the United States. In the San Juan basin of northwestern New Mexico and southwestern Colorado, significant quantities of natural gas are being produced from coal beds of the Upper Cretaceous Fruitland Formation and from adjacent sandstone reservoirs. Analysis of gas samples from the various gas-producing intervals provided a means of determining their origin and of evaluating coal beds as source rocks. The rank of coal beds in the Fruitland Formation in the central part of the San Juan basin, where major gas production occurs, increases to the northeast and ranges from high-volatile B bituminous coal to medium-volatile bituminous coal ( R m values range from 0.70 to 1.45%). On the basis of chemical, isotopic and coal-rank data, the gases are interpreted to be thermogenic. Gases from the coal beds show little isotopic variation ( δ 13 C 1 values range −43.6 to −40.5 ppt), are chemically dry (C 1 /C 1–5 values are > 0.99), and contain significant amounts of CO 2 (as much as 6%). These gases are interpreted to have resulted from devolatilization of the humic-type bituminous coal that is composed mainly of vitrinite. The primary products of this process are CH 4 , CO 2 and H 2 O. The coal-generated, methane-rich gas is usually contained in the coal beds of the Fruitland Formation, and has not been expelled and has not migrated into the adjacent sandstone reservoirs. In addition, the coal-bed reservoirs produce a distinctive bicarbonate-type connate water and have higher reservoir pressures than adjacent sandstones. The combination of these factors indicates that coal beds are a closed reservoir system created by the gases, waters, and associated pressures in the micropore coal structure. In contrast, gases produced from overlying sandstones in the Fruitland Formation and underlying Pictured Cliffs Sandstone have a wider range of isotopic values ( δ 13 C 1 values range from −43.5 to −38.5 ppt), are chemically wetter (C 1 /C 1–5 values range from 0.85 to 0.95), and contain less CO 2 (< 2%). These gases are interpreted to have been derived from type III kerogen dispersed in marine shales of the underlying Lewis Shale and nonmarine shales of the Fruitland Formation. In the underlying Upper Cretaceous Dakota Sandstone and Tocito Sandstone Lentil of the Mancos Shale, another gas type is produced. This gas is associated with oil at intermediate stages of thermal maturity and is isotopically lighter and chemically wetter at the intermediate stage of thermal maturity as compared with gases derived from dispersed type III kerogen and coal; this gas type is interpreted to have been generated from type II kerogen. Organic matter contained in coal beds and carbonaceous shales of the Fruitland Formation has hydrogen indexes from Rock-Eval pyrolysis between 100 and 350, and atomic H:C ratios between 0.8 and 1.2. Oxygen indexes and atomic O:C values are less than 24 and 0.3, respectively. Extractable hydrocarbon yields are as high as 7,000 ppm. These values indicate that the coal beds and carbonaceous shales have good potential for the generation of liquid hydrocarbons. Voids in the coal filled with a fluorescent material that is probably bitumen is evidence that liquid hydrocarbon generation has taken place. Preliminary oil-source rock correlations based on gas chromatography and stable carbon isotope ratios of C 15+ hydrocarbons indicate that the coals and (or) carbonaceous shales in the Fruitland Formation may be the source of minor amounts of condensate produced from the coal beds at relatively low levelsof thermal maturity ( R m =0.7).

International Journal of Coal Geology↗

Organophosphate insecticide poisoning of Canada geese in the Texas panhandle

Sixteen hundred waterfowl, mostly Canada Geese, died near Etter, Texas, in late January 1981 from anticholinesterase poisoning. Winter wheat in the area of the die-off had been treated with organophosphate insecticides to control greenbugs. Cholinesterase (ChE) levels in brains of a sample of geese found dead were 75% below normal, enough to account for death (Ludke et al. 1975). The gastrointestinal (G I) tracts of geese found dead were packed with winter wheat; gas chromatography techniques identified parathion and methyl parathion in the GI tract contents. Residues of both chemicals were confirmed by mass spectrometry. We recommend that less toxic materials, such as malathion, be used on grain crops when waterfowl are in the vicinity of treatment.

Texas↗

Gas-liquid chromatographic determination of kepone in field-collected avian tissues and eggs

A procedure is described for determining Kepone (decachlorooctahydro-l,3,4-metheno-2H-cyclobuta [cd]pentalene-2-one) residues in avian egg, liver, and tissue. Samples were extracted with benzene-isopropanol, and the extract was cleaned up with fuming H 2 SO 4 -concentrated H 2 SO 4 . Kepone was separated from organochlorine pesticides and polychlorinated biphenyls on a Florisil column and analyzed by electron capture gas-liquid chromatography GLC). The average recovery from spiked tissues was 86%. The analyses performed on 14 bald eagle carcasses and livers, 3 bald eagle eggs, and 14 osprey eggs show measurable levels which indicate that Kepone accumulates in the tissues of fish-eating birds. Residues were confirmed by GLC-mass spectrometry.

Journal of the Association of Official Analytical ↗

Liquid-chromatographic determination of sarafloxacin residues in channel catfish muscle-tissue

A liquid chromatographic method is described for the determination of sarafloxacin hydrochloride residues in channel catfish ( Ictalurus punctatus ) fillets. Sarafloxacin was extracted from fillet tissue with acetonitrile–water (1+1). The extract was centrifuged and the supernatant was partitioned with hexane. The aqueous fraction was filtered through a 0.45 μm filter and evaporated to dryness. The sample was redissolved with 20% acetonitrile–methanol (3 + 2) and 80% trifluoroacetic acid (0.1%), centrifuged, and filtered to remove proteins. Samples were analyzed by chromatography with gradient elution on a C 18 column and with fluorescence detection (excitation at 280 nm and emission above 389 nm). Mean recoveries ranged from 85.4 to 104%, and relative standard deviations ranged from 1.06 to 5.58% in samples spiked at concentrations of 10.0–863.8 ng/g. The method detection limit for sarafloxacin was 1.4 ng/g.

Journal of AOAC International↗

Application of brain cholinesterase reactivation to differentiate between organophosphorus and carbamate pesticide exposure in wild birds

Brain cholinesterase activity was measured to evaluate pesticide exposure in wild birds. Thermal reactivation of brain cholinesterase was used to differentiate between carbamate and organophosphorus pesticide exposure. Brain cholinesterase activity was compared with gas chromatography and mass spectrometry of stomach contents. Pesticides were identified and confirmed in 86 of 102 incidents of mortality from 29 states within the USA from 1986 through 1991. Thermal reactivation of cholinesterase activity was used to correctly predict carbamates in 22 incidents and organophosphates in 59 incidents. Agreement ( P < 0.001) between predictions based on cholinesterase activities and GC/MS results was significant.

Journal of Wildlife Diseases↗

Assessing the occurrence and distribution of pyrethroids in water and suspended sediments

The distribution of pyrethroid insecticides in the environment was assessed by separately measuring concentrations in the dissolved and suspended sediment phases of surface water samples. Filtered water was extracted by HLB solid-phase extraction cartridges, while the sediment on the filter was sonicated and cleaned up using carbon and aluminum cartridges. Detection limits for the 13 pyrethroids analyzed by gas chromatography-tandem mass spectrometry were 0.5 to 1 ng L-1 for water and 2 to 6 ng g for the suspended sediments. Seven pyrethroids were detected in six water samples collected from either urban or agricultural creeks, with bifenthrin detected the most frequently and at the highest concentrations. In spiked water samples and field samples, the majority of the pyrethroids were associated with the suspended sediments.

Journal of Agricultural and Food Chemistry↗