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Biomedical subjects

A J Krynitsky

Publications and source records attributed to A J Krynitsky.

18 recordsLinked to original sources

Hepatic glutathione metabolism and lipid peroxidation in response to excess dietary selenomethionine and selenite in mallard ducklings.

Studies were conducted with mallard (Anas platyrhynchos) ducklings to determine the effects of excess dietary selenium (Se) on hepatic glutathione concentration and associated enzymes, and lipid peroxidation. Day-old ducklings were fed 0.1, 10, 20, or 40 ppm Se as seleno-DL-methionine or sodium selenite for 6 wk. Selenium from selenomethionine accumulated in a dose-dependent manner in the liver, resulting in a decrease in the concentration of hepatic-reduced glutathione (GSH) and total hepatic thiols (SH). These effects were accompanied by a dose-dependent increase in the ratio of oxidized glutathione (GSSG) to GSH, and an increase in malondialdehyde concentration as evidence of lipid peroxidation. Hepatic and plasma GSH peroxidase activity was initially elevated at 10 ppm Se as selenomethionine, whereas GSSG reductase activity was elevated at higher dietary concentrations of Se. Selenium from sodium selenite accumulated in the liver to an apparent maximum at 10 ppm in the diet, resulting in an increase in hepatic GSH and GSSG accompanied by a small decrease in total hepatic SH. Sodium selenite resulted in an increase in hepatic GSSG reductase activity at 10 ppm and in plasma GSSG reductase activity at 40 ppm. A small increase in lipid peroxidation occurred at 40 ppm. These findings indicate that excess dietary Se as selenomethionine has a more pronounced effect on hepatic glutathione metabolism and lipid peroxidation in ducklings than does selenite, which may be related to the pattern of accumulation. Effects of Se as selenite appear to be less pronounced in ducklings than reported in laboratory rodents. The effects of selenomethionine, which occurs in vegetation, are of particular interest with respect to the health of wild aquatic birds in seleniferous locations.

Age Factors↗

Selenium contamination of the Grasslands, a major California waterfowl area.

In a recent study at Kesterson Reservoir in California, selenium was shown to cause mortality and deformities in embryos of aquatic birds. The present study was conducted to determine if selenium or other contaminants in agricultural drainwater used for marsh management were likely to cause similar adverse effects in the nearby Grasslands area. Selenium concentrations were elevated (greater than 15 ppm, dry-weight) in livers of some birds of all species collected from the Grasslands. Mean selenium concentrations in all species sampled in the South Grasslands were significantly higher (P less than 0.05) than those from the "control site", the Volta Wildlife Area. Mean selenium levels in black-necked stilts (Himantopus mexicanus) from the South Grasslands (35.6 ppm) were similar (P greater than 0.05) to levels in stilts from Kesterson (46.4 ppm), but means for American avocets (Recurvirostra americana) from the South Grasslands (67.3 ppm) were higher (P less than 0.05) than those from Kesterson (28.4 ppm). Bird eggs and fish from the Grasslands also contained elevated levels of selenium. Concentrations of eight heavy metals in fish generally reflected those patterns previously found in water entering the study areas. Of the organochlorines detected in fish, only DDE occurred at concentrations potentially harmful to birds (6.1 and 3.0 ppm, wet weight, at two South Grassland sites). The effect on avian health or reproduction of the other contaminants, singly or in combination, could not be determined. However, selenium levels were apparently sufficiently elevated in 1984 to have caused adverse effects on avian reproduction in the South Grasslands.

Animals↗

Acute oral toxicity of sodium cyanide in birds.

Sensitivities of six avian species, black vulture (Coragyps atratus), American kestrel (Falco sparverius), Japanese quail (Coturnix japonica), domestic chicken (Gallus domesticus), eastern screech-owl (Otus asio), and European starling (Sturnus vulgaris), to acute poisoning by sodium cyanide (NaCN) were compared by single dose LD50's. Three species, domestic chickens, black vultures, and turkey vultures (Cathartes aura), were dosed with NaCN to determine cyanide residues in those that died and also in survivors, in addition to postmortem fate. Three flesh-eating species (black vulture, American kestrel, and eastern screech-owl; LD50's 4.0-8.6 mg/kg) were more sensitive to NaCN than three species (Japanese quail, domestic chicken, and European starling; LD50's 9.4-21 mg/kg) that fed predominantly on plant material. Elevated concentrations of cyanide were found in the blood of birds that died of cyanide poisoning; however, concentrations in birds that died overlapped those in survivors. Blood was superior to liver as the tissue of choice for detecting cyanide exposure. No gross pathological changes related to dosing were observed at necropsy.

Administration, Oral↗

The effects of heptachlor and lindane on birds, Columbia Basin, Oregon and Washington, 1976-1981.

The effects of heptachlor seed treatments on birds in the vicinity of the Umatilla National Wildlife Refuge, Oregon and Washington, were investigated from 1978 to 1981. An egg was collected from each of 60 nests representing six species. Heptachlor epoxide (HE) residues were detected in 35 eggs and were particularly high (8-13 micrograms g-1) in a few eggs of the black-billed magpie, mallard, and ring-necked pheasant. These residues were within the range that induced reproductive problems in other species in the area. Diagnostically lethal residue levels (greater than or equal to 9 micrograms g-1) of HE were detected in the brains of nine birds (four species). Most of the avifauna in the area contained residues of HE and related compounds. Lindane, the replacement chemical for heptachlor, did not produce adverse effects in birds, and residues were not detected in either their eggs or brains.

Animals↗

Organochlorine pesticide, PCB, and PBB residues and necropsy data for bald eagles from 29 states--1975-77.

During 1975-77, 168 bald eagles (Haliaeetus leucocephalus) found moribund or dead in 29 states were analyzed for organochlorine pesticides and polychlorinated biphenyls (PCBs); 32 specimens from 13 states were analyzed for polybrominated biphenyls (PBBs). PCBs were present in 166 bald eagle carcasses and DDE was found in 165. TDE and dieldrin were identified in 137 samples, trans-nonachlor in 118, and oxychlordane in 90. Brains of five eagles contained possible lethal levels of dieldrin, and two eagles possibly died of endrin poisoning. Nine eagle livers, analyzed because of suspected lead poisoning, contained high levels of lead. Twenty percent of the eagles died from shooting, the most common cause of death; this cause of death, however, has declined.

Animals↗

Organochlorine residues in eggs of loggerhead and green sea turtles nesting at Merritt Island, Florida--July and August 1976.

Eggs from nine clutches of loggerhead turtles (Caretta caretta) and two clutches of green turtles (Chelonia mydas) were collected as they were laid on Merritt Island, Florida. Eggs were incubated, frozen, and analyzed for organochlorines. Levels of DDE and PCB, the major contaminants, averaged less than 0.08 ppm in loggerhead eggs and were even lower in green turtle eggs. These concentrations are far below levels thought to be potentially harmful. Loggerhead eggs were frozen after 43-52 days incubation; both DDE and PCB declined significantly during this interval. Authors estimate that DDE averaged about 0.2 ppm in loggerhead eggs when they were laid. DDE levels in eggs of both turtle species were less than levels in eggs of crocodiles (Crocodylus acutus) from Everglades National Park and in eggs of 13 species of aquatic birds nesting on Merritt Island. The remarkably low residues in the turtle eggs probably indicate that, when not nesting, the turtles live and feed in areas remote from Florida.

Animals↗

Dieldrin and heptachlor residues in dead gray bats, Franklin County, Missouri--1976 versus 1977.

Lethal dieldrin concentrations were found in the brains of dead gray bats (Myotis grisescens) collected during 1976 and 1977 beneath a maternity roost in a Missouri cave. In addition, residues of heptachlor epoxide, oxychlordane, cis-chlordane, and trans-nonachlor increased significantly in both brains and carcasses of bats collected during 1977. These increases appear to reflect a switch by local farmers from aldrin, dieldrin's parent compound, to heptachlor for the control of cutworms. They also constitute an additional threat to this colony of this endangered bat species.

Animals↗

Selenium accumulation and elimination in mallards.

Selenium accumulation and loss were measured in adult mallards (Anas platyrhynchos) fed selenomethionine during two experiments. In Experiment 1, both sexes were fed a diet containing 10 ppm selenium for 6 weeks, followed by 6 weeks on untreated feed. Selenium accumulation in liver and muscle of females was described by C = A(1-e-bt). Concentrations of selenium were predicted to reach 95% of equilibrium faster in liver (7.8 days) than in muscle (81 days). The loss of selenium from liver and muscle of females was described by the exponential loss rate equation: C = Ae-bt, with half-times of 18.7 and 30.1 days, respectively. Males reached similar levels of selenium in liver and breast muscle as females and declined to similar levels once selenium treatment ended. In Experiment 2, females were fed increasing levels of selenium until some died. Survivors were switched to an untreated diet and selenium was measured in blood, liver, and breast muscle over 64 days. The same equation as in Experiment 1, C = Ae-bt, was used to describe the loss of selenium from blood and muscle. Half-times were 9.8 and 23.9 days, respectively. For liver, the equation C = A1e-b1t + A2e-b2t was used. Selenium initially decreased in liver by one-half in 3.3 days, with subsequent half-times of 3.9, 6.0, and 45.1 days.

Animals↗

Capillary electrophoresis determinative and LC-MS confirmatory method for screening selected imidazolinone herbicides from soil.

Residues of imazapyr, imazamox, imazapic, imazethapyr, imazaquin, and imazamethabenz (meta and para) are extracted from soil with 0.5 N sodium hydroxide. The pH is adjusted to 2.0-2.2, and the resulting precipitate is filtered. Compounds are trapped onto a tC18 solid-phase extraction (SPE) cartridge, then eluted from the cartridge and passed through a strong anion exchange (SAX) SPE cartridge onto a benzenesulfonic acid strong cation exchange (SCX) cartridge using ethyl acetate. After eluting the analytes from the SCX cartridge using saturated potassium chloride in methanol, the solution is evaporated and redissolved in 1% formic acid in water. The sample is then desalted using a tC18 SPE cartridge and eluted with methanol. After evaporating the methanol to dryness, the compounds are partitioned from acidic solution (pH 3.5) into methylene chloride. The methylene chloride is evaporated to dryness and the residues are then dissolved in Milli-Q water (Millipore, Bedford, MA, U.S.A.) in preparation for analysis by capillary electrophoresis. Results are calculated by direct comparison of the sample peak heights to the peak heights of bracketing standards. The validated sensitivity of the method (LOQ, limit of quantitation) is 2.0 ppb for each compound. Confirmation for individual residues greater than 2.0 ppb is provided by liquid chromatography-electrospray ionization mass spectrometry (LC-ESMS) of the final extract.

Chromatography, Liquid↗

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 ether-hexane. 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.

Animals↗

Determination of sulfonylurea herbicides in grains by capillary electrophoresis.

A capillary electrophoresis (CE) method was developed to separate and determine residues of 5 sulfonylurea herbicides in grains (wheat, barley, and corn). This work demonstrated the practicality of using CE for residue analysis of sulfonylureas. The method yielded good recoveries and adequate sensitivities at tolerance levels (0.05-0.1 ppm). The compounds investigated were metsulfuron methyl (Ally), thifensulfuron methyl (Harmony), chlorsulfuron (Glean), rimsulfuron (DPX-E9636), and tribenuron methyl (Express). Acetonitrile extracts of grain samples were partitioned with hexane and then cleaned up with cation exchange solid-phase extraction cartridges. Quantitation was performed by micellar electrokinetic capillary chromatography using a high-sensitivity optical cell. Average recoveries at the 0.05 ppm level ranged from 72.9 to 118.5%. The lower limit of detection was approximately 0.02 ppm, except for rimsulfuron and tribenuron methyl, for which the lower limit of detection was 0.035 ppm. The method was less complicated and showed better sensitivity than current single-analyte liquid chromatographic enforcement methods.

Acetonitriles↗

Determination of sulfonylurea herbicides in water by capillary electrophoresis and by liquid chromatography/mass spectrometry.

A capillary electrophoresis (CE) method and an electrospray ionization (ESI) liquid chromatography/mass spectrometry (LC/MS) confirmatory method were developed to analyze 12 sulfonylurea herbicides and one sulfonamide (Flumetsulam) in runoff water. The water used for fortification was collected from a local marsh that contained high levels of potentially interfering compounds. Good recoveries and adequate sensitivity at the 0.2 ppb level (limit of quantitation) were obtained. A portion of the water was acidified and extracted with reversed-phase solid-phase extraction (SPE). Extracts were cleaned up with a tandem system consisting of a strong-anion exchange SPE cartridge stacked on an alumina SPE cartridge. CE/ultraviolet quantitation was achieved by capillary zone electrophoresis at pH 4.75 with 50 mM ammonium acetate buffer and an acetonitrile modifier. ESI LC/MS quantitation was achieved by using a time-scheduled selective-ion monitoring (positive mode) of the M + H ions for each compound. The extraction/cleanup procedure provided extracts such that in-source collision-induced dissociation gave product ions for confirmation at the 0.2 ppb fortification level.

Chromatography, Liquid↗