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Food matrix reference materials for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements: Collagens, flours, honeys, and vegetable oils

An international project developed, quality-tested, and measured isotope–delta values of 10 new food matrix reference materials (RMs) for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements to support food authenticity testing and food provenance verification. These new RMs, USGS82 to USGS91, will enable users to normalize measurements of samples to isotope–delta scales. The RMs include (i) two honeys from Canada and tropical Vietnam, (ii) two flours from C3 (rice) and C4 (millet) plants, (iii) four vegetable oils from C3 (olive, peanut) and C4 (corn) plants, and (iv) two collagen powders from marine fish and terrestrial mammal origins. An errors-in-variables regression model included the uncertainty associated with the measured and assigned values of the RMs, and it was applied centrally to normalize results and obtain consensus values and measurement uncertainties. Utilization of these new RMs should facilitate mutual compatibility of stable isotope data if accepted normalization procedures are applied and documented.

Journal of Agricultural and Food Chemistry

Uptake, metabolism, and elimination of fungicides from coated wheat seeds in Japanese quail (Coturnix japonica)

Pesticides coated to the seed surface potentially pose an ecological risk to granivorous birds that consume incompletely buried or spilled seeds. To assess the toxicokinetics of seeds treated with current-use fungicides, Japanese quail (Coturnix japonica) were orally dosed with commercially coated wheat seeds. Quail were exposed to metalaxyl, tebuconazole, and fludioxonil at either a low (0.07, 0.03, and 0.03 mg/kg body weight) or high dose (0.2, 0.09, and 0.1 mg/kg body weight). Fungicides were rapidly absorbed and distributed to tissues. Tebuconazole was metabolized into t-butylhydroxy-tebuconazole. All compounds were eliminated to below detection limits within 24 h. The high detection frequencies observed in fecal samples potentially offers a noninvasive matrix to monitor pesticide exposure. Summing total body burden across plasma, tissue, and fecal samples, less than 9% of the administered dose was identified as the parent fungicide, demonstrating the importance to monitor both active ingredients and their metabolites in biological samples.

Journal of Agricultural and Food Chemistry

Performance of the goulden large-sample extractor in multiclass pesticide isolation and preconcentration from stream water

The reliability of the Goulden large-sample extractor in preconcentrating pesticides from water was evaluated from the recoveries of 35 pesticides amended to filtered stream waters. Recoveries greater than 90% were observed for many of the pesticides in each major chemical class, but recoveries for some of the individual pesticides varied in seemingly unpredictable ways. Corrections cannot yet be factored into liquid-liquid extraction theory to account for matrix effects, which were apparent between the two stream waters tested. The Goulden large-sample extractor appears to be well suited for rapid chemical screening applications, with quantitative analysis requiring special quality control considerations. ?? 1991 American Chemical Society.

Journal of Agricultural and Food Chemistry

Isolation and identification of trichothecenes from Fusarium compactum suspected in the aetiology of a major intoxication of sandhill cranes

Isoneosolaniol (4,8-diacetoxy-12,13-epoxytrichothec-9-ene-3,15-diol) and other unidentified trichothecene mycotoxins were isolated from culture extracts of two highly toxigenic strains of Fusarium compactum cultured from waste peanuts involved in an acute intoxication of sandhill cranes ( Grus canadensis ). Neosolaniol and other unidentified trichothecenes were detected in waste peanuts collected from affected areas. The structure of isoneosolaniol was determined by 1 H and 13 C NMR analyses and by high-resolution mass spectometry. Isoneosolaniol was hightly toxic to 1-day-old chickens and to a HEp2 cell culture assay. It was concluded that the most logical cause of the sandhill crane intoxication was Fusarium spp. Contaminated peanuts and various trichothecene mycotoxins acting alone or in conjunction with other Fusarium mycotoxins.

Texas

Residues of isobornyl thiocyanoacetate (Thanite) and a metabolite in fish and treated ponds

Isobornyl thiocyanoacetate (Thanite) is an insecticide that induces a surfacing response in fish and therefore has been considered to have potential as a fish collection agent. Analyses for residues of Thanite in carp (Cyprinus carpio) and largemouth bass (Micropterus salmoides) exposed to chemical yielded only a trace of the parent compound. A metabolite, isobornyl a-(methylthio)acetate, was isolated and indentified by GC-MS,and a reference standard for the metabolite was synthesized. Residues of the metabolite were present in largemouth bass muscle tissue within 1 h after exposure to Thanite. The metabolite was also observed in the muscle, blood plasma, and bile of carp. Residues of the metaboliteare rapidly elimanated after the fish are transferred to Thanite-free water. Residues of Thanite in water, algae, and from soil from ponds treated with Thanite declined to undetectable levels within 28 days after treatment.

Journal of Agricultural and Food Chemistry

Mineral composition of small-grain cultivars from a uniform test plot in South Dakota

Seventy-five cultivated varieties (cultivars) of hard red spring wheat (HRS), hard red winter wheat (HRW), durum wheat, oats, and barley were harvested in 1974 from a small-grain trial plot in Harding County, SD, just north of Buffalo. Analysis of the grains reported here includes crude protein for only the wheat cultivars, ash yield, and 17 chemical elements, many of which are not commonly given in the literature (such as B, Cd, Mo, Ni, and Se). Differences in composition between the two classes of hard red wheat indicate that HRS is significantly higher (p < 0.05) than HRW in protein content, ash yield, Ca, K, Mg, Na, P, total S, Sr, and Zn; Cd is significantly higher in the HRW cultivars. For the most part, concentrations were quite uniform within all grain types. Only two cultivars were anomalous: cv. Hi Plains in HRW wheats and cv. Astro in the oat group.

Journal of Agricultural and Food Chemistry

Analysis and detection of the herbicides dimethenamid and flufenacet and their sulfonic and oxanilic acid degradates in natural water

Dimethenamid [2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide] and flufenacet [N-(4-fluorophenyl)-N-(1-methylethyl)-2-(5-(trifluoromethyl)-1,3,4- thiadiazol-2-yl)oxy] were isolated by C-18 solid-phase extraction and separated from their ethanesulfonic acid (ESA) and oxanilic acid (OXA) degradates during their elution using ethyl acetate for the parent compound, followed by methanol for the polar degradates. The parent compounds were detected using gas chromatography-mass spectrometry in selected-ion mode. The ESA and OXA degradates were detected using high-performance liquid chromatography-electrospray mass spectrometry (HPLC-ESPMS) in negative-ion mode. The method detection limits for a 123-mL sample ranged from 0.01 to 0.07 μg/L. These methods are compatible with existing methods and thus allow for analysis of 17 commonly used herbicides and 18 of their degradation compounds with one extraction. In a study of herbicide transport near the mouth of the Mississippi River during 1999 and 2000, dimethenamid and its ESA and OXA degradates were detected in surface water samples during the annual spring flushes. For flufenacet, the only detections at the study site were for the ESA degradates in samples collected at the peak of the herbicide spring flush in 2000. The low frequency of detections in surface water likely is due to dimethenamid and flufenacet being relatively new herbicides. In addition, detectable amounts of the stable degradates have not been detected in ground water.

Journal of Agricultural and Food Chemistry

Rapid loss of lampricide from catfish and rainbow trout following routine treatment

Rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) were exposed to 3-trifluoromethyl-4-nitrophenol (TFM) and Bayluscide (niclosamide) during a sea lamprey control treatment of the Ford River, located in the upper peninsula of Michigan. Caged fish were exposed to a nominal concentration of 0.02 mg/L of niclosamide for a period of approximately 12 h. Samples of fillet tissue were collected from each fish species before treatment and at 6, 12, 18, 24, 48, 96, and 192 h following the arrival of the block of chemical at the exposure site. The fish were dissected, homogenized, extracted, and analyzed by high-performance liquid chromatography. The major residues found in the fillet tissues were TFM and niclosamide. Niclosamide concentrations were highest 12 h after arrival of the chemical block for rainbow trout (0.0395 ?? 0.0251 ??g/g) and 18 h after arrival of the chemical block for channel catfish (0.0465 ?? 0.0212 ??g/g). Residues decreased rapidly after the block of lampricide had passed and were below the detection limits in fillets of rainbow trout within 24 h and channel catfish within 96 h after the arrival of the lampricide.

Journal of Agricultural and Food Chemistry

Presence of organoarsenicals used in cotton production in agricultural water and soil of the Southern United States

Arsenicals have been used extensively in agriculture in the United States as insecticides and herbicides. Mono- and disodium methylarsonate and dimethylarsinic acid are organoarsenicals used to control weeds in cotton fields and as defoliation agents applied prior to cotton harvesting. Because the toxicity of most organoarsenicals is less than that of inorganic arsenic species, the introduction of these compounds into the environment might seem benign. However, biotic and abiotic degradation reactions can produce more problematic inorganic forms of arsenic, such as arsenite [As(III)] and arsenate [As(V)]. This study investigates the occurrences of these compounds in samples of soil and associated surface and groundwaters. Preliminary results show that surface water samples from cotton-producing areas have elevated concentrations of methylarsenic species (>10 ??g of As/L) compared to background areas (<1 ??g of As/L). Species transformations also occur between surface waters and adjacent soils and groundwaters, which also contain elevated arsenic. The data indicate that point sources of arsenic related to agriculture might be responsible for increased arsenic concentrations in local irrigation wells, although the elevated concentrations did not exceed the new (2002) arsenic maximum contaminant level of 10 ??g/L in any of the wells sampled thus far.

Journal of Agricultural and Food Chemistry

Aqueous photolysis of niclosamide

The photodegradation of [ 14 C]niclosamide was studied in sterile, pH 5, 7, and 9 buffered aqueous solutions under artificial sunlight at 25.0 ± 1.0 °C. Photolysis in pH 5 buffer is 4.3 times faster than in pH 9 buffer and 1.5 times faster than in pH 7 buffer. In the dark controls, niclosamide degraded only in the pH 5 buffer. After 360 h of continuous irradiation in pH 9 buffer, the chromatographic pattern of the degradates was the same regardless of which ring contained the radiolabel. An HPLC method was developed that confirmed these degradates to be carbon dioxide and two- and four-carbon aliphatic acids formed by cleavage of both aromatic rings. Carbon dioxide was the major degradate, comprising ∼40% of the initial radioactivity in the 360 h samples from both labels. The other degradates formed were oxalic acid, maleic acid, glyoxylic acid, and glyoxal. In addition, in the chloronitroaniline-labeled irradiated test solution, 2-chloro-4-nitroaniline was observed and identified after 48 h of irradiation but was not detected thereafter. No other aromatic compounds were isolated or observed in either labeled test system.

Journal of Agricultural and Food Chemistry

Metabolism of niclosamide in sediment and water systems

A series of experiments analyzed the kinetics and mechanisms of [ 14C]niclosamide degradation. The aerobic aquatic metabolism of [ 14C]niclosamide was studied in nonsterile river water/sediment mixtures. Test systems, maintained under aerobic conditions, were treated with niclosamide and incubated in the dark at 25.0 ?? 1.0 ??C for 30 days. Half-lives of 4.9 and 5.4 days were calculated for the chlorosalicylic acid- and chloronitroaniline-labeled test systems, respectively. From 0 to 21 days after treatment (DAT), the only metabolism product observed in either test system was aminoniclosamide. At the final sampling interval, five peaks were resolved from the chlorosalicylic acid label, and three peaks were resolved from the chloronitroaniline label test substance. By 30 DAT, sediment-bound residues represented ???70% of the observed radioactivity. For the anaerobic aquatic metabolism of [14C]niclosamide, test systems were incubated under anaerobic conditions for 365 days. Half-lives of 0.65 day for the chlorosalicylic acid label and 2.79 days for the chloronitroaniline label were calculated. From 0 to 3 DAT, niclosamide was first transformed into aminoniclosamide. Aminoniclosamide is readily formed, as it was observed in the chlorosalicylic acid label 0 DAT sampling. Several minor metabolites were observed in the water and sediment extracts. None of these metabolites were formed to a significant amount until the parent niclosamide dissipated below the detection limit. Two of the byproducts from these metabolism studies are polar unknowns eluting at 3 and 5 min by HPLC, similar to the unknowns observed in aqueous photolysis studies.

Journal of Agricultural and Food Chemistry

Anaerobic biotransformation of organoarsenical pesticides monomethylarsonic acid and dimethylarsinic acid

Monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV) are extensively utilized as pesticides, introducing large quantities of arsenic into the environment. Once released into the environment, these organoarsenicals are subject to microbial reactions. Aerobic biodegradation of MMAV and DMAV has been evaluated, but little is known about their fate in anaerobic environments. The objective of this study was to evaluate the biotransformation of MMAV and DMAV in anaerobic sludge. Biologically mediated conversion occurred under methanogenic or sulfate-reducing conditions but not in the presence of nitrate. Monomethylarsonous acid (MMAIII) was consistently observed as an important metabolite of MMAV degradation, and it was recovered in molar yields ranging from 5 to 47%. The main biotransformation product identified from DMAV metabolism was MMAV, which was recovered in molar yields ranging from 8 to 65%. The metabolites indicate that reduction and demethylation are important steps in the anaerobic bioconversion of MMAV and DMAV, respectively. ?? 2006 American Chemical Society.

Journal of Agricultural and Food Chemistry

Effects of sorbate speciation on sorption of selected sulfonamides in three loamy soils

Sorption of sulfamethazine (SMN) and sulfathiazole (STZ) was investigated in three soils, a North Carolina loamy sand, an Iowa sandy loam, and a Missouri loam, under various pH conditions. A significant increase in the sorption coefficient ( K D ) was observed in all three soils, as the sulfonamides converted from an anionic form at higher pH to a neutral/cationic form at lower pH. Above pH 7.5, sulfonamides exist primarily in anionic form and have higher aqueous solubility and no cationic character, thereby consequently leading to lower sorption to soils. The effect of speciation on sorption is not the same for all sulfonamides; it is a function of the pH of the soil and the p K a of the sulfonamides. The results indicate that, for the soils under investigation, SMN has comparatively lower K D values than STZ. The pH-dependent sorption of sulfonamides was observed to be consistent in all three soils investigated. The K D values for each speciated form cationic, neutral, and anionic were calculated using an empirical model in which the species-specific sorption coefficients ( K D0 , K D1 , and K D2 ) were weighted with their respective fractions present at any given pH.

Journal of Agricultural and Food Chemistry

Mercury distribution and lipid oxidation in fish muscle: Effects of washing and isoelectric protein precipitation

Nearly all the mercury (Hg) in whole muscle from whitefish ( Coregonus clupeaformis ) and walleye ( Sander vitreus ) was present as methyl mercury (MeHg). The Hg content in whole muscle from whitefish and walleye was 0.04–0.09 and 0.14–0.81 ppm, respectively. The myofibril fraction contained approximately three-fourths of the Hg in whitefish and walleye whole muscle. The sarcoplasmic protein fraction (e.g., press juice) was the next most abundant source of Hg. Isolated myosin, triacylglycerols, and cellular membranes contained the least Hg. Protein isolates prepared by pH shifting in the presence of citric acid did not decrease Hg levels. Addition of cysteine during washing decreased the Hg content in washed muscle probably through the interaction of the sulfhydryl group in cysteine with MeHg. Primary and secondary lipid oxidation products were lower during 2 °C storage in isolates prepared by pH shifting compared to those of washed or unwashed mince from whole muscle. This was attributed to removing some of the cellular membranes by pH shifting. Washing the mince accelerated lipid peroxide formation but decreased secondary lipid oxidation products compared to that of the unwashed mince. This suggested that there was a lipid hydroperoxide generating system that was active upon dilution of aqueous antioxidants and pro-oxidants.

Journal of Agricultural and Food Chemistry

Rodent repellents, preparation and properties of thiouronium compounds and cyclic imides

Syntheses and bioassays of cyclic imides and thiouronium compounds were carried out as part of a search for materials capable of preventing rodent damage to packaged commodities. Previous studies had shown that repellent activity was associated with functional groups containing nitrogen and sulfur, and was enhanced by the presence of ionic linkages. Twenty-seven thiouronium compounds and 40 imides, including 1 0 compounds not described previously, were prepared for these tests. Ten imides and 26 thiouronium compounds were repellent under the conditions of test. Information obtained in these studies will be utilized in the development and selection of more effective materials for prevention of rodent damage to foods and other commodities.

Journal of Agricultural and Food Chemistry

Pesticide toxicity, effects of chlorinated hydrocarbon insecticides upon quail and pheasants

Previous studies had shown that heavy or repeated applications of DDT resulted in decreases.in bird populations, but long-range effects of this and other chlorinated hydrocarbon insecticides had not been fully evaluated. Experiments were conducted to determine toxiCitY to quail and pheasants of aldrin, dieldrin, endrin, and strobane, and to determine effects of these compounds upon survival, growth, and reproduction....Feeding of diets containing 0.02% DDT to breeding quail resulted in significant decreases in hatchability of eggs and in viability of chiCks. Similar results were obtained by feeding 0.001% dieldrin, but effects upon reproduct.ion of short-term feeding of aldrin and endrin could not be determined....Aldrin, dieldrin, and endrin were lethal to both male and female quail when fed at levels of 0.0005% in the diets. Female pheasants appeared more resistant than males to the effects of these compounds.

Journal of Agricultural and Food Chemistry

Pesticide toxicity, chronic toxicity to quail and pheasants of some chlorinated insecticides

Quantitative report of tests. 'Inclusion of 1 p.p.m, of aldrin, dieldrin, or endrin in diets fed growing quail resulted in high mortality rates, but the birds survived on diets containing 100 p.p.m, of DDT or 50 p.p.m. of strobane. Young pheasants survived on diets containing 50 p.p.m, of DDT or strobane, but failed to survive on diets containing 5 p.p.m, of aldrin, dieldrin, or endrin. No ill effects were noted when quail were fed winter diets containing 50 p.p.m, of strobane, or 1 p.p.m, of dieldrin or endrin, but nearly all birds died when fed diets containing 0.5 p.p.m, of aldrin. Mortality rates among pheasants fed 50 p.p.m, and of quail fed 100 p.p.m. of DDT were higher than for birds receiving normal diets, but none of the birds displayed symptoms characteristic of DDT poisoning. Egg production, fertility, and hatchability were relatively unaffected by inclusion of insecticides in diets fed breeding quail, but chicks from these matings showed high mortality rates even when reared on insecticide-free diets. Lowered viability of quail chicks was most pronounced in groups receiving DDT and strobane in the reproduction diets. Hatchability of pheasant eggs and viability of chicks were adversely affected by inclusion of aldrin, dieldrin, or endrin in the reproduction diets.'

Journal of Agricultural and Food Chemistry