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At least 19 recordsLinked to original sources
USGS2020

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↗
USGS2020

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↗
USGS2002

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↗
USGS2002

Aquatic dissipation of triclopyr in Lake Seminole, Georgia

A field study was conducted to evaluate the environmental dissipation of triclopyr herbicide under aquatic-use conditions. Three 4-h plots in Lake Seminole, Georgia, were selected for use: one control, one aerial plot, and one subsurface plot; both applications were at the maximum aquatic-use rate of 2.5 mg/L. Water, sediment, plants, fish, clams, and crayfish were all analyzed for residues, and water temperature, oxygen levels, pH, and conductivity were monitored. The half-life for aqueous-phase triclopyr ranged from 0.5 to 3.6 days, and the dissipation in surface and bottom waters was equivalent. The intermediate decay product of triclopyr, 3,5,6-trichloro-2-pyridinol (TCP), had an observed aquatic half-life of less than 1 day. No accumulation of triclopyr or TCP on sediment was observed. The half-life of triclopyr metabolized by aquatic plants averaged 4 days. Fish species did not exhibit any bioconcentration of triclopyr or TCP, with only trace amounts of either compound found in fish tissue. Both clams and crayfish contained detectable residues of triclopyr. The elimination of triclopyr from clam tissue was more rapid, with an observed half-life of 1.5 days, vs 12 days for crayfish; retention of triclopyr in the crayfish carcass (carapace, chelopeds, and gills) may have been an important mechanism. There was no detectable decline in water quality in either treatment plot. ?? 1993 American Chemical Society.

Journal of Agricultural and Food Chemistry↗
USGS2002

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↗
USGS2002

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↗
USGS2002

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↗
USGS2002

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↗
USGS2002

Improved method for quantifying the avicide 3-chloro-p-toluidine hydrochloride in bird tissues using a deuterated surrogate/GC/MS method

A method using a deuterated surrogate of the avicide 3-chloro- p -toluidine hydrochloride (CPTH) was developed to quantify the CPTH residues in the gastrointestinal (GI) tract and breast muscle tissues in birds collected in CPTH-baited sunflower and rice fields. This method increased the range of a previous surrogate/gas chromatography/mass spectroscopy method from 0−2 to 0−20 μg/g in tissue samples and greatly simplified the extraction procedure. The modified method also sought to increase recoveries over a range of matrix effects introduced by analyzing tissues from birds collected in the field, where the GI tract contents would be affected by varying diet. The new method was used to determine the CPTH concentration in GI tract samples fortified with CPTH-treated rice bait to simulate the consumption of varying amounts of treated bait by two nontargeted bird species, pigeon ( Columbia livia ) and house sparrow ( Passer domesticus ). The new method was then used to examine the CPTH concentrations in the gizzard contents of the targeted bird species, red-winged black bird ( Agelaius phoeniceus ) and brown-headed cowbird ( Molothrus ater ), that were collected after feeding at a treated bait site. The method proved sufficiently sensitive to quantify CPTH in the breast muscle tissues and the gizzard contents of red-winged blackbirds and brown-headed cowbirds during an operational baiting program. The levels of CPTH determined for these birds in both tissue samples were determined to be highly correlated. The appearance of CPTH in the breast muscle tissue immediately after feeding was not anticipated. The potential secondary hazard posed by the targeted birds to potential scavengers and predators was also evaluated.

Journal of Agricultural and Food Chemistry↗
USGS2002

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↗
USGS2002

Relatively rapid loss of lampricide residues from fillet tissue of fish after routine treatment

The selective sea lamprey ( Petromyzon marinus ) larvicide 3-trifluoromethyl-4-nitrophenol (TFM) is currently used to control parasitic sea lampreys in tributaries to the Great Lakes basin. The concentration and persistence of TFM and its major metabolite, TFM glucuronide (TFM-glu), was determined in fillet tissue of fish after a typical stream application. Rainbow trout ( Oncorhynchus mykiss ) and channel catfish ( Ictalurus punctatus ) were exposed to a nominal concentration of 12.6 nmol/mL TFM for about 12 h during a sea lamprey control treatment of the Ford River in Michigan. Concentrations of TFM and TFM-glu were greatest in the fillet tissues during the exposure period, with greater residues in channel catfish (wet wt; mean, 6.95 nmol/g TFM; mean, 2.40 nmol/g TFM-glu) than in rainbow trout (wet wt; mean, 1.45 nmol/g TFM; mean, 0.93 nmol/g TFM-glu). After the exposure period, residues in both species decreased by 90−99% within 6−12 h and were less than the quantitation limit (<0.03 nmol/g) within 36 h.

Michigan↗
USGS2002

Determination of isoxaflutole (balance) and its metabolites in water using solid phase extraction followed by high-performance liquid chromatography with ultraviolet or mass spectrometry

Balance (isoxaflutole, IXF) belongs to a new family of herbicides referred to as isoxazoles. IXF has a very short soil half-life (<24 h), degrading to a biologically active diketonitrile (DKN) metabolite that is more polar and considerably more stable. Further degradation of the DKN metabolite produces a nonbiologically active benzoic acid (BA) metabolite. Analytical methods using solid phase extraction followed by high-performance liquid chromatography−UV (HPLC-UV) or high-performance liquid chromatography−mass spectrometry (HPLC-MS) were developed for the analysis of IXF and its metabolites in distilled deionized water and ground water samples. To successfully detect and quantify the BA metabolite by HPLC-UV from ground water samples, a sequential elution scheme was necessary. Using HPLC-UV, the mean recoveries from sequential elution of the parent and its two metabolites from fortified ground water samples ranged from 68.6 to 101.4%. For HPLC-MS, solid phase extraction of ground water samples was performed using a polystyrene divinylbenzene polymer resin. The mean HPLC-MS recoveries of the three compounds from ground water samples spiked at 0.05−2 μg/L ranged from 100.9 to 110.3%. The limits of quantitation for HPLC-UV are approximately 150 ng/L for IXF, 100 ng/L for DKN, and 250 ng/L for BA. The limit of quantitation by HPLC-MS is 50 ng/L for each compound. The methods developed in this work can be applied to determine the transport and fate of Balance in the environment.

Journal of Agricultural and Food Chemistry↗
USGS2002

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↗
USGS2004

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↗
USGS2004

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↗
USGS2005

Residues of the lampricides 3-trifluoromethyl-4-nitrophenol and niclosamide in muscle tissue of rainbow trout

Rainbow trout (Oncorhyncus mykiss) were exposed to the 14C- labeled lampricide 3-trifluoromethyl-4-nitrophenol (TFM) (2.1 mg/L) or niclosamide (0.055 mg/L) in an aerated static water bath for 24 h. Fish were sacrificed immediately after exposure. Subsamples of skin-on muscle tissue were analyzed for residues of the lampricides. The primary residues in muscle tissue from fish exposed to TFM were parent TFM (1.08 ?? 0.82 nmol/g) and TFM-glucuronide (0.44 ?? 0.24 nmol/g). Muscle tissue from fish exposed to niclosamide contained niclosamide (1.42 ?? 0.51 nmol/g), niclosamide-glucuronide (0.0644 ?? 0.0276 nmol/g), and a metabolite not previously reported, niclosamide sulfate ester (1.12 ?? 0.33 nmol/g).

Journal of Agricultural and Food Chemistry↗
USGS2006

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↗
USGS2007

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↗