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At least 55 records · Page 3Linked to original sources

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↗

Rodent repellents, correlation between chemical structure and rodent repellency of benzoic acid derivatives

Sixty-five benzoic acid derivatives were either prepared or obtained from commercial concerns, tested for rat repellency, and their indices of repellency computed. The data from these tests were considered analytically for any correlation between chemical structure and rat repellency. The results suggest a qualitative relationship which is useful in deciding probability of repellency in other compounds.

Journal of Agricultural and Food Chemistry↗

Analysis of chlorothalonil and three degradates in sediment and soil

A method has been developed for the simultaneous extraction of chlorothalonil and three of its degradates (4-hydroxy-2,5,6-trichloroisophthalonitrile, 1-carbamoyl-3-cyano-4-hydroxy-2,5,6-trichlorobenzene, and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene) from soils and sediments; the compounds were extracted using sonication with acetone and isolation of the parent compound and matrix interferences from the degradates by solid phase extraction (SPE). The chlorothalonil fraction underwent further coextracted matrix interference removal with Florisil. The degradates were derivatized with N , O- bis(trimethylsilyl) trifluoroacetamide (BSTFA) and chlorotrimethylsilane (TMCS). All compounds were analyzed by gas chromatography–mass spectrometry (GC-MS). Recoveries on a spiked (20 and 200 µg kg −1 ) sediment ranged from 80% to 91% with calculated limits of detection of 1−5 µg kg −1 dry weight sediment. An additional 20 sediment samples were collected in watersheds from the Southeastern United States where chlorothalonil is used widely on peanuts and other crops. None of the target compounds were detected. Laboratory fortified recoveries of chlorothalonil and its degradates in these environmental sediment samples ranged from 75% to 89%.

Journal of Agricultural and Food Chemistry↗

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↗

Nuclear magnetic resonance identification of new sulfonic acid metabolites of chloroacetanilide herbicides

The detection of the sulfonic acid metabolites of the chloroacetanilide herbicides acetochlor, alachlor, butachlor, propachlor, and, more recently, metolachlor in surface and ground water suggests that a common mechanism for dechlorination exists via the glutathione conjugation pathway. The identification of these herbicides and their metabolites is important due to growing public awareness and concern about pesticide levels in drinking water. Although these herbicides are regulated, little is known about the fate of their metabolites in soil. The sulfonic acid metabolites were synthesized by reaction of the parent compounds with an excess of sodium sulfite. Acetochlor, alachlor, butachlor, metolachlor, and propachlor and their sulfonic acid metabolites were studied by nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. This paper provides a direct method for the preparation and characterization of these compounds that will be useful in the analysis and study of chloracetanilide herbicides and their metabolites.

Journal of Agricultural and Food Chemistry↗

Determination of niclosamide residues in rainbow trout (Oncorhynchus mykiss) and channel catfish (Ictalurus punctatus) fillet tissue by high-performance liquid chromatography

Bayluscide [the ethanolamine salt of niclosamide (NIC)] is a registered piscicide used in combination with 3-(trifluoromethyl)-4-nitrophenol (TFM) to control sea lamprey populations in streams tributary to the Great Lakes. A high-performance liquid chromatography (HPLC) method was developed for the determination of NIC residues in muscle fillet tissues of fish exposed to NIC and TFM during sea lamprey control treatments. NIC was extracted from fortified channel catfish and rainbow trout fillet tissue with a series of acetone extractions and cleaned up on C 18 solid-phase extraction cartridges. NIC concentrations were determined by HPLC with detection at 360 and 335 nm for rainbow trout and catfish, respectively. Recovery of NIC from rainbow trout ( n = 7) fortified at 0.04 μg/g was 77 ± 6.5% and from channel catfish ( n = 7) fortified at 0.02 μg/g was 113 ± 11%. NIC detection limit was 0.0107 μg/g for rainbow trout and 0.0063 μg/g for catfish. Percent recovery of incurred radioactive residues by this method from catfish exposed to [ 14 C]NIC was 89.3 ± 4.1%. Percent recoveries of NIC from fortified storage stability tissue samples for rainbow trout ( n = 3) analyzed at 5 and 7.5 month periods were 78 ± 5.1 and 68 ± 2.4%, respectively. Percent recoveries of NIC from fortified storage stability tissue samples for channel catfish ( n = 3) analyzed at 5 and 7.5 month periods were 88 ± 13 and 76 ± 21%, respectively.

Great Lakes↗

Comparison of enzyme-linked immunosorbent assay and gas chromatography procedures for the detection of cyanazine and metolachlor in surface water samples

Enzyme-linked immunosorbent assay (ELISA) data from surface water reconnaissance were compared to data from samples analyzed by gas chromatography for the pesticide residues cyanazine (2-[[4-chloro-6-(ethylamino)-l,3,5-triazin-2-yl]amino]-2-methylpropanenitrile ) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide). When ELISA analyses were duplicated, cyanazine and metolachlor detection was found to have highly reproducible results; adjusted R2s were 0.97 and 0.94, respectively. When ELISA results for cyanazine were regressed against gas chromatography results, the models effectively predicted cyanazine concentrations from ELISA analyses (adjusted R2s ranging from 0.76 to 0.81). The intercepts and slopes for these models were not different from 0 and 1, respectively. This indicates that cyanazine analysis by ELISA is expected to give the same results as analysis by gas chromatography. However, regressing ELISA analyses for metolachlor against gas chromatography data provided more variable results (adjusted R2s ranged from 0.67 to 0.94). Regression models for metolachlor analyses had two of three intercepts that were not different from 0. Slopes for all metolachlor regression models were significantly different from 1. This indicates that as metolachlor concentrations increase, ELISA will over- or under-estimate metolachlor concentration, depending on the method of comparison. ELISA can be effectively used to detect cyanazine and metolachlor in surface water samples. However, when detections of metolachlor have significant consequences or implications it may be necessary to use other analytical methods.

Journal of Agricultural and Food Chemistry↗

Herbicides and nitrate in near-surface aquifers in the midcontinental United States, 1991

The occurrence and distribution of selected herbicides, atrazine metabolites, and nitrate were determined for near-surface aquifers (within 50 feet of land surface) in the corn- and soybean-producing region of the midcontinental United States. The study region included all or parts of Illinois, Indiana, Iowa, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Dakota, Ohio, South Dakota, and Wisconsin. Water samples were collected during the spring and summer of 1991 from 303 wells completed in near-surface unconsolidated and near-surface bedrock aquifers. At least one herbicide or atrazine metabolite was detected in 24 percent of 579 water samples analyzed for herbicides, based on a reporting limit of 0.05 microgram per liter. However, no herbicide concentration exceeded the U.S. Environmental Protection Agency's maximum contaminant levels or health advisory levels for drinking water. The most frequently detected herbicide compound was desethylatrazine, an atrazine metabolite (18.1 percent), followed by atrazine (17.4 percent); deisopropylatrazine, an atrazine metabolite (5.7 percent); prometon (5.0 percent); metolachlor (2.7 percent); alachlor (1.7 percent); simazine (1.0 percent); metribuzin (1.0 percent); and cyanazine (0.7 percent). The herbicides ametryn, prometryn, propazine, and terbutryn were not detected during this study. Nitrate concentrations equal to or greater than 3.0 milligrams per liter (excess nitrate) were detected in 29 percent of the 599 nitrate analyses, and ammonium concentrations equal to or greater than 0.01 milligram per liter were detected in 78 percent of the 584 ammonium analyses. Nitrate concentrations equal to or greater than the U.S. Environmental Protection Agency's maximum contaminant level for drinking water of 10 milligrams per liter were found in 6 percent of the samples. The frequency of herbicide detection was, in part, affected by the analytical method's reporting limit. Results from this study show that the frequency of atrazine detection increases as the reporting limit decreases. Herbicide metabolite concentrations are critical to understanding the detection of herbicide residues. The frequency of detection of atrazine residue (atrazine + desethylatrazine + deisopropylatrazine) was 22.1 percent, which was more than the frequency of detection of atrazine alone (17.4 percent). Prometon was detected more frequently than every other herbicide except atrazine. The prometon appears to be derived from areas of nonagricultural land use, such as golf courses and residential areas. Herbicides and excess nitrate were both rarely detected in the eastern part of the study region, even though this is an area of intense herbicide and nitrogen-fertilizer use. Hydrogeologic factors, land use, agricultural practices, local features, and water chemistry were analyzed for possible relation to herbicide and excess-nitrate detections. Herbicides and excess nitrate were detected more frequently in near-surface unconsolidated aquifers than in nearsurface bedrock aquifers. The depth to the top of the aquifer was inversely related to the frequency of detection of herbicides and excess nitrate. The proximity of streams to sampled wells also affected the frequency of herbicide detection. Significant seasonal differences were determined for the frequency of herbicide detection, but not for the frequency of excess nitrate.

Illinois, Indiana, Iowa, Kansas, Michigan, Minneso↗

Comprehensive water quality of the Boulder Creek Watershed, Colorado, during high-flow and low-flow conditions, 2000

Executive Summary The Boulder Creek Watershed, Colorado, is 1160 square kilometers in area and ranges in elevation from 1480 to 4120 meters above sea level. Streamflow originates primarily as snowmelt near the Continental Divide, and thus discharge varies seasonally and annually (Chapter 1). Most of the water in Boulder Creek is diverted for domestic, agricultural, and industrial use. Some diverted water is returned to the creek as wastewater effluent and by ditch returns, and additional water enters as groundwater and by transbasin diversions. These diversions and returns lead to complex temporal and spatial variations in discharge. The variations in discharge, along with natural factors such as geology and climate, and anthropogenic factors such as wastewater treatment, agriculture, mining, and urbanization, can affect water chemistry. As with many watersheds in the American West, dependable water quality and sufficient water supply are issues facing local water managers and users. Detailed water-quality and sediment sampling allows the identification of sources and sinks of chemical constituents and an understanding of the processes at work in a river system. This study, the most comprehensive water-quality analysis performed for Boulder Creek to date, was a cooperative effort of the U.S. Geological Survey (USGS) and the city of Boulder. Geographic information systems and modeling programs were used to delineate watershed boundaries, land cover, and geology (Chapter 2). During high-flow (June 2000) and low-flow (October 2000) conditions, researchers evaluated 226 water-quality variables, including basic water-quality indicators (Chapter 3), major ions and trace elements (Chapter 4), wastewater-derived organic compounds (Chapter 5), and pesticides (Chapter 6). Discharge (Chapter 1) and bed-sediment particle size and mineralogy (Chapter 7) were also evaluated. This cooperative study was facilitated by the Boulder Area Sustainability Information Network (BASIN), which provides public access to environmental information about the Boulder Creek Watershed on a website, www.basin.org. In addition to the USGS and city of Boulder data, researchers at the Institute of Arctic and Alpine Research at the University of Colorado provided water chemistry data for the headwaters of North Boulder Creek, upstream of the reach of the USGS/city of Boulder sampling sites (Chapter 8). Snowmelt produces high flows in Boulder Creek in late spring to early summer (Chapter 1). Because precipitation falling in the headwaters is very dilute (specific conductance about 5 microsiemens per centimeter), most chemical constituents are present in lower concentrations during high flows (Chapters 3, 4, 5, 6, and 8). However, concentrations of some constituents, such as total suspended solids (Chapter 3) and organic carbon (Chapter 5), increase during the spring snowmelt flush. The upper basin, which consists of alpine, subalpine, montane, and foothills regions west of the mouth of Boulder Canyon, is underlain by Precambrian igneous and metamorphic rocks (Chapter 1). Major dissolved inorganic constituents in headwater sites were found to be enriched by factors of 10 to 20 relative to precipitation; this is consistent with minor weathering of the local crystalline bedrock (Chapter 4). Some anthropogenic input is observed in the headwaters; precipitation introduces nitrogen derived from fossil fuel combustion and agricultural activities (Chapter 8). The lower basin, which consists of the plains region east of the mouth of Boulder Canyon, is underlain by Mesozoic sedimentary rock and Quaternary alluvium, and has substantially more anthropogenic sources. Concentrations of most dissolved inorganic constituents increased in the lower basin. Differentiation between natural and anthropogenic sources of some dissolved constituents is difficult because both sources contribute to the water composition in this region. The increase of most major constituents (bicarbonate, calcium, chloride, magnesium, sodium, and sulfate) is consistent with weathering of the underlying sedimentary bedrock (Chapter 4). It is likely that anthropogenic loading of constituents in this reach occurs during storm events. Fecal coliform concentrations were variable and in some cases exceeded state standards, primarily during low-flow conditions (Chapter 3). Effluent from Boulder’s 75th Street Wastewater Treatment Plant (WWTP) has a substantial impact on the water chemistry of lower Boulder Creek. The WWTP increases the concentrations of nutrients such as nitrogen and phosphorus (Chapter 3), major ions and trace metals (Chapter 4), and organic carbon (Chapter 5) in Boulder Creek. The effluent contained a spike in gadolinium, a rare earth element that is ingested for magnetic resonance imaging as a contrasting agent and then excreted to the urban wastewater system. The effluent also contained trace organic compounds such as surfactants, pharmaceuticals, hormones (Chapter 5), and pesticides (Chapter 6), which also were detected at downstream Boulder Creek sites. Water chemistry of Boulder Creek downstream of the WWTP is largely controlled by the degree of dilution of the wastewater effluent, which varies depending on the baseflow of Boulder Creek, the volume of wastewater effluent, and depletion by agricultural diversions. Coal Creek, a tributary of Boulder Creek, contains wastewater effluent from four additional WWTPs, and increases the load of many constituents in Boulder Creek. In addition to the impact from wastewater effluent, lower Boulder Creek is affected by agricultural land use. Eleven of 84 analyzed pesticides were detected in Boulder Creek or its inflows, primarily in the eastern section of the watershed (Chapter 6). This collaborative study provides an in-depth evaluation of the hydrology, water chemistry, and sediment mineralogy of North Boulder Creek, Middle Boulder Creek, Boulder Creek, and major inflows. The detailed sampling and analysis in this report provide a baseline for future reference, as well as information on the effect of land use and geology on water chemistry.

Colorado↗