Gas chromatographic determination of systemic fungicide tricyclazole in soil and water

A method is described for determination of tricyclazole residues in soil and water. Tricyclazole is extracted from soil by refluxing with ethyl acetate-acetone (80 + 20 v/v) and from water by partitioning into dichloromethane. The soil extract is purified by coagulation. The compound is detected and measured by gas chromatography using a flame photometer operated in the sulfur mode. Detection limits are 8 ppb for soil and 0.8 ppb for water. Recoveries for control samples fortified with tricyclazole at 0.1-5.0 ppm averaged 97.1% for soil and 108.1% for water.     

Gas-liquid chromatographic determination of kepone residues in finfish, shellfish, and crustaceans.

Finfish, shellfish, and crustacean samples are extracted with isopropanol and benzene; the extract is filtered and then concentrated. The extract, dissolved in hexane, is treated with oleum and extracted with aqueous alkali. The aqueous phase is acidified and extracted with petroleum ether-ethyl ether (1 + 1). The Kepone residue is determined by electron capture gas-liquid chromatography (GLC). Recoveries obtained by 8 laboratories from 15 species of finfish fortified at 0.02-0.23 ppm ranged from 37 to 107% with a mean +/- relative standard deviation of 79.4 +/- 14.5%. For oysters fortified at 0.01-0.10 ppm, recoveries range from 63 to 129% with a mean of 78.8 +/- 20.8%. For crustaceans fortified at 0.05-0.26 ppm, recoveries ranged from 52 to 110% with a mean of 78 +/- 16.4%. The approximate limits of quantitation for finfish and for shellfish and crustaceans are 0.02 and 0.05 ppm, respectively, under the GLC conditions used in this study.     

Liquid chromatographic determination of melamine in beverages

A liquid chromatographic method is described for the determination of melamine in beverages. Melamine is separated by column chromatography using cation and anion exchange resin and determined by ion-pair liquid chromatography using an ODS column and a mixture of acetonitrile and 0.05M phosphate buffer (pH 3.0) containing 0.005M sodium 1-laurylsulfate (1 + 4, v/v) as mobile phase. Recoveries of melamine ranged between 90.3 +/- 7.8 and 102.1 +/- 5.6% at levels of 0.6 to 2.4 ppm in 4 kinds of beverages. The quantitation limit was 2.5 micrograms melamine in 50 mL beverage. The method was applied to the migration test of melamine from melamine-formaldehyde resin products to the beverages.     

Levels of available micro-nutrient metals in some Japanese soils as measured by aspergillus niger with special reference to their threshold values

This paper presents the levels of available amounts of zinc, copper, and molybdenum as measured by Asp. niger (Mulder strain) in soils of Japan with special regard to their threshold values. Results obtained are as follow: 1) Levels of available zinc in soils examined ranged from 0.4 to 27 ppm. The threshold value for available zinc is adequelty represented as a function of the soil pH value, and was estimated to be around “0.5 × (soil pH value)-0.5” ppm (soil pH value >1). 2) Levels of available copper in soils examined ranged from 0.3 to 5 ppm, and the threshold value for available copper lies near 0.5 ppm. However, the value is more suitably represented as a function of the soil carbon content. This value was shown to be around “0.1 × (carbon % in the soil)” ppm. 3) Levels of available molybdenum in soils examined ranged from 0.01 to 0.13 ppm with the average about 0.10 ppm. The threshold value for available molybdenum is well expressed as a function of the soil pH. The value was estimated to be around “-0.04 × (soil pH value)+0.30” ppm (soil pH value <7.5).     

Determination of phenol in honey by liquid chromatography with amperometric detection

A sensitive, selective analytical method has been developed for determination of phenol in honey by liquid chromotography (LC) with amperometric detection (AMD). Phenol is extracted with benzene from the distillate of honey. The benzene extract is washed with 1% sodium bicarbonate solution and then reextracted with 0.1N sodium hydroxide followed by cleanup on a C18 cartridge. Phenol is determined by reverse-phase LC with amperometric detection. An Inertsil ODS column (150 X 4.6 mm, 5 microns) is used in the determination. The mobile phase is a mixture (20 + 80 v/v) of acetonitrile and 0.01M sodium dihydrogen phosphate containing 2mM ethylenediaminetetraacetic acid, disodium salt (EDTA) with the pH adjusted to 5.0. The flow rate is 1 mL/min under ambient conditions. The applied potential of the AMD using a glassy carbon electrode is 0.7 V vs an Ag/AgCl reference electrode. Average recoveries of phenol added to honey were 79.8% at 0.01 ppm spiking level, 90.4% at 0.1 ppm, and 91.0% at 1.0 ppm. Repeatabilities were 3.4, 1.3, and 1.8%, respectively. The detection limit of phenol in honey was 0.002 ppm. For analysis of 112 commercial honey samples, the range and average values of 32 detected samples were 0.05-5.88 ppm and 0.71 ppm, respectively.     

Soil testing of horticultural substrates for cyclamen and poinsettia

Abstract

The 1: 1.5 water, Spurway and saturated media extract procedures were evaluated for cyclamen and 1: 1.5 water extract for poinsettia growing in bark, peat and peat + soil using nutrient uptake as the criterion. In addition, the N, P, and K desirable values (DV) to give maxi Timm dry wt in two harvests and to give maximum growth rate for various growing periods, in samples taken at the start of the trial and midway through the trial, were determined using a quadratic function for both crops. The relationships between N, P and K uptake and the soil test values were generally very good, although the methods overestimated N uptake and underestimated P uptake in bark‐relative to peat. Underestimation of P uptake in peat + soil was even greater. The initial desirable N soil test value in relation to midterm harvest (IDVM) for cyclamen in peat varied from 100–104 ppm for water, 303–312 ppm for saturated media and 44–46 for Spurway extraction. The midterm soil test value in relation to final harvest (MDVF) values varied from 125–136 ppm for water, 471–502 for saturated media and 44–53 ppm for Spurway extraction. Corresponding values in bark were generally higher. The IDVM and MDVF values using the water extract for poinsettia were 180–225 ppm and 155–215 ppm in peat and bark respectively. It was not possible to determine phosphorus IDVM values for cyclamen due to the poor fit of the response curve. The phosphorus MDVF values in peat for cyclamen were 8.1–8.8 ppm for water, 24.5–26.7 ppm for saturated media and 3.2–3.5 ppm for Spurway extraction. The corresponding values in bark were about half of those values and even lower in peat + soil. The phosphorus MDVF values in peat for poinsettia were 14–19 ppm and in bark 4–4.5 ppm for the water extraction. It was not possible to determine K desirable values for cyclamen because of lack of adequate plant response from K application. Potassium IDVF and MDVF values for poinsettia in peat were 100–136 and 80–126 ppm respectively. The DV obtained using growth data were broadly similar to those using plant dry wt. The desirable plant nutrient levels for maximum dry wt of cyclamen at final harvest varied from 1.9–2.4% for N, 0.10–0.17% for P and 1.0–1.7% for K. The DV values for poinsettia at mid harvest were 3.6–4.6% N, and at final harvest 2.7–3.6% N and 0.18–0.37% P.     

Liquid chromatographic determination of monensin in chicken tissues with fluorometric detection and confirmation by gas chromatography-mass spectrometry

An accurate, sensitive method is described for the determination of monensin residue in chicken tissues by liquid chromatography (LC), in which monensin is derivatized with a fluorescent labeling reagent, 9-anthryldiazomethane (ADAM), to enable fluorometric detection. Samples are extracted with methanol-water (8 + 2), the extract is partitioned between CHCl3 and water, and the CHCl3 layer is cleaned up by silica gel column chromatography. Free monensin, obtained by treatment with phosphate buffer solution (pH 3) at 0 degrees C, is derivatized with ADAM and passed through a disposable silica cartridge. Monensin-ADAM is identified and quantitated by normal phase LC using fluorometric detection. The detection limit is 1 ppb in chicken tissues. Recoveries were 77.6 +/- 1.8% at 1 ppm, 56.7 +/- 7.1% at 100 ppb, and 46.5 +/- 3.7% at 10 ppb fortification levels in chicken. Gas chromatography-mass spectrometry is capable of confirming monensin methyl ester tris trimethylsilyl ether in samples containing residues greater than 5 ppm.     

Rapid screening method for detection of deoxynivalenol

A rapid method for detecting deoxynivalenol (DON), also known as vomitoxin, was developed. DON was extracted from grains and other samples with acetonitrile-4% potassium chloride solution (9 + 1). Impurities that would interfere with detection were removed on a C18 silica gel reverse phase column. Water was removed from eluates on a hydrophilic matrix column. DON was detected by thin layer chromatography using an aluminum chloride solution to develop the blue response characteristic of the mycotoxin. Total time involved is approximately 30 min. The method was applicable to corn, wheat, and barley at detection levels of 1 ppm, and oats at 1.5 ppm. It is applicable to environmental samples (soil, green plants, and water) at detection levels of 0.75 ppm.     

Gas chromatographic determination of residue levels of the herbicides trifluralin, benefin, ethalfluralin, and isopropalin in soil with confirmation by mass selective detection

A method is presented for the simultaneous or individual determination of the dinitroaniline herbicides trifluralin, benefin, ethalfluralin, and isopropalin in soil. The herbicides are extracted with acetonitrile-water (99 + 1), and the extracts are purified with small, disposable Florisil cartridges prior to analysis by gas chromatography using an electron capture detector or a mass selective detector. When electron capture detection is used as the primary detection system, confirmation with selective detection can be obtained using gas chromatography-mass spectrometry with a mass selective detector and a capillary column operated in the split mode. The limit of detection is 0.01 ppm, and recoveries averaged 95-112% for the 4 herbicides in several different soil types fortified at levels of 0.01-0.33 ppm.     

Tissue distribution, metabolism, and residue depletion study in Atlantic salmon following oral administration of [3H]emamectin benzoate

Atlantic salmon (approximately 1.3 kg) maintained in tanks of seawater at 5 +/- 1 degrees C were dosed with [3H]emamectin B1 benzoate in feed at a nominal rate of 50 microg of emamectin benzoate/kg/day for 7 consecutive days. Tissues, blood, and bile were collected from 10 fish each at 3 and 12 h and at 1, 3, 7, 15, 30, 45, 60, and 90 days post final dose. Feces were collected daily from the tanks beginning just prior to dosing to 90 days post final dose. The total radioactive residues (TRR) of the daily feces samples during dosing were 0.25 ppm maximal, and >97% of the TRR in pooled feces covering the dosing period was emamectin B1a. Feces TRR then rapidly declined to approximately 0.05 ppm by 1 day post final dose. The ranges of mean TRR for tissues over the 90 days post dose period were as follows: kidney, 1.4-3 ppm; liver, 1.0-2.3 ppm; skin, 0.04-0.09 ppm; muscle, 0.02-0.06 ppm; and bone, <0.01 ppm. The residue components of liver, kidney, muscle, and skin samples pooled by post dose interval were emamectin B1a (81-100% TRR) and desmethylemamectin B1a (0-17% TRR) with N-formylemamectin B1a seen in trace amounts (<2%) in some muscle samples. The marker residue selected for regulatory surveillance of emamectin residues was emamectin B1a. The emamectin B1a level was quantified in individual samples of skin and muscle using HPLC-fluorometry and was below 85 ppb in all samples analyzed (3 h to 30 days post dose).     

FIELD STUDIES OF THE SOIL ATMOSPHERE

A study was made of the concentrations of ethylene and oxygen in the soil atmosphere under field conditions at three contrasting sites. The duration of the experiments ranged from 6 weeks to 9 months. A clear relationship between high moisture content and both the production of ethylene and the depression of oxygen levels was found in a sandy loam, although there was great variability between replicate sampling points. Concentrations of oxygen in a heavy clay soil remained below 10 per cent (v/v) throughout the winter and spring, followed by a gradual rise to near-atmospheric levels. Concentrations of ethylene were not correlated with those of oxygen, except in the winter, but rose logarithmically with soil temperature during the spring, increasing by twenty times over the range 4-1 I °C. There was no significant difference between plots which had been subjected to different drainage treatments, and again there was great variability from point to point. In a more permeable clay soil, however, the levels of oxygen were higher, and were related to the proximity to drains and the height of the water table, but not to the levels of ethylene. The concentration of ethylene showed a similar logarithmic increase with temperature to that observed in the heavy clay, and exceeded I ppm throughout the period May-July. The factors which have the greatest influence on the concentrations of ethylene in the soil were considered to be temperature, depression of oxygen concentration, the availability of substrates for microbial activity and the effect of soil moisture content on the air-filled porosity of the soil. Concentrations of ethylene greatly in excess of those which, under some circumstances, inhibit root growth, are likely to be of widespread occurrence in heavy soils during the spring and early summer and in light soils when unusually wet.     

Vanillin content in boiled peanuts

A high-performance liquid chromatographic (HPLC) method for determination of vanillin in boiled peanuts has been developed. Vanillin was extracted with acetonitrile by blending at high speed followed by purification of an aliquot of the extract on a minicolumn packed with Al(2)O(3). Vanillin was quantitated by HPLC on silica gel with n-hexane/2-propanol/water/acetic acid (2100/540/37/2, v/v) as a mobile phase. The recovery of vanillin added to fresh peanut hulls at 0.50 and 2.50 microg/g was 78.7 +/- 2.7 and 79.9 +/- 3.1%, respectively. The detection limit of vanillin in boiled peanuts was estimated at 0.05 microg/g. UV-detector response to vanillin was linear to at least 2.5 microg/injection. Free vanillin has been found in two commercial brands of boiled peanuts at low ppm levels. Both the kernels and the hulls contained vanillin, which was formed during hydrolysis of lignin, one of the major constituents of the peanut hulls. Since vanillin has a low flavor threshold, it could be considered as one of the major ingredients that determines the flavor of boiled peanuts.     

Effects of soluble fractions of drilling fluids on development of crabs,Rhithropanopeus harrisii and Callinectes sapidus

The mud aqueous fraction (MAF) and suspended particulate phase (SPP) of low-density lignosulfonate type mud with úerrochrome added were nontoxic to larvae during the complete larval development of Rhithropanopeus harrisii. Five percent (5000 ppm, 0.5 % v/v mud in water) MAF and SPP were not toxic to Callinectes sapidus. Survival of C. sapidus larvae decreased as concentrations of MAF and SPP increased from 5 % (5000 ppm, 0.5 v/v mud in water) to 50% (50000 ppm, 5 % v/v mud in water). No larvae reached the 1st crab stage in 100% (100000 ppm, 10% v/v mud in water) MAF and SPP. Statistical analysis of the data on survival, mortality, and behavior are presented. Blue crab larval behavior is affected by exposure to MAF and SPP with the general effect being a decline in swimming speed. A significant reduction was only observed in 100% MAF but was noticed in 5, 25, 50, and 100% SPP.     

前期不同水分状况对土壤氧化亚氮排放的影响

田间采集的新鲜土壤样品分别在室温下风干(土样D)和淹水(土样S)保存110d后,将二者的含水量分别调至20%、40%、60%、80%、100%持水量(WHC,Water Holding Capacity),在25℃下培育138h,设置不通和通入10%(v/v)乙炔的处理。结果显示,在20%～80%WHC下培育时,土样S的氧化亚氮(N2O)排放量为土样D的2.48倍～6.36倍(p<0.01),而在100%WHC水分含量下培育时,土样S的N2O排放量仅为土样D的19%(p<0.01),通入乙炔不但未使土样D的N2O排放量增加,反而显著减少。通入乙炔的处理,培养结束后硝态氮的含量增加。随培育水分含量的升高,土样S和土样D的二氧化碳排放量增大。供试土样可能存在异养硝化作用。前期水分的差异显著影响土壤N2O排放量,故在田间测定土壤N2O排放量时,要考虑土壤前期水分的差异。     

Photochemical degradation of acifluorfen in aqueous solution

To elucidate the photochemical behavior of diphenyl ether herbicides in superficial waters, the photodegradation of acifluorfen, 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzo?c acid (CAS Registry No. 50594-66-6), was studied in water and acetonitrile. All experiments were carried out under laboratory conditions using a solar simulator (xenon arc) or jacket Pyrex reaction cell equipped with a 125 W high-pressure mercury lamp. The calculated polychromatic quantum efficiencies (Phi(solvent)) of acifluorfen in different solvents are as follows (units are degraded molecules photon(-1)): Phi(water) = 10(-4), Phi(acetonitrile) = 10(-4), Phi(methanol) = 10(-4), and Phi(hexane) = 10(-2). The results obtained in this work are in good agreement with the literature value of monochromatic quantum yield. HPLC-MS analysis (APCI and ESI in positive and negative modes) was used to identify acifluorfen photoproducts. These results suggest that the photodegradation of acifluorfen proceeds via a number of reaction pathways: (1) decarboxylation, (2) dehalogenation, (3) substitution of chlorine group by hydroxyl or hydrogen groups, and (4) cleavage of ether linkage, giving phenols. Photorearrangement products were studied by other investigators. No such products were observed. In addition, it was found that the trifluoro functional group on acifluorfen was not affected by any transformation, and no products of a nitro group reduction were found.     

Sephadex LH-20 cleanup, high pressure liquid chromatographic assay, and fluorescence detection of zearalenone in animal feeds

A high pressure liquid chromatographic (HPLC) method is described to determine zearalenone in animal feeds at levels as low as 0.01 ppm. Samples are extracted with chloroform-ethanol and initially purified using a SEP-PAK silica cartridge, followed by column chromatography using Sephadex LH-20. Separation by normal phase HPLC is followed by fluorescence detection. Recoveries at levels of 1.0-0.01 ppm averaged greater than 90%. Confirmation included HPLC analysis of the sample and a zearalenone standard, using 3 different excitation wavelengths, and comparison of fluorescence responses obtained. The method was successfully applied to the analysis of 1 corn and 3 cornmeal samples. Zearalenone was detected in all 4 samples at levels of 0.379-19.2 ppm.     

Development of a gas chromatographic method for fungicide cymoxanil analysis in dried hops

An analytical method for detecting cymoxanil [2-cyano-N-[(ethylamino)carbonyl]-2-(methoxyimino)acetamide] residues in dried hops was developed utilizing liquid-liquid partitioning, automated gel permeation chromatography (GPC), solid phase extraction (SPE) cleanup, and gas chromatography (GC). Method validation recoveries from dried hops were 96 +/- 12, 108 +/- 11, and 136 +/- 8% over three levels of fortification (0.05, 0.5, and 1.0 ppm, respectively). The hop samples from three field sites, which were treated with cymoxanil, had residue levels ranging from 0.146 to 0.646 ppm. The detection limit and the quantitation limit of the method developed in the present study were 0.022 and 0.050 ppm, respectively.     

Validation of a method for determination of tetracycline antibiotics in salmon muscle tissue

A method was validated for analysis of oxytetracycline (OTC), tetracycline (TC), and chlortetracycline (CTC) in fortified salmon muscle tissue. Recoveries of OTC were 100 +/- 6, 86 +/- 6, and 82 +/- 5% (n = 6) at fortification levels of 1.0, 0.5, and 0.2 ppm, respectively. Recoveries of TC were 68 +/- 4, 65 +/- 6, and 66 +/- 7%; recoveries of CTC were 45 +/- 9, 48 +/- 8, and 0%, respectively. Detection limits for OTC and TC were 0.08 and 0.09 ppm, respectively.     

Determination of sulfite in food by flow injection analysis

A method is described for the determination of sulfite levels in food products by flow injection analysis (FIA). The method is based on the decolorization of malachite green by SO2, which is isolated from the flowing sample stream by means of a gas diffusion cell. The FIA method has a detection limit in food sample extracts of 0.1 ppm SO2 (3 times peak height of blank), which corresponds to 1-10 ppm SO2 in a food product, depending on the extraction procedure used. At the 5 ppm SO2 level in a food extract, the precision of replicate injections is +/- 1-2%. The method was tested on a variety of both sulfite-treated and untreated food products and the results compared favorably with those obtained by the Monier-Williams, colorimetric (pararosaniline), and enzymatic (sulfite oxidase) methods. The average differences from the FIA results were 19, 11, and 12%, respectively, for those samples (n = 12) above 50 ppm SO2. At lower levels the results were somewhat more erratic due to inaccuracies of the various methods at low concentrations.     

Collaborative study of an extension of the Mills et al. method for the determination of pesticide residues in foods.

Fifteen laboratories collaboratively determined parathion, o,p'-DDT, p,p'-DDT, and p,p'-DDE in kale, and lindane, dieldrin, heptachlor epoxide, and p,p'-DDE in eggs, using electron capture gas-liquid chromatography (potassium chloride thermionic detector for parathion). Pesticide levels ranged from 0.033 ppm heptachlor epoxide to 3.32 ppm p,p'-DDT. Mean recoveries (+/- standard deviations) were: parathion 91+/-15%, o,p'-DDT 99+/-8%, P,P'-DDT 97+/-8%, lindane 94+/-4%, dieldrin 106+/-8%, heptachloro epoxide 106+/-5%, p,p'-DDE 94+/-8% in eggs and 101+/-9% in kale. The methods have been adopted as official first action.