Rapid sensitive speciation analysis of butyl- and phenyltin compounds in water by capillary gas chromatography atomic emission spectrometry (GC-AES) after in-situ ethylation and in-liner preconcentration

Summary A rapid, simple and sensitive method has been developed for the simultaneous determination of butyl- and phenyltin species in environmental waters. The ionic organotin compounds are ethylated in the aqueous phase using sodium tetraethylborate (NaBEt₄) and extracted with hexane. A 25 l aliquot of the extract is injected at a low temperature into a Tenax filled liner. After solvent venting the analytes are transferred onto the capillary column using programmed temperature vaporization (PTV) injection. Detection is done by means of a microwave induced plasma atomic emission detector (MIP AED). The method allows the determination of butyl- and phenyltin compounds in water samples down to the level of 0.1 ng/l (as Sn) while 50 ml of sample is sufficient for analysis. The accuracy of the method was confirmed by GC-AAS after chelation and Grignard derivatization.     

A Simple Method for the Speciation of Organotin Compounds in Water Samples Using Ethylation and GC-QFAAS

 A simple method for the extraction of organotin compounds from water samples was developed in which both the instrumental parameters and the extraction/derivatization step were optimized. Organotin compounds (butyl-, phenyl- and octyl-) in tap water samples were ethylated with the addition of 2.5 ml of 0.4% w/v NaBEt₄ at pH 5.00 and subsequently extracted two times, for 10 min, with 3 and 2 ml of hexane. The combined extracts were analyzed with on-column capillary GC-QFAAS. The recoveries were quantitative for di- and tri- alkyltin compounds, whereas between 67 and 86% of the monoalkyltin compounds were recovered. The detection limits obtained ranged from 110 pg for monobutyltin to 500 pg for triphenyltin, as sensitivities were found to be compound dependent. The preparation of ethylated standards was also optimized. It was found that two subsequent extractions, with 1.0 and 0.5 ml of hexane were necessary for the quantitative recovery of the ethylated organotin compounds.     

High-pressure liquid chromatographic analysis of carbofuran and two non-conjugated metabolites in crops as fluorescent dansyl derivatives

Carbofuran, and non-conjugated 3-hydroxycarbofuran and 3-ketocarbofuran were extracted from carrots, corn and potatoes with acetone and partitioned into hexane-methylene chloride. The organic extract was evaporated to a small volume for clean-up on a 2% deactivated Florisil column. All three carbamates were eluted with 15% acetone in hexane. The pesticide residues were hydrolysed to their corresponding phenols with 0.1 M sodium carbonate followed by derivatization with dansyl chloride in acetone. The derivatives were extracted and analysed by high-pressure liquid chromatography with fluorescence detection (excitation, 360 nm; emission, greater than 400 nm). Absolute recoveries for all three compounds were between 50 and 65% for spiked samples by the extraction method used. Detection limits approached 0.01 ppm in the foods studied.     

Residues Analysis of Post-Harvest Imidazole Fungicides in Citrus Fruit by H PLC and GLC

Abstract

The determination of imazalil and prochloraz fungicide residues has been carried out by HPLC with an UV detector at 204 nm and by GLC with an electron capture detector (ECD).

In both cases fungicide residues were extracted with hexane/acetone (90:10, v/v) after pH adjustment and purified by a liquid-liquid partitioning process. When HPLC was used for prochloraz and imazalil analysis, it was necessary to eliminate the interfering substances with a further clean-up process. This was also required when samples with low residue levels were analyzed by GLC.

Recovery was always higher than 70%. The detection limit was 0.04 ppm for the HPLC method and 0.02 for the GLC method.

Imazalil and prochloraz residues in “Washington Navel” oranges and “Hernandina” clementine fruits, dipped in a 1000 ppm fungicide solution, are reported.     

Determination of thiamphenicol residues in chicken muscles by column liquid chromatography

A column liquid chromatographic (CLC) method for the determination of thiamphenicol residues in chicken muscles was developed. The drug is extracted from minced muscles with ethyl acetate and the extract is evaporated to dryness. The residue is dissolved in 10% sodium chloride solution and partitioned with n-hexane. Thiamphenicol is extracted with ethyl acetate and, after evaporation of the solvent, the residue is cleaned up by alumina column chromatography. CLC analysis is carried out on a Nucleosil C18 column with ultraviolet detection of thiamphenicol at 230 nm. The average recoveries of thiamphenicol added to muscles at 0.2 and 0.1 ppm were 92.8 and 90.0%, respectively. The detection limit was 5 ng for thiamphenicol standard, which corresponds to 0.05 ppm in muscles.     

Residues analysis of post-harvest imidazole fungicides in citrus fruit by HPLC and GLC

The determination of imazalil and prochloraz fungicide residues has been carried out by HPLC with an UV detector at 204 nm and by GLC with an electron capture detector (ECD). In both cases fungicide residues were extracted with hexane/acetone (90:10, v/v) after pH adjustment and purified by a liquid-liquid partitioning process. When HPLC was used for prochloraz and imazalil analysis, it was necessary to eliminate the interfering substances with a further clean-up process. This was also required when samples with low residue levels were analyzed by GLC. Recovery was always higher than 70%. The detection limit was 0.04 ppm for the HPLC method and 0.02 for the GLC method. Imazalil and prochloraz residues in "Washington Navel" oranges and "Hernandina" clementine fruits, dipped in a 1000 ppm fungicide solution, are reported.     

Simultaneous screening and confirmation of multiple classes of drug residues in fish by liquid chromatography-ion trap mass spectrometry

LC-ion trap mass spectrometry was used to screen and confirm 38 compounds from a variety of drug classes in four species of fish: trout, salmon, catfish, and tilapia. Samples were extracted with acetonitrile and hexane. The acetonitrile phase was evaporated, redissolved in water and acetonitrile, and analyzed by gradient chromatography on a phenyl column. MS² or MS³ spectra were monitored for each compound. Qualitative method performance was evaluated by the analysis over several days of replicate samples of control fish, fish fortified with a drug mixture at 1 ppm, 0.1 ppm and 0.01 ppm, and fish dosed with a representative from each drug class. Half of the 38 drugs were confirmed at 0.01 ppm, the lowest fortification level. This included all of the quinolones and fluoroquinolones, the macrolides, malachite green, and most of the imidazoles. Florfenicol amine, metronidazole, sulfonamides, tetracyclines, and most of the betalactams were confirmed at 0.1 ppm. Ivermectin and penicillin G were only detectable in the 1 ppm fortified samples. With the exception of amoxicillin, emamectin, metronidazole, and tylosin, residue presence was confirmed in all the dosed fish.     

High-Performance Liquid Chromatographic Determination of TCNB in Potatoes

Abstract

A high-performance liquid chromatographic (HPLC) method was developed for the determination of TCNB (tetrachloronitrobenzene), a sprout inhibitor, in potato peels and flesh fortified at levels of 0.16 to 53.5 ppm. TCNB was analyzed on a u Bondapak C₁₈ column with UV detection at 210 nm. The mobile phase was acetonitrile-methanol-water (35:35:30) at a flow rate of 1.0 ml/min. Retention time was approximately 10 min. TCNB was extracted by blending for 5 min in acetone. Samples at a level of 1 ppm or higher were directly injected whereas samples below 1 ppm were partitioned into hexane followed by passage through an alumina column. Average recoveries varied from 85.6 to 96.8% with coefficients of variation ranging from 2.18 to 11.68%. A study conducted to test 23 pesticides for possible interferences with TCNB demonstrated that none of them co-chromatographed. The lower limit of detection was 0.08 ppm.     

Analysis of triallate residues in cereals and soil by gas chromatography with ion-trap detection.

Triallate residues in barley seedlings and soil samples were determined by gas chromatography with ion-trap detection. Soil was extracted with methanol on a mechanical shaker, and plants were extracted with acetonitrile in a Sorvall homogenizer. After evaporation of the organic solvents, the residue was dissolved in hexane, and plants extracts were cleaned-up on an alumina column. Gas chromatographic analysis was carried out using a BP-1 fused-silica capillary column with helium as carrier gas. To quantitate residues the total-ion chromatogram was obtained and then the selected-ion monitoring chromatograms were displayed at m/z 86 for triallate and at m/z 154 for the internal standard, methyl-(4-amino-2-chloro)-benzoate. The average recovery through the method from barley and soil samples was always higher than 80%. The limit of detection in the selected-ion mode was 0.01 mg/kg. Barley and soil samples treated with triallate were also analysed. A good agreement was observed between results obtained by this method and by gas chromatography with nitrogen-phosphorus detection.     

Direct analysis of fenvalerate isomers by liquid chromatography. Application to formulation and residue analysis of fenvalerate

Summary The separation of the optical isomers of fenvalerate [cyano(3-phenoxyphenyl)methyl 2-(4-chlorophenyl)-3-methylbutyrate] has been carried out by high-performance liquid chromatography (HPLC) on a chiral column with (R)-N-3,5-dinitrobenzoyl-phenyl-glycine (DNBPG) covalently bonded on aminopropyl silica and eluted with mixtures of methanol, 2-propanol, and hexane. The system was applied to the analysis of Pydrin^®, an emulsifiable concentrate formulation of fenvalerate, and to the residue analysis of fenvalerate in milk samples. For the analysis of Pydrin^® the only requirement was the proper dilution of Pydrin^® with hexane. For the analysis of residues in milk, fenvalerate was extracted with hexane after precipitating the milk proteins with acetonitrile and removing the precipitate by filtration; the hexane extract was concentrated to small volume and filtered before being analyzed by HPLC.     

SFC-UV determination of diflubenzuron residues,teflubenzuron and triflumuron in apple and pear pulps for baby food

Summary A method to determine residues of diflubenzuron (DFB), teflubenzuron (TFB), triflumuron (TFM) at 0.01 ppm with recoveries above 60% in apple and pear pulps for baby food is described. DFB, TFB and TFM are extracted with methanol, and cleaned up by SPE using C18 stationary phase and methanol mobile phase. Analysis of the three pesticides is by SFC-UV at 254 nm using a Diol column, and CO₂ at 30 MPa and 40°C modified with acetonitrile (10%) mobile phase.     

Derivatization of Humic Compounds: An Analytical Approach for Bound Organic Residues

Abstract

Bound residues of pesticides and their metabolites are defined as being nonextractable with organic solvents, but partly extractable together with the humic matrix by NaOH or other solvents suitable to extract humic compounds. Recently, an improvement in humus extraction from soils was achieved upon derivatization of the organic matter with silylating reagents at room temperature. By this method 70–90% of the organic carbon or nitrogen either from soil or from humin became soluble in organic solvents. The extracts were analyzed by means of ¹³C NMR-spectroscopy. The spectra were well resolved with signal-separation of less than 1 ppm. The extracted humic compounds were of rather low molecular weight, ranging from 300 to 4000 to 6000 d or more.

¹⁴C-labeled residues of pesticides or other xenobiotics found to be nonextractable after exhaustive organic solvent extraction became readily dissolved along with most of the humic matrix using this derivatization procedure. Between 60–80% of ¹⁴C anilazine residues or of ¹⁴C-labeled chlorinated phenols or anilines originating from both previously solvent extracted soil samples or from humin became solubilized in organic solvents.     

The determination of polychlorinated biphenyl in small samples of monkey milk and tissues. II. Extraction efficiency

The extraction efficiency of benzene, toluene, dichloromethane, acetone:hexane and chloroform:methanol with respect to lipids and polychlorinated biphenyls was investigated using small samples of monkey adipose tissue, liver, kidney, brain, skin, feces and milk. The most efficient solvents were: acetone:hexane and chloroform:methanol for brain, feces, kidney, liver and milk; acetone:hexane and dichloromethane for adipose tissue; acetone:hexane and toluene for blood and dichloromethane for skin tissue. Within these solvent pairs acetone:hexane was the most outstanding with respect to an average of 90% PCB recoveries from fortified samples in the range of 0.02-2 ppm. In addition, a comparison was made between the lipid determination before and after Florisil column chromatography. Only adipose and blood lipids were sufficiently recovered from Florisil to make a lipid determination after chromatography feasible.     

Extraction and determination of linear alkylbenzenesulfonate detergents from the aquatic environment using a membrane disk and gas chromatography

Levels of linear alkylbenzenesulfonate (LAS) detergents have been measured in Anzali lagoon water sampled at fourteen stations. All samples were extracted with octadecyl-bonded silica membrane disks. Extraction efficiency, maximum capacity, and the effect of the solvent used to extract the LAS from the membrane disks were evaluated. Extraction efficiencies > 95% were obtained by elution of the disks with minimal amounts of solvent. It was demonstrated that membrane disk extraction introduced less error into analytical results than liquid – liquid extraction. Quantitative determination of total LAS levels and measurement of the distribution of LAS homologs with C₁₀? C₁₃ alkyl chains were performed by high resolution gas chromatography with flame ionization detection after derivatization of the detergents with sulfonyl chloride. The total level of LAS ranged from 0.01 to 0.89 ppm.     

GLC multiresidue analysis of postharvest fungicides in citrus fruit

Summary A simple GLC multiresidue method for the analysis of fenpropimorph, thiabendazole, imazalil, propiconazole and prochloraz residues in citrus fruit, with a limit of detection of 0.1 ppm, is reported.The fungicides are extracted with hexane: ethyl acetate (90:10, v/v) after pH-adjustment of the fruit homogenate. The GLC-separation is carried out using a bonded phase, SE-54, fused silica capillary column and fungicides are determined with a nitrogen-phosphorus detector.Recovery was always higher than 80% with standard deviation equal or lower than 7%. The method is suitable to determine residues in citrus, whole fruit or peel, treated with these fungicides at usual concentrations to avoid citrus decay.

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GLC-Verfahren zur Bestimmung mehrerer Fungicide in Citrusfrüchten nach der Ernte

     

固相萃取-气相色谱法同时测定花生中18种有机氯农药残留

利用气相色谱(GC)建立了花生中18种有机氯农药同时测定的方法。花生中有机氯农药残留通过乙腈提取,减压浓缩后过弗罗里固相萃取柱净化,采用正己烷-丙酮(体积比为9∶1)溶液淋洗,淋洗液氮吹近干后以正己烷定容,应用微池电子捕获检测器(μECD)检测。氟氯氰菊酯和溴氰菊酯的检出限分别为50和100g/kg,其余16种有机氯农药检出限均为10μg/kg。在花生样品中添加检测限水平有机氯混标溶液,加标回收率为71.28%～116.58%,测定结果的相对标准偏差为4.08%～18.16%(n=4或5)。     

GLC analysis of thiabendazole residues in citrus fruit

Analysis of thiabendazole (TBZ) residues in citrus fruit is performed using a bonded phase, SE-54, fused-silica capillary column. The fungicide is extracted with hexane: ethyl acetate (90:10, v/v) at high pH and, after a short cleanup, determined by gas-liquid chromatography with a nitrogen-phosphorus detector (NPD). Recoveries through the method are always higher than 80% and the limit of detection is 0.01 mg/Kg. TBZ residues are determined in whole fruit, peel, and pulp of "Washington Navel" oranges and "Hernandina" clementines treated with 1500 mg/L fungicide. Residues found in these samples and their changes during storage are reported. TBZ analysis in samples with high residue levels (peel and whole fruit) is also carried out by direct determination in the crude extracts. Results obtained with this shorter method are similar to those of the former proposed method.     

Dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry determination of polychlorinated biphenyls and polybrominated diphenyl ethers in milk

An effective multi‐residue pretreatment technique, solid‐phase extraction (SPE) combined with dispersive liquid–liquid microextraction (DLLME), was proposed for the trace analysis of 14 polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk samples using gas chromatography–mass spectrometry (GC‐MS). Interesting analytes in milk samples were extracted with hexane after protein precipitation. The hexane extracts were loaded on an LC‐Florisil column to isolate analytes from the milk matrix. The elutes were dried and dissolved in acetone, which was used as the disperser solvent in subsequent DLLME procedures. The effects of several important parameters on the extraction efficiency were evaluated. Under the optimized conditions, a linear relationship was obtained in the range of 0.02–10.00 μg/L (PCBs) and 0.5–100.00 μg/L (PBDEs). The LOD (S/N=3) and relative standard deviations (RSDs, n=5) for all analytes were 0.01–0.4 μg/L and 0.6–8.5%, respectively. The recoveries of the standards added to raw bovine milk samples were 74.0–131.8%, and the repeatabilities of the analysis results were 1.12–17.41%. This method has been successfully applied to estimating PCBs and PBDEs in milk samples.     

HPLC—UV determination of pesticide residues at 0.01 ppm in apple and pear pulp used for baby food

Two distinct methods are described for determination of residues of ethiofencarb and triforine, and of diflubenzuron, teflubenzuron, and triflumuron at the 0.01 ppm level in apple and pear pulp used for baby food;recoveries are above 50%. Diflubenzuron, teflubenzuron, and triflumuron are extracted with a 1:1 mixture of dichloromethane and acetone, and the extracts are cleaned by SPE using C₁₈ as stationary phase and methanol as mobile phase. Ethiofencarb and triforine are extracted with dichloromethane, and the extracts cleaned using the same stationary phase but a 1:1 mixture of acetonitrile and water as mobile phase. Analysis of both groups of pesticides is by isocratic HPLC—UV at 210 nm using an RP-18 column and acetonitrile-water as mobile phase.     

气相色谱-质谱法检测沉积物中自由态与束缚态多溴联苯醚和四溴双酚-A

建立了一种同时测定沉积物中不同赋存形态的多溴联苯醚(PBDEs)和四溴双酚A(TBBPA)的分析方法.样品由等体积的丙酮和正己烷混合溶剂抽提得到自由态目标物,再通过碱性水解反应释放束缚态目标化合物.通过调节酸度(pH值)实现PBDEs和TBBPA的分离和提取.PBDEs由复合硅胶柱净化,运用气相色谱-质谱(负离子化学源)-分时段选择离子监测技术测定;TBBPA经重氮甲烷衍生化反应后由酸性硅胶柱预纯化,运用气相色谱-质谱(电子轰击源)-分时段选择离子监测技术测定.8种低溴联苯醚(BDE28,-47,-66,-100,-99,-154,-153,-183),十溴联苯醚(BDE209)和TBBPA的检出限分别为0.6～12.5 pg/g,172 pg/g,4 2 pg/g.方法具有良好的准确度和精确度,回收率均在74%～106%之间,RSD≤10%.对东江沉积物样品的分析表明,本方法能够实现不同形态的PBDEs 和TBBPA的有效检测.