离子色谱—三重四极杆质谱测定环境水样中有机磷

建立了一种非衍生—离子色谱—三重四极杆质谱法测定环境水样中有机磷（草甘膦、氨甲基膦酸、草铵膦、杀木膦和乙烯利）的方法。环境水样经RP-C18固相萃取柱和Ba柱除去杂质后，滤液无须衍生化，可直接进行定量分析。有机磷通过AS 19阴离子色谱柱分离，在负离子模式下以多反应监测方式（MRM）进行检测。结果表明，草甘膦、氨甲基膦酸和草铵膦在0.10～10.0 μg/L范围内的线性相关系数（r）均＞0.999，检出限分别为0.02，0.03和0.03 μg/L，相对标准偏差（RSD）分别为2.8%～4.7%，5.4%～11.7%和5.1%～7.4%。杀木膦和乙烯利在0.02～2.00 μg/L范围内的 r 值均＞0.999，检出限分别为0.007和0.004 μg/L，RSD分别为3.7%～5.8%和2.1%～13.2%。对实际水样进行测定，各目标物的加标回收率为70.0%～120%。该方法操作简便，精密度好，准确度高，适用于环境水样中5种极性有机磷的测定。     

水中草甘膦和氨甲基膦酸的柱前衍生-液相色谱方法研究

建立柱前衍生-液相色谱-荧光检测法同时测定水中草甘膦和氨甲基膦酸的方法。水样经芴甲氧羰酰氯衍生化后取上清液进样,采用ODS C18柱,以水(5 mmol/L乙酸铵)-乙腈作为流动相进行梯度洗脱,采用荧光检测器进行检测。实验通过加入柠檬酸三钠,解决了实际水样中金属阳离子的干扰问题。草甘膦和氨甲基膦酸在一定范围内线性良好(r=0.997 3~0.999 0),回收率为92.2%~102%,相对标准偏差为4.3%~8.5%,方法检出限为1.29μg/L和1.84μg/L。     

离子色谱-串联质谱法测定4类水质中7种极性有机磷

应用离子色谱-串联质谱法(IC-MS/MS)同时测定了地下水、地表水、生活污水和工业废水等4类水质中的草甘膦、草铵膦、氨甲基膦酸、杀木膦、乙烯利、双甘膦和增甘膦.这7种有机磷极性和水溶性强,用常规气相或液相的方法需要经衍生化后才能测定,且要严格控制前处理条件.该法水样用微孔滤膜和离子净化柱过滤后直接进样,经Ion Pa...     

高效液相色谱法测定水中草甘膦

水样中草甘膦经柠檬酸三钠络合金属离子,固相萃取柱净化,与FMOC-Cl(9-芴甲基氯甲酸酯)进行衍生化反应,用二氯甲烷萃取去除衍生化副产物后,经高效液相色谱分离,荧光检测器检测,以保留时间定性,外标法定量。结果表明,在10μg/L～500μg/L范围内线性良好,检出限为1.2μg/L,相对标准偏差为0.91%～2.23%,实际水样加标回收率为97.0%～102%。该方法检测草甘膦灵敏度和准确度高,精密度良好。     

五氟苯甲酰氯衍生-气相色谱-质谱法测定地表水中一甲基肼

建立了五氟苯甲酰氯衍生-气相色谱-质谱法测定地表水中一甲基肼的方法。取200ml水样,调节后的pH为10,加入20ml衍生剂,在室温下剧烈振荡衍生1h,40ml二氯甲烷萃取10min,浓缩至1.0ml后用气相色谱-质谱联用分析。方法在5～500μg/L浓度范围内线性良好,相关系数大于0.996,方法检出限为2.67μg/L;加标水样的相对标准偏差为9.54%和8.38%;加标水样回收率为79.08%～102.96%。     

电导和直流安培双检测器离子色谱法测定清洁水样中的碘化物

选用配备了2种不同检测器(电导检测器和直流安培检测器)的离子色谱仪对稀释后过0.22μm滤膜的水样进行分析。配备有直流安培检测器的离子色谱仪测定水中碘化物的方法在0.100~20.0μg/L范围内线性关系良好,相关系数(r)=0.9999,方法检出限为0.030μg/L,测定下限为0.120μg/L,样品加标回收率为95.0%~104%,相对标准偏差为1.06%~1.64%;配备有电导检测器的离子色谱仪测定水中碘化物的方法在20.0~2.00×105μg/L范围内线性关系良好,相关系数(r)=0.9995,方法检出限为2.00μg/L,测定下限为8.00μg/L,样品加标回收率为99.0%~110%,相对标准偏差为0.71%~3.12%。离子色谱-直流安培检测器法测定水中碘化物的方法准确度高、灵敏度高、精密度好,检出限相对较低,适用于测定ρ(碘化物)≤20.0μg/L的清洁水样;离子色谱-电导检测器法主要适用于测定ρ(碘化物)≥20.0μg/L的水样。     

固相萃取-液相色谱/紫外法测定地表水中百草枯和敌草快

利用固相萃取和液相色谱,建立地表水中百草枯和敌草快的分析方法。该方法不使用离子对试剂即可对目标物进行分离,百草枯和敌草快的回收率分别为107.6%±6.90%、100.5%±9.93%,在0.04~10μg/ml范围内,有很好的线性相关性,百草枯和敌草快的检出限均为0.05μg/L,定量限为0.2μg/L。水样需在7天内完成前处理。     

柱前衍生化-固相萃取-气相色谱法快速测定水中五氯酚

建立了柱前衍生化-固相萃取-气相色谱法快速测定水样中五氯酚的方法。结果表明,目标化合物在气相色谱条件下可以实现很好的基线分离,五氯酚在质量浓度0. 05~50. 0μg/L范围内呈现良好的线性关系,相关系数r=0. 998,方法检出限为0. 006μg/L,测定下限为0. 024μg/L,相对标准偏差均10%。该方法具有较高的精密度和准确度,且简便高效,适用于水体中五氯酚的测定。     

原子荧光光谱法同时测定环境水体中痕量锡和锌

采用原子荧光光谱法同时测定环境水样中痕量锡和锌,优化了试验条件。锡在1.00μg/L～10.0μg/L、锌在20.0μg/L～200μg/L范围内线性良好,方法检出限锡为0.13μg/L,锌为1.76μg/L,锡和锌标准溶液测定的相对标准偏差分别为2.9%和4.0%,环境水样加标回收率锡为96.4%～106%,锌为92.0%～111%。     

溴化衍生-三重四极杆气质联用法测定地表水中丙烯酰胺

采用溴化衍生-液液萃取法处理地表水,用三重四极杆气相色谱质谱联用仪测定样品中α,β-二溴丙烯酰胺,再换算成丙烯酰胺的质量浓度,该方法在20.0μg/L~500μg/L范围内线性良好,相关系数r为0.998,方法检出限为0.08μg/L。实际水样2个质量浓度水平的平均加标回收率分别为87.5%和92.2%,7次测定结果的RSD分别为9.1%和6.1%。用该方法测定黄河兰州段的黄河水和实验室自来水,结果均未检出。     

分光光度法测定废水中草甘膦的探讨

探讨了亚硝基衍生化紫外分光光度法测定废水中草甘膦的适用性,考察了硫酸加入体积对亚硝化反应的影响,提出应根据样品碱度调整硫酸用量。方法与高效液相色谱法测定值的重现性较好,应用于实际废水中草甘膦测定的加标回收率为95%～105%,平行测定的RSD≤1.3%,检出限为0.069 mg/L,检测上限为50.0 mg/L,废水中可能存在的伯胺和叔胺类物质对测定无明显干扰。     

Monitoring of glyphosate and AMPA in soil samples from two olive cultivation areas in Greece: aspects related to spray operators activities

The persistence of glyphosate and its primary metabolite AMPA (aminomethylphosphonic acid) was monitored in two areas in Southern Greece (Peza, Crete and Chora Trifilias, Peloponnese) with a known history of glyphosate use, and the levels of residues were linked to spray operators’ activities in the respective areas. A total of 170 samples were collected and analysed from both areas during a 3-year monitoring study. A new method (Impact Assessment Procedure - IAP) designed to assess potential impacts to the environment caused by growers’ activities, was utilised in the explanation of the results. The level of residues was compared to the predicted environmental concentrations in soil. The ratio of the measured concentrations to the predicted environmental concentrations (MCs/PECs) was >?1 in Chora the first 2 years of sampling and <?1 in the third year, whilst the MCs/PECs ratio was <?1 in Peza, throughout the whole monitoring period. The compliance to the instructions for best handling practices, which operators received during the monitoring period, was reflected in the amount of residues and the MCs/PECs ratio in the second and especially the third sampling year. Differences in the level of residues between areas as well as sampling sites of the same area were identified. AMPA persisted longer than the parent compound glyphosate in both areas.     

Adsorption-desorption and leaching potential of glyphosate and aminomethylphosphonic acid in acidic Malaysian soil amended with cow dung and rice husk ash

This study investigates adsorption-desorption and the leaching potential of glyphosate and aminomethylphosphonic acid (AMPA) in control and amended—addition of cow dung or rice husk ash—acidic Malaysian soil with high oxide mineral content. The addition of cow dung or rice husk ash increased the adsorptive removal of AMPA. The isotherm data of glyphosate and AMPA best fitted the Freundlich model. The constant K_f for glyphosate was high in the control soil (544.873 mg g^?1) followed by soil with cow dung (482.451 mg g^?1) then soil with rice husk ash (418.539 mg g^?1). However, for AMPA, soil with cow dung was high (166.636 mg g^?1) followed by soil with rice husk ash (137.570 mg g^?1) then the control soil (48.446 mg g^?1). The 1/n values for both glyphosate and AMPA adsorptions were <?1 indicating their strong affinity for adsorbents. Desorption of both glyphosate and AMPA occurred only in the control soil. The compounds were not detected in soils with added cow dung or rice husk ash. The addition of cow dung or rice husk ash increased glyphosate mobility. However, ground water ubiquity scores for both control and amended soils were <?2.8. This indicated glyphosate is a transitional herbicide; therefore, its leaching potential in the soil is low, despite the addition of cow dung or rice husk ash. Addition of these wastes decreased the mobility and leaching potential of AMPA. The addition of cow dung or rice husk ash could be beneficial in increasing adsorption and enhancing degradation of these compounds.     

The occurrence of glyphosate, atrazine, and other pesticides in vernal pools and adjacent streams in Washington, DC, Maryland, Iowa, and Wyoming, 2005–2006

Vernal pools are sensitive environments that provide critical habitat for many species, including amphibians. These small water bodies are not always protected by pesticide label requirements for no-spray buffer zones, and the occurrence of pesticides in them is poorly documented. In this study, we investigated the occurrence of glyphosate, its primary degradation product aminomethylphosphonic acid, and additional pesticides in vernal pools and adjacent flowing waters. Most sampling sites were chosen to be in areas where glyphosate was being used either in production agriculture or for nonindigenous plant control. The four site locations were in otherwise protected areas (e.g., in a National Park). When possible, water samples were collected both before and after glyphosate application in 2005 and 2006. Twenty-eight pesticides or pesticide degradation products were detected in the study, and as many as 11 were identified in individual samples. Atrazine was detected most frequently and concentrations exceeded the freshwater aquatic life standard of 1.8 micrograms per liter (microg/l) in samples from Rands Ditch and Browns Ditch in DeSoto National Wildlife Refuge. Glyphosate was measured at the highest concentration (328 microg/l) in a sample from Riley Spring Pond in Rock Creek National Park. This concentration exceeded the freshwater aquatic life standard for glyphosate of 65 microg/l. Aminomethylphosphonic acid, triclopyr, and nicosulfuron also were detected at concentrations greater than 3.0 microg/l.     

Genotoxic effects of the herbicide Roundup® in the fish Corydoras paleatus (Jenyns 1842) after short-term, environmentally low concentration exposure

The glyphosate-based herbicide, Roundup^®, is one of the most used pesticides worldwide. In concert with the advent of transgenic crops resistant to glyphosate, the use of this pesticide has led to an increase in agricultural yields. The objective of this study was to evaluate the genotoxic effect that the herbicide Roundup^® (at a concentration of 6.67 μg/L, corresponding to 3.20 μg/L glyphosate) can have on the fish Corydoras paleatus. Treatment groups were exposed for 3, 6, and 9 days, and effects were analyzed using the piscine micronucleus test (PMT) and comet assay. A group subjected to filtered water only was used as a negative control. The PMT did not show differences between the control and exposed groups for any of the treatment times. In contrast, the comet assay showed a high rate of DNA damage in group exposed to Roundup^® for all treatment times, both for blood and hepatic cells. We conclude that for the low concentration used in this research, the herbicide shows potential genotoxic effects. Future research will be important in evaluating the effects of this substance, whose presence in the environment is ever-increasing.     

Mass Spectrometric Detection and Identification of Polar Pesticides and their Degradation Products - A Comparison of Different Ionization Methods

Due to increasing use of polar pesticides, they are found together with their degradation products in ground- and surface waters serving for drinking water treatment. The triazine derivatives acetamido-atrazine, ametryne, atrazine, cyanazine, deethylatrazine, deethyldeisopropyl-hydroxyatrazine, deethyl-hydroxyatrazine, deisopropyl-atrazin, deisopropyl-hydroxyatrazine, desmetryn, hydroxyatrazine, prometryne, propazine, simazine, terbumeton, terbutryne and terbutylazine, and the pesticides 2,4-D, dichlorprop, isoproturon, diuron, metolachlor, glyphosate, metsulfuronmethyl and dalapon, all of them belonging to this type of pesticides, have been studied. For determination of triazine derivatives UV detection by means of diode array detector (DAD) as well as mass spectrometric (MS) detection coupled by thermospray interface (TSP) have been used successfully after liquid chromatoraphic (LC) separation. Interfaces like thermospray (TSP), electrospray (ESP) and atmospheric pressure chemical ionisation (APCI) were examined with regard to their suitability for substance-specific detection of polar pesticides by flow injection analysis (FIA) with MS- and tandem mass spectroscopic detection (MS/MS) without preceding LC separation. Optimised detection conditions for these pesticides using FIA are presented, and solutions for occurring problems are offered.     

流动注射-氢化物发生-原子荧光光谱法测定土壤中铅

采用流动注射-氢化物发生-原子荧光光谱法测定土壤中的铅,工作曲线线性关系良好,检出限为0.25 mg/kg,相对标准偏差＜3.5%,加标回收率为93.0%～105%.该方法简便快速,测定结果准确可靠.     

柱前衍生-EI源串联四极杆气质联用测定地表水中的丙烯酰胺

建立了地表水中痕量丙烯酰胺的柱前衍生-EI源串联四极杆气质联用测定方法。丙烯酰胺的双键经溴化衍生成2,3-二溴丙酰胺,加入硫酸钠盐析,乙酸乙酯萃取,浓缩取1μl进样,由串联四极杆气相色谱质谱联用仪测定。通过MRM(150→70.0/107.0)多反应监测实现定性和外标法定量分析。与其他方法相比,该方法具有定性准确、灵敏度高的特点。方法检出限为0.03μg/L,线性范围在0.030~40μg/L;相关系数r=0.9998;六次测定值RSD在14.3%;回收率在89%~196%之间,结果满意。     

Optimizing a dansylhydrazine (DNSH) based method for measuring airborne acrolein and other unsaturated carbonyls

The Passive Aldehydes and Ketones Sampler (PAKS) method has been developed to measure airborne carbonyls (aldehydes and ketones) by derivatizing the carbonyls with dansylhydrazine (DNSH) on a solid sorbent. The method collection efficiencies are approximately 100% for most saturated carbonyls, but are significantly lower for unsaturated carbonyls. In this study, we examined the mechanisms of DNSH reactions with unsaturated carbonyls, focusing on acrolein. With a better understanding of these mechanisms, we modified the sampling substrate conditions and HPLC analysis conditions of the original PAKS method, resulting in substantially improved collection efficiencies for acrolein and crotonaldehyde. Evaluated under a variety of conditions (temperature, humidity, presence of ozone), the modified PAKS method had a collection efficiency of 99%+/- 5% for acrolein (N= 36) and 96%+/- 20% for crotonaldehyde (N= 6). The acrolein-DNSH derivative was stable within 9.6% of the initial amount, after 14 days of storage at 4 degrees C, on the collection medium; and stable within 2.8% of the initial amount, after 16 days of storage at room temperature, in extract.     

SPE-GCMS法分析饮用水源水中痕量半挥发性有机物

采用C 18固相萃取柱富集,乙酸乙酯、二氯甲烷和丙酮混合溶剂以1∶1∶1比例洗脱、自动固相萃取的前处理方法,气相色谱质谱连用,分析水源水中33种半挥发性有机物,并与液液萃取前处理方法进行比较。结果表明:在500~5 000μg/L范围内,33种SVOC线性良好,相关系数0.990,回收率为70.1%~114.2%,相对标准偏差为2.4%~13.4%,方法检出限为0.06~0.25μg/L;而且该方法较液液萃取,检出样品种类多。适用于饮用水源水中半挥发性有机物的监测。