化合物的土壤柱色谱保留因子与其土壤／水吸附系数的关联

利用土壤柱液相色谱方法,对19种不同类型的农药和化学品在土壤柱上的保留进行了测定,并考察了流动相对保留的影响。对土壤柱液相色谱法测定的化合物的保留因子与批量平衡法测定的土壤/水吸附系数的相关性进行了研究,在条件一致的情况下,批量平衡法和土壤柱液相色谱法测定的数据间存在很好的相关性。研究表明,土壤柱液相色谱法可以用于土壤/水吸附系数的快速测定和筛选。     

莠去津吸附的土壤淋溶柱色谱法研究

采用新发展的土壤淋溶柱色谱法,研究农药在水－土壤体系中的吸附。用土壤装填成液相色谱柱,以农药水溶液为流动相,以除草剂莠去津（２－氯－４－乙胺基－６－异丙胺基－ｓ－三嗪）为例,质量浓度从１９．７３μｇ／Ｌ至２９．６０ｍｇ／Ｌ,紫外检测器监测吸附平衡。吸附相中莠去津的质量浓度经甲醇淋洗液的测定值扣除柱内液相中的质量浓度后得到。对于极稀溶液,可采用在ＯＤＳ柱上富集－液相色谱台阶梯度法测定。莠去津在沙壤土上的吸附行为符合Ｆｒｅｕｎｄｌｉｃｈ方程式,其吸附常数Ｋｆ＝８４２．６ｍＬ／ｋｇ。     

高效液相色谱法同时测定土壤中多菌灵、吡虫啉和甲基托布津的残留

建立了高效液相色谱法同时测定土壤中多菌灵、吡虫啉和甲基托布津残留的快速分析方法。利用甲醇-0.1mol.L-1HCl从土壤中提取,C18柱分离,紫外检测,在7min内实现了3种农药的同时分离测定。3种农药的平均回收率为87%、97%和92%,相对标准偏差为9.8%、8.1%和11.0%。     

加速溶剂萃取-气相色谱测定土壤中有机磷农药

提出了气相色谱法测定土壤中8种有机磷农药含量的方法。样品以水为分散剂、丙酮-二氯甲烷（1+4）混合溶剂为萃取剂,经加速溶剂萃取仪在60℃静态萃取5 min。采用DB17色谱柱分离,火焰光度检测器测定有机磷农药。8种有机磷农药的检出限（3S/N）在3.0～7.2μg·L^-1之间。以土壤样品为基体,进行加标回收试验,回收率在73.3%～110%之间,相对标准偏差（n=7）在5.9%～15%之间。     

NANO碳净化-超高效液相色谱-串联质谱法测定东北黑土壤中多农残含量

本文使用NANO碳净化柱对土壤中的31种农药进行净化,并且通过超高效液相色谱-串联质谱法(UPLC-MS/MS)进行测定。土壤样品经过NANO碳净化柱,净化效果良好。31种农药的检出限为0.001~0.01mg/kg,定量限为0.003~0.033mg/kg,添加回收率在70%~120%之间,相对标准偏差(RSD)在0%~10%之间。结果表明,该方法简单、快捷、灵敏度高,线性范围、回收率和精密度均适合土壤中的31种农药残留检测,在土壤农药残留筛查中具有较好的应用前景。     

土壤柱液相色谱多级吸附法测定污染物的土壤有机碳吸附常数

建立了利用土壤柱液相色谱多级吸附测定污染物的土壤有机碳吸附常数(KOC)的新方法。用这种方法通过一次实验就可获得多个不同浓度的样品在土壤中的吸附量,从而通过吸附等温线计算出KOC。用该法测定的戊唑醇、保棉磷、敌草隆、莠去津、扑草净、苯酚、萘在欧洲3#标准土壤中的log KOC分别为2.70,2.87,2.47,2.26,3.09,1.51和2.77,与文献值基本一致。     

气相色谱法测定土壤中21种有机氯农药和4种有机磷农药

应用气相色谱法测定土壤中21种有机氯农药和4种有机磷农药(OCP′s及OPP′s)的含量。土壤样品(10g)以丙酮-正己烷(1+1)混合液(200mL)在65℃用索氏提取7h。提取液蒸缩至约2mL,用经固相萃取小柱净化。用上述混合液6mL分3次从柱上洗脱,洗脱液浓缩至1mL供气相色谱分析。测定OCP′s时用CLPⅡ型毛细管色谱柱分离,电子捕获检测器检测;测定OPP′s时用1701型毛细管色谱柱分离,火焰光度检测器检测。21种OCP′s和4种OPP′s在一定的质量浓度范围内与其峰面积呈线性关系,方法的检出限(3S/N)在0.14~0.38μg·kg-1之间。加标回收率在68.0%~125%之间,测定值的相对标准偏差(n=10)在2.8%~5.9%之间。     

超声提取反相高效液相色谱测定土壤中微量灭多威

ｌ引言灭多威（Ｍｅｔｈｏｍｙｌ）是一种具有触杀和胃毒作用的氨基甲酸酯类杀虫剂，是目前防治棉铃虫的主要农药品种之一。有关灭多威的分析已报道的有气相色谱法和高效液相色谱法，但土壤中微量灭多威的分析尚未见报道。本文研究了采用超声提取，反相高效液相色谱测定土壤中微量灭多威的方法，取得较满意的结果。与传统的索氏提取相比，超声提取具有方便、快速的特点。２实验部分２．１仪器和试剂贝克曼３３４型高效液相色谱仪；ＣＱ２５０型超声波清洗器；ＺＦＱ８５Ａ型旋转蒸发器。灭多威标样（含量９８．８％，沈阳化工研究院）；甲醇…     

离子液体微波辅助液相萃取-高效液相色谱法同时测定土壤中5种微量有机氧农药

采用离子液体([BMIm]PF6)微波辅助液相萃取-高效液相色谱法建立同时测定土壤中5种有机氧农药(6-糠氨基嘌呤、咪唑乙烟酸、2,4-二氯苯氧乙酸、苄嘧磺隆、烯效唑)的残留分析方法。研究了离子液体的种类和浓度、微波功率、时间、温度对色谱峰面积的影响。并检测了西安近郊地区苹果园和葡萄园土壤样品,在2种浓度添加水平2.00和20.0μg/mL下,5种有机氧农药的平均回收率分别为76.4%～125.0%和86.2%～117.0%,相对标准偏差(RSD)为1.2%～13%和3.9%～17%(n=6),方法检出限为0.03～0.13μg/mL。研究表明离子液体微波辅助液相微萃取可有效地萃取土壤中有机氧农药的残留。     

超声波萃取-SPE净化-双柱双检测器测定土壤和沉积物中的20种有机氯

建立了超声波萃取-SPE硅胶小柱净化-双柱双检测器气相色谱法测定土壤和沉积物中20种有机氯农药的方法。样品中添加高纯铜粉除硫,二氯甲烷超声萃取9 min,使用SPE硅胶小柱,9 mL丙酮:正己烷(1:9)洗脱净化。采用单进样口,双色谱柱双μ-ECD同时分离测定。土壤和沉积物样品中的方法检出限为0.001 mg/kg,平均回收率为73.17%～112.5%,相对标准偏差为0.33%～16%。     

Prediction of soil organic carbon partition coefficients by soil column liquid chromatography

To avoid the limitation of the widely used prediction methods of soil organic carbon partition coefficients (KOC) from hydrophobic parameters, e.g., the n-octanol/water partition coefficients (KOW) and the reversed phase high performance liquid chromatographic (RP-HPLC) retention factors, the soil column liquid chromatographic (SCLC) method was developed for KOC prediction. The real soils were used as the packing materials of RP-HPLC columns, and the correlations between the retention factors of organic compounds on soil columns (ksoil) and KOC measured by batch equilibrium method were studied. Good correlations were achieved between ksoil and KOC for three types of soils with different properties. All the square of the correlation coefficients (R2) of the linear regression between log ksoil and log KOC were higher than 0.89 with standard deviations of less than 0.21. In addition, the prediction of KOC from KOW and the RP-HPLC retention factors on cyanopropyl (CN) stationary phase (kCN) was comparatively evaluated for the three types of soils. The results show that the prediction of KOC from kCN and KOW is only applicable to some specific types of soils. The results obtained in the present study proved that the SCLC method is appropriate for the KOC prediction for different types of soils, however the applicability of using hydrophobic parameters to predict KOC largely depends on the properties of soil concerned.     

A New Method for Determination of Adsorption and Desorption Coefficients of Pesticides with Soil Column Liquid Chromatography

Agricultural chemicals such as pesticides were extensively applied in the fields. Pesticides effectively protect the crops, only as long as they remain in the root zone of soil. In case a portion of the chemicals leaves root zone and especially leaches through soil pores. They may pollute groundwater and be a serious environmental problem1. This problem has got widespread concern in the world. In soils the fate of organic compounds such as pesticides is governed by hydraulic transport coupled…     

Retention of ionizable compounds on HPLC. 6. pH measurements with the glass electrode in methanol-water mixtures

The relationship, delta values, between the two rigorous pH scales, S(S)pH (pH measured in a methanol-water mixture and referred to the same mixture as standard state) and S(W)pH (pH measured in a methanol-water mixture but referred to water as standard state), in several methanol-water mixtures was determined (delta = S(W)pH-S(S)pH). Delta values were measured using a combined glass electrode and a wide set of buffer solutions. The results are consistent with those obtained with the hydrogen electrode. This confirms the aptness of the glass electrode to achieve rigorous pH measurements in methanol-water mixtures. An equation that relates delta and composition of methanol-water mixtures, and allows delta computation at any composition by interpolation, is proposed. Therefore, S(S)pH can be achieved from the experimental S(W)pH value and delta at any mobile phase composition. S(S)pH (or S(W)pH) values are related to the chromatographic retention of ionizable compounds through their thermodynamic acid-base constants in the methanol-water mixture used as mobile phase. These relationships were tested for the retention variation of several acids and bases with the pH of the mobile phase. Therefore, the optimization of the mobile phase acidity for any analyte can be easily reached avoiding the disturbances observed when W(W)pH is used.     

高效液相色谱法构建定量结构-保留关系预测中药肝肾毒性组分的正辛醇-水分配系数值

构建了定量结构-保留关系(QSRR)测定马兜铃酸A、马兜铃酸B、马兜铃内酰胺及白黎芦醇的正辛醇-水分配系数(K_(ow))。采用反相高效液相色谱(RP-HPLC)法,以甲醇-水为流动相,以16种已知K_(ow)值的酸性和中性苯系物为模型化合物,以保留时间两点校正法(DP-RTC)校正保留时间,并由Snyder-Soczewinski方程得100%水相保留因子k_w,建立了表观正辛醇-水分配系数K_(ow)″与k_w的定量关系(QSRR模型),并对模型进行了内、外部验证。结果显示,不同pH下的QSRR模型线性相关性良好(相关系数R~2为0.980~0.987),内部验证(交叉验证相关系数R_(cv)~2为0.982~0.988)和外部验证结果(6种验证化合物的相对误差RE为0.6%~10.9%)令人满意。将建立的QSRR模型应用于中药中4种潜在肝肾毒性化合物的K_(ow)测定,并与软件计算值、摇瓶法(SFM)实验值比较,结果显示该方法准确性更高,且简单快捷。该文提出的采用中性及酸性苯系物建立QSRR模型,通过对结构与性质相似的中药材组分进行RP-HPLC分析,得到各待测组分的保留时间即可获得其K_(ow)值的简便策略,解决了中药组分复杂且难以分离、无法通过SFM测定其K_(ow)值的问题,为通过定量-构效关系(QSAR)模型实现快速预测中药组分的肝肾毒性提供了可靠的K_(ow)数据。     

Modelling retention in liquid chromatography as a function of solvent composition and pH of the mobile phase

The aim of this work was to develop a model that accurately describes retention in liquid chromatography (LC) as a function of pH and solvent composition throughout a large parameter space. The variation of retention as a function of the solvent composition, keeping other factors constants, has been extensively studied. The linear relationship established between retention factors of solutes and the polarity parameter of the mobile phase, E(N)T, has proved to predict accurately retention in LC as a function of the organic solvent content. Moreover, correlation between retention and the mobile phase pH, measured in the hydroorganic mixture, can be established allowing prediction of the chromatographic behavior as a function of the eluent pH. The combination of these relationships could be useful for modelling retention in LC as a function of solvent composition and pH. For that purpose, the retention behavior on an octadecyl silica column of a group of diuretic compounds covering a wide range of physico-chemical properties were studied using acetonitrile as organic modifier. The suggested model accurately describes retention of ionizable solutes as concomitant effects of variables included and is applicable to all solutes studied. We also aimed to establish an experimental design that allows to reproduce to a good approximation the real retention surface from a limited number of experiments, that is from a limited number of chromatograms. Ultimately, our intention is to use the model and experimental design for the simultaneous interpretive optimization of pH and proportion of organic solvent of the mobile phase to be used in the proposed separation.     

基于养分指标相关性的土壤有机质预测模型研究

为探究土壤间各养分指标间的相互关系,选取了天津市宁河区不同区域的种植土壤,基于行业标准规定的检测方法,对主要养分指标进行了测定,并研究各指标间的相关性。结果表明,各区域土壤pH值变异系数最小,整体均呈碱性;有机质、全氮及速效钾变异系数属于中等;有效磷的变异系数最高。各研究区域土壤有机质含量与全氮含量呈显著正相关(P<0.01),与pH值呈显著负相关(P<0.01),而与其他指标间不具备普遍且显著的相关性。基于多元线性回归分析建立了土壤有机质与全氮及pH值之间的预测模型,通过模型计算出的预测值与实际测定值的拟合性较好;另取土壤样品进行验证表明,预测模型具有良好的可靠性和准确性。     

A New Rapid Determination Method of Soil Organic Carbon Adsorption Coefficients of Pesticides with Soil Column Liquid Chromatography

Recent legislation in many countries requires extensive testing of all manufactured chemicals for environmental evaluation and registration. Among the requirements are water solubility, solvent (usually octanol) - water partition coefficient, soil adsorption and bioconcentration factors in aquatic organisms. Soil adsorption influences the extent of vaporization of a compound from the soil surface and its lateral (run-off) or vertical transport including groundwater contamination. Additionally,…     

Separation of potentially therapeutic peptide hormones by liquid chromatography. Optimisation of the composition and pH of the mobile phase

The aim of this work is to optimise the proportion of the organic modifier and the pH of the mobile phase, in order to separate a series of peptide hormones with therapeutic interest in the molecular mass range from 500 to 6000. The composition of the mobile phase was optimised by establishing relationships between retention parameters and either the scale of solvent polarity, or the Kamlet–Taft multiparameter solvent scale of the eluent, using linear solvation energy relationships. Likewise, linear correlations between the chromatographic retention and Reichardt’s E^N_T parameter were obtained. These relationships allowed an important reduction of the experimental retention data needed for developing a given separation. In addition, a model describing the effect of the correctly measured pH of the mobile phase on retention in LC was established and tested for the series of selected peptides using an octadecylsilica column. The proposed equations permit the prediction of the optimum pH and also permit the determination of the acidity constants of the peptides in the hydro-organic mixtures using a minimum number of measurements.     

Retention behaviour of peptides, quinolones, diuretics and peptide hormones in liquid chromatography. Influence of ionic strength and pH on chromatographic retention

Peptides, quinolones, diuretics and peptide hormones are important substances of biomedical interest. In this work a model describing the effect of pH on retention in liquid chromatography (LC) is established and tested for these compounds using an octadecylsilica column. The suggested model uses the pH value measured in the hydro-organic mixture used as mobile phase instead of the pH value in water and takes into account the effect of the activity coefficients. The proposed equations permit the prediction of the pH optimum using a minimum number of measurements and also permit the determination of the acidity constants of the compounds considered in the medium used as mobile phase. Moreover, these equations can be combined with the previously derived equations, that relate the retention with the solvent composition of the mobile phase, to establish a general model that relates the elution behaviour of the solute with the significant mobile phase properties: composition, pH and ionic strength.