超声提取-离子选择电极法测定铝渣中的氟化物

目前铝渣中的氟化物对环境的影响已经成为人们关注重点之一。为了能够准确测定铝渣中的氟化物含量,实验对超声时间、固液比以及Al~(3+)和Ca~(2+)同时存在下的干扰进行了研究。确定了最佳超声时间为20min,以固液比为1∶20进行超声提取,提取液移取体积为5mL,加入总离子强度溶液15mL的方法来消除质量浓度不大于25mg/L Al~(3+)和Ca~(2+)的干扰,运用离子选择电极法准确测定铝渣中的氟化物,得到标准曲线线性相关系数为0.999 9,方法检出限为0.3mg/kg,相对标准偏差(n=6)小于2%,加标回收率在90.8%～108%。同时用超声提取法对样品进行前处理,分别运用离子选择电极法和离子色谱法对铝渣中的氟化物进行测定,两者测定结果一致,方法的准确度良好。     

离子色谱法快速测定土壤中的亚硝酸盐氮和硝酸盐氮

建立离子色谱法快速测定土壤中亚硝酸盐氮和硝酸盐氮的方法。土壤样品采用250 mL 0.01 moL/L氯化钙溶液提取,于20℃水浴振荡60 min,静置离心。采用Ion Pac AS19离子色谱柱,以20 mmoL/L氢氧化钾溶液为淋洗液,流量为1.0 mL/min,进样体积为25μL,以电导检测器进行检测。亚硝酸盐氮和硝酸盐氮的质量浓度在0.20～5.00 mg/L范围内与色谱峰面积呈良好的线性关系,线性相关系数均为0.999 9,方法检出限分别为0.005,0.007mg/L。样品的加标回收率为95.0%～97.4%,测定结果的相对标准偏差为0.89%～2.11%(n=12)。该方法适用于土壤中亚硝酸盐氮和硝酸盐氮含量的快速测定。     

高效液相色谱法同时测定染发剂中8种合成染料

使用甲醇对样品进行超声提取,以乙腈-0.02 mol/L乙酸铵溶液为流动相,采用XB-C18色谱柱分离,二极管阵列检测器检测,外标法定量,建立了同时测定染发剂中8种合成染料的高效液相色谱分析方法。HC红3号、分散黑9、HC黄2号、分散紫1及HC橙1号的检测波长设为240 nm,HC黄4号设为410nm,HC蓝7号为450 nm,HC红1号为270 nm。8种染料在0.5~100.0μg/m L范围内具有良好线性,相关系数(r2)均不小于0.999 3。HC红3号、HC黄4号、HC橙1号和分散紫1的检出限均为0.70 mg/kg,分散黑9、HC黄2号、HC蓝7号和HC红1号的检出限分别为2.50,0.60,0.35,0.50 mg/kg。样品的平均回收率为85.4%~99.8%,相对标准偏差(n=6)为1.1%~3.6%。方法的精密度、准确度、回收率和基质效应均符合染发剂样品测定的要求,用于实际样品测定,结果满意。该方法快速简便、定量准确,能满足染发剂中8种合成染料含量的分析检测要求。     

离子色谱法测定海产品中磷酸盐、焦磷酸盐、偏磷酸盐和总磷

建立了离子色谱法测定海产品中磷酸盐、焦磷酸盐、偏磷酸盐和总磷的分析方法。样品经100 mmol/L NaOH溶液浸提,固相萃取柱去除有机物、阳离子、中和OH~后用于海产品中磷酸盐、焦磷酸盐和偏磷酸盐的测定;样品经干灰化法消化,固相萃取柱净化后用于总磷测定。考察了提取溶液的pH、有机物和共存离子对测定结果的影响。该方法的线性范围为0.3～60 mg/L,检出限为2.1～2.3 mg/kg,相对标准偏差为1.6%～2.6%。海鱼和虾仁样品中目标物的加标回收率为81.8%～100.0%。该方法选择性好,灵敏度高,用于实际样品测定结果令人满意。     

密闭熔融–离子色谱法测定土壤中氟化物

建立测定土壤中氟化物的离子色谱法。在0.100 0 g土壤样品中加入0.800 g氢氧化钠和1 mL去离子水,于220 ℃下密闭熔融土壤样品6 h,采用Ion Pac AS19型离子色谱柱,以20 mmol/L氢氧化钾溶液为淋洗液,利用离子色谱法测定土壤中的氟化物含量。氟离子质量浓度在0～10 mg/L范围内与色谱峰面积线性关系良好,相关系数为0.999 8,方法检出限为2.5 mg/kg。氟化物测定结果的相对标准偏差为1.49%～5.53%(n=7)。采用所建方法对标准物质GBW 07446、GBW 07388和GBW 07407进行测定,测定值与标准值的相对误差为1.09%～1.83%。该方法具有高效率、低危险、低污染、低成本的特点,适用于土壤样品中氟化物的测定。     

高效液相色谱法测定肌肉组织中的磷酸肌酸

 采用反相离子对液相色谱法测定肌肉组织中的磷酸肌酸 (PCr)的含量。样品经高氯酸溶液沉淀蛋白 ,匀浆后离心 ,上清液用KOH溶液中和后用反相液相色谱法分离测定。方法的最低检测限为 2mg/L(S/N≥ 3) ,PCr在 5mg/L～ 10 0mg/L范围内与其峰面积呈良好的线性关系 (r =0 .9992 ) ;PCr的平均回收率为 99.34 % ;测定结果的日内RSD <4.42 % ,日间RSD <8.6 7%。方法准确、灵敏、快速 ,适用于动物和人体肌肉组织中PCr含量的测定。     

超声辅助提取/离子色谱法测定铬污染土壤中的六价铬

建立了超声辅助提取/离子色谱法测定铬污染场地中铬（Ⅵ）的方法。选用0.3 mol/L的KCl溶液作提取剂,对12组土壤样品中的铬（Ⅵ）进行超声辅助提取20 min。采用Metrosep A Supp 4-250（250 mm×4.0mm）型阴离子分离柱,以4 mmol/L Na₂CO₃-1 mmol/L NaHCO₃混合溶液为淋洗液对样品进行分离分析。铬（Ⅵ）在0.01²0 mg/L浓度范围有较好的线性关系,相关系数（r²）为0.999 8;该方法的检出限为0.003 mg/L,加标回收率为96.4%¹06.8%,相对标准偏差（RSD,n=3）为0.56%。该方法具有简便、快速、准确等优点,适用于铬污染场地的监测与调查。     

离子色谱法及聚类分析研究主流烟气中的有机酸

建立了超声辅助萃取-离子色谱法同时测定卷烟主流烟气中主要有机酸的方法.采用20 mL 30 mmol/L J NaOH溶液在50℃下对捕集了卷烟主流烟气的剑桥滤片超声萃取50 min,AS11-HC分离柱、Ion AG11-HC保护柱、ASRS-ULTRAⅡ抑制器,KOH溶液为淋洗液,用电导检测器同时测定了卷烟主流烟气中的乳酸、甲酸、乙酸、丙酸、苹果酸和草酸的含量.方法的线性范围1.0～400 mg/L,相关系数为0.9990～0.9995,相对标准偏差1.4%～4.8%,检出限0.03～0.09 mg/L,回收率为92%～104%.采用此方法测定了19种不同规格卷烟样品主流烟气中6种有机酸的含量,并且以6种有机酸为指标对样品进行了聚类分析.结果表明,6种有机酸的含量分布特征可反映不同等级卷烟产品的特性,可用于不用等级卷烟产品的比较和分类.     

反相离子对高效液相色谱法测定心肌组织中的三磷酸腺苷

 采用反相离子对高效液相色谱法测定心肌组织中三磷酸腺苷 (ATP)的含量。样品经高氯酸溶液沉淀蛋白 ,上清液用KOH溶液中和后用反相离子对高效液相色谱法分离测定。色谱柱为SpherisorbODS2柱 ,流动相为甲醇 KH2 PO4缓冲液 (内含 5mmol/LIPR A离子对试剂 ) ,在 2 59nm波长处检测。方法最低检测限为 2mg/L,在 5mg/L～ 1 0 0 mg/L范围内有良好的线性关系 (r=0 9998) ,方法的回收率为 97 8%～ 1 0 4 % ,日内精密度 <4 85% ,日间精密度 <8 81 %。方法准确、灵敏、快速 ,适用于动物和人心肌组织中ATP含量的测定。     

固相萃取–离子色谱法测定人尿液中钙、镁、氟、磷酸根离子

建立固相萃取–离子色谱法测定人尿液中钙、镁两种阳离子和氟、磷酸根两种阴离子。采用C₁₈固相萃取柱去除样品中杂质以消除干扰,以CS12 A型阳离子交换柱为分离柱,以甲基磺酸溶液为淋洗液,等度洗脱,测定钙、镁离子;以AS15型阴离子交换柱为分离柱,以KOH溶液为淋洗液,梯度洗脱,测定氟、磷酸根离子。钙、镁离子的质量浓度在0.25～10 mg/L范围内,氟、磷酸根离子的质量浓度分别在0.002 5～0.05 mg/L、1.25～50 mg/L范围内与色谱峰面积具有良好的线性关系,相关系数均大于0.999 0,方法检出限为0.002～0.2 mg/L。样品加标回收率为86.0%～99.5%,测定结果的相对标准偏差为0.12%～5.50%(n=6)。该方法操作简便,灵敏度高。     

气相色谱-质谱法同时测定氧化型染发剂中的17种染料

建立了氧化型染发剂中17种染料中间体(包括苯二胺类、氨基酚类、苯二酚类、萘酚和氨基吡啶类等)的气相色谱-质谱检测方法. 采用体积分数为50%的乙醇超声提取染发剂中的染料中间体, 加入还原剂连二亚硫酸钠防止待测物变质, 选择DB\|WAX毛细管柱实现了在25 min内同时分离17种水溶性和醇溶性染料. 结果表明, 本方法对所测物质的检出限(LOD)为2～380 mg/kg, 定量限(LOQ)为7.5～1267.5 mg/kg. 在1, 2, 10, 20或100倍LOQ 4个添加水平下的平均回收率在81.1％～103.7％之间, 相对标准偏差(n=6)在0.67%～3.73%之间.     

Ultrasound-assisted matrix solid-phase dispersive liquid extraction for the determination of intermediates in hair dyes with ion chromatography

A novel one-step sample preparation technique called ultrasound-assisted matrix solid-phase dispersive liquid extraction was developed. After sample matrices being dispersed, target analytes were extracted into acid solutions and fat and lipin were dissolved in n-hexane while the interfering components were retained by dispersing sorbent. The extraction process could be rapidly accomplished within 9 min with high sample throughput under the synergistic effects of vibration, ultrasound action and heating. The extraction efficiency of approach was demonstrated for the determination of intermediates in commercial hair dyes with ion chromatography. Linearity ranges of 0.2–100 mg L⁻¹ and detection limits varying from 0.019 to 0.048 mg L⁻¹ were achieved. The recoveries ranged from 85.7 to 107.0% with the relative standard deviations (RSDs) of 0.31–3.7%. These results showed that the method was simple, time-saving, reliable and suitable for the routine analysis of intermediates in large numbers of hair dyes.     

高效液相色谱-二极管阵列检测器同时测定化妆品中的九种染料及中间体

建立了用高效液相色谱-二极管阵列检测器(HPLC-PDA)同时检测9种染料及中间体的系统方法。首先采用超声提取的方法处理样品,对提取溶剂和提取时间进行了选择,确定用甲醇-0.01 mol/L 乙酸铵(体积比为2∶1)作提取溶剂,超声提取20 min。然后,采用C18柱,以甲醇-0.01 mol/L乙酸铵(pH 6.2)为流动相梯度洗脱,用PDA检测。以保留时间定性,并以紫外吸收光谱图辅助定性,以外标法定量。定量检测波长为230 nm,15 min内可对9种目标物同时进行测定,且各化合物都达到基线分离(分离度大于1.5)。经测定,该方法的平均回收率(n=8)为81.0%～105.6%,相对标准偏差（RSD）为0.8%～4.9%,检出限(以信噪比为3计)为0.1～2 μg。该方法简单、快速,能有效提取和分离测定化妆品中9种染料及中间体。将该方法用于实际化妆品样品的检测,结果令人满意。     

高效液相色谱法测定氧化型染发产品中40种染发剂

氧化型染发产品中的多种染发剂具有不同程度的致敏性及其他毒性,建立快速、准确检测多种染发剂的方法,为该类产品监管提供有效的技术手段,十分必要。该研究建立了氧化型染发类产品中40种染发剂的高效液相色谱测定方法。染发产品经含70%乙醇的亚硫酸氢钠水溶液涡旋、超声提取,并经亚硫酸氢钠水溶液稀释后,以0.02 mol/L乙酸铵水溶液(含4%乙腈)和乙腈为流动相,采用Waters Atlantis^® T3 MV Kit色谱柱(250 mm×4.6 mm, 5 μm)分离,配合柱温变化进行梯度洗脱,二极管阵列检测器检测,检测波长为235 nm和280 nm,外标法定量。结果表明,40种染发剂在各自范围内线性关系良好,相关系数均大于0.999; 40种染发剂的检出限为5~168 μg/g,定量限为16~504 μg/g;各染发剂在3个添加水平下的平均回收率为81.4%~109.6%, RSD均小于5%;各染发剂标准溶液在24 h内稳定性良好,RSD为0.2%~2.2%。与现行标准检验方法相比,该方法较大程度地增加了单一液相色谱条件下可测定的染发剂,特别是准用染发剂种类(36种),提高了检测效率,并可保证检测结果的灵敏度与准确性,适用于氧化型染发产品中多种染发剂的检测分析。     

Simultaneous determination of p-phenylenediamines and aminophenols in hair dye products: interlaboratory study

An isocratic HPLC method routinely used in the National Laboratory for Food and Drug Analysis of Taiwan was validated for the simultaneous determination of six aminophenols and phenylenediamines in commercial hair dyes. After extraction of the commercial hair dye product, the dye intermediates were determined by HPLC. Recoveries from the extraction were between 91.6 and 96.5%. The method was then evaluated in an interlaboratory collaborative study according to AOAC guidelines. Five laboratories in Taiwan participated in the study that analyzed the test product, which was preanalyzed by two laboratories to ensure acceptable homogeneity. The RSD(r) and RSD(R) values of the measurements obtained for the dye intermediates in the product were < or = 3.75 and < or = 5.95%, respectively. The method demonstrated acceptable reproducibility, as evidenced by HorRat values of 0.82- 0.97. The applicability of the method to the determination of oxidative hair dye components was further demonstrated in analyses of two different products. The method is thus proposed to be used by manufacturers and laboratories to evaluate the quality of commercial hair dyes containing the six aminophenols and phenylenediamines.     

Polypyrrole‐magnetite dispersive micro‐solid‐phase extraction combined with ultraviolet‐visible spectrophotometry for the determination of rhodamine 6G and crystal violet in textile wastewater

Polypyrrole‐magnetite dispersive micro‐solid‐phase extraction method combined with ultraviolet‐visible spectrophotometry was developed for the determination of selected cationic dyes in textile wastewater. Polypyrrole‐magnetite was used as adsorbent due to its thermal stability, magnetic properties, and ability to adsorb Rhodamine 6G and crystal violet. Dispersive micro‐solid‐phase extraction parameters were optimized, including sample pH, adsorbent amount, extraction time, and desorption solvent. The optimum polypyrrole‐magnetite dispersive micro‐solid phase‐extraction conditions were sample pH 8, 60 mg polypyrrole‐magnetite adsorbent, 5 min of extraction time, and acetonitrile as the desorption solvent. Under the optimized conditions, the polypyrrole‐magnetite dispersive micro‐solid‐phase extraction with ultraviolet‐visible method showed good linearity in the range of 0.05–7 mg/L (R ² > 0.9980). The method also showed a good limit of detection for the dyes (0.05 mg/L) and good analyte recoveries (97.4–111.3%) with relative standard deviations < 10%. The method was successfully applied to the analysis of dyes in textile wastewater samples where the concentration found was 1.03 mg (RSD ±7.9%) and 1.13 mg/L (RSD ± 4.6%) for Rhodamine 6G and crystal violet, respectively. It can be concluded that this method can be adopted for the rapid extraction and determination of dyes at trace concentration levels.     

GC-MS法测定氧化型染发剂中的苯二胺

建立了气相色谱-质谱同时测定氧化型染发剂中邻苯二胺、间苯二胺和对苯二胺的方法。以乙酸乙酯提取氧化型染发剂中苯二胺,用气相色谱-质谱方法进行定性和定量分析。该方法对氧化型染发剂中的3种苯二胺的检出限为20 mg/kg,线性范围为0.2~10 mg/L,线性相关系数为0.999 2~0.999 9。方法的回收率为75%~110%,满足氧化型染发剂中3种苯二胺检测的需要。     

毛细管电泳-场强放大样品堆积法检测染发剂中的7种苯胺类物质

建立了毛细管电泳-场强放大样品堆积测定染发剂中4,4′-二氨基二苯甲烷、苯胺、邻甲氧基苯胺、对氨基苯甲醚、3,4-二甲基苯胺、间氨基苯酚、1-萘胺7种苯胺类物质的分析方法。在优化的缓冲溶液体系(0.15 mol/L NaH2PO4,0.015 mol/L 三乙醇胺, pH 2.3)下7种分析物在6.5 min内实现基线分离。考察了样品中添加的磷酸浓度和乙腈浓度、水柱长度、电动进样时间与电压对场强放大富集效率及重现性的影响。最佳的富集条件为: 水柱注入3.45 kPa(0.5 psi)×6 s,样品中添加40%(v/v)乙腈和0.6×10~3mol/L磷酸,进样电压与进样时间为10 kV×10 s。线性范围为3～1000 μg/L(R2＞0.996),检出限为0.26～2.75 μg/L,将已有方法的检测灵敏度提高了1～3个数量级。在2种市售黑色染发剂中均检测到间氨基苯酚,含量分别为7.32 mg/g和1.34 mg/g。平均加标回收率为74%～108%。该方法灵敏度高、快速、重现性好、成本低,可供多种样品基质中痕量苯胺类污染物及其他阳离子物质的测定借鉴使用。     

A method for the analysis of intermediates of oxidative hair dyes in cosmetic products

A method has been developed and validated for the analysis of some commonly used intermediates of oxidative hair dyes: phenylenediamines, toluenediamines, aminophenols, 1-Naphthol, resorcinol, and hydroquinone. The target analytes are ion-paired prior to HPLC analysis with gradient elution employing phosphate buffer-acetonitrile as mobile phase and detection in the wavelength range 220–400 nm by a photodiode array detector. A spectral-library, consisting of 220–400 nm spectra of the target substances and their HPLC retention times, has been prepared for the identification. A method of sample preparation was established and applied to the analysis of a series of cosmetic formulations for hair dyeing. The method has been found to be suitable for routine analysis of the target intermediates of oxidative hair dyes, and it may also be suitable for the analysis of some non-target intermediates of these substances.     

超高效液相色谱-串联质谱法同时测定染发剂中6种染料

建立了同时测定染发剂中4,4'-二氨基二苯胺硫酸盐和2,4-二氨基苯酚硫酸盐等6种染料的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法.以水为提取剂进行超声提取,用Waters BEH-C₁₈柱(100 mm×2.1 mm, 1.7 μm)分离,以10 mmol/L的乙酸铵和乙腈为流动相进行梯度洗脱.在电喷雾正离子模式下,采用多反应监测(MRM)模式进行定性和定量分析.6种染料在相应的质量浓度范围内线性关系良好,线性相关系数(R²)均大于0.99,检出限为0.26~4.6 mg/kg,回收率为83.0%~92.2%,相对标准偏差为5.4%~11.2%.方法精密度、准确度、回收率和基质效应均符合染发剂样品测定的要求,用于实际样品测定,结果满意.本方法准确、简便、快速,适用于染发剂中6种染料的分析测定.