CN105548081A - 一种测定水中溶解性腐殖酸分子量分布的方法 - Google Patents
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Abstract
本发明公开了一种测定水中溶解性腐殖酸分子量分布的方法,包括如下步骤:1)用总有机碳分析仪测定水溶液中溶解性腐殖酸的总有机碳值；取溶解性腐殖酸水溶液，用去离子水分别稀释；2)用进样器取10ml注入后面串联有多角度激光光散射仪和紫外可见光检测器的非对称场流分析仪中，进行检测；3)利用非对称场流分析仪自带软件对多角度激光光散射仪检测得到的光散射信号峰和紫外可见光检测器检测得到的紫外可见光信号峰进行积分，得腐殖酸分子量分布图。本发明的方法根据粒子大小进行分离，分离过程没有固定相填料，不存在固定相与样品的剪切作用，有利于保留颗粒的完整性。能够获得溶解性腐殖酸的连续性分布，操作简单，成本低。
Description
技术领域
本发明涉及水体溶解性有机物的测定，具体涉及一种测定水中溶解性腐殖酸分子量分布的方法。
背景技术
腐殖酸是水体有机污染物的主要组成部分，主要来源于动植物残体的分解。腐殖酸在天然水体中主要以胶体形式存在，含量约数十毫克每升。它是以多元酚及醌为芳香中心的多聚物，结构十分复杂，没有固定的分子式和分子量，具有疏松的“海绵状”结构，所以具有巨大的表面积和表面能；对痕量金属具有较强的络合能力，可以与众多金属离子形成络合物或鳌合物，对水体其他污染物的迁移转化和毒性具有重要影响。腐殖酸含有较多的活性官能团，其形态特征容易受水环境条件(pH、浓度、阴阳离子浓度、固体颗粒等)的影响，腐殖酸本身的特性是影响其与其他物质络合的根本因素。了解腐殖酸在水环境中的大小及分布对于腐殖酸的特性及其迁移转化规律具有十分重要的意义。
有机物分子量分布常采用凝胶尺寸排阻法进行测定，其原理主要是根据溶液中样品组分的流体力学体积大小进行分离的，由于不同分子量组分所拥有的流体力学体积不同，其在色谱柱中所受到的固定相的阻力也不同，使得被分离样品组分按分子量大小先后流出色谱柱。然而，对于高分子量粒子的分离，尺寸排阻法由于孔径排阻的作用不能将其完全分开。
非对称流动场场流分析仪，是用一个没有固定相的、空心的、扁平的分离通道代替了传统的凝胶渗透色谱柱，同时在垂直于样品流的方向上施加一个分离力，从而实现对样品的分离。目前，尚未有用非对称流动场场流分析仪对水中溶解性腐殖酸分子量分布测定的报道。
发明内容
本发明的目的是克服现有技术的不足，提供一种测定水中溶解性腐殖酸分子量分布的方法。
本发明的技术方案概述如下：
一种测定水中溶解性腐殖酸分子量分布的方法，包括如下步骤:
1)用总有机碳分析仪测定溶解性腐殖酸水溶液中溶解性腐殖酸的总有机碳值；取溶解性腐殖酸水溶液，用去离子水分别稀释至溶解性腐殖酸浓度为10mg/L-20mg/L；
2)用进样器取10ml步骤1)所得溶液注入后面串联有多角度激光光散射仪和紫外可见光检测器的非对称场流分析仪中，进行检测；
3)利用非对称场流分析仪自带软件对多角度激光光散射仪检测得到的光散射信号峰和紫外可见光检测器检测得到的紫外可见光信号峰进行积分，得腐殖酸分子量分布图。
非对称场流分析仪采用300DaPES(聚醚砜)膜；分离系统的参数：进样过程主流流速为0.5ml/min，交叉流流速为3.0ml/min；洗脱过程采用梯度洗脱，交叉流流速在20min内从3ml/min线性降为0.25ml/min，又在2.5min内降至0.1ml/min，最后在3.5min内降到0.01ml/min后保持恒定。
步骤1)所得溶液在多角度激光光散射器和紫外可见光检测器内的流速均为0.4ml/min，紫外可见光检测器的吸收波长设为254nm。
本发明具有以下优点：
1.根据粒子大小进行分离，分离过程没有固定相填料，不存在固定相与样品的剪切作用，有利于保留颗粒的完整性。
2.能够获得溶解性腐殖酸的连续性分布，了解溶解性腐殖酸的分子量分布及其相对含量，且操作简单，成本低。
附图说明
图1为溶解性腐殖酸分子量分布(图1A：10mg/L；图1B：15mg/L；图1C：20mg/L)
具体实施方式
下面结合具体实施例对本发明作进一步地说明。
实施例1
溶解性腐殖酸水溶液的配制：准确称取腐殖酸样品0.5g，加入0.1mol/LNaOH水溶液20ml；搅拌24小时，通过孔径为0.45μm的滤膜过滤，得滤液；加水定容至1000毫升得溶解性腐殖酸水溶液。所述腐殖酸样品购自天津市莱博生物公司。
实施例2
一种测定水中溶解性腐殖酸分子量分布的方法，包括如下步骤:
1)用总有机碳分析仪(TOC-VCPH)测定溶解性腐殖酸水溶液中溶解性腐殖酸的总有机碳值(TOC)；取溶解性腐殖酸水溶液，用去离子水分别稀释至溶解性腐殖酸浓度为10mg/L、15mg/L、20mg/L；
2)三个浓度的样品分别测定，用进样器取10ml步骤1)所得其中一种溶液注入后面串联有多角度激光光散射仪和紫外可见光检测器的非对称场流分析仪中，进行检测；
3)利用非对称场流分析仪自带软件对多角度激光光散射仪检测得到的光散射信号峰和紫外可见光检测器检测得到的紫外可见光信号峰进行积分，得腐殖酸分子量分布图，结果见图1，结果表明，溶解性腐殖酸浓度为10mg/L时，分子量主要在104-107范围内，其中105-106范围内含量最大；当腐殖酸浓度为15mg/L时，分子量基本都集中在105-106范围内；腐殖酸浓度为20mg/L时，分子量分布与浓度为15mg/L时相似。
优选的，非对称场流分析仪采用300Da聚醚砜膜；分离系统的参数：进样过程主流流速为0.5ml/min，交叉流流速为3.0ml/min；洗脱过程采用梯度洗脱，交叉流流速在20min内从3.0ml/min线性降为0.25ml/min，又在2.5min内降至0.1ml/min，最后在3.5min内降到0.01ml/min后保持恒定。
步骤1)所得溶液在多角度激光光散射器和紫外可见光检测器内的流速均为0.4ml/min，紫外可见光检查器的吸收波长设为254nm。
非对称场流分离技术原理：非对称场流分离是依靠流体力学作用进行分离，它将流体与外场联合作用于待分离物质，利用样品质量、大小和密度等性质的差异实现分离。最初是在1986年提出，样品的分离通道为长为25-90cm，宽为2cm左右，厚度在50-500μm之间的扁平带状流道，流动相由泵从流道的入口注入，在流道中携带样品以抛物线型的层流流动，流道上壁面是透明的玻璃板，下壁面由多孔的熔块和其上面溶剂可以透过的半透膜组成，在交叉流泵的抽力作用下形成垂直主流的交叉流；样品在交叉流的作用下向下壁面积聚。由于扩散作用，使得不同大小的样品分子离开累积壁的距离不同，其在主流方向上的流速也不同，距离累积壁面较远的组分速度较大，会先被洗脱出来，这样不同的样品组分就会被分离开。
Claims (3)
1.一种测定水中溶解性腐殖酸分子量分布的方法,其特征是包括如下步骤:
1)用总有机碳分析仪测定溶解性腐殖酸水溶液中溶解性腐殖酸的总有机碳值；取溶解性腐殖酸水溶液，用去离子水分别稀释至溶解性腐殖酸浓度为10mg/L-20mg/L；
2)用进样器取10ml步骤1)所得溶液注入后面串联有多角度激光光散射仪和紫外可见光检测器的非对称场流分析仪中，进行检测；
3)利用非对称场流分析仪自带软件对多角度激光光散射仪检测得到的光散射信号峰和紫外可见光检测器检测得到的紫外可见光信号峰进行积分，得腐殖酸分子量分布图。
2.根据权利要求1所述的方法,其特征是非对称场流分析仪采用300Da聚醚砜膜；
分离系统的参数：进样过程主流流速为0.5ml/min，交叉流流速为3.0ml/min；
洗脱过程采用梯度洗脱，交叉流流速在20min内从3ml/min线性降为0.25ml/min，又在2.5min内降至0.1ml/min，最后在3.5min内降到0.01ml/min后保持恒定。
3.根据权利要求1所述的方法，其特征是步骤1)所得溶液在多角度激光光散射器和紫外可见光检测器内的流速均为0.4ml/min，紫外可见光检查器的吸收波长设为254nm。
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| MATS ANDERSSON: "Ultrahigh Molar Mass Component Detected in Ethylhydroxyethyl Cellulose by Asymmetrical Flow Field-Flow Fractionation Coupled to Multiangle Light Scattering", 《ANAL.CHEM.》 * |
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