CN101021515A - Method for in-situ sampling, separating enriching and measuring heavy metal ion in water body - Google Patents

Method for in-situ sampling, separating enriching and measuring heavy metal ion in water body Download PDF

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CN101021515A
CN101021515A CN 200710010553 CN200710010553A CN101021515A CN 101021515 A CN101021515 A CN 101021515A CN 200710010553 CN200710010553 CN 200710010553 CN 200710010553 A CN200710010553 A CN 200710010553A CN 101021515 A CN101021515 A CN 101021515A
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water
heavy metal
metal ions
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2ml
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CN 200710010553
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CN101021515B (en
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隋殿鹏
孙挺
范洪涛
刘畅
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东北大学
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Abstract

A method to sample in situ, separate, enrich and measure heavy metal ion in waters. Its steps contain: (1) Puts some high-molecular compound being capable of occurring chemical reaction with heavy metal ion into device and uses a semi-permeable membrane being able to permeate heavy metal ion to cover it. (2) Puts device into waters and detaches it from waters by membrane. (3) Sets in waters for a period of time. Recur to osmosis of membrane, heavy metal ion enters into back of device to occur chemical reaction with high-molecular compound. (4) Takes out device located in waters to measure concentration and mean concentration of heavy metal in waters by atomic absorption spectrometry. It is characterized in that simple, economical, providing concentration and measurement in situ for much heavy metal, has selectivity.

Description

一种在水体中原位取样、分离、富集、测量重金属离子的方法 A water-situ sampling, separation, enriching, measuring method of heavy metal ions

技术领域 FIELD

本发明涉及化学及环境监测技术领域,特别涉及一种在水体中原位取样、分离、富集、测量重金属离子的方法。 The present invention relates to chemical and environmental monitoring technology, and particularly relates to a water-situ sampling, separation, enriching, measuring method of heavy metal ions.

背景技术 Background technique

环境中的无机污染物以重金属比较突出,主要是由于重金属不能被微生物分解并且易于积累转化。 Inorganic heavy metal pollutants in the environment to more prominent, mainly due to the heavy metals can not be decomposed by microorganisms and the conversion tend to accumulate. 有的甚至能通食物链在人体内以有害浓度积累。 Some even can accumulate through the food chain to harmful concentrations in the human body. 环境中重金属污染主要有汞、镉、铅、铜、铬、砷、镍、铁(砷虽然不属于重金属,但因其来源、危害都与重金属相似,故通常列入重金属行列讨论)。 Heavy Metal pollution mainly mercury, cadmium, lead, copper, chromium, arsenic, nickel, iron (although not arsenic metal, but because the source of harmful heavy metals are similar, it is usually included in the ranks of heavy metals discussed). 天然水中痕量金属离子的可靠测量对于污染和痕量元素回收的研究具有重要意义。 Reliable measurement of trace metal ions in natural water is important for the study of contamination of trace elements and recovered. 但由于环境样品被测物浓度低、组分复杂、干扰物多、同一元素以多元形式存在、易受环境影响而变化,通常检测方法都要经过复杂的前处理后才能进行分析测定。 However, due to the low concentration of analyte environmental samples, complex components, multiple interferent, the same elements are present in the form of polyols, environmentally sensitive, and is generally go through the complicated method of detecting the front handling to analysis. 经典的前处理方法不仅要靠人工操作,工作强度大,处理周期长,需要大量有机溶剂,而且重现性差,为分析工作带来了很大的误差。 The classic pretreatment methods rely on manual operation only, work intensity, long processing cycle, requires a large amount of organic solvents, and poor reproducibility, a big error analysis. 因此减少前处理过程的新技术的研究对环境分析化学乃至分析化学都具有重要的意义。 So the research of new technologies to reduce the pre-treatment process of environmental analytical chemistry and the chemical analysis has important significance.

发明内容 SUMMARY

针对现有技术存在的问题,本发明提供一种在水体中原位取样、分离、富集、测量重金属离子的方法。 For the presence of the prior art, the present invention provides an in situ water sampling, separation, enrichment, measurement method of heavy metal ions.

本发明在水溶液中原位取样、富集和定量测量重金属离子的方法主要利用高分子化合物上的特性基团与外界水溶液中被监测物质或被监测物质上的特性基团的化学反应,达到原位取样、富集和定量测量的目的。 The present invention in situ in an aqueous solution sample, and quantitative measurement of the enrichment of heavy metal ions of the main characteristics of using a chemical reaction on the outside with an aqueous solution of a polymer compound groups are groups of the material characteristics of the monitor or the monitored substances, to achieve in situ sampling purposes, enrichment and quantitative measurements.

本发明方法包括:(1)取一定量能够与重金属离子发生化学反应的高分子化合物放入装置内,用能够透过重金属离子的半透膜将装置封好;(2)将上述含有高分子化合物的装置放入含有重金属离子的水体中,使装置内的高分子化合物与水体被膜分开;(3)在水体中放置一段时间,利用膜的渗透作用,水体中的重金属离子进入到被膜隔离的装置内部后,与高分子化合物发生化学反应;(4)取出放在水体中的装置,用原子吸收光谱法测定重金属的浓度,并计算放置时间内水体中重金属的平均浓度。 The method of the present invention comprises: a polymer compound (1) a certain amount capable of chemically reacting with heavy metal ions into the apparatus, with the heavy metal ions can be through the semipermeable membrane of the seal means good; (2) The above polymer comprising It means a compound containing water of heavy metal ions into the body of water in the polymer compound coating apparatus separated; (3) placed in the water for some time, using osmosis membrane, heavy metal ions into the water film isolated after the inside of the device, a polymer compound with a chemical reaction occurs; (4) water extraction device is placed, the concentration of heavy metals was measured by atomic spectroscopy absorption, and calculates the average concentration of heavy metals in water is placed within the time.

本发明中能与重金属离子反应的高分子化合物为羧甲基纤维素、羧甲基壳聚糖、聚丙烯酸钠。 The polymer compound of the present invention can react with heavy metal ions is a carboxymethyl cellulose, carboxymethyl chitosan, sodium polyacrylate.

本发明的方法中所述水溶液包括:天然淡水、天然矿化水、污水、饮用水、回用水、生物体内水、沉积物和土壤中的水。 The method of the present invention comprises an aqueous solution of: natural fresh water, natural mineral water, waste water, drinking water, water for back-vivo water, sediment and soil water.

本发明方法所用的装置为一种原位取样、分离、富集、测量的装置,如附图所示:该装置是在容器内装有高分子化合物,然后用半透膜将其封好,并通过橡皮垫和夹紧器将其固定即可。 The method of the present invention, apparatus is used in an in-situ sampling, separation, enriching, measuring apparatus, as shown in the drawings: the apparatus is a polymer compound in the container contents, and then a semipermeable membrane which is sealed, and by the rubber mat and the clamp can be fixed.

溶液中的物质可通过一个简单的方程式来表示:M+nL→ M(L)nM:被监测物质;L:结合相(过量);M(L)n:被监测物质与高分子化合物形成的络合物。 Substances in solution may be represented by a simple equation: M + nL → M (L) nM: the substance being monitored; L: Phase binding (excess); M (L) n: monitoring material and a polymer compound is formed complex.

在本发明中,大分子的扩散可能被半透膜影响。 In the present invention, the diffusion of macromolecules may be semi-permeable membranes. 但是简单的金属离子或小分子有机化合物则可以自由地扩散,并产生一个有效的扩散系数。 But the simple metal ions or small organic molecules can diffuse freely, and produces an effective diffusion coefficient. 这与它们在水中的扩散没有区别。 It makes no difference in the diffusion of water with them. 因此本发明允许分子体积小于半透膜孔道的可溶性物质自由扩散。 Thus the present invention allows the molecules of soluble substances semipermeable membrane pore volume is less than the free diffusion.

本发明方法中,能够渗透被监测物质的半透膜有透析膜、色谱纸、渗析膜、生物膜、胶棉薄膜、玻璃纸、羊皮纸、动物膀胱膜等。 The method of the present invention, are capable of penetrating semi-permeable membrane material has monitored a dialysis membrane, paper chromatography, dialysis membranes, the biofilm, collodion film, glassine paper, parchment, film or animal bladder. 能透过重金属离子的半透膜为各种类型半透膜或选择性透过膜,其允许透过分子量大于或等于2000。 A semipermeable membrane permeable for all types of heavy metal ions or semipermeable membrane selectively permeable membrane which permits passage of molecular weight greater than or equal to 2000.

本发明方法中,在膜内侧含有能够与被监测物质相结合的高分子:其平均分子量应大于3000,其水溶液浓度为0.0001-1.0mol·L-1。 The method of the present invention, the inner membrane contains a polymer capable of being monitored substance combination: an average molecular weight greater than 3000, an aqueous solution thereof at a concentration of 0.0001-1.0mol·L-1. 如果半透膜孔隙小,则所用高分子的平均分子量可小些,如果半透膜孔隙大,则所用高分子的平均分子量应大些,总的原则只能允许被监测物质自由通过半透膜扩散,而不能使膜内侧的高分子渗透到外界水相中。 If the semipermeable membrane pores is small, the average molecular weight of the polymer used can be smaller, if the semipermeable membrane pores large, then the average molecular weight of polymer used should be larger, the general principle only allow the substance to be monitored through a semipermeable membrane consisting of diffusion, the polymer film can not permeate to the outside of the inner aqueous phase. 放入水体中的时间为1小时~1年。 Into a body of water for 1 hour to 1 year. 在一个被监测物质浓度不断变化的水体中长期放置,可得到在此时间(t)范围内体系中被监测物质的平均浓度(Cm),Cm=Csample/t,式中Csample为测量浓度。 Long-term placement in a monitored substance concentration is constantly changing body of water, is obtained this time (t) is the average concentration of the substance monitored (Cm is) in the range of the system, Cm = Csample / t, where Csample concentration measurement.

本发明方法中的被监测重金属离子,例如:Cu,Cd,Co,Zn,Pb,Ni,Cr,Fe,U,Mn,Ag,Hg,Be,Tl,Tu,Re,V,Ti。 Heavy metal ions to be monitored in the method of the present invention, for example: Cu, Cd, Co, Zn, Pb, Ni, Cr, Fe, U, Mn, Ag, Hg, Be, Tl, Tu, Re, V, Ti.

本发明方法中,所用高分子化合物的特点是它们都能与被监测物质发生化学反应,并与被监测物质牢牢结合,使得膜内侧的高分子溶液中游离被监测物质的浓度始终保持为零。 The method of the present invention, the polymer compound feature is that they can react chemically with the monitored substances, and are firmly bound substance and monitored, so that the polymer solution inside the membrane is monitored concentration of free substance remains zero .

本方法的主要优点有:(1)简单,经济。 The main advantages of this method are: (1) simple and economical.

(2)可以提供原位浓度。 (2) may be provided in situ concentration.

(3)可以测量多种物质。 (3) a variety of substances can be measured.

(4)具有选择性。 (4) selective. 不是测量自然水中所有的物质,只能测量那些在结合相中能被富集的物质。 Not measure all the natural substances in water, it can only measure those substances that can be combined phase enrichment.

(5)定量测量与结合相摄取的被监测物质的动力学和半透膜的特性有关。 (5) quantitative measurements of binding properties with kinetics and uptake was monitored semipermeable membrane related substances.

(6)如果一个适当的半透膜厚度被选定,物质的传输只与分子扩散有关,物质传输过程与流体动力学无关。 (6) if a proper thickness of the semipermeable membrane is selected, only the transport substance related to molecular diffusion, mass transfer process is independent of fluid dynamics.

附图说明 BRIEF DESCRIPTION

附图为本发明水体中原位取样、分离、富集、测量装置结构示意图。 BRIEF situ water sampling, separation, enriching, measuring a schematic structure of the apparatus of the present invention.

图中:1聚四氟乙烯容器、2高分子化合物水溶液、3半透膜、4垫片、5夹紧器具体实施方式实施例1取2mL0.0001M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 FIG: a Teflon container, an aqueous solution of the polymer compound 2, the semipermeable membrane 3, the spacer 4, 5 clamp the specific embodiments Example 1 embodiment taken 2mL0.0001M carboxymethylcellulose (calculated as carboxyl group concentration) load capacity of the apparatus 2mL of polypropylene, with a dialysis membrane means sealing the well, a total of three, of the device into a body of water contaminated with heavy metals 1h taken place, by atomic absorption spectrometry concentration of heavy metals, and calculates the average concentration of heavy metals is placed within a body of water.

实施例2取2mL0.0001M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 2 taken after 2mL0.0001M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume of embodiment, the paper by chromatography good sealing means, a total of three, of the device into the body of heavy metals in polluted water 1h placed taken out by atomic absorption spectrometry concentration of heavy metals, and the average concentration of heavy metals in the water storage time.

实施例3取2mL 0.0001M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 EXAMPLE 3 After 2mL 0.0001M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume of embodiment, with the collodion film good sealing means, a total of three, of the device into the heavy metal pollution placing a body of water removed 1h, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例4取2mL 0.01M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 EXAMPLE 4 After 2mL 0.01M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume of embodiment, with a dialysis membrane means sealing the well, a total of three, of the device into the body of water contaminated with heavy metals 12h taken placed, by atomic absorption spectrometry concentration of heavy metals, and the average concentration of heavy metals in the water storage time.

实施例5取2mL 0.01M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 5 after taking 2mL 0.01M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, the paper by chromatography good sealing means, a total of three, of the device into the body of heavy metals in polluted water 12h taken placed, by atomic absorption spectrometry concentration of heavy metals, and the average concentration of heavy metals in the water storage time.

实施例6取2mL 0.01M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 6 After taking apparatus 2mL 0.01M carboxymethylcellulose 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a collodion film good sealing means, a total of three, of the device into the heavy metal pollution 12h taken place the water, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例7取2mL 0.02M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 After taking 2mL Example 7 0.02M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a dialysis membrane means sealing the well, a total of three, of the device into the body of heavy metals in polluted water 12h taken placed, by atomic absorption spectrometry concentration of heavy metals, and the average concentration of heavy metals in the water storage time.

实施例8取2mL 0.02M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 8 taken after 2mL 0.02M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, the paper by chromatography good sealing means, a total of three, of the device into the body of heavy metals in polluted water 12h taken placed, by atomic absorption spectrometry concentration of heavy metals, and the average concentration of heavy metals in the water storage time.

实施例9取2mL 0.02M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 9 taken after 2mL 0.02M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a collodion film good sealing means, a total of three, of the device into the heavy metal pollution 12h taken place the water, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例10取2mL 0.0001M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 10 After 0.0001M sodium polyacrylate apparatus taken 2mL 2mL polypropylene (based on monomer concentration) was charged volume, with a dialysis membrane means sealing the well, a total of three, of the device into a body of water contaminated with heavy metals 1h taken place, by atomic absorption spectrometry concentration of heavy metals, and calculates the average concentration of heavy metals in water is placed within the time.

实施例11取2mL 0.0001M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 11 taken after 2mL 0.0001M sodium polyacrylate apparatus 2mL polypropylene (based on monomer concentration) was charged volume, the paper by chromatography good sealing means, a total of three, of the device into a body of water contaminated with heavy metals 1h taken place, by atomic absorption spectrometry concentration of heavy metals, and calculates the average concentration of heavy metals in water is placed within the time.

实施例12取2mL 0.0001M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 12 taken 0.0001M Sodium 2mL polypropylene (calculated as monomer concentration) was charged to a volume of 2mL the apparatus polypropylene, with a good collodion film sealing means, a total of three, of the device into the heavy metal pollution water taken place 1h, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例13取2mL 0.01M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 13 After taking 2mL 0.01M sodium polyacrylate (based on monomer concentration) was charged to a volume of 2mL apparatus of polypropylene, with a dialysis membrane means sealing the well, a total of three, of the device into a body of water contaminated with heavy metals 12h taken place, by atomic absorption spectrometry concentration of heavy metals, and calculates the average concentration of heavy metals in water is placed within the time.

实施例14取2mL 0.01M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 14 0.01M sodium polyacrylate taken after 2mL apparatus 2mL polypropylene (based on monomer concentration) was charged volume, the paper by chromatography good sealing means, a total of three, of the device into a body of water contaminated with heavy metals 12h taken place, by atomic absorption spectrometry concentration of heavy metals, and calculates the average concentration of heavy metals in water is placed within the time.

实施例15取2mL 0.01M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 15 Polypropylene taken after 0.01M sodium 2mL 2mL apparatus polypropylene (based on monomer concentration) was charged volume, with a collodion film good sealing means, a total of three, of the device into the heavy metal pollution water 12h taken place, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例16取2mL 0.02M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 16 After taking 2mL 0.02M sodium polyacrylate (based on monomer concentration) was charged to a volume of 2mL apparatus of polypropylene, with a dialysis membrane means sealing the well, a total of three, of the device into a body of water contaminated with heavy metals 12h taken place, by atomic absorption spectrometry concentration of heavy metals, and calculates the average concentration of heavy metals in water is placed within the time.

实施例17取2mL 0.02M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 After 17 embodiment taken 2mL 0.02M sodium polyacrylate (based on monomer concentration) was charged to a volume of 2mL embodiment apparatus polypropylene, paper chromatography using the good sealing means, a total of three, of the device into a body of water contaminated with heavy metals 12h taken place, by atomic absorption spectrometry concentration of heavy metals, and calculates the average concentration of heavy metals in water is placed within the time.

实施例18取2mL 0.02M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 18 taken 0.02M sodium 2mL polypropylene (calculated as monomer concentration) was charged to a volume of 2mL the apparatus polypropylene, with a good collodion film sealing means, a total of three, of the device into the heavy metal pollution water 12h taken place, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例19取2mL0.0001M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 After taking 2mL0.0001M Example 19 Carboxymethyl apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume of embodiment, with a dialysis membrane means sealing the well, a total of three, of the device into the heavy metal pollution water taken place 1h, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例20取2mL0.0001M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 20 Carboxymethyl 2mL0.0001M after taking apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, paper chromatography using the sealed apparatus, a total of three, of the device into the heavy metal pollution water taken place 1h, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例21取2mL 0.0001M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置1h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 After taking 2mL 0.0001M Example 21 Carboxymethyl apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a collodion film good sealing means, a total of three, heavy metal into a device 1h contaminated water taken place, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例22 Example 22

取2mL 0.01M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 After taking 2mL 0.01M Carboxymethyl apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a dialysis membrane means sealing the well, a total of 3, the device is placed into water of heavy metal pollution 12h taken out by atomic absorption spectrometry concentration of heavy metals, and the average concentration of heavy metals in the water storage time.

实施例23取2mL 0.01M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 23 0.01M taken 2mL carboxymethyl chitosan (calculated as carboxyl group concentration) was charged to a volume of 2mL the apparatus polypropylene, paper chromatography using the sealed apparatus, a total of three, of the device into the heavy metal pollution water 12h taken place, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例24取2mL 0.01M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 After taking 2mL Example 24 Carboxymethyl apparatus 0.01M 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a collodion film good sealing means, a total of three, heavy metal into a device 12h contaminated water taken place, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例25取2mL 0.02M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 After taking 2mL Example 25 Carboxymethyl apparatus 0.02M 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a dialysis membrane means sealing the well, a total of three, of the device into the heavy metal pollution water 12h taken place, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例26取2mL 0.02M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 Example 26 0.02M taken 2mL carboxymethyl chitosan (calculated as carboxyl group concentration) was charged to a volume of 2mL the apparatus polypropylene, paper chromatography using the sealed apparatus, a total of three, of the device into the heavy metal pollution water 12h taken place, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例27取2mL0.02M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共3个,将装置放入重金属污染的水体中放置12h取出,利用原子吸收光谱法测定重金属的浓度,并计算在放置时间内水体中重金属的平均浓度。 After taking 2mL0.02M Example 27 Carboxymethyl apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a collodion film good sealing means, a total of three, heavy metal into a device 12h contaminated water taken place, the concentration of heavy metals was measured by atomic absorption spectrometry, and the average concentration of heavy metals in the water storage time.

实施例28取2mL0.02M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 Example 28 After taking 2mL0.02M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a dialysis membrane means sealing the well, a total of 21, the natural water bodies or heavy metal into the device polluted water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and the average concentration of metal ions in the aqueous system storage time.

实施例29取2mL0.02M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 Example 29 After taking 2mL0.02M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume of embodiment, the paper by chromatography good sealing means, a total of 21, the natural water bodies or heavy metal into the device polluted water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and the average concentration of metal ions in the aqueous system storage time.

实施例30取2mL 0.02M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 Example 30 After taking apparatus 2mL 0.02M carboxymethylcellulose 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a collodion film good sealing means, a total of 21, the natural water bodies into the device or heavy metal polluted water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and calculating the mean concentration time placed in an aqueous metal ions.

实施例31取2mL0.02M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 Example 31 after the apparatus taken 2mL0.02M sodium polyacrylate 2mL polypropylene (based on monomer concentration) was charged volume, with a dialysis membrane means sealing the well, a total of 21, the heavy metal contamination of the device or into natural waters water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and the average concentration of metal ions in the aqueous system storage time.

实施例32取2mL0.02M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 After taking 2mL0.02M Example 32 Sodium polyacrylate (calculated as monomer concentration) was charged to a volume of 2mL embodiment apparatus of polypropylene, the paper by chromatography good sealing means, a total of 21, the heavy metal contamination of the device or into natural waters water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and the average concentration of metal ions in the aqueous system storage time.

实施例33取2mL 0.02M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 After Example 33 0.02M sodium polyacrylate apparatus taken 2mL 2mL polypropylene (based on monomer concentration) was charged volume, with a collodion film good sealing means, a total of 21, or the apparatus into natural water heavy metals in polluted water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and the average concentration of metal ions in the aqueous system storage time.

实施例34取2mL0.02M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 After taking 2mL0.02M Example 34 Carboxymethyl apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a dialysis membrane means sealing the well, a total of 21, or the apparatus into natural water heavy metals in polluted water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and the average concentration of metal ions in the aqueous system storage time.

实施例35取2mL 0.02M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 After Example 35 Carboxymethyl taken 2mL 0.02M apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, the paper by chromatography good sealing means, a total of 21, or the apparatus into natural water heavy metals in polluted water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and the average concentration of metal ions in the aqueous system storage time.

实施例36取2mL0.02M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用火棉胶薄膜将装置封好,共21个,将装置放入自然水体或重金属污染水体中,放置1周,每天取出3个,利用原子吸收光谱法测定水体中金属离子、并计算在放置时间内水系中金属离子的平均浓度。 Example 36 Carboxymethyl 2mL0.02M after taking apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a collodion film good sealing means, a total of 21, into the natural means water or heavy metal polluted water, for one week, a day out of three, the metal ion water was measured by atomic absorption spectrometry, and the average concentration of metal ions in the aqueous system storage time.

实施例37取2mL 0.05M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共36个,将装置放入自然水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定自然水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 37 taken 2mL 0.05M carboxymethylcellulose apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume of embodiment, with a dialysis membrane means sealing the well, a total of 36, a device placed in a natural water system, in a place, remove the 3 month, natural water determined by atomic absorption spectrometry of the metal ion, and calculate the rest time in the average concentration of metal ions in aqueous and can understand the relationship between the concentration of metal ions and metal ion concentrations seasons changes in the year.

实施例38取2mL 0.05M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共36个,将装置放入被监测水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定自然水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 Example 38 After taking apparatus 2mL 0.05M carboxymethylcellulose 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, the paper by chromatography good sealing means, a total of 36, of the device into the aqueous system to be monitored , placed in 1, taken three month, natural water determined by atomic absorption spectrometry of the metal ion, and calculate the rest time in the average concentration of metal ions in aqueous and can understand the relationship between the concentration of metal ions and metal ions and seasonal concentration changes throughout the year.

实施例39取2mL 0.05M羧甲基纤维素(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用胶棉薄膜将装置封好,共36个,将装置放入被监测水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定自然水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 Example 39 After taking apparatus 2mL 0.05M carboxymethylcellulose 2mL of polypropylene (calculated as carboxyl group concentration) was charged to a volume, will be better with a collodion film sealing means, a total of 36, a device to be monitored into an aqueous allowed to stand for 1 year, month 3 taken, natural water determined by atomic absorption spectrometry of the metal ion, and calculate the rest time in the average concentration of metal ions in aqueous and can understand the relationship between the concentration of metal ions and metal seasons ion concentration changes throughout the year.

实施例40取2mL 0.05M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共36个,将装置放入自然水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定自然水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 Example 40 0.05M sodium polyacrylate taken after 2mL apparatus 2mL polypropylene (based on monomer concentration) was charged volume, with a dialysis membrane means sealing the well, a total of 36, a device placed in a natural water system, is placed 1 year, 3 month removed, determined by atomic nature of metal ions in the aqueous absorption spectrometry, and calculating the mean concentration time placed in an aqueous metal ions can understand the relationship between the concentration of metal ions and metal ion concentration in the season changes throughout the year.

实施例41取2mL 0.05M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共36个,将装置放入被监测水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定自然水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 41 taken 0.05M sodium polyacrylate Example 2mL apparatus after 2mL polypropylene (based on monomer concentration) was charged volume, paper chromatography using the sealed apparatus, a total of 36, of the device into the aqueous system to be monitored, in a place, remove the 3 month, natural water determined by atomic absorption spectrometry of the metal ion, and calculate the rest time in the average concentration of metal ions in aqueous and can understand the relationship between the concentration of metal ions and metal ion concentrations seasons changes in the year.

实施例42取2mL 0.05M聚丙烯酸钠(按单体浓度计算)装入容积为2mL的聚丙烯的装置后,用胶棉薄膜将装置封好,共36个,将装置放入被监测水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定自然水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 Example 42 0.05M sodium polyacrylate after taking 2mL 2mL apparatus polypropylene (based on monomer concentration) was charged to a volume, will be better with a collodion film sealing means, a total of 36, of the device into the aqueous system to be monitored , placed in 1, taken three month, natural water determined by atomic absorption spectrometry of the metal ion, and calculate the rest time in the average concentration of metal ions in aqueous and can understand the relationship between the concentration of metal ions and metal ions and seasonal concentration changes throughout the year.

实施例43取2mL0.05M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用透析膜将装置封好,共36个,将装置放入被监测水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定自然水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 After taking 2mL0.05M Example 43 Carboxymethyl apparatus 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, with a dialysis membrane means sealing the well, a total of 36, a device to be monitored into an aqueous allowed to stand for 1 year, month 3 taken, natural water determined by atomic absorption spectrometry of the metal ion, and calculate the rest time in the average concentration of metal ions in aqueous and can understand the relationship between the concentration of metal ions and metal seasons ion concentration changes throughout the year.

实施例44取2mL 0.05M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用色谱纸将装置封好,共36个,将装置放入自然水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定被监测水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 After taking 2mL Example 44 Carboxymethyl apparatus 0.05M 2mL of polypropylene (calculated as carboxyl group concentration) was charged volume, the paper by chromatography good sealing means, a total of 36, a device placed in an aqueous Nature , placed in 1, 3 month removed, by atomic absorption spectrometry was monitored in an aqueous metal ion, and calculate the rest time in the average concentration of metal ions in aqueous and can understand the relationship between the concentration of metal ions and metal seasons ion concentration changes throughout the year.

实施例45取2mL 0.05M羧甲基壳聚糖(按羧基浓度计算)装入容积为2mL的聚丙烯的装置后,用胶棉薄膜将装置封好,共36个,将装置放入自然水系中,放置1年,每个月取出3个,利用原子吸收光谱法测定被监测水系中金属离子、并计算在放置时间内水系中金属离子的平均浓度并可了解金属离子浓度与季节的关系以及金属离子浓度在全年的变化情况。 After taking 2mL Example 45 Carboxymethyl apparatus 0.05M 2mL of polypropylene (calculated as carboxyl group concentration) was charged to a volume, will be better with a collodion film sealing means, a total of 36, of the device into natural water allowed to stand for 1 year, month 3 taken, by atomic absorption spectrometry was monitored in an aqueous metal ion, and calculate the rest time in the average concentration of metal ions in aqueous and can understand the relationship between the concentration of metal ions and seasons metal ion concentration changes throughout the year.

Claims (7)

1.一种在水体中原位取样、分离、富集、测量重金属离子的方法,其特征在于该方法包括以下步骤:(1)取一定量能够与重金属离子发生化学反应的高分子化合物放入装置内,用能够透过重金属离子的半透膜将装置封好,所述能与重金属离子反应的高分子化合物为羧甲基纤维素或羧甲基壳聚糖或聚丙烯酸钠;(2)将上述含有高分子化合物的装置放入含有重金属离子的水体中,使装置内的高分子化合物与水体被膜分开;(3)在水体中放置一段时间,利用膜的渗透作用,水体中的重金属离子进入到被膜隔离的装置内部后,与高分子化合物发生化学反应;(4)取出放在水体中的装置,测定重金属的浓度,并计算放置时间内水体中重金属的平均浓度。 An in situ sampling in the water, separation, enrichment, measurement method of heavy metal ions, characterized in that the method comprises the steps of: (1) a certain amount capable of chemically reacting with a polymer compound of the heavy metal ions into the apparatus the use of heavy metal ions can be through the semipermeable membrane will be better seal means, said heavy metal ions can react with the polymer compound is carboxymethylcellulose or sodium polyacrylate or carboxymethyl chitosan; (2) said means containing a polymer compound of the heavy metal ions into the water containing the polymer compound with water in the coating apparatus separated; (3) placed in the water for some time, using osmosis membrane, heavy metal ions into the water after the inside of the device isolation film, a chemical reaction occurs with the polymer compound; (4) water extraction device is placed, the concentration of heavy metals was measured, and calculates the average concentration of heavy metals in water is placed within the time.
2.如权利要求1所述的在水体中原位取样、分离、富集、测量重金属离子的方法,其特征在于所述能与重金属离子反应的高分子化合物,其平均分子量大于3000,其水溶液浓度为0.0001-1.0mol·L-1。 2. The aqueous solution of its water-situ sampling in claim 1, separate, enrich, method of measurement of heavy metal ions, wherein the polymer compound capable of reacting with heavy metal ions having an average molecular weight greater than 3000, It is 0.0001-1.0mol·L-1.
3.如权利要求1所述的在水体中原位取样、分离、富集、测量重金属离子的方法,其特征在于所述能透过重金属离子的半透膜为各种类型半透膜或选择性透过膜,其允许透过分子量大于或等于2000。 In claim 1, said water-situ sampling, separation, enrichment, measurement method of heavy metal ions, wherein said heavy metal ion-permeable semipermeable membrane is a semipermeable membrane, or various types of selective permeable membrane which permits passage of molecular weight greater than or equal to 2000.
4.如权利要求3所述的在水体中原位取样、分离、富集、测量重金属离子的方法,其特征在于所述各种类型半透膜或选择性透过膜,包括透析膜、色谱纸、渗析膜、生物膜、胶棉薄膜、玻璃纸、羊皮纸、动物膀胱膜。 4. In situ sampling of the body of water 3, separation, enrichment, measurement method of heavy metal ions, characterized in that the various types of permselective membrane or a semipermeable membrane, comprising a dialysis membrane, as claimed in claim chromatography paper , dialysis membrane, biofilm, collodion film, glassine paper, parchment, animal bladder membrane.
5.如权利要求1所述的在水体中原位取样、分离、富集、测量重金属离子的方法,其特征在于所述装置放入水体中的时间为1小时~1年。 5. In situ sampling of the body of water 1, separation, enrichment, measurement method of heavy metal ions, characterized in that said apparatus into a body of water for 1 hour to 1 year claims.
6.如权利要求1所述的在水体中原位取样、分离、富集、测量重金属离子的方法,其特征在于所述重金属离子包括:Cu,Cd,Co,Zn,Pb,Ni,Cr,Fe,U,Mn,Ag,Hg,Be,Tl,Tu,Re,V,Ti。 In water according to claim 1, said situ sampling, separation, enrichment, measurement method of heavy metal ions, wherein said heavy metal ions comprising: Cu, Cd, Co, Zn, Pb, Ni, Cr, Fe , U, Mn, Ag, Hg, Be, Tl, Tu, Re, V, Ti.
7.如权利要求1所述的在水体中原位取样、分离、富集、测量重金属离子的方法,其特征在于所述水体包括:天然淡水、天然矿化水、污水、饮用水、回用水、生物体内水、沉积物和土壤中的水。 In water according to claim 1, said situ sampling, separation, enrichment, measurement method of heavy metal ions, characterized in that said body of water comprising: a natural fresh water, natural mineral water, waste water, drinking water, recycled water, vivo water, sediment and soil water.
CN 200710010553 2007-03-09 2007-03-09 Method for in-situ sampling, separating enriching and measuring heavy metal ion in water body CN101021515B (en)

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CN102841062B (en) * 2012-08-24 2015-02-25 渤海大学 Method for selectively and quantitatively collecting and measuring chromium (VI) in aquatic environment
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