CN104677977A - Method for measuring trace mercury and cadmium in water by cloud point extraction-inductively coupled plasma (ICP)-mass spectrometry (MS) combination - Google Patents
Method for measuring trace mercury and cadmium in water by cloud point extraction-inductively coupled plasma (ICP)-mass spectrometry (MS) combination Download PDFInfo
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Abstract
The invention discloses a method for measuring trace mercury and cadmium in water by cloud point extraction-inductively coupled plasma (ICP)-mass spectrometry (MS) combination, wherein the cloud point extraction comprises the steps of heating, centrifuging, carrying out ice-bath, layering and diluting which are carried out strictly in sequence; the method is simple in operation, does not use an organic solvent and is capable of reducing a matrix effect; the method is a technology which is simple, low in cost, efficient and environment-friendly; and the method has a wide application prospect in the field of trace analysis.
Description
Technical field
The invention belongs to analytical chemistry field, be specifically related to a kind of method that cloud point extraction-ICP-MS coupling measures Determination of Trace Mercury In Water, cadmium.
Background technology
Heavy metal pollution, after industry is risen, is a problem be concerned always.The toxigenous scope of general heavy metal is greatly between 1-10mg/L, and the metal that toxicity is stronger mass concentration scope as toxigenous in mercury, cadmium etc. is between 0.01-0.001mg/L.The source of mercury and cadmium has a lot, and as old and useless battery contains the heavy metal such as mercury, cadmium noxious material, if carry out landfill to old and useless battery, along with passage of time, the shell of battery can be corroded perforation, causes objectionable impurities to enter in soil, water body, to environment; Factory, not according to index sewage effluent, causes Heavy Metals in Waters content overproof.Mercury and cadmium can accumulate in vivo, have neurotoxicity, are usually absorbed by the body by skin, respiratory tract and alimentary canal, have carcinogenesis.Minamata disease is exactly the one of mercury poisoning.
The pre-treatment of heavy metal Hg, cadmium and detection, adopt main cold atomic absorbent spectrophotometry method, atomic absorption method and the atomic fluorescence method etc. adopted in traditional dithizone spectrophotometry and GB/T 7468-1987, GB/T 7475-1987 water-quality determination and relevant criterion at present, wherein part of standards method can not meet trace analysis requirement in sensitivity, precision, accuracy more.Dithizone spectrophotometry is used widely because of advantages such as its cost are lower, instrument is easy to use, accuracy is higher, reappearance is better, but this method needs to use a large amount of organic solvent (chloroform) to carry out liquid-liquid extraction regrettably, to realize concentration and separation, so not only do not embody selectivity, expend time in longer, waste reagent, and widely using of chloroform also can cause certain harm and impact to environment and human body.
People start to strengthen environmental protection consciousness in recent years, and cloud point extraction (being called for short CPE) becomes the extracting process of a kind of environment-friendly type that experimenters parent in recent years looks at gradually.The principle of cloud point extraction is dissolution properties according to hydrophobic in neutral surface active agent, hydrophilic radical and cloud point phenomenon, by changing experiment parameter as pH, temperature etc., the analytical approach of a kind of purifying of hydrophobic, hydroaropic substance is separated, its suitable for mass production from aqueous phase.Cloud point extraction, relative to traditional liquid-liquid extractive technique, has following several advantage: the scope 1. used is comparatively extensive, and high from the extraction efficiency object, enrichment times is larger; 2. without the need to using poisonous and harmful organic reagent, the theory of green test is met, with low cost, there is higher economic benefit; 3. experimental implementation is simple and convenient, and the time consumed is shorter; 4. with instrumental method coupling convenience etc.
Inductively coupled plasma mass spectrometry (ICP-MS) has the advantages such as extremely low detection limit, the wider range of linearity, rapid multi-element analysis, is generally approve the Environmental Water method for analyzing very small amount of element with widespread use in the world.Therefore, in the technical field of environmental detection of China, adopt ICP-MS method to replace additive method is imperative.
Summary of the invention
The object of the present invention is to provide a kind of cloud point extraction-ICP-MS coupling to measure the method for Determination of Trace Mercury In Water, cadmium, for purification and enriched sample, the method accumulation ability is high, simple to operate, and not with an organic solvent, detectability is low, can the multiple element of Simultaneously test.
For achieving the above object, the present invention adopts following technical scheme:
A kind of cloud point extraction-ICP-MS coupling measures Determination of Trace Mercury In Water, the method for cadmium comprises the following steps:
1) first in the centrifugal plastic tube of the round bottom that 10 mL are with cover, add the Triton X-114 solution that 5.0 mL sample solutions (pH=6.5), 0.8mL 3mM ammonium pyrrolidine dithiocarbamate (APDC) solution and 0.2mL volume fraction are 10%, be diluted to 10mL with deionized water;
2) centrifuge tube lid is covered tightly fully to shake up afterwards, be placed in water-bath, heating balance 10min at 60 DEG C;
3) place in hydro-extractor with the centrifugal 5min of 4000r/min after heating balance;
4) centrifugal rear taking-up is put into ice-water bath immediately and is cooled 10min, and the liquid phase making surfactant become viscous mutually sticks on tube wall, careful reversing centrifugal pipe aqueous phase discarded;
5) be diluted to 2mL with 5% salpeter solution, shake up and directly carry out ICP-MS analysis afterwards.
Described plastic tube is the centrifugal plastic tube of round bottom with cover, and with cover avoiding is vibrated and loss of liquid in centrifugal process, and round bottom construction is convenient to the absorption of centrifugal rear surface activating agent at the bottom of bottle;
Described sample solution will carry out cloud point extraction under the condition of pH 6.5, and the complexing agent added is APDC, and the surfactant added is Triton X-114;
Described cloud point extraction step will be carried out in strict accordance with the order of heating-centrifugal-ice bath-layering-dilution;
Described stick to surfactant on tube wall mutually with 5% nitric acid dilution, with dissolve surfactant phase completely and reduce mercury, cadmium residual, also reduce during ICP-MS detects the matrix effect produced;
Described detection method is for using ICP-MS(inductivity coupled plasma mass spectrometry), its spectral line is simple, efficient, and detection limit is low, can carry out multiple element quick, detect simultaneously.
Remarkable advantage of the present invention is:
(1) this method can effectively be carried out preenrichment concentrate the heavy metal Hg in water, cadmium, reduces matrix to the interference of detection signal;
(2) this method does not consume organic solvent, is a kind of eco-friendly technology;
(3) this method device is simple, and cost is low.
Accompanying drawing explanation
Fig. 1 is cloud point extraction schematic diagram;
Fig. 2 is cloud point extraction-ICP-MS step schematic diagram.
Embodiment
Cloud point extraction-ICP-MS step schematic diagram of the present invention is as Fig. 1, and its device comprises a centrifugal plastic tube of round bottom with cover, a water-bath, a hydro-extractor.In the centrifugal plastic tube of round bottom that 10 mL are with cover, first in the centrifugal plastic tube of the round bottom that 10 mL are with cover, add the Triton X-114 solution that 5.0 mL sample solutions (pH 6.5), 0.8mL 3mM APDC solution and 0.2mL volume fraction are 10%, be diluted to 10mL with deionized water; Centrifuge tube lid is covered tightly and fully to shake up afterwards, be placed in water-bath, heating balance 10min at 60 DEG C; Place in hydro-extractor with the centrifugal 5min of 4000r/min after heating balance; Centrifugal rear taking-up is put into ice-water bath immediately and is cooled 10min, and the liquid phase making surfactant become viscous mutually sticks on tube wall, careful reversing centrifugal pipe aqueous phase discarded; Be diluted to 2mL with 5% salpeter solution, shake up and directly carry out ICP-MS analysis afterwards.
The present invention is utilized to measure heavy metal Hg, the cadmium of underwater trace.
5mL is sampled to Environmental Water (mineral water, tap water, river), after 0.22 μm of membrane filtration, adds 0.8mL 3mM APDC solution respectively and 0.2mL pH is the phosphate buffered solution of 6.5; After slight oscillatory, add the Triton X-114 solution that 0.2mL volume fraction is 10% respectively, be diluted to 10mL with deionized water; Respectively centrifuge tube lid is screwed and fully to shake up afterwards, be placed in water-bath, at 60 DEG C after heating balance 10min, in centrifuges with the centrifugal 5min of 4000r revolution, centrifugal rear taking-up is put into ice-water bath immediately and is cooled 10min, and the liquid phase making surfactant become viscous mutually sticks on tube wall, careful reversing centrifugal pipe aqueous phase discarded, be diluted to 2mL with 5% salpeter solution, shake up and directly to detect on ICP-MS afterwards.
ICP-MS condition: radio frequency (RF) power 1400W, sampling depth 10mm, cooling gas flow 13.0L/min, assisted gas flow 0.90L/min, atomization gas flow 0.91L/min, scan mode is for jumping peak; 3 points/quality, multiplicity is 3 times.
In the present invention, cloud point extraction-ICP-MS method is used for the detection of underwater trace heavy metal Hg, cadmium, and simple to operate, good stability, detectability is low.Consider that in environmental water sample, these two kinds of constituent contents are extremely low, for ensureing the accuracy of trace analysis, have chosen low concentration standard curve range herein, during mensuration, also actual conditions per sample can suitably adjust typical curve concentration range.The range of linearity of mercury, cadmium and regression equation, related coefficient are in table 1.Measure 11 times after being chosen at the standard substance preparation near quantitative limit, calculate detection limit and the quantitative limit of 2 kinds of elements, refer to table 2.
The correlation parameter of table 1 typical curve
The detection limit of table 2 method and quantitative limit
Take 5mL mineral water, tap water, river sample respectively, add finite concentration mercury, cadmium mark liquid, the recovery that after measuring by this law, in calculating mineral water, mercury, cadmium measure is respectively 96.7%, 98.7%, the recovery that in tap water, mercury, cadmium measure is respectively 98.3%, 100.7%, the recovery that in river, mercury, cadmium measure is respectively 101.1%, 99.6%, refers to table 3.
Table 3 recovery experimental result (μ g/L)
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. cloud point extraction-ICP-MS coupling measures a method for Determination of Trace Mercury In Water, cadmium, it is characterized in that: comprise the following steps:
First in the centrifugal plastic tube of the round bottom that 10 mL are with cover, add the Triton X-114 solution that the sample solution of 5.0 mL pH=6.5,0.8mL 3mM ammonium pyrrolidine dithiocarbamate solution and 0.2mL volume fraction are 10%, be diluted to 10mL with deionized water;
Centrifuge tube lid is covered tightly and fully to shake up afterwards, be placed in water-bath, heating balance 10min at 60 DEG C;
Be positioned in hydro-extractor with the centrifugal 5min of 4000r/min;
Put into ice-water bath immediately and cool 10min, the liquid phase making surfactant become viscous mutually sticks on tube wall, careful reversing centrifugal pipe aqueous phase discarded;
Surfactant is diluted to 2mL with the salpeter solution that volume fraction is 5% mutually, shakes up directly to carry out ICP-MS analysis afterwards.
2. cloud point extraction-ICP-MS coupling according to claim 1 measures the method for Determination of Trace Mercury In Water, cadmium, it is characterized in that: in step (1), ammonium pyrrolidine dithiocarbamate is complexing agent, and Triton X-114 is surfactant.
3. cloud point extraction-ICP-MS coupling according to claim 1 measures the method for Determination of Trace Mercury In Water, cadmium, it is characterized in that: cloud point extraction step will be carried out in strict accordance with the order of heating-centrifugal-ice bath-layering-dilution.
4. cloud point extraction-ICP-MS coupling according to claim 1 measures the method for Determination of Trace Mercury In Water, cadmium, it is characterized in that: the surfactant sticked in step (5) on tube wall dilutes with the salpeter solution of 5% mutually, with dissolve surfactant phase completely and reduce mercury, cadmium residual, also reduce during ICP-MS detects the matrix effect produced.
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| CN108593758A (en) * | 2018-07-10 | 2018-09-28 | 南方医科大学 | A method of measuring trace metal content in biological tissue and body fluid |
| CN108760454A (en) * | 2018-06-01 | 2018-11-06 | 广西壮族自治区海洋环境监测中心站 | A kind of preparation method of low-heavy metal content seawater |
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| CN108760454A (en) * | 2018-06-01 | 2018-11-06 | 广西壮族自治区海洋环境监测中心站 | A kind of preparation method of low-heavy metal content seawater |
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