CN104007076A - Method for detecting mercury in sewage - Google Patents
Method for detecting mercury in sewage Download PDFInfo
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- CN104007076A CN104007076A CN201410252294.7A CN201410252294A CN104007076A CN 104007076 A CN104007076 A CN 104007076A CN 201410252294 A CN201410252294 A CN 201410252294A CN 104007076 A CN104007076 A CN 104007076A
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- mercury
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- standard
- hydrochloric acid
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Abstract
The invention discloses a method for detecting mercury in sewage and belongs to the technical field of analytic chemistry. The method comprises the following basic detection steps: selecting a standard liquid medium, preparing a standard stock solution, preparing a standard use liquid, preparing a NaBH4 reducing-agent solution, pretreating a sample and connecting mercury atoms of generated cold steam into a cold-atom absorbing and mercury-detecting instrument. The method disclosed by the invention has the advantages that a hydrochloric acid (HCl) medium is adopted for preparing a standard solution of mercury, so that the mercury generates extremely-stable hydrogen mercury chloride (HHgCl3) complex in the hydrochloric acid medium; in addition, sodium borohydride is used as a reducing agent, and the operation is more convenient and faster.
Description
Technical field
The present invention relates to technical field of analytical chemistry, is to utilize the cold mercury ion atom of sodium borohydride reduction to measure the detection method of mercury content specifically.
Background technology
Mercury pollution, refers in people's commercial production and life because human body and the destroyed phenomenon of environment ineffective to the processing of mercury and that cause.Element mercury is substantially nontoxic, and inorganic mercury Zhong Noboru mercury is extremely toxic substance, and phenyl mercury in machine mercury decomposes very fast, and toxicity is little, and methyl mercury enters human body and is easy to be absorbed, and is difficult for degraded, drains very slowly, particularly easily in brain, accumulates toxicity maximum.
China is that big country is produced and used to mercury, and data show 2005,2006, and mercury in China output accounts for 60% left and right of global total mercury output, and mercury demand accounts for 30%～40%, all occupies first place, the whole world.Meanwhile, China is also global mercury emissions big country.End 2010, the annual human activity in the whole world has 2000 tons to the mercury emission of atmosphere, the wherein about 500-600 ton of China's annual discharge mercury, account for global mercury emissions total amount 1/4 more than.
In atmosphere, the mercury of gaseous state and particulate form flies away with the wind, a part by wet deposition or dry deposition fall earthward or water body in.The volatilizable atmosphere that enters of mercury in soil, also can be entered in the day water and underground water by Rainfall washout.A mercury part in the day water is because volatilization enters atmosphere, and major part sedimentation enters bed mud.Mercury in bed mud, no matter be which kind of form,---mercury metal, inorganic mercury, organic mercury---all can directly or indirectly be converted into methyl mercury or dimethylmercury under the effect of microorganism.Dimethylmercury can be decomposed into methyl mercury under acid condition.Methyl mercury water soluble, gets back to water from bed mud again.The methyl mercury that hydrobiont is taken in, can accumulate in vivo, and by the continuous enrichment of food chain (biomagnification).
The methyl mercury that hydrobiont is taken in, can accumulate in vivo, and by the continuous enrichment of food chain.Fish in mercury contaminated water body, up to ten thousand times of height in the interior comparable water of methyl mercury concentration of body.By volatilizing, dissolve, methylate, the effect such as sedimentation, Rainfall washout, mercury is constantly carrying out exchange and is shifting between atmosphere, soil, water.
Water is the necessity of human survival, has left water, and the mankind have not just had the material base of depending on for existence.Therefore, extremely important for people's life to the processing of contaminant water.Particularly, for mercury heavy metal, health is had to great impact; So the development of the treatment technology of sewage is more and more.
At present, conventional technology is: Determination of Mercury by Atomic Absorption Spectrophotometry method, the medium of its standard solution is 5% nitric acid+0.05% potassium bichromate solution, to ensure standard solution stable of mercury.
Measuring principle is using stannous chloride as reductive agent, and mercury is discharged and becomes cold atom mercuryvapour, and body reaction equation is as follows:
Sn
2++8Cl
-+2Hg
2 +＝[SnCl
6]
2-+Hg
2Cl
2
Sn
2++4Cl
-+Hg
2Cl
2＝2Hg+[SnCl6]
2-
The mercury vapour discharging enters Testing Mercury by cold Atom Absorphotometry instrument and measures.
Above-mentioned technical scheme has good effect to mercurous water treatment, but also has very large weak point, as:
1, taking nitric acid+potassium dichromate as medium, mercury standard solution concentration still can reduce gradually, is difficult to long-time preservation, and potassium dichromate is noxious material.
2, in the process of Reduction with Stannous Chloride high price mercury release mercury vapour, there is defect:
Stannous chloride must just have higher reduction effect under relatively low acidity (lower than 1mol/L), but low acidity easily causes stannous chloride hydrolytic precipitation and loses reducing power; In the time that raising acidity ensures that stannous chloride is not hydrolyzed, the reduction efficiency of stannous chloride can reduce again, affects the release of mercuryvapour, makes measurement result on the low side, unstable, even cannot detect.
Summary of the invention
The present invention, in order to overcome the deficiencies in the prior art, provides a kind of sewage to survey mercury method, its objective is and improves stability and the accuracy of measuring mercury, ensures analyzing and testing quality, makes operation more convenient.
In order to solve above-mentioned technical matters, basic solution technical scheme of the present invention is: a kind of sewage is surveyed mercury method, comprises step,
S1: selection standard liquid medium, this titer medium comprises HCl solution, potassium dichromate hydrochloric acid solution and tartaric acid solution; The concentration of wherein said HCl solution is 0.5mol/L; Described potassium dichromate hydrochloric acid solution is by the K of 0.56g
2cr
2o
7be dissolved in 30ml water, to add 15ml concentration be 35% hydrochloric acid and add water to 100ml configuration and form; The concentration of described tartaric acid solution is 40%;
S2: use the HCl solution allocation standard stock solution in S1 step, this standard stock solution comprises HgCl
2solution, its concentration is 10 μ g/ml;
S3: selecting the standard stock solution in S2 step is that raw material outfit standard uses liquid, and this standard solution is HgCl
2solution, its concentration is 10ng/ml;
S4: with NaBH
4reductant solution, its concentration is 0.05mol/L;
S5: sample pretreatment: get mercurous water sample and be put in color comparison tube, the volume of this mercury water sample accounting colour tube 1/3rd, and add the potassium dichromate hydrochloric acid solution described in 0.4molS1 step, adds the tartaric acid solution described in 0.8mol step S1 after 5 minutes, shake up;
S6: toward the NaBH that adds the 0.5mol in S4 step through step S5 sample after treatment
4, there is redox reaction in reductant solution, then the cold steam mercury atom access Testing Mercury by cold Atom Absorphotometry instrument producing is detected.
Sewage of the present invention is surveyed in mercury method, the HgCl described in step S2
2the preparation method of solution adopts in silica gel drier to place 12 hours above HgCl20.1354g, is dissolved in 0.5mol/L HCl, and dilutes and be settled to 1L with this HCl.
The present invention, using sodium borohydride as reductive agent, discharges mercury to become cold atom mercury vapour, and its ion-reaction equation is:
2BH
4-+2H
2O＝6[H]+2B(OH)
3
Hg
2++2[H]＝Hg↑+H
2
The invention has the beneficial effects as follows:
1, the present invention adopts the standard solution of hydrochloric acid (HCl) medium preparation mercury, makes mercury in hydrochloric acid medium, generate extremely stable mercuric chloride hydrogen (HHgCl
3) complex, facts have proved, in hydrochloric acid medium, it is unchanged that the standard stock solution of 10ng/ml mercury stores 1 year its concentration at normal temperatures, boils also non-volatile loss even if mercuric chloride hydrogen complex heats in hydrochloric acid medium.
2, the reduction of mercury discharges and adopts hydrochloric acid medium, and with sodium borohydride, as reductive agent, preparation is simple, and reduction efficiency is high, not affected by acidity of medium, analyzes quality and is easy to ensure.
3, in the time adopting Testing Mercury by cold Atom Absorphotometry instrument and reagent, to use stannous chloride solution in the past, but the hydrolytic precipitation gradually of stannous chloride solution can make, pump line inwall is rough causes sample introduction to have some setbacks and unstable meeting with attenuating, and the present invention uses sodium borohydride for reductive agent, its faster and more convenient operation.
Brief description of the drawings
Fig. 1 is the step schematic diagram that sewage of the present invention is surveyed mercury method.
Embodiment
In order to make technical matters to be solved by this invention, technical scheme and beneficial effect clearer, clear, below in conjunction with drawings and Examples, the present invention is further elaborated, specific embodiment described herein only, in order to explain the present invention, is not intended to limit the present invention.
Contrast Fig. 1, the basic step that the present invention's sewage is surveyed mercury method comprises:
S1: selection standard liquid medium;
This titer medium comprises HCl solution, potassium dichromate hydrochloric acid solution and tartaric acid solution; The concentration of wherein said HCl solution is 0.5mol/L; Described potassium dichromate hydrochloric acid solution is by the K of 0.56g
2cr
2o
7be dissolved in 30ml water, to add 15ml concentration be 35% hydrochloric acid and add water to 100ml configuration and form; The concentration of described tartaric acid solution is 40%;
S2: configuration standard stock solution;
This standard stock solution comprises HgCl
2solution, its concentration is 10 μ g/ml;
S3: selecting the standard stock solution in S2 step is that raw material outfit standard uses liquid;
This standard solution is HgCl2 solution, and its concentration is 10ng/ml;
S4: the NaBH that outfit concentration is 0.05mol/L
4reductant solution;
S5: sample pretreatment:
Get mercurous water sample and be put in color comparison tube, add the potassium dichromate hydrochloric acid solution described in 0.4molS1 step, after a period of time, add the tartaric acid solution described in 0.8mol step S1, shake up;
S6: carry out redox reaction and use Testing Mercury by cold Atom Absorphotometry instrument to detect;
Toward the NaBH that adds the 0.5mol in S4 step through step S5 sample after treatment
4, there is redox reaction in reductant solution, then the cold steam mercury atom access Testing Mercury by cold Atom Absorphotometry instrument producing is detected.
The present invention adopts the standard solution of hydrochloric acid (HCl) medium preparation mercury, makes mercury in hydrochloric acid medium, generate extremely stable mercuric chloride hydrogen (HHgCl
3) complex, facts have proved, in hydrochloric acid medium, it is unchanged that the standard stock solution of 10ng/ml mercury stores 1 year its concentration at normal temperatures, boils also non-volatile loss even if mercuric chloride hydrogen complex heats in hydrochloric acid medium.The reduction of mercury discharges and adopts hydrochloric acid medium, and with sodium borohydride, as reductive agent, preparation is simple, and reduction efficiency is high, not affected by acidity of medium, analyzes quality and is easy to ensure.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change and revise above-mentioned embodiment.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition,, although used some specific terms in this instructions, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (2)
1. sewage is surveyed a mercury method, it is characterized in that: comprise step,
S1: selection standard liquid medium, this titer medium comprises HCl solution, potassium dichromate hydrochloric acid solution and tartaric acid solution; The concentration of wherein said HCl solution is 0.5mol/L; Described potassium dichromate hydrochloric acid solution is by the K of 0.56g
2cr
2o
7be dissolved in 30ml water, to add 15ml concentration be 35% hydrochloric acid and add water to 100ml configuration and form; The concentration of described tartaric acid solution is 40%;
S2: use the HCl solution allocation standard stock solution in S1 step, this standard stock solution comprises HgCl
2solution, its concentration is 10 μ g/ml;
S3: selecting the standard stock solution in S2 step is that raw material outfit standard uses liquid, and this standard solution is HgCl
2solution, its concentration is 10ng/ml:
S4: with NaBH
4reductant solution, its concentration is 0.05mol/L;
S5: sample pretreatment: get mercurous water sample and be put in color comparison tube, the volume of this mercury water sample accounting colour tube 1/3rd, and add the potassium dichromate hydrochloric acid solution described in 0.4molS1 step, adds the tartaric acid solution described in 0.8mol step S1 after 5 minutes, shake up;
S6: toward the NaBH that adds the 0.5mol in S4 step through step S5 sample after treatment
4, there is redox reaction in reductant solution, then the cold steam mercury atom access Testing Mercury by cold Atom Absorphotometry instrument producing is detected.
2. sewage is as claimed in claim 1 surveyed mercury method, it is characterized in that: the HgCl described in step S2
2the preparation method of solution places 12 hours above HgCl in employing silica gel drier
20.1354g, is dissolved in 0.5mol/L HCl, and dilutes and be settled to 1L with this HCl.
Priority Applications (1)
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|---|---|---|---|
| CN201410252294.7A CN104007076A (en) | 2014-06-06 | 2014-06-06 | Method for detecting mercury in sewage |
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|---|---|---|---|
| CN201410252294.7A CN104007076A (en) | 2014-06-06 | 2014-06-06 | Method for detecting mercury in sewage |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105548152A (en) * | 2015-12-04 | 2016-05-04 | 清华大学 | Kit for detection of mercury ions in sewage by colorimetric method and detection method thereof |
| CN109253996A (en) * | 2018-10-31 | 2019-01-22 | 中国石油天然气股份有限公司 | A kind of the mercury isotope test method and its device of crude oil |
| CN111829970A (en) * | 2020-07-28 | 2020-10-27 | 上海安杰环保科技股份有限公司 | Method for measuring mercury content by gas phase molecular absorption spectrometer |
| CN112665933A (en) * | 2020-12-04 | 2021-04-16 | 安徽大学 | Pretreatment method for mercury isotope determination of environmental sample |
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2014
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105548152A (en) * | 2015-12-04 | 2016-05-04 | 清华大学 | Kit for detection of mercury ions in sewage by colorimetric method and detection method thereof |
| CN109253996A (en) * | 2018-10-31 | 2019-01-22 | 中国石油天然气股份有限公司 | A kind of the mercury isotope test method and its device of crude oil |
| CN109253996B (en) * | 2018-10-31 | 2021-05-28 | 中国石油天然气股份有限公司 | Mercury isotope testing method and device for crude oil |
| CN111829970A (en) * | 2020-07-28 | 2020-10-27 | 上海安杰环保科技股份有限公司 | Method for measuring mercury content by gas phase molecular absorption spectrometer |
| WO2022021867A1 (en) * | 2020-07-28 | 2022-02-03 | 上海安杰环保科技股份有限公司 | Mercury content measurement method using gas-phase molecular absorption spectrometer |
| CN112665933A (en) * | 2020-12-04 | 2021-04-16 | 安徽大学 | Pretreatment method for mercury isotope determination of environmental sample |
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Application publication date: 20140827 |