CN104297173A - Method for rapid detection of mercury content in ocean sediments - Google Patents
Method for rapid detection of mercury content in ocean sediments Download PDFInfo
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- CN104297173A CN104297173A CN201310304081.XA CN201310304081A CN104297173A CN 104297173 A CN104297173 A CN 104297173A CN 201310304081 A CN201310304081 A CN 201310304081A CN 104297173 A CN104297173 A CN 104297173A
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Abstract
The invention discloses a method for rapid detection of mercury content in ocean sediments. The method includes the following steps: a) weighing a wet sample of ocean sediments and preparing a liquid sample to be tested; b) digesting the liquid sample by a sulfuric acid-nitric acid-potassium permanganate digestion method, completely transforming mercury ions into divalent mercury, and reducing excessive oxidant; c) reducing the divalent mercury in the liquid sample to be tested into metallic mercury by using boron hydride; and d) detecting the mercury content in the liquid sample by using a hydride atomic absorption spectrophotometry. The invention provides a determination method with high degree of automation, and can rapidly determine mercury content in a variety of sample sources; and compared with the conventional method, the method is more labor-saving and time-saving in operation, and has high accuracy and high sensitivity.
Description
Technical field
The present invention relates to chemical analysis technology field, specifically, relate to a kind of method of quick detection Mercury in Marine Sediment content.
Background technology
Mercury is the toxic element with savings property, and it is accumulated in after entering human body in nervous centralis, liver and kidney, causes associated organ to damage with poisoning.Mercury poisoning has acute and chronic dividing.Heavy dose of mercury vapour sucks or mercury compound is taken in, then acute poisoning occurs, can threat to life time serious.This acute poisoning is actually rare now, mainly occurs in productivity poisoning as in the direct labors such as mercury ore exploitation, mercury alloy smelting.In fact, more common, it is then all unknown by the people for threatening larger to the general public, from the chronic mercury poisoning of surrounding environment.
Due to mercury at occurring in nature not only with metal form, more extensively exist with the form of all organomercury compounds.Along with natural evolution, in each factor of environment, all may contain mercury, form the size selective sampling of mercury.In the earth's crust, the average abundance of mercury is 0.08ppm, is 0.03 ~ 0.3ppm in soil, is 0.1 ~ 1.0ppt in air.Mercury is in an atmosphere in steam-like, and thus also have mercury in rainwater, mean concentration is 0.2ppb (1ppb is the per mille of 1ppm).The background concentration of mercury in water, inland underground water is 0.1ppb, and seawater is 0.03 ~ 2ppb, and spring can reach more than 80ppb, and lake water, river are generally no more than 0.1ppb.
The activity in production of the mankind obviously can increase the weight of the pollution of mercury to environment.Though this kind of artificial pollution proportion is not very big, discharge is concentrated, therefore harm is serious far beyond natural pollution.Nuisance disease can be caused, as minamata disease to the pollution of rivers,lakes and seas containing Mercury sewage.Nowadays mercury quantity through food intake human body reached for 20 ~ 30 μ g/ days, and even up to 200 ~ 300 μ g/ ﹐, this constitutes a serious threat to human health in severe contamination area, therefore mercury poisoning control has become the important topic of countries in the world facing.
Cause the chronic mercury poisoning of the public to prevent the pollution of the environment, so adopt certain technological means, all kinds of mercury contents in testing environment become very important.
Due to the expansion of human being's production life scope in modern society, day by day violent on the impact of marine environment.Due in different waters, the dynamic condition of material carrying is different.Terrigenous clastic rock enters the carrying in extra large mainly river, is secondly the carrying of the geologic function such as floating ice and wind-force.Enter sea along with land pollutant, the mercury content of oceanic sediment is also growing with each passing day.Therefore, in detection field, especially environmental evaluation standard and environmental monitoring field, the mercury content of oceanic sediment to survey project.
The assay method of mercury content is more, and conventional has atomic absorption spectrography (AAS), atomic fluorescence spectrometry, electrochemical process, chromatography, ICP2 mass spectroscopy etc.In standard GB/T/T15555.1-1995, the mensuration of mercury content adopts cold atomic absorbent spectrophotometry, and mercury vapor analyzer measures.The method operation more complicated, need add sample and Reduction with Stannous Chloride agent in reaction bulb, and reading will dig-in display during mensuration at every turn, write down mxm., reacted mercury absorbs through liquor potassic permanganate, therefore often will change absorbing liquid, seems and extremely bothers.
Hydride generated atomic absorption spectroscopic methodology is a kind of new Analytical Methods of Trace, the features such as tool is highly sensitive, co-existing element interference is few, and method is simple and quick; But detect report there are no mercury content the method be applied in oceanic sediment.
Summary of the invention
For the problems referred to above that prior art exists, the object of this invention is to provide a kind of method of quick detection Mercury in Marine Sediment content, the mercury content in oceanic sediment is detected by New Hydrogen compound generation atomic absorption spectrography (AAS), the method automaticity is high, simple to operate, there is higher sensitivity and accuracy.
For achieving the above object, the technical solution used in the present invention is as follows:
The invention provides a kind of method of quick detection Mercury in Marine Sediment content, specifically comprise the following steps:
A) take oceanic sediment to wet sample, obtained testing liquid sample;
B) sulfonitric-potassium permanganate resolution method is adopted to clear up after the complete mercury ion of described testing liquid sample is all converted into bivalent mercury, by the oxidant reduction of surplus;
C) adopt hydroborate that the bivalent mercury in described testing liquid sample is reduced into mercury metal;
D) mercury content in testing liquid sample described in hydride atomic absorption spectrophotometry is adopted.
Preferably, described steps d) in the concrete operations of hydride atomic absorption spectrophotometric method as follows: in an acidic solution, with potassium borohydride (KBH
4) as reductive agent, make mercury be reduced to mercury atom steam, be loaded in flame atomizer by carrier gas, be decomposed into the resonance line of atomic state mercury vapour absorbing wavelength 253.7nm, its uptake is directly proportional to mercury content, quantitatively records mercury content with typical curve systematic comparison.
More preferably, described steps d) in carrier gas be argon gas, during mensuration, load volume is 150mL/min.
Preferably, described step c) described in hydroborate be potassium borohydride or sodium borohydride, and concentration should be 15 ~ 25g/L, is preferably 20g/L.
More preferably, described step c) described in hydroborate be hydroborate configuration liquid, also containing 0.2%wt NaOH in described hydroborate configuration liquid.
Compared with prior art, the invention provides the assay method that a kind of automaticity is high, the mercury content in the sample of energy Fast Measurement various sources, compared with conventional method, it is more time saving and energy saving to operate, and has higher sensitivity and accuracy; Employing hydride generated atomic absorption spectroscopic methodology detects the mercury content in oceanic sediment, adopt mercury in hydride-atomic absorption spectroscopy determination water, simple, convenient, quick, the effect of METHOD FOR CONTINUOUS DETERMINATION can be reached, data are accurate, and have flame (survey peak area) and flame micro-sampling (survey peak height) two kinds of assay methods continuously, and flame surveys high concentration continuously, flame micro-sampling surveys low concentration, and the detection limit of low concentration is lower; Potassium borohydride or sodium borohydride are than stannous chloride reaction acutely, reduction effect is also more satisfactory, can avoid adopting survey arsenic and mercury to be used alternatingly, stannous chloride and potassium borohydride react and produce turbidity and precipitation thing, cleaning up is more difficult, comparatively large to hydride generator damage ratio, the problem such as easily result in blockage; The method automaticity is high, simple to operate, has higher sensitivity and accuracy, and therefore its application prospect is very wide.
Embodiment
Do to illustrate in detail, intactly further to the present invention below in conjunction with embodiment.
The reagent adopted in embodiment be analyze pure or analyze pure more than, water is distilled water or deionized water.Glassware used all uses volume fraction 50%HNO
3soak more than 24 hours again with distilled water flushing totally and dry.In following examples if no special instructions, reagent and instrument all adopt commercially available kind and operate to specifications.
Embodiment 1
1, the preparation of oceanic sediment sample
1.1 instruments and material
50mL beaker; Distilled water; Glass stirring rod
1.2 preparation process
Take 1g marine sediment samples to wet sample, stir and evenly mix with distilled water in 50mL beaker, obtained testing liquid sample.
2, the clearing up of testing liquid sample
Use sulfonitric-potassium permanganate resolution method, get a certain amount of fluid sample in 150mL conical flask, add sulfonitric nitration mixture and liquor potassic permanganate, plug funnel, be placed in heating on electric hot plate and boil 10 minutes, period keeps potassium permanganate purple not take off, and need add potassium permanganate amount if fade, after having cleared up, with the oxidant reduction of oxammonium hydrochloride by surplus.
3, the content of mercury is measured with hydride generator and atomic absorption spectrophotometer (AAS)
3.1 instruments and material
Shimadzu atomic spectrophotometer AA-6300C (Shimadzu Corp)
Generator for mobile injection of hydride WHG-102A (making institute during the writing brush of Beijing)
10, clean 100mL volumetric flask, 2,500mL volumetric flask, 200mL plastic bottle 2,2mL and 5mL, 10mL transfer pipet several; Sulfuric acid, hydrochloric acid, potassium borohydride, NaOH, potassium permanganate, distilled water or deionized water;
3.2 experimental procedure
3.2.1.1% the configuration of carrier fluid: use 500mL volumetric flask, adds 5mL hydrochloric acid, is settled to 500mL.
3.2.2. blank configuration: use 500mL volumetric flask, add 20mL sulfuric acid, be settled to 500mL, add appropriate potassium permanganate, be as the criterion with the micro-purple of color, this is the sulfuric acid solution of 4%.
3.2.3. 1 μ g/mL/Hg mother liquor is configured: the mark liquid Hg mother liquor configuring 1 μ g/mL according to the content of mark liquid.
3.2.4. the configuration of standard series: the volumetric flask getting out 6 100mL, adds the Hg standard mother liquor of 0mL, 1mL, 2mL, 4mL, 6mL, 8mL respectively, is dissolved to 100mL with the sulfuric acid of configured 4%.This for series concentration be 0.0,10.0, the standard solution of 20.0,40.0,60.0,80.0 μ g/L.
3.2.5. blank use has configured, with remaining 4% sulfuric acid solution.
3.2.6. the configuration of potassium borohydride: take 2g potassium borohydride and put into plastic bottle, then add 0.2g NaOH, adding distil water is dissolved to 200mL, is namely made into the potassium borohydride of 1% concentration.(preserving the operating period is 1 week)
3.2.7. the dilution configuration of sample: with sample acid adjustment degree to 4% sulfuric acid dissolved.Be diluted to again within the range of linearity.
3.2.8. sample blank: sample blank is identical in vain with mark liquid air.
3.2.9. sample detection:
A) according to optimum configurations atomic spectrophotometer in lower list:
| Wavelength | Lamp current mA | The wide nm of slit | Carrier gas flux mL/min |
| 253.7 | 4 | 0.7 | 150 |
B) testing standard product and sample
Preheating main frame, connects main frame and hydride generator, and by selected condition of work setting instrument, fine setting burner position, ensures ceiling capacity by the quartzy absorption tube do not heated, three of hydride generator pipes are inserted liquid to be measured, KBH respectively
4in liquid and carrier fluid, press start key, generator can suck three kinds of solution by automatic ration, the rear metallic mercury vapor that generates of reaction of joining is brought into gas-liquid separation pipe by carrier gas, combination gas enters the quartz ampoule on flame burner, main frame with peak height method reading, by standard series order sequentially determining standard solution, blank and sample light absorption value is measured, with typical curve standard measure after drawing standard curve.
In testing liquid sample, the computing method of mercury concentration are as follows:
The concentration of mercury is calculated by following company
In formula: the concentration in C-water, mg/L;
ρ
1-check in concentration value by curve, mg/L;
V
1-constant volume, L;
V
2-sample volume, L.
C) test findings
Table 1 sample determination
4, interpretation of result
4.1 potassium borohydride concentration select the impact on mercury absorption signal
The solution of potassium borohydride of variable concentrations is adopted to make reductive agent, according to the absorbance of determination of experimental method 10ng/mL mercury standard working solution.Test findings shows, when the concentration of solution of potassium borohydride is 20g/L, absorbance reaches maximal value, then increases its concentration, and absorbance is substantially constant; But when the concentration of solution of potassium borohydride is 30g/L, measurement result is unstable, and relative standard deviation increases.This experimental selection concentration is 20g/L solution of potassium borohydride.
In 100mL20g/L solution of potassium borohydride, add 0.2 ~ 0.7g NaOH respectively as stabilizing agent, find that the consumption of NaOH is little on measurement result impact.This experimental selection adds 0.4g NaOH at 100mL20g/L solution of potassium borohydride.
4.2 carrier gas fluxes are on the impact of mercury absorption signal
According to experimental technique, 10ng/mL mercury standard working solution is tested, measure carrier gas flux to the impact of absorbance.Test finds, when carrier gas flux is 80 ~ 120mL/min, along with the increase of carrier gas flux, the amplification of absorbance is very large; When carrier gas flux is 120 ~ 150mL/min, along with the increase of carrier gas flux, the amplification of absorbance reduces relatively; When carrier gas flux is greater than 150mL/min, along with the increase of carrier gas flux, absorbance declines.This experimental selection carrier gas flux is 150mL/min.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (7)
1. detect a method for Mercury in Marine Sediment content fast, it is characterized in that, specifically comprise the following steps:
A) take oceanic sediment to wet sample, obtained testing liquid sample;
B) sulfonitric-potassium permanganate resolution method is adopted to clear up after the complete mercury ion of described testing liquid sample is all converted into bivalent mercury, by the oxidant reduction of surplus;
C) adopt hydroborate that the bivalent mercury in described testing liquid sample is reduced into mercury metal;
D) mercury content in testing liquid sample described in hydride atomic absorption spectrophotometry is adopted.
2. the method for quick detection Mercury in Marine Sediment content according to claim 1, is characterized in that: described step c) described in hydroborate be potassium borohydride or sodium borohydride, and concentration is 15 ~ 25g/L.
3. the method for quick detection Mercury in Marine Sediment content according to claim 2, is characterized in that: described step c) described in borohydride concentration be 20g/L.
4. the method for quick detection Mercury in Marine Sediment content according to claim 1, is characterized in that: described step c) described in hydroborate be hydroborate configuration liquid, also containing 0.2%wt NaOH in described hydroborate configuration liquid.
5. the method for quick detection Mercury in Marine Sediment content according to claim 1, is characterized in that: described steps d) in the concrete operations of hydride atomic absorption spectrophotometric method as follows: in an acidic solution, with potassium borohydride (KBH
4) as reductive agent, make mercury be reduced to mercury atom steam, be loaded in flame atomizer by carrier gas, be decomposed into the resonance line of atomic state mercury vapour absorbing wavelength 253.7nm, its uptake is directly proportional to mercury content, quantitatively records mercury content with typical curve systematic comparison.
6. the method for quick detection Mercury in Marine Sediment content according to claim 5, is characterized in that: described steps d) in carrier gas be argon gas, during mensuration, load volume is 150mL/min.
7. the method for quick detection Mercury in Marine Sediment content according to claim 5, is characterized in that: the mensuration formula of described mercury content is:
in formula: mercury concentration (mg/L) in C-testing liquid sample, ρ 1-checks in quantitative concentrations value (mg/L) by typical curve, V1-constant volume (L), V2-sample volume (L).
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Cited By (7)
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| CN104819971A (en) * | 2015-05-21 | 2015-08-05 | 山东格林检测股份有限公司 | Detection method for mercury in water |
| CN106546585A (en) * | 2016-11-09 | 2017-03-29 | 江南大学 | Mercury ion, total mercury and organomercurial detection method and detection kit |
| CN106814039A (en) * | 2017-01-23 | 2017-06-09 | 重庆民泰香料化工有限责任公司 | A kind of Cadmium detrmination method in Midew preventive for feed |
| CN107064028A (en) * | 2017-01-23 | 2017-08-18 | 重庆民泰香料化工有限责任公司 | The assay method of mercury in a kind of Midew preventive for feed |
| CN109253994A (en) * | 2018-10-31 | 2019-01-22 | 中国石油天然气股份有限公司 | A kind of oil-gas-source mercury isotope detection method and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104819971A (en) * | 2015-05-21 | 2015-08-05 | 山东格林检测股份有限公司 | Detection method for mercury in water |
| CN106546585A (en) * | 2016-11-09 | 2017-03-29 | 江南大学 | Mercury ion, total mercury and organomercurial detection method and detection kit |
| CN106546585B (en) * | 2016-11-09 | 2019-04-16 | 江南大学 | The detection method and detection kit of mercury ion, total mercury and organic mercury |
| CN106814039A (en) * | 2017-01-23 | 2017-06-09 | 重庆民泰香料化工有限责任公司 | A kind of Cadmium detrmination method in Midew preventive for feed |
| CN107064028A (en) * | 2017-01-23 | 2017-08-18 | 重庆民泰香料化工有限责任公司 | The assay method of mercury in a kind of Midew preventive for feed |
| CN109253994A (en) * | 2018-10-31 | 2019-01-22 | 中国石油天然气股份有限公司 | A kind of oil-gas-source mercury isotope detection method and device |
| CN109253994B (en) * | 2018-10-31 | 2021-05-28 | 中国石油天然气股份有限公司 | Oil and gas source mercury isotope detection method and device |
| US11119085B2 (en) | 2018-10-31 | 2021-09-14 | Petrochina Company Limited | Methods and devices for detecting mercury isotopes in oil-gas sources |
| CN110346192A (en) * | 2019-06-27 | 2019-10-18 | 青岛海洋地质研究所 | A kind of ocean combustible ice deposit Volatile Elements test pre-treating method |
| CN110346192B (en) * | 2019-06-27 | 2020-04-17 | 青岛海洋地质研究所 | Pretreatment method for testing volatile elements in marine combustible ice sediment |
| CN111495282A (en) * | 2020-04-22 | 2020-08-07 | 重庆川仪自动化股份有限公司 | Device and method for generating gaseous ionic mercury |
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Application publication date: 20150121 |