CN101571523B - Method for measuring various types of unknown pollutants in sewage - Google Patents
Method for measuring various types of unknown pollutants in sewage Download PDFInfo
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- CN101571523B CN101571523B CN2009100984669A CN200910098466A CN101571523B CN 101571523 B CN101571523 B CN 101571523B CN 2009100984669 A CN2009100984669 A CN 2009100984669A CN 200910098466 A CN200910098466 A CN 200910098466A CN 101571523 B CN101571523 B CN 101571523B
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Abstract
The invention discloses a method for applying a gas phase chromatography-combined with gas spectrometry to measure various types of unknown pollutants in sewage, belonging to the technical field of environmental detection. The invention firstly proposes a method for synchronous extraction and pretreatment; the sewage applies the gas phase chromatography-combined with gas spectrometry after being treated by purification and concentration and the specific parameters of measuring work with gas phase chromatography-combined with gas spectrometry are respectively proposed. By the analysis of the above instruments, an obtained molecular fragment peak value is compared with an NIST library, and then the qualitative analysis can be made to a plurality of unknown pollutants so as to determine the pollutants and have important functions for finding the sources of the pollutants and investigation, handling and identification of pollution accidents.
Description
Technical field
The invention discloses a kind of method of measuring multiple types of unknown pollutants in the sewage, belong to the environment measuring technical field.
Background technology
Along with China's economy develop rapidly; Each industry heats up rapidly; Industrial development is especially outstanding, and this just inevitably brings some negative effects, comprises the pollution to environment; Only the pollution to the fishery ecologic environment all will cause the loss more than several hundred million yuan every year, and the accident polluting that discharge of industrial wastes causes takes place again and again.But the authenticate technology of accident development is slow relatively, particularly pollution source confirm and dirt qualitative aspect, often, accident is identified is lagged behind because data support does not timely cause lack of evidence, accident can not get dealing carefully with, and causes the certain social problem.
Traditional detection method such as gas chromatography, liquid chromatography, AAS etc. are often felt simply helpless in the face of unknown pollutant, perhaps can only carry out analyzing and testing to a pollutant.And from contaminated actual, multiple often rather than single pollutant is playing contamination, thereby above-mentioned method is the current reality of incompatibility.
During types of unknown pollutants, sample pre-treatments mainly is to separate determinand and matrix in order to reach, and determinand is carried out purifying, enrichment, reduces the influence of other materials to instrument detecting in analyzing sewage.Aspect sewage analaysis; Mostly adopt liquid-liquid extraction to combine with SPE; But this method can not extract the different types of unknown pollutants of character simultaneously, as extracting and need repeatedly handle multiple types of unknown pollutants, has so not only influenced ageing but also has increased the laboratory cost.Thereby, the improved needs of raising are arranged.And nearly GC-MS that began to use in 2 years can solve the problem of this respect well.The GC-MS method can detect polytype pollutant simultaneously, and can be accurately qualitative, quantitative to detected object.
Summary of the invention
For solving the technology that present traditional detection technique can not detect, analyze multiple types of unknown pollutants, though and the GC-MS method can detect polytype pollutant simultaneously, extracting pretreatment technology simultaneously is the problem that must at first solve.The present invention will find a kind of method that can carry out pre-treatment simultaneously to types of unknown pollutants; This method both can not cause background interference to follow-up instrument detecting; The analytical approach that is set by instrument in the time of carrying out qualitative analysis to types of unknown pollutants is again accepted, and what the first step promptly of the present invention will solve is the pre-treating method that extracts simultaneously, on this basis; Second step was a mensuration running parameter of selecting gas chromatography-mass spectrography, thereby accomplished the object of the invention.
The pretreatment technology that extracts simultaneously of the present invention is following: behind 500mL sewage mechanical filter; Water sample places separating funnel; Divide three extractions with methylene chloride-sherwood oil mixed liquor 40mL, 40mL, 20mL, behind the combining extraction liquid extract is divided into two parts, a with 0.1mol/L sulfuric acid accent pH to 3; A with 0.125mol/L sodium hydroxide solution accent pH to 11, extract purifies with the 30g/L metabisulfite solution.Again two parts of extracts are passed through alumina chromatographic column, collect filtered fluid and be concentrated into 2mL at 40 ℃ of water-bath rotary evaporations, subsequent use.
Above-mentioned concentrate is after treatment carried out the qualitative analysis of types of unknown pollutants.The instrument that uses is a gas chromatography-mass spectrography; The vaporizer temperature of traditional analysis method is constant high temperature; Gas phase of the present invention partly utilizes the temperature programme of vaporizer that the pollutant of different boiling can not decomposed under the different temperature condition, and the temperature programme of gas chromatographic column can be separated each pollutant preferably.The mensuration running parameter of gas chromatography: the injection port initial temperature is a normal temperature, keeps 0.75min, and 200 ℃/min rises to 280 ℃; Keep 1min, initial split ratio 1: 20,0.01min split ratio 1: 100; 0.75min the split ratio of closing, 3.00min split ratio 1: 100; Column flow rate 1.2mL/min; Temperature programme, 55 ℃ of initial column temperatures are kept 1min, and 5 ℃/min is warming up to 280 ℃, keeps 14min.Running parameter is measured in the mass spectrum aspect: 200 ℃ of ion trap temperature; 45 ℃ of menifold temperature; 200 ℃ of transmission line temperature; Ionization mode: EI, 70ev; Solvent delay 10min; Sweep limit 40～650, autoscan.Through comparing, just can correctly carry out qualitative at last to types of unknown pollutants in the sewage with the NIST storehouse.On positive determinacy basis, can seek the source of pollutant, to the evaluation of contamination accident, handle important evidential function is arranged to pollutant.Its advantage is: simple to operate, practical, good separating effect, pretreatment technology is enhanced about more than once analyzing and testing efficient simultaneously, can be used as the foundation that contamination accident is handled.
The practical implementation method
At first, extract pre-treating method simultaneously: get the sewage 500ml that need to detect, with 500ml sewage through mechanical filter; Filtered sewage is placed separating funnel; Divide three extractions with methylene chloride-sherwood oil mixed liquor 40mL, 40mL, 20mL, behind the combining extraction liquid extract is divided into two parts, a with 0.1mol/L sulfuric acid accent pH to 3; A with 0.125mol/L sodium hydroxide solution accent pH to 11, extract purifies with the 30g/L metabisulfite solution.Again two parts of extracts are passed through alumina chromatographic column, collect filtered fluid and be concentrated into 2mL at 40 ℃ of water-bath rotary evaporations, subsequent use.
Second step: use gas chromatography-mass spectrography above-mentioned treated sewage is carried out qualitative analysis, its mensuration running parameter is:
1, gas chromatography parameter: the injection port initial temperature is a normal temperature, keeps 0.75min, and 200 ℃/min rises to 280 ℃, keeps 1min, initial split ratio 1: 20, and 0.01min split ratio 1: 100,0.75min closes split ratio, 3.00min split ratio 1: 100; Column flow rate 1.2mL/min; Temperature programme, 55 ℃ of initial column temperatures are kept 1min, and 5 ℃/min is warming up to 280 ℃, keeps 14min.
2, mass spectrum parameter: 200 ℃ of ion trap temperature; 45 ℃ of menifold temperature; 200 ℃ of transmission line temperature; Ionization mode: EI, 70ev; Solvent delay 10min; Sweep limit 40～650, autoscan.
With scanning result, through comparing, just can correctly carry out qualitatively to multiple types of unknown pollutants in the sewage with the NIST storehouse, just can confirm which hazards of pollutants.
By the invention described above method many contamination accidents are detected; Detected classes of compounds such as group thiophosphate, pyrazoles, organophosphorus pesticide class, chrysanthemum ester class, pyridines, benzene series thing and chlorobenzene class, phenol, phenyl amines, for the contaminated solution accident provides the data support.Blank interpolation test is carried out to 48 kinds of organophosphoruss and organo-chlorine pesticide in the laboratory, and utilization the inventive method is carried out check and analysis, and 48 kinds of organism all detect, detection limit scope 0.02 μ g/L-0.2 μ g/L.
Aspect the caused legal dispute of contaminated solution,, support the present invention of following illustration is arranged simultaneously through the enforcement of the invention described above:
Illustration 1:2004; Mass mortality repeatedly appears in the aquaculture organism in Longwan District mudflat aquaculture district, Wenzhou City, Zhejiang Province; Loss surpasses 1,000 ten thousand yuan, suspects relevantly with near the blowdown of industrial park, but this industrial park does not provide the condition of production and the pollutant data of factory.Through the waste water of gathering this Craft in Chemical Industrial Area sewage draining exit, the seawater of culture zone; Measure and analyze according to method of the present invention, in waste water and culture zone seawater, all detect agricultural chemicals and a large amount of agricultural chemicals synthetic intermediate, raw materials such as chlopyrifos, methidathion, Hostathion.Confirm through searching data; There is overt toxicity in these chemical substances to the biology of culture zone; Confirm through social investigation simultaneously; Be this industrial park relevant enterprise with the detected organism of this method and produce product, raw material, intermedium, thereby the death that the garden aquatic biological is cultured in very fast affirmation causes just because of the industrial park blowdown.
Illustration 2:2005, the white shrimp mass mortality of spine end of culturing in the pool in the white shrimp aquaculture of Putuo District, Zhoushan City, Zhejiang Province spine end field lose hundreds thousand of units, and near the shrimp that other culture the pool is all safe and sound, and the raiser is very puzzled to the cause of death of the white shrimp of spine end.The inventor has gathered in this breed pool 1 bottle of water sample, carries out check and analysis according to the inventive method, detects to contain Hostathion and two kinds of agricultural chemicals to the high poison of the white shrimp of spine end of sulfotep in the water body, and clue is investigated in view of the above, is that agricultural chemicals is improper to be caused because near peasant household uses.
Illustration 3:2007, the Penaeus Vannmei generation mass mortality that the Putuo District, Zhoushan City, Zhejiang Province raiser cultures is lost more than 10 ten thousand yuan, and the raiser suspects has the people to poison, and reports public security organ immediately, but because of pollutant is not clear investigation is had reached an impasse.The inventor has gathered water sample in this breed pool, carries out check and analysis according to the inventive method, in water body, detects fenvalerate.Clue in view of the above, public security organ has arrested the molecule of poisoning very soon, makes it obtain the sanction of law.
Claims (1)
1. a method of measuring multiple types of unknown pollutants in the sewage is characterized in that, this method follows these steps to operation:
One, extract pre-treating method simultaneously, get the sewage 500ml that need to detect, with 500ml sewage behind mechanical filter; Filtered sewage is placed separating funnel; Divide three extractions with methylene chloride-sherwood oil mixed liquor 40mL, 40mL, 20mL, behind the combining extraction liquid extract is divided into two parts, a with 0.1mol/L sulfuric acid accent pH to 3; A with 0.125mol/L sodium hydroxide solution accent pH to 11; Extract purifies with the 30g/L metabisulfite solution, again two parts of extracts is passed through alumina chromatographic column, collects filtered fluid and is concentrated into 2mL at 40 ℃ of water-bath rotary evaporations;
Two, use gas chromatography-mass spectrography, the concrete mensuration running parameter of instrument is:
A, gas chromatography parameter: the injection port initial temperature is a normal temperature, keeps 0.75min, and 200 ℃/min rises to 280 ℃, keeps 1min, initial split ratio 1: 20, and 0.01min split ratio 1: 100,0.75min closes split ratio, 3.00min split ratio 1: 100; Column flow rate 1.2mL/min; Temperature programme, 55 ℃ of initial column temperatures are kept 1min, and 5 ℃/min is warming up to 280 ℃, keeps 14min;
B, mass spectrum parameter: 200 ℃ of ion trap temperature; 45 ℃ of menifold temperature; 200 ℃ of transmission line temperature; Ionization mode: EI, 70ev; Solvent delay 10min; Sweep limit 40～650, autoscan.
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| CN102183596B (en) * | 2011-03-02 | 2013-11-20 | 江南大学 | Method for detecting antibiotic residue in honey based on rapid classification extraction technology |
| US20190257068A1 (en) * | 2014-01-24 | 2019-08-22 | Waterup Pty Ltd | A system for environmental spills protection |
| CN104502497B (en) * | 2014-12-04 | 2016-05-25 | 苏州国环环境检测有限公司 | The residual detection method of methidathion in a kind of ripe orange |
| CN108061681A (en) * | 2017-12-25 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | The detection method of Manganese in Waste Water ion |
| CN111537651A (en) * | 2020-06-16 | 2020-08-14 | 青岛海关技术中心 | Method for detecting heavy oil pollutants in aquatic products |
| CN113945650A (en) * | 2021-09-09 | 2022-01-18 | 国家粮食和物资储备局科学研究院 | Method for simultaneously analyzing persistent organic pollutants in grains |
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| CN101000330A (en) * | 2007-01-12 | 2007-07-18 | 清华大学 | Method for investigating estrogen active constribution material in sewage |
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| CN101000330A (en) * | 2007-01-12 | 2007-07-18 | 清华大学 | Method for investigating estrogen active constribution material in sewage |
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| 乔玉霜等.污水处理厂污泥中几种典型酚类内分泌干扰物的调查.《环境化学》.2007,第26卷(第5期),671-674. * |
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