CN103076417A - Method for synchronously extracting organic pollutants in water sample - Google Patents
Method for synchronously extracting organic pollutants in water sample Download PDFInfo
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- CN103076417A CN103076417A CN2012105391816A CN201210539181A CN103076417A CN 103076417 A CN103076417 A CN 103076417A CN 2012105391816 A CN2012105391816 A CN 2012105391816A CN 201210539181 A CN201210539181 A CN 201210539181A CN 103076417 A CN103076417 A CN 103076417A
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Abstract
The invention relates to a method for synchronously extracting organic pollutants in a water sample. The method is suitable for the pretreatment process of the water sample through a gas chromatography-mass spectrometry analyzer. The method for synchronously extracting organic pollutants in the water sample comprises the following steps: 1, sample dehydration: putting 10-20mL of a sample filtered through a 0.45mum filter membrane into a watch glass, and placing in a 40-50DEG C baking box for 10h to completely evaporate water in the sample in the watch glass; and 2, organic matter dissolving: carrying out ultrasonic crushing, carrying out oscillation dissolving, centrifuging, and taking the obtained supernatant in a sample bottom as a sample for the gas chromatography-mass spectrometry analyzer. The method for synchronously extracting organic pollutants in the water sample has the advantages of simple and convenient operation, less organic solvent consumption, high extraction efficiency, low cost and the like.
Description
Technical field:
The present invention relates to the synchronous extracting process of organic contaminant in a kind of water sample, belong to the environmental monitoring field.
Background technology:
Along with the fast development of China's industry, the discharge capacity of organic wastewater increases day by day, and the kind of organic contaminant is also increasingly sophisticated.Organic contaminant in the water body mainly comprises phenolic compound, amino benzenes compounds, total organic halogen, polycyclic arene compound etc.Some Organic Pollutants can in the medium-term and long-term accumulation of environment, cause serious threat to ecologic environment and human health.Important prerequisite to its quantitative test and risk assessment to the qualitative analysis of Organic Pollutants In Water.At present, mainly adopt organic contaminant pre-service-gas chromatograph-mass spectrometer (GCMS) (GC-MS) that organic contaminant is carried out qualitative analysis.
The pretreated fundamental purpose of water sample is the extraction of organic contaminant and concentrates.After pretreatment, could adopt GC-MS that organic contaminant is carried out the qualitative detection analysis.At present, extracting process commonly used mainly contains liquid-liquid extraction, Solid-Phase Extraction, solid-phase microextraction etc.
Liquid-liquid extraction method mainly is to utilize the different solubility of organism in water and organic solvent, selects suitable organic solvent that the organism in the water sample is extracted.Liquid-liquid extraction method is traditional organism extracting process, but needs to consume a large amount of poisonous organic solvents, be detrimental to health, and contaminated environment, cost is higher, and reappearance is relatively poor.
Solid phase extraction (SPE) is the Sample Pretreatment Technique Used that development in recent years is got up, and the advantage such as have that device is simple, solvent-oil ratio is few can be used for pre-treatment and the enrichment of trace in the environmental sample or micro-content organism.Develop at present polytype commercialization solid-phase extraction column, comprised nonpolar, polarity, cation exchange, preparing anion exchange extracting post etc.But use a kind of extraction column can only extract the organism of a certain type in the water sample, may cause the loss of part target contaminant.Simultaneously, the activation of Solid-Phase Extraction process need, loading, drip washing, wash-out and the operation such as concentrated, consuming time longer, complex operation.
Solid phase micro-extraction technique (SPME) is the non-solvent selective extraction method that grows up the nineties in 20th century, mainly utilize the fiber head in the solid-phase microextraction post to immerse in the sample solution or a period of time in the head space gas, agitating solution is to accelerate two alternate equilibrium rates simultaneously, behind the ready to balance gas chromatography vaporizer, the material that adsorbs on the thermal desorption coating are inserted in the fiber head taking-up.Because related micro-extraction post and micro-extraction device are expensive, and single micro-extraction post is high to organic selectivity in the water sample, has limited its widespread use in the actual complex water sample.
Summary of the invention:
The invention reside in and overcome the problem that exists in the background technology, and the synchronous extracting process of organic contaminant in a kind of water sample is provided.The synchronous extracting process of organic contaminant in this water sample can be realized the synchronous extraction of multiple organic contaminant of different nature in the actual complex water sample, and extraction efficiency is high, and cost is lower, thereby has good application prospect.
The present invention solves its problem and can reach by following technical solution: the synchronous extracting process of organic contaminant in a kind of water sample may further comprise the steps:
(1) sample dehydration
With water sample to be measured through 0.45 μ m filtering with microporous membrane, water sample is in surface plate after getting the filter of 10～20mL, surface plate is positioned in a conventional oven, temperature setting is set to 40～50 ℃, drying time is about 10h, the moisture that guarantees sample in the surface plate is evaporated to dried fully, and the trace in the water sample or the organism of trace will remain on the surface plate;
(2) organism dissolving
A. ultrasonication
In surface plate, add the organic solvent of 2mL, surface plate is placed the ultrasonic 10min of Ultrasound Instrument, make the organism residue on the surface plate broken, in order to be dissolved in the organic solvent that adds;
B. vibration dissolving
With the sample in the surface plate, comprise not consoluet organism residue, all be transferred in the centrifuge tube of 2mL; Centrifuge tube is placed the 10min that vibrates on the vortex oscillation device, accelerate the dissolving of organism in organic solvent;
C. centrifuging
Centrifuge tube is positioned over centrifugal 5min in the small-sized high speed centrifugal machine, and centrifugal speed is 10000 rev/mins;
Centrifugally get supernatant in the centrifuge tube with pipettor afterwards, namely can be used as the sample of gas chromatography-mass spectrography analyser, the organism in the former water sample is carried out qualitative or quantitative test.
Described organic solvent is a kind of in formamide, acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, pyridine, acetone, tetrahydrofuran, ethyl acetate, ether, diphenyl ether, methylene chloride, chloroform, ethylene dichloride, toluene, benzene, phenixin, carbon disulphide, cyclohexane or the sherwood oil.Can according to the character of organic contaminant in the actual water sample, select the close organic solvent of polarity.
The present invention makes at first that hydrone fully evaporates in the water sample, then add suitable organic solvent and make organism dissolving residual in the water sample, and adopt ultrasonic-vortex oscillation to accelerate the course of dissolution of organism in organic solvent, and carrying out at last high speed centrifugation, the sample that can obtain GC-MS detects.
Know-why of the present invention is:
(1) evaporation of moisture in the water sample
The surface area of the evaporation of moisture and the temperature of moisture surface, liquid is relevant with the flowing velocity of liquid surface.With water sample to be measured through 0.45 μ m filtering with microporous membrane after, get the filter of 10～20mL after water sample in surface plate, can greatly increase the surface area of water sample.Surface plate is placed baking oven, and temperature setting is set to 40～50 ℃.On the one hand, selected evaporating temperature can guarantee to be higher than room temperature, with the speed of the evaporation that moisturizes, does not cause again the organism volatilization in the water; On the other hand, the Air Flow in the baking oven also can accelerate the evaporation of moisture in the water sample.In the confined space of baking oven, the evaporation process that can guarantee water sample is not subjected to interference and the pollution of suspended particle in the outside air.
(2) organic dissolving in the water sample
The dissolving in organic solvent of the dehydration of water sample and organism is that substep carries out among the present invention, has improved the dissolution degree of organism in organic solvent.After moisture evaporated fully in the water sample, organic substance residues was on surface plate.According to the similar principle that mixes, select the organic solvent similar to organic polarity in the water sample to be measured, in surface plate, add organic solvent 2mL.
Because the organism in the water sample exists with the solid residue form, has affected its dissolution velocity in organic solvent.Place Ultrasound Instrument to carry out ultrasonic processing 10min surface plate, can the organism residue is effectively broken.Then the sample in the surface plate and not consoluet organism all are transferred in the centrifuge tube of 2mL.Centrifuge tube is placed the 10min that vibrates on the vortex oscillation device, make organism fully dissolving in organic solvent.
(3) sample is centrifugal
Above-mentioned 2mL centrifuge tube is positioned over centrifugal 5min in the small-sized high speed centrifugal machine, and centrifugal speed is 10000 rev/mins.Get the centrifuge tube supernatant in sample bottle, as the test sample of GC-MS, organic cycles of concentration is about 10 in the sample.
The synchronous extracting process of organic contaminant can be applicable to the pre-service of actual complex water sample in the water sample of the present invention.
The present invention compares with the above-mentioned background technology can have following beneficial effect: the synchronous extracting process of organic contaminant in this water sample, all adopt the laboratory conventional equipment, and do not need extra equipment, operating process is simple, good reproducibility; The consumption of organic solvent is little among the present invention, and cost is low, can not produce secondary pollution; The loss of analyte is little among the present invention, only needs less water sample can reach the requirement of trace or organic micro-pollutant extraction; The present invention can select dissimilar organic solvents to dissolve according to the character of target analytes when reality is used, and realizes the synchronous extraction of Some Organic Pollutants in the complicated water sample.Can realize synchronous enrichment and the extraction of Some Organic Pollutants in potable water, surface water and the industrial waste water water sample.This extracting process environmental friendliness has good economy and environment benefit.
Description of drawings
Fig. 1 is the extraction procedure figure of organic contaminant in the water sample of the present invention;
Fig. 2 is that waste water from dyestuff adopts GC-MS to detect the resulting chromatogram of analysis after extraction process pre-service of the present invention.
Embodiment:
The invention will be further described below in conjunction with the accompanying drawings and the specific embodiments:
Embodiment 1
As shown in Figure 1, get the water sample behind the azo dyes acid orange 7 oxidative degradation 3h, extract in accordance with the following steps: water sample gets that water sample is in the surface plate of 15cm to diameter after the 20mL filter behind 0.45 μ m filtering with microporous membrane; Surface plate is placed baking oven about 10h under 45 ℃ of conditions, make that the moisture of sample evaporates fully in the surface plate; Surface plate is taken out from baking oven, and add the methyl alcohol of 2mL, surface plate is positioned over ultrasonic 10min in the Ultrasound Instrument; Sample in the surface plate is transferred in the centrifuge tube of 2mL, centrifuge tube is placed the 10min that vibrates on the vortex oscillation device; Centrifuge tube is placed the centrifugal 5min of small-sized high speed centrifugal machine, and centrifugal speed is 10000 rev/mins, gets supernatant in sample bottle after centrifugal; Sample after adopting GC-MS to extraction carries out qualitative analysis and detects, and the GC-MS gas phase separation adopts DB-5 capillary column (30mm * 320 μ m * 0.5 μ m), and mass detector (MSD) adopts EI ionization source (70eV), and ion source temperature is 230 ℃.Carrier gas (He) flow is 1.0mL/min, and sample size is 1 μ L, and injector temperature is 250 ℃, adopts not shunt mode.The chromatographic column adopting temperature programme, heating schedule is as follows: 40 ℃ keep 2min, and the speed with 10 ℃/min is warming up to 150 ℃ again, keep 2min, and then the speed with 8 ℃/min is warming up to 200 ℃, and keep 5min.The NIST08 standard spectrum picture library that the evaluation of catabolite adopts GC-MS to carry, matching degree is greater than 90%.
GC-MS analysis result to this sample shows that this waste water from dyestuff still contains multiple compound fragrant hydrocarbon after treatment, and analysis of spectra as shown in Figure 2.The organic contaminant relevant information that detects is as shown in table 1, and a is coumarone in the spectrogram, and b is 1 (3) hydrogen-isobenzofuranone, and c is 1,3-indandione, d are paranitroanisole, and e is cumarin, f is repefral, and g is phthalimide, and h is the 1-aminoidan.Therefore, the present invention all has higher extraction efficiency to Some Organic Pollutants in the waste water from dyestuff.
The organic contaminant information that table 1 detects
Claims (3)
1. the synchronous extracting process of organic contaminant in the water sample may further comprise the steps:
(1) sample dehydration
With water sample to be measured through 0.45 μ m filtering with microporous membrane, water sample is in surface plate after getting the filter of 10 ~ 20 mL, surface plate is positioned in a conventional oven, temperature setting is set to 40 ~ 50 ℃, drying time is about 10 h, the moisture that guarantees sample in the surface plate is evaporated to dried fully, and the trace in the water sample or the organism of trace will remain on the surface plate;
(2) organism dissolving
A. ultrasonication
In surface plate, add the organic solvent of 2 mL, surface plate is placed ultrasonic 10 min of Ultrasound Instrument, make the organism residue on the surface plate broken, in order to be dissolved in the organic solvent that adds;
B. vibration dissolving
With the sample in the surface plate, comprise not consoluet organism residue, all be transferred in the centrifuge tube of 2 mL; Centrifuge tube is placed vibration 10 min on the vortex oscillation device, accelerate the dissolving of organism in organic solvent;
C. centrifuging
Centrifuge tube is positioned over centrifugal 5 min in the small-sized high speed centrifugal machine, and centrifugal speed is 10000 rev/mins;
Centrifugally get supernatant in the centrifuge tube with pipettor afterwards, namely can be used as the sample of gas chromatography-mass spectrography analyser, the organism in the former water sample is carried out qualitative or quantitative test.
2. the synchronous extracting process of organic contaminant in a kind of water sample according to claim 1 is characterized in that: described organic solvent is a kind of in formamide, acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, pyridine, acetone, tetrahydrofuran, ethyl acetate, ether, diphenyl ether, methylene chloride, chloroform, ethylene dichloride, toluene, benzene, phenixin, carbon disulphide, cyclohexane or the sherwood oil.
3. the synchronous extracting process of organic contaminant is used for extraction and the enrichment of actual complex water sample organic contaminant in a kind of water sample claimed in claim 1.
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| CN108362791A (en) * | 2018-01-30 | 2018-08-03 | 中国农业科学院茶叶研究所 | Phthalimide detection method in a kind of tealeaves |
| CN114441700A (en) * | 2021-12-24 | 2022-05-06 | 江苏赫尔斯检测技术有限公司 | Method for determining deltamethrin in water based on gas-mass linkage method |
| CN114965799A (en) * | 2022-08-02 | 2022-08-30 | 山东杰诺检测服务有限公司 | Method for rapidly determining residual quantity of various pesticides in food |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108362791A (en) * | 2018-01-30 | 2018-08-03 | 中国农业科学院茶叶研究所 | Phthalimide detection method in a kind of tealeaves |
| CN108362791B (en) * | 2018-01-30 | 2020-07-28 | 中国农业科学院茶叶研究所 | Method for detecting phthalimide in tea |
| CN114441700A (en) * | 2021-12-24 | 2022-05-06 | 江苏赫尔斯检测技术有限公司 | Method for determining deltamethrin in water based on gas-mass linkage method |
| CN114965799A (en) * | 2022-08-02 | 2022-08-30 | 山东杰诺检测服务有限公司 | Method for rapidly determining residual quantity of various pesticides in food |
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