CN105044236B - Dispersive solid-phase extraction gas chromatography method for polychlorinated biphenyls in soil and sediment - Google Patents
Dispersive solid-phase extraction gas chromatography method for polychlorinated biphenyls in soil and sediment Download PDFInfo
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Abstract
Belonging to the technical field of soil and sediment pollution detection, the invention relates to a dispersive solid-phase extraction gas chromatography method for polychlorinated biphenyls (PCBs) in soil and sediment. The method includes: adding n-hexane into a soil or sediment sample to conduct ultrasonic extraction, when the extraction liquid is basically colorless and transparent, subjecting the extraction liquid to rotary evaporation till dry, adding n-hexane, then adding 50-200mg of a N-propylethylenediamine solid phase adsorption agent to carry out dispersive solid-phase extraction, performing centrifugal layering, and introducing 1microliter of the supernatant into a gas chromatography-electron capture detector to conduct detection, otherwise adding a concentrated sulfuric acid purification step after ultrasonic extraction. The detection limit of 7 polychlorinated biphenyls is 0.02-0.03 microgram/kg, the recovery rate is 72-115%, and the relative standard deviation (n=5) is 3.5-6.9%. The method provided by the invention is simple and sensitive, and can quickly realize batch detection of PCBs in soil and sediment.
Description
Technical field
The invention belongs to soils and sediments pollution detection technical field, be related to PCB28 in a kind of soils and sediments,
The dispersive solid-phase extraction of PCB52, PCB101, PCB118, PCB153, PCB138, PCB1807 kind " indicative Polychlorinated biphenyls " monomer
Gas-chromatography detection method.
Background technology
Polychlorinated biphenyls as a kind of typical persistence organic pollutant be widely distributed in water, air, soil, bed mud,
In the surrounding mediums such as organism, there is stronger " three-induced effect " to human body, once by as heat exchanging agent, lubricant, transformator and
Dielectric, plasticizer in capacitor, paraffin expand agent, binding agent, organic diluent, dedusting agent, cutting oil and carbon-free
The important chemical products such as carbon paper, are widely used in the fields such as electric power, plastic processing, chemical industry and printing, to human health and
Ecological environment constitutes grave danger, is May calendar year 2001《Convention of Stockholm》One of 12 kinds of priority pollutants.Although many
Chlordiphenyl is stopped using for many years, but because the characteristics such as its persistency and hydrophobicity cause it to remain in the environment and accumulate.Soil
Earth and bed mud be Polychlorinated biphenyls in the environment the important carrier of Transport And Transformation, home to return to and savings storehouse.Therefore, analysis determines soil
Or Polychlorinated biphenyls are just of great significance in bed mud.
At present, both at home and abroad mainly using oscillation extraction, surname extraction, ultrasonic extraction, microwave auxiliary extraction, plus quick-dissolving agent
The abstraction techniques such as extraction, supercritical fluid extraction, Subcritical Water Extraction, ooze with reference to concentrated acid sulfonation purification, Solid-Phase Extraction, gel
One or two purification methods such as saturating chromatograph, solid-phase microextraction, headspace solid-phase microextraction, dispersive liquid-liquid microextraction, then using gas
The technologies such as phase chromatograph electron capture detection method, GC-MS, gas chromatogram tandem mass spectrometry are carried out in soil or bed mud
Polychlorinated biphenyls are detected.
Soil or bed mud sample matrices are complicated, and pre-treatment and purifying step become the pass that residual polychlorinated biphenyl is analyzed in sample
Key.But traditional extracting process long processing period such as oscillation extraction, surname extraction, solvent-oil ratio are big.Microwave auxiliary extraction, plus
The instruments such as quick-dissolving agent extraction, supercritical fluid extraction and technical costss are of a relatively high.And ultrasonic extraction can not only be effectively
Constitutionally stable Organic substance is extracted from solid sample, and it is cheap, simple to operate etc. excellent with efficiency high, instrument price
Point, is much reported at present with Polychlorinated biphenyls in the method extraction soil or bed mud.Gel permeation chromatography cleaning equipment is held high relatively
Expensive, process cycle is longer, and need to consume a large amount of eluting solvents.Solid-phase microextraction and headspace solid-phase microextraction, extracting head cost compared with
Height, extraction coating is easy to wear, and sample needs parsing after extraction, and service life is shorter, is used for multiple times and cross-contamination issue also exist,
And solid-phase microextraction cannot be directly used to the process of solid sample, it is necessary to first Jing liquid-solid extraction.Dispersive liquid-liquid microextraction is mainly fitted
Simple Liquid matrix sample is closed, for the process of complicated solid matrix needs is converted into fluid matrix, and matrix effect is also easy to produce.Cause
And, for the removal of the impurity such as the pigment in soil or bed mud, oils and fatss, document report it is most be after concentrated sulfuric acid purification in conjunction with
Solid phase extraction.Concentrated sulfuric acid cleanup method can remove most interference impurity, but have impurity to have interference to PCB52 all the time,
Sometimes interference is also had to PCB28.Although preferably, complex operation needs to carry out extraction column work solid phase extraction clean-up effect
The processes such as change, loading, drip washing, eluting, it is time-consuming longer, be not suitable for mass sample treatment.Dispersive solid-phase extraction has quick, letter
Single, cheap, effective, reliable and safe the characteristics of, various organic dirts in various agricultural byproducts and surrounding medium have progressively been applied to
Dye analyte detection.But current domestic and foreign literature is consulted, not yet has document report that dispersive solid-phase extraction is applied to into soil or deposit
Analysis of PCBs purification in sample.
The content of the invention
For the deficiency of the studies above present situation, the present invention is according to analysis of PCBs present situation in soils and sediments, there is provided
The dispersive solid-phase extraction gas-chromatography detection method of Polychlorinated biphenyls in a kind of soils and sediments, the method is successively including sample
Collection and sample preparation, sampling and ultrasonic extraction, concentrated sulfuric acid purification concentrates constant volume, dispersive solid-phase extraction purification, gas chromatogram-electricity
Sub- acquisition detector detection, Specification Curve of Increasing, sample and determination of recovery rates.
The inventive method is comprised the following steps：
Step (1). the collection and sample preparation of sample：
Soils and sediments sample to be detected is placed in freezer dryer and is dried 12~24h, took out 80~100 mesh
Stainless steel sift, is placed in be measured in exsiccator；
Described soils and sediments sample to be detected can adopt clean In Aluminium Foil Packing and be sealed in polyethylene bags
In transported；
Step (2). sampling and ultrasonic extraction：
10.00g testing samples are weighed, 20~40mL normal hexane is added, be vortexed 1~3min, with 400~500W power in 30
~40 DEG C of 20~40min of ultrasonic extraction；When the ambient interferences of sulfur-containing compound in sample, 1~3g copper powders ultrasound can be added
Desulfurization, 3000~6000r/m, 3~5min of high speed centrifugation, takes supernatant, as hexane extract；Observation extracting solution color, if
It is substantially colorless transparent, directly carry out step (4) concentration constant volume, i.e., only need a step to purify, otherwise carry out step (3) concentrated sulphuric acid net
Change, that is, need two steps to purify；
Described copper powder first removes its surface film oxide using front with dilute hydrochloric acid process, then is removed with distilled water flushing attached
In a small amount of acid on its surface, finally flow down with acetone rinsing and in high pure nitrogen (v/v, 99.99 ﹪) and dry up, in case copper powder is by again
Secondary oxidation；
Described step purification is that, when extracting solution color is substantially colorless transparent, sample purification only needs to carry out dispersed solid phase
Extracting operation；
Described two steps purification is that, when extracting solution color is not substantially colorless transparent, sample needs to carry out concentrated sulphuric acid simultaneously
Purification and dispersive solid-phase extraction purification；
Step (3). concentrated sulfuric acid purification：
1~3mL of concentrated sulphuric acid is added in the hexane extract that step (2) is obtained, 1~3min is vibrated, stratification is abandoned
Sub-cloud concentrated sulphuric acid waste liquid, can repeatedly add concentrated sulfuric acid purification colourless to concentrated sulphuric acid layer as needed, then use 30g/L aqueous sodium sulfates
Liquid washs hexane extract to neutrality；
Step (4). concentration constant volume：
By hexane extract anhydrous sodium sulfate dehydration, then in pump vacuum 0.08~0.09MPa of degree, bath temperature 35
~40 DEG C, under 50~100rpm of rotating speed, it is evaporated to dryness with Rotary Evaporators, adds n-hexane dissolution, is settled to 1.0mL, is obtained
N-hexane dissolution liquid；
Step (5). dispersive solid-phase extraction is purified：
50~200mg N- propyl group ethylenediamine solid-phase adsorbents are added in 1mL n-hexane dissolution liquid, be vortexed 30~60s,
3000~6000r/m, 1~3min of high speed centrifugation, take supernatant；
Step (6). gas chromatography-electron capture detector is detected：
Sample introduction needle extracts above-mentioned supernatant, is detected according to the gas chromatography-electron capture detector condition for setting；
Chromatographic condition is：Injector temperature is 260 DEG C；Electron capture detector temperature is 300 DEG C；Carrier gas be high pure nitrogen (v/v,
99.999 ﹪), flow velocity is 1mL/min；Sampling volume is 1 μ L；Input mode is Splitless injecting samples, and after 0.75min, split ratio is
50:1；Gas chromatographic column heating schedule is：120 DEG C of holding 1min, 10 DEG C/min is warming up to 200 DEG C, then is warming up to 2 DEG C/min
240 DEG C, finally 270 DEG C are warming up to 15 DEG C/min, keep 1min, total run time is 32min.
Described gas chromatographic column is from the CD-5MS capillary gas chromatographies that specification is 30m × 0.25mm × 0.25 μm
Post, fixing phase is the mixed liquor of diphenyl and dimethyl polysiloxane, and wherein the mass fraction of diphenyl is 5 ﹪, and dimethyl gathers
The mass fraction of siloxanes is 95 ﹪, can realize efficiently separating for 7 kinds of Polychlorinated biphenyls；
Step (7). Specification Curve of Increasing：It is qualitative with retention time, quantified by external standard method
When retention time is qualitative, standard solution is carried out operating obtaining standard solution according to the requirement of above-mentioned steps (6)
Gas chromatogram, and carry out retention time with the gas chromatogram of single analyte and compare, when determining the reservation of 7 kinds of Polychlorinated biphenyls
Between；When the retention time of this 7 kinds of Polychlorinated biphenyls is to as quantified by external standard method, the foundation of 7 kinds of Polychlorinated biphenyls chromatographic peak identifications.
Solute is Polychlorinated biphenyls in described standard solution, and solvent is normal hexane, and concentration is 10 μ g/L；Wherein many chlorine connection
Benzene includes PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180.
The step of preparing standard solution can be：Take the Polychlorinated biphenyls hybrid standard that concentration is 100 μ g/L and use the μ of liquid 100
L, with normal hexane 1mL is settled to, and obtains standard solution.
During quantified by external standard method, by the standard curve serial solution of six kinds of different spiked levels, according to the Polychlorinated biphenyls for adding
The corresponding relation of concentration and peak area sets up standard curve.
Solute is Polychlorinated biphenyls in described standard curve serial solution, and solvent is normal hexane, and concentration range is 1.25
~100 μ g/L.
The preparation steps of standard curve serial solution are：Taking the Polychlorinated biphenyls hybrid standard that concentration is 100 μ g/L respectively makes
With the μ L of liquid 12.5,25,50,100,500,1000,1mL is settled to normal hexane, obtains six spiked levels scopes and be 1.25
The standard curve serial solution of~100 μ g/L.
Table 1 is the equation of linear regression, the range of linearity, correlation coefficient and detection limit of the inventive method.As shown in Table 1, respectively
Polychlorinated biphenyls, with good linear relationship, meet analysis method requirement in the corresponding range of linearity.
The equation of linear regression of the inventive method of table 1, the range of linearity, correlation coefficient and detection limit
Wherein, a：Y and x represent respectively the theoretical concentration of the peak area and analyte of analyte in 1mL normal hexane；b：Line
Property scope represents concentration of the analyte in standard curve serial solution；
Step (8). sample and determination of recovery rates：
By the actual sample for collecting, operated according to the requirement of above-mentioned steps (1)~(6), and with above-mentioned steps (7)
The standard curve for obtaining compares, and by conversion the content of 7 kinds of Polychlorinated biphenyls in actual sample is finally given；
By the mark-on sample of different spiked levels, five parallel behaviour are carried out respectively according to the requirement of above-mentioned steps (2)~(6)
Make, and the standard curve obtained with above-mentioned steps (7) compares, 7 kinds of Polychlorinated biphenyls are finally given in mark-on sample by conversion
Determine concentration；Response rate calculating is carried out according to the following formula：
In formula：R --- the response rate, ﹪；
Cs--- the measure concentration of 7 kinds of Polychlorinated biphenyls, μ g/kg in mark-on sample；
C0--- the concentration of 7 kinds of Polychlorinated biphenyls in actual sample, μ g/kg；
C --- the theoretical spiked levels of 7 kinds of Polychlorinated biphenyls, μ g/kg in mark-on sample；
Described mark-on sample is the sample Jing after adding Polychlorinated biphenyls in the pretreated actual sample of step (1).
Beneficial effects of the present invention：
The present invention determines soil using ultrasonic extraction, dispersive solid-phase extraction purification, gas chromatogram electron capture detection method
With the Polychlorinated biphenyls in deposit, the method is simple to operate, can be rapidly completed sample pre-treatments, when extracting solution color it is substantially colorless
When transparent, step purification (dispersive solid-phase extraction purification) is selected, otherwise need two steps purification (concentrated sulfuric acid purification+dispersed solid phase extraction
Take purification), wherein dispersive solid-phase extraction purification process only needs to 5min, and as a result accurately, the detection of 7 kinds of Polychlorinated biphenyls is limited to 0.02~
0.03 μ g/kg, the response rate is 72~115 ﹪, and relative standard deviation (n=5) is 3.6~6.9 ﹪, with higher sensitivity and
The gratifying response rate and repeatability, can be used for the assay of Polychlorinated biphenyls in soils and sediments.
Description of the drawings
Fig. 1 is the gas chromatogram of 7 kinds of Polychlorinated biphenyls standard solution (10 μ g/L)；
Fig. 2 is the soil sample (A) of the Zhujiajian I., zhoushan Islands first vegetable plot of embodiment 2 collection and the collection of mark-on Zhujiajian I., zhoushan Islands first vegetable plot
The gas chromatogram of soil sample (B)；
Fig. 3 is that the mud sample (A) of the Zhoushan Dai Quyang enhancement releasings marine site of embodiment 3 collection and mark-on Zhoushan Dai Quyang propagation are put
The gas chromatogram of the mud sample (B) of stream marine site collection；
Fig. 4 is sample analysis flow chart；
Wherein, 1.PCB28；2.PCB52；3.PCB101；4.PCB118；5.PCB153；6.PCB138；7.PCB180.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
The instrument and equipment that example below is used mainly has the GC-450 gas chromatograpies that Varian companies of the U.S. produce
(configuration electron capture detector).
Embodiment 1.
Step (1). the collection and sample preparation of sample：
Will collection soils and sediments sample, with clean In Aluminium Foil Packing and be sealed in polyethylene bags, Ran Houyong
Portable refrigerating box transports laboratory back, then sample is placed in freezer dryer is dried 24h, takes out 100 mesh stainless steel sifts, puts
It is to be measured in exsiccator.
Step (2). sampling and ultrasonic extraction：
10.00g testing samples are weighed, in being placed in 50mL centrifuge tubes, 30mL normal hexane, vortex 2min, with 480W work(is added
Rate, when the ambient interferences of sulfur-containing compound in sample, can add 1~3g copper powders ultrasound de- in 30 DEG C of ultrasonic extraction 30min
Sulfur, 6000r/m high speed centrifugation 5min；Observation extracting solution color, if substantially colorless transparent, directly carries out step (4) concentration constant volume,
Only need a step to purify, otherwise carry out step (3) concentrated sulfuric acid purification, that is, need two steps to purify.
Described copper powder first removes its surface film oxide using front with dilute hydrochloric acid process, then is removed with distilled water flushing attached
In a small amount of acid on its surface, finally flow down with acetone rinsing and in high pure nitrogen (v/v, 99.99 ﹪) and dry up, in case copper powder is by again
Secondary oxidation.
Described step purification is, when extracting solution color is substantially colorless transparent, sample purification only needs to carry out disperseing solid
Phase extracting operation.
Described two steps purification is, when extracting solution color is not substantially colorless transparent, sample needs to carry out dense sulfur simultaneously
Acid purification and dispersive solid-phase extraction are purified.
When extraction way choice is carried out, it is contemplated that traditional extracting process such as oscillation extraction, surname extraction processes week
Phase length, solvent-oil ratio are big.The instruments such as microwave auxiliary extraction, accelerated solvent extraction, supercritical fluid extraction and technical costss phase
To higher.And ultrasonic extraction effectively can not only extract constitutionally stable Organic substance from solid sample, and have
Effective percentage is high, instrument price is cheap, simple operation and other advantages, with Polychlorinated biphenyls in the method extraction soil or bed mud not at present
Understatement road.Therefore, the present invention selects ultrasonic extraction extraction soil or the Polychlorinated biphenyls in bed mud.
When purification style selection is carried out, it is contemplated that GPC cleaning equipments are relatively expensive, and process cycle is longer, and need to consume
A large amount of eluting solvents.Solid-phase microextraction and headspace solid-phase microextraction, extracting head is relatively costly, and extraction coating is easy to wear, after extraction
Sample needs parsing, and service life is shorter, is used for multiple times and cross-contamination issue also exist, and solid-phase microextraction cannot be directly used to
The process of solid sample, it is necessary to first Jing liquid-solid extraction.Dispersive liquid-liquid microextraction is mainly suitable for simple Liquid matrix sample, for multiple
Miscellaneous solid matrix needs are processed and are converted into fluid matrix, and are also easy to produce matrix effect.Thus, for the color in soil or bed mud
The removal of the impurity such as element, oils and fatss, document report it is most be in conjunction with Solid phase extraction after concentrated sulfuric acid purification.Concentrated sulfuric acid purification
Method can remove most interference impurity, but have impurity to have interference to PCB52 all the time, also have interference to PCB28 sometimes.Though
So solid phase extraction clean-up effect is preferable, but complex operation, needs to carry out the processes such as extraction column activation, loading, drip washing, eluting,
It is time-consuming longer, be not suitable for mass sample treatment.The present invention substitutes solid phase extraction procedure using dispersive solid-phase extraction, it is only necessary to
Appropriate suitable adsorbent adsorbing contaminant is added in extraction concentrated solution, purification purpose is just can reach.Whole dispersive solid-phase extraction process
5min is at most only needed to, and conventional solid extraction generally needs 50min, greatly shortens the pre-treatment time.
When sample is after ultrasonic extraction, according to the color of extract, step purification or the purification of two steps are flexibly selected, this
It is according to a large amount of sample test experiences.This is because when extract color is substantially colorless transparent, adding concentrated sulfuric acid purification
Afterwards, concentrated sulphuric acid layer is substantially colorless, now regardless of whether carrying out concentrated sulfuric acid purification, the mainly PCB28 of impact analysis analyte detection
With the impurity near PCB52, as long as and carry out dispersive solid-phase extraction purification just can reach clean-up effect.
Step (3). concentrated sulfuric acid purification：
Concentrated sulphuric acid 2mL is added in extracting solution, 2min is vibrated, stratification discards lower floor's concentrated sulphuric acid waste liquid, as needed,
Can repeatedly add concentrated sulfuric acid purification colourless to concentrated sulphuric acid layer, then hexane extract is washed to neutrality with 30g/L aqueous sodium persulfate solutions.
Step (4). concentration constant volume：
After by extracting solution anhydrous sodium sulfate dehydration, at pump vacuum degree 0.09MPa, 35 DEG C of bath temperature, rotating speed
80rpm, is evaporated to dryness with Rotary Evaporators, is added n-hexane dissolution, is settled to 1.0mL, obtains n-hexane dissolution liquid.
Step (5). dispersive solid-phase extraction is purified：
Addition 50~200mg N- propyl group ethylenediamine solid-phase adsorbents in 1mL n-hexane dissolution liquid, vortex 30s,
6000r/m high speed centrifugation 2min, take supernatant.
When dispersive solid-phase extraction purification is carried out, the species and consumption of solid-phase adsorbent are optimized.Compare
The clean-up effect of 100mg N- propyl group ethylenediamine adsorbents and 100mg C18 adsorbents.As a result show, C18 adsorbents pair
PCB28, PCB52 impurity purification nearby there is not effect, and PSA adsorbents can effectively eliminate the interference that impurity is detected to PCB28, PCB52.
This is possibly due to N- propyl group ethylenediamines adsorbent and can effectively remove affect the carbohydrate of target analyte detection, fatty acid, have
The interference of machine acid, phenols, saccharide and some polarity pigments, it is nonpolar that C18 adsorbents are mainly used in removal fat and esters etc.
Chaff interference, and concentrated sulfuric acid purification has removed most pigment and fat, and regardless of whether carry out concentrated sulfuric acid purification, PCB28,
PCB52 goes out peak position can have a certain degree of impurity interference.Then, investigate N- propyl group ethylenediamine in the range of 0~200mg to inhale
Impact of the attached agent content to clean-up effect.As a result show, with the increase of N- propyl group ethylenediamine adsorbent amounts, clean-up effect has
Increased, after reaching to a certain degree, adsorbent increases, response rate change is little.But due to N- propyl group ethylenediamine adsorbent meetings
The certain normal hexane of absorption, PSA dosage increases, and after centrifugation, supernatant is reduced, if the steps of final sample Jing two purification (dense sulfur
The purification of acid purification+dispersive solid-phase extraction) when select 50~150mg, if selecting during the steps of Jing mono- purification (only dissipating Solid phase extraction)
100~200mg, now can reach preferable clean-up effect, and the higher response rate is can guarantee that again.
Step (6). gas chromatography-electron capture detector is detected：
Sample introduction needle extracts above-mentioned supernatant, is detected according to the gas chromatography-electron capture detector condition for setting.
Chromatographic condition is：Injector temperature is 260 DEG C；Electron capture detector temperature is 300 DEG C；Carrier gas is high pure nitrogen
(99.999 ﹪), flow velocity is 1mL/min；Sampling volume is 1 μ L；Input mode is Splitless injecting samples, after 0.75min, split ratio
For 50:1；Gas chromatographic column heating schedule is：120 DEG C of holding 1min, 10 DEG C/min are warming up to 200 DEG C, then with 2 DEG C/min intensifications
To 240 DEG C, finally 270 DEG C are warming up to 15 DEG C/min, keep 1min, total run time is 32min.
Described gas chromatographic column is from the CD-5MS capillary gas chromatographies that specification is 30m × 0.25mm × 0.25 μm
Post, fixing phase is the mixed liquor of diphenyl and dimethyl polysiloxane, and wherein the mass fraction of diphenyl is 5 ﹪, and dimethyl gathers
The mass fraction of siloxanes is 95 ﹪, can realize efficiently separating for 7 kinds of Polychlorinated biphenyls.
Step (7). Specification Curve of Increasing：It is qualitative with retention time, quantified by external standard method.
When retention time is qualitative, take concentration be the PCB28 of 100 μ g/L, PCB52, PCB101, PCB118, PCB153,
The Polychlorinated biphenyls hybrid standard of PCB138, PCB180 uses the μ L of liquid 100, and with normal hexane 1mL is settled to, and obtains standard solution, obtains
The standard solution of 10 μ g/L is to concentration.Standard solution is carried out into operation according to the requirement of above-mentioned steps (6), and to obtain standard molten
The gas chromatogram of liquid, and carry out retention time with the gas chromatogram of single analyte and compare, determine the guarantor of 7 kinds of Polychlorinated biphenyls
Stay the time；When the retention time of this 7 kinds of Polychlorinated biphenyls is to as quantified by external standard method, 7 kinds of Polychlorinated biphenyls chromatographic peak identifications according to
According to.Accompanying drawing 1 is the gas chromatogram of standard solution.
During quantified by external standard method, take respectively Polychlorinated biphenyls hybrid standard that concentration is 100 μ g/L use liquid 12.5,25,50,
100th, 500,1000 μ L, with normal hexane 1mL is settled to, and obtains the standard that six spiked levels scopes are 1.25~100 μ g/L
Series of curves solution.By the standard curve serial solution of six kinds of different spiked levels, according to the Polychlorinated biphenyls concentration and peak that add
The corresponding relation of area sets up standard curve.
Table 1 is the equation of linear regression, the range of linearity, correlation coefficient and detection limit of the inventive method.As shown in Table 1, respectively
Polychlorinated biphenyls, with good linear relationship, meet analysis method requirement in the corresponding range of linearity.
The equation of linear regression of the inventive method of table 1, the range of linearity, correlation coefficient and detection limit
Wherein, a：Y and x represent respectively the theoretical concentration of the peak area and analyte of analyte in 1mL normal hexane.
b：The range of linearity represents concentration of the analyte in standard curve serial solution；
Step (8). sample and determination of recovery rates：
Actual sample (the soil sample and Zhoushan Dai Quyang propagation of Zhujiajian I., zhoushan Islands vegetable plot collection of two kinds of different substrates of collection
Release the mud sample of marine site collection), operated according to the requirement of above-mentioned steps (1)~(6), and obtain with above-mentioned steps (7)
Standard curve compares, and by conversion the content of 7 kinds of Polychlorinated biphenyls in testing sample is finally given.
Using above-mentioned actual sample, after processing according to the requirement of (1) step, take 10.00g, be separately added into 12.5,100,
The 100 μ g/L Polychlorinated biphenyls hybrid standards of 1000 μ L use liquid, are configured to low (0.125 μ g/kg), in it is (1.00 μ g/kg) and high
The mark-on sample of (10.0 μ g/kg) three kinds of addition concentration levels, is carried out respectively five times according to the requirement of above-mentioned steps (2)~(6)
Operation repetitive, and the standard curve obtained with above-mentioned steps (7) compares, and by conversion chlorine more than 7 kinds in mark-on sample is finally given
The measure concentration of biphenyl；Response rate calculating is carried out according to the following formula：
In formula：R --- the response rate, ﹪；
Cs--- the measure concentration of 7 kinds of Polychlorinated biphenyls, μ g/kg in mark-on sample；
C0--- the concentration of 7 kinds of Polychlorinated biphenyls in actual sample, μ g/kg；
C --- the theoretical spiked levels of 7 kinds of Polychlorinated biphenyls, μ g/kg in mark-on sample；
After testing, in the soil sample of Zhujiajian I., zhoushan Islands vegetable plot collection and the mud sample of Zhoushan Dai Quyang enhancement releasings marine site collection
7 kinds of Polychlorinated biphenyls concentration are and do not detect, the different substrates actual sample (soil sample and Zhou Shandai of Zhujiajian I., zhoushan Islands vegetable plot collection
The mud sample of thoroughfare ocean enhancement releasing marine site collection) in the recovery testu of different spiked levels levels the results are shown in Table 2.Zhoushan Zhu Jia
The soil sample and the gas chromatogram of the soil sample of mark-on Zhujiajian I., zhoushan Islands vegetable plot collection that certain vegetable plot of point gathers is shown in accompanying drawing 2, Zhou Shandai
The gas chromatogram of the mud sample of thoroughfare ocean enhancement releasing marine site collection and the mud sample of mark-on Zhoushan Dai Quyang enhancement releasings marine site collection
See accompanying drawing 3, whole sample analysis flow chart is shown in accompanying drawing 4.
7 kinds in the soil sample of the Zhujiajian I., zhoushan Islands vegetable plot of table 3 collection and the mud sample of Zhoushan Dai Quyang enhancement releasings marine site collection
The recovery of standard addition of Polychlorinated biphenyls and the precision (n=5) of method
The mud sample of Zhoushan Dai Quyang enhancement releasings marine site collection
Note：A. the unit of measured value is μ g/kg
The measure of 7 kinds of Polychlorinated biphenyls in the soil sample of the Zhujiajian I., zhoushan Islands first vegetable plot of embodiment 2. collection
(1) collection and sample preparation of sample：The soil sample of Zhujiajian I., zhoushan Islands first vegetable plot collection, with clean In Aluminium Foil Packing and seals
In polyethylene bags, then laboratory is transported back with portable refrigerating box, then sample is placed in freezer dryer is dried 24h,
100 mesh stainless steel sifts were taken out, was placed in be measured in exsiccator.
The soil sample of mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection：The Zhujiajian I., zhoushan Islands first vegetable plot collection handled well to 10.00g
Soil sample, the 100 μ g/L Polychlorinated biphenyls hybrid standards for being separately added into 12.5,100,1000 μ L use liquid, are configured to low (0.125 μ g/
Kg), the mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection of (1.00 μ g/kg) and high (10.0 μ g/kg) three kinds of addition concentration levels in
Soil sample.
(2) sampling and ultrasonic extraction：Weigh the Zhujiajian I., zhoushan Islands first vegetable plot collection that 10.00g above-mentioned steps (1) are handled well
Soil sample or mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection soil sample, in being placed in 50mL centrifuge tubes, add 30mL normal hexane, be vortexed
2min, with 480W power in 30 DEG C of ultrasonic extraction 30min, adds 1g copper powder ultrasound desulfurizations, 6000r/m high speed centrifugation 5min；
Extracting solution color is more yellow, carries out two step purifications.
(3) concentrated sulfuric acid purification：Concentrated sulphuric acid 2mL is added in extracting solution, 2min is vibrated, stratification discards lower floor's concentrated sulphuric acid
Waste liquid, repeats said process 3 times, colourless to concentrated sulphuric acid layer, then washs hexane extract with 30g/L aqueous sodium persulfate solutions into
Property.
(4) constant volume is concentrated：After by extracting solution anhydrous sodium sulfate dehydration, in pump vacuum degree 0.09MPa, bath temperature 35
DEG C, under rotating speed 80rpm, it is evaporated to dryness with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution
Liquid.
(5) dispersive solid-phase extraction purification：100mg N- propyl group ethylenediamine solid phase adsorptions are added in 1mL n-hexane dissolution liquid
Agent, vortex 30s, 6000r/m high speed centrifugation 2min, takes supernatant.
(6) gas chromatography-electron capture detector detection：Sample introduction needle extracts the μ L of supernatant 1 that above-mentioned steps (5) are obtained,
Gas chromatography-electron capture detector condition according to setting is detected.Chromatographic condition is：Injector temperature is 260 DEG C；
Electron capture detector temperature is 300 DEG C；Carrier gas is high pure nitrogen (v/v, 99.999 ﹪), and flow velocity is 1mL/min；Sampling volume
For 1 μ L；Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1；Gas chromatographic column heating schedule is：120℃
1min is kept, 10 DEG C/min is warming up to 200 DEG C, then is warming up to 240 DEG C with 2 DEG C/min, is finally warming up to 270 with 15 DEG C/min
DEG C, 1min is kept, total run time is 32min.
Described gas chromatographic column is from the CD-5MS capillary gas chromatographies that specification is 30m × 0.25mm × 0.25 μm
Post, fixing phase is the mixed liquor of diphenyl and dimethyl polysiloxane, and wherein the mass fraction of diphenyl is 5 ﹪, and dimethyl gathers
The mass fraction of siloxanes is 95 ﹪, can realize efficiently separating for 7 kinds of Polychlorinated biphenyls.
(7) Specification Curve of Increasing：It is qualitative with retention time, quantified by external standard method.When retention time is qualitative, takes concentration and be
The Polychlorinated biphenyls hybrid standard of PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L is used
The μ L of liquid 100, with normal hexane 1mL is settled to, and obtains standard solution, obtains the standard solution that concentration is 10 μ g/L.Standard is molten
Liquid carries out operating the gas chromatogram for obtaining standard solution according to the requirement of above-mentioned steps (6), and with the gas phase of single analyte
Chromatogram carries out retention time comparison, determines the retention time of 7 kinds of Polychlorinated biphenyls；The retention time of this 7 kinds of Polychlorinated biphenyls to
During as quantified by external standard method, the foundation of 7 kinds of Polychlorinated biphenyls chromatographic peak identifications.Accompanying drawing 1 is the gas chromatogram of standard solution.
During quantified by external standard method, take respectively Polychlorinated biphenyls hybrid standard that concentration is 100 μ g/L use liquid 12.5,25,50,
100th, 500,1000 μ L, with normal hexane 1mL is settled to, and obtains the standard that six spiked levels scopes are 1.25~100 μ g/L
Series of curves solution.By the standard curve serial solution of six kinds of different spiked levels, according to the Polychlorinated biphenyls concentration and peak that add
The corresponding relation of area sets up standard curve.Table 1 is the equation of linear regression of the inventive method, the range of linearity, correlation coefficient and
Detection limit.As shown in Table 1, each Polychlorinated biphenyls, with good linear relationship, meet analysis method in the corresponding range of linearity
Require.
(8) sample and determination of recovery rates：The soil sample of Zhujiajian I., zhoushan Islands first vegetable plot collection is according to above-mentioned steps (1)~(6)
After requirement is operated, the standard curve obtained with above-mentioned steps (7) compares, and by conversion Zhujiajian I., zhoushan Islands first dish is finally given
The measure concentration of 7 kinds of Polychlorinated biphenyls is and does not detect in the soil sample of ground collection.The soil sample of mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection
Requirement according to above-mentioned steps (1)~(6) carries out respectively five operation repetitives, and the standard curve obtained with above-mentioned steps (7)
Relatively, the measure concentration of 7 kinds of Polychlorinated biphenyls in the soil sample of mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection is finally given by conversion, and
Calculate the response rate, the relative standard deviation of five parallel assays.As shown in Table 2, the soil of mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection
The sample response rate is 72~107 ﹪, and relative standard deviation (n=5) is 3.5~5.8 ﹪, meets analysis method to the response rate and reproduction
Property require.
The measure of 7 kinds of Polychlorinated biphenyls in the mud sample of the Zhoushan Dai Quyang enhancement releasings marine site of embodiment 3. collection
(1) collection and sample preparation of sample：The mud sample of Zhoushan Dai Quyang enhancement releasings marine site collection, with clean In Aluminium Foil Packing
And be sealed in polyethylene bags, then transport laboratory back with portable refrigerating box, then sample is placed in freezer dryer dry
Dry 24h, took out 100 mesh stainless steel sifts, was placed in be measured in exsiccator.
The mud sample of mark-on Zhoushan Dai Quyang enhancement releasings marine site collection：Put to the Zhoushan Dai Quyang propagation that 10.00g is handled well
The mud sample of stream marine site collection, the 100 μ g/L Polychlorinated biphenyls hybrid standards for being separately added into 12.5,100,1000 μ L use liquid, prepare
Into low (0.125 μ g/kg), in (1.00 μ g/kg) and high (10.0 μ g/kg) three kinds of addition concentration levels mark-on Zhoushan Dai Quyang
The mud sample of enhancement releasing marine site collection.
(2) sampling and ultrasonic extraction：Weigh the Zhoushan Dai Quyang enhancement releasings sea that 10.00g above-mentioned steps (1) are handled well
The mud sample of domain collection or the mud sample of mark-on Zhoushan Dai Quyang enhancement releasings marine site collection, in being placed in 50mL centrifuge tubes, add 30mL
Normal hexane, vortex 2min, with 480W power in 30 DEG C of ultrasonic extraction 30min, 6000r/m high speed centrifugation 5min；Extracting solution face
Color base this water white transparency, carries out a step purification.
(3) constant volume is concentrated：After by extracting solution anhydrous sodium sulfate dehydration, in pump vacuum degree 0.09MPa, bath temperature 35
DEG C, under rotating speed 80rpm, it is evaporated to dryness with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution
Liquid.
(4) dispersive solid-phase extraction purification：100mg N- propyl group ethylenediamine solid phase adsorptions are added in 1mL n-hexane dissolution liquid
Agent, vortex 30s, 6000r/m high speed centrifugation 2min, takes supernatant.
(5) gas chromatography-electron capture detector detection：Sample introduction needle extracts the μ L of supernatant 1 that above-mentioned steps (5) are obtained,
Gas chromatography-electron capture detector condition according to setting is detected.Chromatographic condition is：Injector temperature is 260 DEG C；
Electron capture detector temperature is 300 DEG C；Carrier gas is high pure nitrogen (v/v, 99.999 ﹪), and flow velocity is 1mL/min；Sampling volume
For 1 μ L；Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1；Gas chromatographic column heating schedule is：120℃
1min is kept, 10 DEG C/min is warming up to 200 DEG C, then is warming up to 240 DEG C with 2 DEG C/min, is finally warming up to 270 with 15 DEG C/min
DEG C, 1min is kept, total run time is 32min.
Described gas chromatographic column is from the CD-5MS capillary gas chromatographies that specification is 30m × 0.25mm × 0.25 μm
Post, fixing phase is the mixed liquor of diphenyl and dimethyl polysiloxane, and wherein the mass fraction of diphenyl is 5 ﹪, and dimethyl gathers
The mass fraction of siloxanes is 95 ﹪, can realize efficiently separating for 7 kinds of Polychlorinated biphenyls.
(6) Specification Curve of Increasing：It is qualitative with retention time, quantified by external standard method.When retention time is qualitative, takes concentration and be
The Polychlorinated biphenyls hybrid standard of PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L is used
The μ L of liquid 100, with normal hexane 1mL is settled to, and obtains standard solution, obtains the standard solution that concentration is 10 μ g/L.Standard is molten
Liquid carries out operating the gas chromatogram for obtaining standard solution according to the requirement of above-mentioned steps (5), and with the gas phase of single analyte
Chromatogram carries out retention time comparison, determines the retention time of 7 kinds of Polychlorinated biphenyls；The retention time of this 7 kinds of Polychlorinated biphenyls to
During as quantified by external standard method, the foundation of 7 kinds of Polychlorinated biphenyls chromatographic peak identifications.Accompanying drawing 1 is the gas chromatogram of standard solution.
During quantified by external standard method, take respectively Polychlorinated biphenyls hybrid standard that concentration is 100 μ g/L use liquid 12.5,25,50,
100th, 500,1000 μ L, with normal hexane 1mL is settled to, and obtains the standard that six spiked levels scopes are 1.25~100 μ g/L
Series of curves solution.By the standard curve serial solution of six kinds of different spiked levels, according to the Polychlorinated biphenyls concentration and peak that add
The corresponding relation of area sets up standard curve.Table 1 is the equation of linear regression of the inventive method, the range of linearity, correlation coefficient and
Detection limit.As shown in Table 1, each Polychlorinated biphenyls, with good linear relationship, meet analysis method in the corresponding range of linearity
Require.
(7) sample and determination of recovery rates：Zhoushan Dai Quyang enhancement releasings marine site collection mud sample according to above-mentioned steps (1)~
(5) after requirement is operated, the standard curve obtained with above-mentioned steps (6) compares, and by conversion Zhoushan Dai Qu is finally given
The measure concentration of 7 kinds of Polychlorinated biphenyls is and does not detect in the mud sample of foreign enhancement releasing marine site collection.Mark-on Zhoushan Dai Quyang breeds
Release the mud sample of marine site collection carries out respectively five operation repetitives, and and above-mentioned steps according to the requirement of above-mentioned steps (1)~(5)
(6) standard curve for obtaining compares, and is finally given by conversion 7 in the mud sample of mark-on Zhoushan Dai Quyang enhancement releasings marine site collection
The measure concentration of Polychlorinated biphenyls is planted, and calculates the response rate, the relative standard deviation of five parallel assays.As shown in Table 2, mark-on boat
Mountain Mount Tai Qu Yang enhancement releasings marine site collection the mud sample response rate be 88~115 ﹪, relative standard deviation (n=5) be 3.7~
6.9 ﹪, meet analysis method and the response rate and repeatability are required.
The measure of 7 kinds of Polychlorinated biphenyls in the soil sample of the Zhujiajian I., zhoushan Islands second vegetable plot of embodiment 4. collection
(1) collection and sample preparation of sample：The In Aluminium Foil Packing of the soil sample cleaning of Zhujiajian I., zhoushan Islands second vegetable plot collection is simultaneously sealed
In polyethylene bags, then laboratory is transported back with portable refrigerating box, then sample is placed in freezer dryer is dried 12h,
80 mesh stainless steel sifts were taken out, was placed in be measured in exsiccator.
The soil sample of mark-on Zhu family point second vegetable plot collection：The soil sample of the Zhu family's point second vegetable plot collection handled well to 10.00g, point
Not Jia Ru the 100 μ g/L Polychlorinated biphenyls hybrid standards of 12.5,100,1000 μ L use liquid, be configured to low (0.125 μ g/kg), in
The soil sample of the mark-on Zhu family point second vegetable plot collection of (1.00 μ g/kg) and high (10.0 μ g/kg) three kinds of addition concentration levels.
(2) sampling and ultrasonic extraction：Weigh the soil of Zhu family's point second vegetable plot collection that 10.00g above-mentioned steps (1) are handled well
Sample or the soil sample of mark-on Zhu family point second vegetable plot collection, in being placed in 50mL centrifuge tubes, addition 20mL normal hexane, vortex 1min, with
400W power is in 35 DEG C of ultrasonic extraction 40min；There are the ambient interferences of sulfur-containing compound, add 1g copper powder ultrasound desulfurizations,
3000r/m high speed centrifugation 3min；Extracting solution color is more yellow, carries out two step purifications.
(3) concentrated sulfuric acid purification：Concentrated sulphuric acid 1mL is added in extracting solution, 1min is vibrated, stratification discards lower floor's concentrated sulphuric acid
Waste liquid, repeats said process 2 times, colourless to concentrated sulphuric acid layer, then washs hexane extract with 30g/L aqueous sodium persulfate solutions into
Property.
(4) constant volume is concentrated：After by extracting solution anhydrous sodium sulfate dehydration, in pump vacuum degree 0.08MPa, bath temperature 40
DEG C, under rotating speed 100rpm, it is evaporated to dryness with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain normal hexane molten
Solution liquid.
(5) dispersive solid-phase extraction purification：50mg N- propyl group ethylenediamine solid phase adsorptions are added in 1mL n-hexane dissolution liquid
Agent, vortex 60s, 3000r/m high speed centrifugation 3min, takes supernatant.
(6) gas chromatography-electron capture detector detection：Sample introduction needle extracts the μ L of supernatant 1 that above-mentioned steps (5) are obtained,
Gas chromatography-electron capture detector condition according to setting is detected.Chromatographic condition is：Injector temperature is 260 DEG C；
Electron capture detector temperature is 300 DEG C；Carrier gas is high pure nitrogen (v/v, 99.999 ﹪), and flow velocity is 1mL/min；Sampling volume
For 1 μ L；Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1；Gas chromatographic column heating schedule is：120℃
1min is kept, 10 DEG C/min is warming up to 200 DEG C, then is warming up to 240 DEG C with 2 DEG C/min, is finally warming up to 270 with 15 DEG C/min
DEG C, 1min is kept, total run time is 32min.
Described gas chromatographic column is from the CD-5MS capillary gas chromatographies that specification is 30m × 0.25mm × 0.25 μm
Post, fixing phase is the mixed liquor of diphenyl and dimethyl polysiloxane, and wherein the mass fraction of diphenyl is 5 ﹪, and dimethyl gathers
The mass fraction of siloxanes is 95 ﹪, can realize efficiently separating for 7 kinds of Polychlorinated biphenyls.
(7) Specification Curve of Increasing：It is qualitative with retention time, quantified by external standard method.When retention time is qualitative, takes concentration and be
The Polychlorinated biphenyls hybrid standard of PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L is used
The μ L of liquid 100, with normal hexane 1mL is settled to, and obtains standard solution, obtains the standard solution that concentration is 10 μ g/L.Standard is molten
Liquid carries out operating the gas chromatogram for obtaining standard solution according to the requirement of above-mentioned steps (6), and with the gas phase of single analyte
Chromatogram carries out retention time comparison, determines the retention time of 7 kinds of Polychlorinated biphenyls；The retention time of this 7 kinds of Polychlorinated biphenyls to
During as quantified by external standard method, the foundation of 7 kinds of Polychlorinated biphenyls chromatographic peak identifications.
During quantified by external standard method, take respectively Polychlorinated biphenyls hybrid standard that concentration is 100 μ g/L use liquid 12.5,25,50,
100th, 500,1000 μ L, with normal hexane 1mL is settled to, and obtains the standard that six spiked levels scopes are 1.25~100 μ g/L
Series of curves solution.By the standard curve serial solution of six kinds of different spiked levels, according to the Polychlorinated biphenyls concentration and peak that add
The corresponding relation of area sets up standard curve.
(8) sample and determination of recovery rates：The soil sample of Zhu family's point second vegetable plot collection according to above-mentioned steps (1)~(6) requirement
After being operated, the standard curve obtained with above-mentioned steps (7) compares, and by conversion the vegetable plot collection of Zhu family's point second is finally given
The measure concentration of 7 kinds of Polychlorinated biphenyls is and does not detect in soil sample.The soil sample of mark-on Zhu family point second vegetable plot collection is according to above-mentioned steps
(1) requirement of~(6) carries out respectively five operation repetitives, and the standard curve obtained with above-mentioned steps (7) compares, by conversion
The measure concentration of 7 kinds of Polychlorinated biphenyls in the soil sample of mark-on Zhu family point second vegetable plot collection is finally given, and calculates the response rate, five times flat
The relative standard deviation that row is determined.The soil sample response rate of mark-on Zhu family point second vegetable plot collection is 76~110 ﹪, relative standard deviation
(n=5) it is 3.9~6.4 ﹪, meets analysis method and the response rate and repeatability are required.
The measure of 7 kinds of Polychlorinated biphenyls in the soil sample of the third vegetable plot of Zhujiajian I., zhoushan Islands of embodiment 5. collection
(1) collection and sample preparation of sample：The In Aluminium Foil Packing of the soil sample cleaning of the vegetable plot of Zhujiajian I., zhoushan Islands third collection is simultaneously sealed
In polyethylene bags, then laboratory is transported back with portable refrigerating box, then sample is placed in freezer dryer is dried 20h,
100 mesh stainless steel sifts were taken out, was placed in be measured in exsiccator.
The soil sample of mark-on Zhu family point second vegetable plot collection：The soil sample of Zhu family's point the third vegetable plot collection handled well to 10.00g, point
Not Jia Ru the 100 μ g/L Polychlorinated biphenyls hybrid standards of 12.5,100,1000 μ L use liquid, be configured to low (0.125 μ g/kg), in
The soil sample of mark-on Zhu family point the third vegetable plot collection of (1.00 μ g/kg) and high (10.0 μ g/kg) three kinds of addition concentration levels.
(2) sampling and ultrasonic extraction：Weigh the soil of Zhu family's point the third vegetable plot collection that 10.00g above-mentioned steps (1) are handled well
Sample or the soil sample of mark-on Zhu family point the third vegetable plot collection, in being placed in 50mL centrifuge tubes, addition 40mL normal hexane, vortex 3min, with
500W power is in 40 DEG C of ultrasonic extraction 20min；There are the ambient interferences of sulfur-containing compound, add 3g copper powder ultrasound desulfurizations,
3000r/m high speed centrifugation 5min；Extracting solution color is substantially colorless, carries out two step purifications.
(3) concentrated sulfuric acid purification：Concentrated sulphuric acid 3mL is added in extracting solution, 3min is vibrated, stratification discards lower floor's concentrated sulphuric acid
Waste liquid, repeats said process 2 times, colourless to concentrated sulphuric acid layer, then washs hexane extract with 30g/L aqueous sodium persulfate solutions into
Property.
(4) constant volume is concentrated：After by extracting solution anhydrous sodium sulfate dehydration, in pump vacuum degree 0.09MPa, bath temperature 40
DEG C, under rotating speed 50rpm, it is evaporated to dryness with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution
Liquid.
(5) dispersive solid-phase extraction purification：150mg N- propyl group ethylenediamine solid phase adsorptions are added in 1mL n-hexane dissolution liquid
Agent, vortex 60s, 6000r/m high speed centrifugation 1min, takes supernatant.
(6) gas chromatography-electron capture detector detection：Sample introduction needle extracts the μ L of supernatant 1 that above-mentioned steps (5) are obtained,
Gas chromatography-electron capture detector condition according to setting is detected.Chromatographic condition is：Injector temperature is 260 DEG C；
Electron capture detector temperature is 300 DEG C；Carrier gas is high pure nitrogen (v/v, 99.999 ﹪), and flow velocity is 1mL/min；Sampling volume
For 1 μ L；Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1；Gas chromatographic column heating schedule is：120℃
1min is kept, 10 DEG C/min is warming up to 200 DEG C, then is warming up to 240 DEG C with 2 DEG C/min, is finally warming up to 270 with 15 DEG C/min
DEG C, 1min is kept, total run time is 32min.
Described gas chromatographic column is from the CD-5MS capillary gas chromatographies that specification is 30m × 0.25mm × 0.25 μm
Post, fixing phase is the mixed liquor of diphenyl and dimethyl polysiloxane, and wherein the mass fraction of diphenyl is 5 ﹪, and dimethyl gathers
The mass fraction of siloxanes is 95 ﹪, can realize efficiently separating for 7 kinds of Polychlorinated biphenyls.
(7) Specification Curve of Increasing：It is qualitative with retention time, quantified by external standard method.When retention time is qualitative, takes concentration and be
The Polychlorinated biphenyls hybrid standard of PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L is used
The μ L of liquid 100, with normal hexane 1mL is settled to, and obtains standard solution, obtains the standard solution that concentration is 10 μ g/L.Standard is molten
Liquid carries out operating the gas chromatogram for obtaining standard solution according to the requirement of above-mentioned steps (6), and with the gas phase of single analyte
Chromatogram carries out retention time comparison, determines the retention time of 7 kinds of Polychlorinated biphenyls；The retention time of this 7 kinds of Polychlorinated biphenyls to
During as quantified by external standard method, the foundation of 7 kinds of Polychlorinated biphenyls chromatographic peak identifications.
During quantified by external standard method, take respectively Polychlorinated biphenyls hybrid standard that concentration is 100 μ g/L use liquid 12.5,25,50,
100th, 500,1000 μ L, with normal hexane 1mL is settled to, and obtains the standard that six spiked levels scopes are 1.25~100 μ g/L
Series of curves solution.By the standard curve serial solution of six kinds of different spiked levels, according to the Polychlorinated biphenyls concentration and peak that add
The corresponding relation of area sets up standard curve.
(8) sample and determination of recovery rates：Zhu family point the third vegetable plot collection soil sample according to above-mentioned steps (1)~(6) requirement
After being operated, the standard curve obtained with above-mentioned steps (7) compares, and by conversion the third vegetable plot collection of Zhu family's point is finally given
The measure concentration of 7 kinds of Polychlorinated biphenyls is and does not detect in soil sample.The soil sample of mark-on Zhu family point the third vegetable plot collection is according to above-mentioned steps
(1) requirement of~(6) carries out respectively five operation repetitives, and the standard curve obtained with above-mentioned steps (7) compares, by conversion
The measure concentration of 7 kinds of Polychlorinated biphenyls in the soil sample of mark-on Zhu family point the third vegetable plot collection is finally given, and calculates the response rate, five times flat
The relative standard deviation that row is determined.Mark-on Zhu family point the third vegetable plot collection the soil sample response rate be 73~105 ﹪, relative standard deviation
(n=5) it is 3.2~6.3 ﹪, meets analysis method and the response rate and repeatability are required.
The measure of 7 kinds of Polychlorinated biphenyls in the mud sample of the Zhoushan Dai Quyang enhancement releasings marine site of embodiment 6. collection
(1) collection and sample preparation of sample：The mud sample of Zhoushan Dai Quyang enhancement releasings marine site collection, with clean In Aluminium Foil Packing
And be sealed in polyethylene bags, then transport laboratory back with portable refrigerating box, then sample is placed in freezer dryer dry
Dry 24h, took out 100 mesh stainless steel sifts, was placed in be measured in exsiccator.
The mud sample of mark-on Zhoushan Dai Quyang enhancement releasings marine site collection：Put to the Zhoushan Dai Quyang propagation that 10.00g is handled well
The mud sample of stream marine site collection, the 100 μ g/L Polychlorinated biphenyls hybrid standards for being separately added into 12.5,100,1000 μ L use liquid, prepare
Into low (0.125 μ g/kg), in (1.00 μ g/kg) and high (10.0 μ g/kg) three kinds of addition concentration levels mark-on Zhoushan Dai Quyang
The mud sample of enhancement releasing marine site collection.
(2) sampling and ultrasonic extraction：Weigh the Zhoushan Dai Quyang enhancement releasings sea that 10.00g above-mentioned steps (1) are handled well
The mud sample of domain collection or the mud sample of mark-on Zhoushan Dai Quyang enhancement releasings marine site collection, in being placed in 50mL centrifuge tubes, add 40mL
Normal hexane, vortex 2min, with 400W power in 40 DEG C of ultrasonic extraction 20min, 6000r/m high speed centrifugation 5min；Extracting solution face
Color base this water white transparency, carries out a step purification.
(3) constant volume is concentrated：After by extracting solution anhydrous sodium sulfate dehydration, in pump vacuum degree 0.08MPa, bath temperature 40
DEG C, under rotating speed 80rpm, it is evaporated to dryness with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution
Liquid.
(4) dispersive solid-phase extraction purification：200mg N- propyl group ethylenediamine solid phase adsorptions are added in 1mL n-hexane dissolution liquid
Agent, vortex 30s, 6000r/m high speed centrifugation 2min, takes supernatant.
(5) gas chromatography-electron capture detector detection：Sample introduction needle extracts the μ L of supernatant 1 that above-mentioned steps (5) are obtained,
Gas chromatography-electron capture detector condition according to setting is detected.Chromatographic condition is：Injector temperature is 260 DEG C；
Electron capture detector temperature is 300 DEG C；Carrier gas is high pure nitrogen (v/v, 99.999 ﹪), and flow velocity is 1mL/min；Sampling volume
For 1 μ L；Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1；Gas chromatographic column heating schedule is：120℃
1min is kept, 10 DEG C/min is warming up to 200 DEG C, then is warming up to 240 DEG C with 2 DEG C/min, is finally warming up to 270 with 15 DEG C/min
DEG C, 1min is kept, total run time is 32min.
Described gas chromatographic column is from the CD-5MS capillary gas chromatographies that specification is 30m × 0.25mm × 0.25 μm
Post, fixing phase is the mixed liquor of diphenyl and dimethyl polysiloxane, and wherein the mass fraction of diphenyl is 5 ﹪, and dimethyl gathers
The mass fraction of siloxanes is 95 ﹪, can realize efficiently separating for 7 kinds of Polychlorinated biphenyls.
(6) Specification Curve of Increasing：It is qualitative with retention time, quantified by external standard method.When retention time is qualitative, takes concentration and be
The Polychlorinated biphenyls hybrid standard of PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L is used
The μ L of liquid 100, with normal hexane 1mL is settled to, and obtains standard solution, obtains the standard solution that concentration is 10 μ g/L.Standard is molten
Liquid carries out operating the gas chromatogram for obtaining standard solution according to the requirement of above-mentioned steps (5), and with the gas phase of single analyte
Chromatogram carries out retention time comparison, determines the retention time of 7 kinds of Polychlorinated biphenyls；The retention time of this 7 kinds of Polychlorinated biphenyls to
During as quantified by external standard method, the foundation of 7 kinds of Polychlorinated biphenyls chromatographic peak identifications.
During quantified by external standard method, take respectively Polychlorinated biphenyls hybrid standard that concentration is 100 μ g/L use liquid 12.5,25,50,
100th, 500,1000 μ L, with normal hexane 1mL is settled to, and obtains the standard that six spiked levels scopes are 1.25~100 μ g/L
Series of curves solution.By the standard curve serial solution of six kinds of different spiked levels, according to the Polychlorinated biphenyls concentration and peak that add
The corresponding relation of area sets up standard curve.
(7) sample and determination of recovery rates：Zhoushan Dai Quyang enhancement releasings marine site collection mud sample according to above-mentioned steps (1)~
(5) after requirement is operated, the standard curve obtained with above-mentioned steps (6) compares, and by conversion Zhoushan Dai Qu is finally given
The measure concentration of 7 kinds of Polychlorinated biphenyls is and does not detect in the mud sample of foreign enhancement releasing marine site collection.Mark-on Zhoushan Dai Quyang breeds
Release the mud sample of marine site collection carries out respectively five operation repetitives, and and above-mentioned steps according to the requirement of above-mentioned steps (1)~(5)
(6) standard curve for obtaining compares, and is finally given by conversion 7 in the mud sample of mark-on Zhoushan Dai Quyang enhancement releasings marine site collection
The measure concentration of Polychlorinated biphenyls is planted, and calculates the response rate, the relative standard deviation of five parallel assays.Mark-on Zhoushan Dai Quyang increases
Grow release marine site collection the mud sample response rate be 79~112 ﹪, relative standard deviation (n=5) be 3.2~6.5 ﹪, meet analysis
Method is required the response rate and repeatability.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment, as long as meeting for the restriction of the present invention
Application claims, belong to protection scope of the present invention.
Claims (5)
1. in a kind of soils and sediments Polychlorinated biphenyls dispersive solid-phase extraction gas-chromatography detection method, it is characterised in that the party
Method is comprised the following steps：
Step (1). the collection and sample preparation of sample：
Soils and sediments sample to be detected is placed in freezer dryer and is dried 12~24h, took out 80~100 mesh stainless
Steel is sieved, and is placed in be measured in exsiccator；
Step (2). sampling and ultrasonic extraction：
10.00g testing samples are weighed, 20~40mL normal hexane is added, be vortexed 1~3min, with 400~500W power in 30~40
DEG C 20~40min of ultrasonic extraction；When the ambient interferences of sulfur-containing compound in sample, 1~3g copper powder ultrasound desulfurizations are added,
3000~6000r/m, 3~5min of high speed centrifugation, take supernatant, as hexane extract；Observation extracting solution color, if colourless
It is transparent, directly carry out step (4) concentration constant volume, i.e., only need a step to purify, otherwise carry out step (3) concentrated sulfuric acid purification, that is, need two
Step purification；
Step (3). concentrated sulfuric acid purification：
1~3mL of concentrated sulphuric acid is added in hexane extract, 1~3min is vibrated, stratification discards lower floor's concentrated sulphuric acid waste liquid, root
According to needing, multiple plus concentrated sulfuric acid purification is colourless to concentrated sulphuric acid layer, then washs hexane extract extremely with 30g/L aqueous sodium persulfate solutions
It is neutral；
Step (4). concentration constant volume：
After by hexane extract anhydrous sodium sulfate dehydration, in pump vacuum 0.08~0.09MPa of degree, bath temperature 35~40
DEG C, under 50~100rpm of rotating speed, be evaporated to dryness with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain just oneself
Alkane lysate；
Step (5). dispersive solid-phase extraction is purified：
50~200mg N- propyl group ethylenediamine solid-phase adsorbents are added in 1mL n-hexane dissolution liquid, be vortexed 30~60s, 3000
~6000r/m 1~3min of high speed centrifugation, take supernatant；
Step (6). gas chromatography-electron capture detector is detected：
Sample introduction needle extracts above-mentioned supernatant, is detected according to the gas chromatography-electron capture detector condition for setting；
Step (7). Specification Curve of Increasing：It is qualitative with retention time, quantified by external standard method；
When retention time is qualitative, standard solution is carried out operating the gas phase for obtaining standard solution according to the requirement of above-mentioned steps (6)
Chromatogram, and carry out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of Polychlorinated biphenyls；
When the retention time of this 7 kinds of Polychlorinated biphenyls is to as quantified by external standard method, the foundation of 7 kinds of Polychlorinated biphenyls chromatographic peak identifications；
Solute is Polychlorinated biphenyls in described standard solution, and solvent is normal hexane, and concentration is 10 μ g/L；
During quantified by external standard method, by the standard curve serial solution of different spiked levels, according to the Polychlorinated biphenyls concentration and peak that add
The corresponding relation of area sets up standard curve；
Solute is Polychlorinated biphenyls in described standard curve serial solution, and solvent is normal hexane, and concentration range is 1.25~100
μg/L；
Step (8). sample and determination of recovery rates：
By the actual sample for collecting, operated according to the requirement of above-mentioned steps (1)~(6), and obtained with above-mentioned steps (7)
Standard curve compare, the content of 7 kinds of Polychlorinated biphenyls in actual sample is finally given by conversion；
By the mark-on sample of different spiked levels, five operation repetitives are carried out respectively according to the requirement of above-mentioned steps (2)~(6),
And the standard curve obtained with above-mentioned steps (7) compares, the measure of 7 kinds of Polychlorinated biphenyls in mark-on sample is finally given by conversion
Concentration；Response rate calculating is carried out according to the following formula：
In formula：R --- the response rate, ﹪；
Cs--- the measure concentration of 7 kinds of Polychlorinated biphenyls, μ g/kg in mark-on sample；
C0--- the concentration of 7 kinds of Polychlorinated biphenyls in actual sample, μ g/kg；
C --- the theoretical spiked levels of 7 kinds of Polychlorinated biphenyls, μ g/kg in mark-on sample；
Described mark-on sample is the sample Jing after adding Polychlorinated biphenyls in the pretreated actual sample of step (1).
2. in a kind of soils and sediments as claimed in claim 1 Polychlorinated biphenyls dispersive solid-phase extraction gas chromatographic detection side
Method, it is characterised in that step (6) gas chromatography-electron capture detector detection chromatographic condition be：Injector temperature is 260
℃；Electron capture detector temperature is 300 DEG C；Carrier gas is the ﹪ high pure nitrogens of volume content 99.999, and flow velocity is 1mL/min；Enter
Sample volume is 1 μ L；Input mode is Splitless injecting samples, and after 0.75min, split ratio is 50:1；Gas chromatographic column heating schedule
For：120 DEG C of holding 1min, 10 DEG C/min is warming up to 200 DEG C, then is warming up to 240 DEG C with 2 DEG C/min, finally with 15 DEG C/min liters
Temperature keeps 1min to 270 DEG C, and total run time is 32min；
Described gas chromatographic column selects the CD-5MS capillary gas chromatographic columns that specification is 30m × 0.25mm × 0.25 μm, Gu
Fixed is mutually the mixed liquor of diphenyl and dimethyl polysiloxane, and the wherein mass fraction of diphenyl is 5 ﹪, dimethyl polysiloxane
Mass fraction be 95 ﹪, efficiently separating for 7 kinds of Polychlorinated biphenyls can be realized.
3. the dispersive solid-phase extraction gas chromatogram of Polychlorinated biphenyls is examined in a kind of soils and sediments as claimed in claim 1 or 2
Survey method, it is characterised in that described Polychlorinated biphenyls include PCB28, PCB52, PCB101, PCB118, PCB153, PCB138,
PCB180。
4. the dispersive solid-phase extraction gas chromatogram of Polychlorinated biphenyls is examined in a kind of soils and sediments as claimed in claim 1 or 2
Survey method, it is characterised in that if selecting 50~150mg N- propyl group ethylenediamine solid-phase adsorbents when the steps of Jing two are purified, if the steps of Jing mono-
100~200mg N- propyl group ethylenediamine solid-phase adsorbents are selected during purification.
5. the dispersive solid-phase extraction gas chromatogram of Polychlorinated biphenyls is examined in a kind of soils and sediments as claimed in claim 1 or 2
Survey method, it is characterised in that described copper powder first removes its surface film oxide using front with dilute hydrochloric acid process, then uses distilled water
Rinse to remove and be attached to a small amount of acid on its surface, finally flow down with acetone rinsing and in the ﹪ high pure nitrogens of volume content 99.999 and blow
It is dry, in case copper powder again be oxidized.
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| CN110031561A (en) * | 2019-04-25 | 2019-07-19 | 浙江省海洋水产研究所 | The dispersive solid-phase extraction gaschromatographic mass spectrometry detection method of organic tin environmental hormone in a kind of marine product |
| CN110412156B (en) * | 2019-06-28 | 2022-08-16 | 宁波大学 | Method for determining polychlorinated biphenyl in soil |
| CN111474261B (en) * | 2020-04-24 | 2023-02-24 | 山东省济南生态环境监测中心 | Method for measuring aniline in soil and sediment |
| CN114660208A (en) * | 2020-12-23 | 2022-06-24 | 沈阳沈化院测试技术有限公司 | Gas chromatography method for simultaneously measuring polychlorinated biphenyl in bottom mud |
| CN113311083B (en) * | 2021-05-24 | 2022-12-16 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | Method for determining seven indicative polychlorinated biphenyls in fish scales |
| CN115343401A (en) * | 2022-07-11 | 2022-11-15 | 浙江格临检测股份有限公司 | Method for measuring adsorbable organic halogen AOX in soil and sediment |
| CN116236818B (en) * | 2023-01-10 | 2023-12-19 | 北京师范大学珠海校区 | Solid-phase microextraction probe and preparation method and application thereof |
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