CN105044236A - 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, relate to the dispersive solid-phase extraction gas-chromatography detection method of PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB1807 kind in a kind of soils and sediments " indicative polychlorinated biphenyl " monomer.
Background technology
Polychlorinated biphenyl is distributed in water widely as the typical persistence organic pollutant of one, air, soil, bed mud, in the surrounding mediums such as biosome, have stronger " three-induced effect " human body, once by as heat exchanging agent, lubricant, insulating medium in transformer and capacitor, plastifier, paraffin expands agent, bonding agent, organic diluent, dedusting agent, the chemical products that cutting oil and no carbon paper etc. are important, be widely used in electric power, plastic processing, the field such as chemical industry and printing, grave danger is formed to human health and ecologic environment, one of May calendar year 2001 " Convention of Stockholm " 12 kinds of priority pollutants.Although polychlorinated biphenyl has been stopped using for many years, because its characteristic such as persistence and hydrophobicity causes it remain in the environment and accumulate.Soil and bed mud be polychlorinated biphenyl in the environment the important carrier of Transport And Transformation, home to return to savings storehouse.Therefore, analyze polychlorinated biphenyl in mensuration soil or bed mud to be just of great significance.
At present, mainly adopt the abstraction techniques such as oscillation extraction, surname extraction, ultrasonic extraction, microwave auxiliary extraction, accelerated solvent extraction, supercritical fluid extraction, Subcritical Water Extraction both at home and abroad, in conjunction with one or both purification methods such as concentrated acid sulfonation purification, Solid-Phase Extraction, gel permeation chromatography, solid-phase microextraction, headspace solid-phase microextraction, dispersive liquid-liquid microextractions, then the technology such as gas chromatography electron capture detection method, GC-MS, gas chromatography tandem mass spectrometry are adopted to carry out polychlorinated biphenyl detection in soil or bed mud.
Soil or bed mud sample matrices complexity, pre-treatment and purifying step become the key that in sample, residual polychlorinated biphenyl is analyzed.But the traditional extracting process long processing period such as oscillation extraction, surname extraction, solvent-oil ratio are large.The instruments such as microwave auxiliary extraction, accelerated solvent extraction, supercritical fluid extraction and technical costs relatively high.And constitutionally stable organism can not only extract by ultrasonic extraction effectively from solid sample, and have that efficiency is high, instrument price is cheap, simple operation and other advantages, at present with the existing many reports of polychlorinated biphenyl in this method extraction soil or bed mud.Gel permeation chromatography cleaning equipment is relatively costly, and treatment cycle is longer, and need consume a large amount of eluting solvent.Solid-phase microextraction and headspace solid-phase microextraction, extracting head cost are higher, and extraction coating is easy to wear, and after extraction, sample needs to resolve, serviceable life is shorter, repeatedly use and also there is cross-contamination issue, and solid-phase microextraction can not be directly used in the process of solid sample, must first through liquid-solid extraction.Dispersive liquid-liquid microextraction is mainly applicable to simple Liquid matrix sample, needs process to be converted into fluid matrix, and easily produce matrix effect for complicated solid matrix.Thus, for the removal of the impurity such as the pigment in soil or bed mud, grease, what bibliographical information was maximum is again in conjunction with Solid phase extraction after concentrated sulfuric acid purification.Concentrated sulfuric acid cleanup method can remove most interference impurity, but has impurity to have interference to PCB52 all the time, sometimes also has interference to PCB28.Although solid phase extraction clean-up effect is better, complicated operation, needs to carry out the processes such as extraction column activation, loading, drip washing, wash-out, consuming time longer, is not suitable for mass sample preparation.Dispersive solid-phase extraction has quick, simple, cheap, effective, reliable and safe feature, is progressively applied to various organic contaminant in various agricultural byproducts and surrounding medium and detects.But consult current domestic and foreign literature, not yet have bibliographical information dispersive solid-phase extraction to be applied to analysis of PCBs purification in soil or sediment sample.
Summary of the invention
For the deficiency of above-mentioned present Research, 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 biphenyl in a kind of soils and sediments, the method comprises collection and the sample preparation of sample successively, sampling and ultrasonic extraction, concentrated sulfuric acid purification, concentrated constant volume, dispersive solid-phase extraction purifies, and gas chromatography-electron capture detector detects, Specification Curve of Increasing, sample and determination of recovery rates.
The inventive method comprises the following steps:
Step (1). the collection of sample and sample preparation:
Soils and sediments sample to be detected is placed in the dry 12 ~ 24h of freeze drier, took out 80 ~ 100 order stainless steel sifts, and be placed in exsiccator to be measured;
Described soils and sediments sample to be detected can adopt clean In Aluminium Foil Packing and be sealed in polyethylene bags and transport;
Step (2). sampling and ultrasonic extraction:
Take 10.00g testing sample, add 20 ~ 40mL normal hexane, vortex 1 ~ 3min, extract 20 ~ 40min with 400 ~ 500W power in 30 ~ 40 DEG C of ultrasound waves; When the background interference of sulfocompound in sample, can add 1 ~ 3g copper powder ultrasound desulfurization, 3000 ~ 6000r/m high speed centrifugation, 3 ~ 5min, gets supernatant, is hexane extract; Observe extract color, if basic water white transparency, directly carry out the concentrated constant volume of step (4), namely only need a step purification, otherwise carry out step (3) concentrated sulfuric acid purification, namely need two step purifications;
Described copper powder before using first with watery hydrochloric acid process to remove its surface film oxide, a small amount of acid on its surface is attached to again with distilled water flushing removing, finally flow down with acetone rinsing and at high pure nitrogen (v/v, 99.99 ﹪) and dry up, in case copper powder again be oxidized;
A described step purification is for when the basic water white transparency of extract color, and sample purification only needs to carry out dispersive solid-phase extraction operation;
Two described step purifications are not for when extract color is basic water white transparency, and sample needs to carry out concentrated sulfuric acid purification and dispersive solid-phase extraction purification simultaneously;
Step (3). concentrated sulfuric acid purification:
The concentrated sulphuric acid 1 ~ 3mL is added in the hexane extract that step (2) obtains, vibration 1 ~ 3min, stratification, discard lower floor's concentrated sulphuric acid waste liquid, can repeatedly add concentrated sulfuric acid purification as required colourless to concentrated sulphuric acid layer, then with 30g/L aqueous sodium persulfate solution washing hexane extract to neutral;
Step (4). concentrated constant volume:
By hexane extract anhydrous sodium sulfate dehydration, again pump vacuum degree 0.08 ~ 0.09MPa, bath temperature 35 ~ 40 DEG C, under rotating speed 50 ~ 100rpm, be evaporated to dry with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid;
Step (5). dispersive solid-phase extraction purifies:
In 1mL n-hexane dissolution liquid, add 50 ~ 200mgN-propyl group ethylenediamine solid-phase adsorbent, vortex 30 ~ 60s, 3000 ~ 6000r/m high speed centrifugation 1 ~ 3min, gets supernatant;
Step (6). gas chromatography-electron capture detector detects:
Sample introduction needle extracts above-mentioned supernatant, detects according to the gas chromatography-electron capture detector condition set; 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 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 keep 1min, and 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 DEG C with 15 DEG C/min, and keep 1min, total run time is 32min.
Described gas chromatographic column selects specification to be the CD-5MS capillary gas chromatographic column of 30m × 0.25mm × 0.25 μm, Stationary liquid is the mixed liquor of diphenyl and dimethyl polysiloxane, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 7 kinds of polychlorinated biphenyl;
Step (7). Specification Curve of Increasing: qualitative with retention time, quantified by external standard method
When retention time is qualitative, standard solution is carried out operating the gas chromatogram obtaining standard solution according to the requirement of above-mentioned steps (6), and carry out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of polychlorinated biphenyl; The retention time of these 7 kinds of polychlorinated biphenyl in order to during as quantified by external standard method, the foundation of 7 kinds of polychlorinated biphenyl chromatographic peaks identification.
In described standard solution, solute is polychlorinated biphenyl, and solvent is normal hexane, and concentration is 10 μ g/L; Wherein polychlorinated biphenyl comprises PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180.
The step of preparing standard solution can be: get the polychlorinated biphenyl hybrid standard use liquid 100 μ L that concentration is 100 μ g/L, be settled to 1mL, obtain standard solution with normal hexane.
During quantified by external standard method, by the typical curve serial solution of six kinds of different spiked levels, according to the corresponding relation Criterion curve of the polychlorinated biphenyl concentration added and peak area.
In described typical curve serial solution, solute is polychlorinated biphenyl, and solvent is normal hexane, and concentration range is 1.25 ~ 100 μ g/L.
The preparation steps of typical curve serial solution is: get polychlorinated biphenyl hybrid standard use liquid 12.5,25,50,100,500, the 1000 μ L that concentration is 100 μ g/L respectively, be settled to 1mL with normal hexane, obtain the typical curve serial solution that six spiked levels scopes are 1.25 ~ 100 μ g/L.
Table 1 is the equation of linear regression of the inventive method, the range of linearity, related coefficient and detection limit.As shown in Table 1, each polychlorinated biphenyl, in the corresponding range of linearity, has good linear relationship, meets analytical approach requirement.
The equation of linear regression of table 1 the inventive method, the range of linearity, related coefficient and detection limit
Wherein, a:y and x represents the peak area and the theoretical concentration of analysis thing in 1mL normal hexane of analyzing thing respectively; B: the concentration of thing in typical curve serial solution is analyzed in range of linearity representative;
Step (8). sample and determination of recovery rates:
By the actual sample collected, operate according to the requirement of above-mentioned steps (1) ~ (6), and compare, by the content finally obtaining 7 kinds of polychlorinated biphenyl in actual sample that converts with the typical curve that above-mentioned steps (7) obtains;
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 compare with the typical curve that above-mentioned steps (7) obtains, the mensuration concentration finally obtaining 7 kinds of polychlorinated biphenyl in mark-on sample by converting; Carry out recovery calculating according to the following formula:
In formula: R---the recovery, ﹪;
C
s---the mensuration concentration of 7 kinds of polychlorinated biphenyl in mark-on sample, μ g/kg;
C
0---the concentration of 7 kinds of polychlorinated biphenyl in actual sample, μ g/kg;
C---the theoretical spiked levels of 7 kinds of polychlorinated biphenyl in mark-on sample, μ g/kg;
Described mark-on sample is the sample after adding polychlorinated biphenyl in step (1) pretreated actual sample.
Beneficial effect of the present invention:
The present invention adopts ultrasonic extraction, dispersive solid-phase extraction purifies, gas chromatography electron capture detection method measures the polychlorinated biphenyl in soils and sediments, the method is simple to operate, sample pre-treatments can be completed fast, when the basic water white transparency of extract color, select step purification (dispersive solid-phase extraction purification), otherwise need two step purifications (concentrated sulfuric acid purification+dispersive solid-phase extraction purification), wherein dispersive solid-phase extraction purification process only needs 5min, result is accurate, 7 kinds of polychlorinated biphenyl detect and are limited to 0.02 ~ 0.03 μ g/kg, the recovery is 72 ~ 115 ﹪, relative standard deviation (n=5) is 3.6 ~ 6.9 ﹪, there is higher sensitivity and the gratifying recovery and reappearance, the assay of polychlorinated biphenyl in soils and sediments can be used for.
Accompanying drawing explanation
Fig. 1 is the gas chromatogram of 7 kinds of polychlorinated biphenyl standard solution (10 μ g/L);
Fig. 2 is the gas chromatogram of the soil sample (A) of embodiment 2 Zhujiajian I., zhoushan Islands first vegetable plot collection and the soil sample (B) of mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection;
Fig. 3 is the gas chromatogram of the mud sample (A) of Dai Quyang enhancement releasing marine site, embodiment 3 Zhoushan collection and the mud sample (B) of Dai Quyang enhancement releasing marine site, mark-on Zhoushan collection;
Fig. 4 is sample analysis process flow diagram;
Wherein, 1.PCB28; 2.PCB52; 3.PCB101; 4.PCB118; 5.PCB153; 6.PCB138; 7.PCB180.
Embodiment
Below in conjunction with 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 embodiment uses below mainly contains the GC-450 gas chromatograph (configuration electron capture detector) that Varian company of the U.S. produces.
Embodiment 1.
Step (1). the collection of sample and sample preparation:
By the soils and sediments sample gathered, be sealed in polyethylene bags by the In Aluminium Foil Packing of cleaning, then transport laboratory back with portable refrigerating box, then sample is placed in the dry 24h of freeze drier, took out 100 order stainless steel sifts, be placed in exsiccator to be measured.
Step (2). sampling and ultrasonic extraction:
Take 10.00g testing sample, be placed in 50mL centrifuge tube, add 30mL normal hexane, vortex 2min, extracts 30min, when the background interference of sulfocompound in sample with 480W power in 30 DEG C of ultrasound waves, 1 ~ 3g copper powder ultrasound desulfurization can be added, 6000r/m high speed centrifugation 5min; Observe extract color, if basic water white transparency, directly carry out the concentrated constant volume of step (4), namely only need a step purification, otherwise carry out step (3) concentrated sulfuric acid purification, namely need two step purifications.
Described copper powder before using first with watery hydrochloric acid process to remove its surface film oxide, a small amount of acid on its surface is attached to again with distilled water flushing removing, finally flow down with acetone rinsing and at high pure nitrogen (v/v, 99.99 ﹪) and dry up, in case copper powder again be oxidized.
A described step purification is that, when the basic water white transparency of extract color, sample purification only needs to carry out dispersive solid-phase extraction operation.
Two described step purifications are, when extract color is not basic water white transparency, sample needs to carry out concentrated sulfuric acid purification and dispersive solid-phase extraction purification simultaneously.
When carrying out extraction way choice, consider that the traditional extracting process long processing period such as oscillation extraction, surname extraction, solvent-oil ratio are large.The instruments such as microwave auxiliary extraction, accelerated solvent extraction, supercritical fluid extraction and technical costs relatively high.And constitutionally stable organism can not only extract by ultrasonic extraction effectively from solid sample, and have that efficiency is high, instrument price is cheap, simple operation and other advantages, at present with the existing many reports of polychlorinated biphenyl in this method extraction soil or bed mud.Therefore, the present invention selects the polychlorinated biphenyl in ultrasonic extraction extraction soil or bed mud.
When carrying out purification style and selecting, consider that GPC cleaning equipment is relatively costly, treatment cycle is longer, and need consume a large amount of eluting solvent.Solid-phase microextraction and headspace solid-phase microextraction, extracting head cost is higher, and extraction coating is easy to wear, after extraction, sample needs to resolve, and serviceable life is shorter, repeatedly uses and also there is cross-contamination issue, and solid-phase microextraction can not be directly used in the process of solid sample, must first through liquid-solid extraction.Dispersive liquid-liquid microextraction is mainly applicable to simple Liquid matrix sample, needs process to be converted into fluid matrix, and easily produce matrix effect for complicated solid matrix.Thus, for the removal of the impurity such as the pigment in soil or bed mud, grease, what bibliographical information was maximum is again in conjunction with Solid phase extraction after concentrated sulfuric acid purification.Concentrated sulfuric acid cleanup method can remove most interference impurity, but has impurity to have interference to PCB52 all the time, sometimes also has interference to PCB28.Although solid phase extraction clean-up effect is better, complicated operation, needs to carry out the processes such as extraction column activation, loading, drip washing, wash-out, consuming time longer, is not suitable for mass sample preparation.The present invention adopts dispersive solid-phase extraction to substitute solid phase extraction procedure, only needs to add appropriate suitable adsorbent adsorbing contaminant in extraction concentrate, just can reach purification object.Whole dispersive solid-phase extraction process at most only needs 5min, and conventional solid extraction needs 50min usually, greatly shortens the pre-treatment time.
When sample is after ultrasonic extraction, according to the color of extract, select a step purification or the purification of two steps flexibly, this is according to a large amount of sample test experience.This is because when the basic water white transparency of extract color, after adding concentrated sulfuric acid purification, concentrated sulphuric acid layer is substantially colourless, now no matter whether carry out concentrated sulfuric acid purification, impact analysis quality testing survey all mainly PCB28 and PCB52 near impurity, as long as and carry out dispersive solid-phase extraction purification just can reach clean-up effect.
Step (3). concentrated sulfuric acid purification:
Add concentrated sulphuric acid 2mL in extract, vibration 2min, stratification, discards lower floor's concentrated sulphuric acid waste liquid, as required, can repeatedly add concentrated sulfuric acid purification colourless to concentrated sulphuric acid layer, then with 30g/L aqueous sodium persulfate solution washing hexane extract to neutral.
Step (4). concentrated constant volume:
After extract anhydrous sodium sulfate dehydration, at pump vacuum degree 0.09MPa, bath temperature 35 DEG C, rotating speed 80rpm, is evaporated to dry with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtains n-hexane dissolution liquid.
Step (5). dispersive solid-phase extraction purifies:
In 1mL n-hexane dissolution liquid, add 50 ~ 200mgN-propyl group ethylenediamine solid-phase adsorbent, vortex 30s, 6000r/m high speed centrifugation 2min, gets supernatant.
When carrying out dispersive solid-phase extraction purification, the kind of solid-phase adsorbent and consumption are optimized.Compare the clean-up effect of 100mgN-propyl group ethylenediamine adsorbent and 100mgC18 adsorbent.Result shows, C18 adsorbent does not have effect to impurity purification near PCB28, PCB52, and PSA adsorbent effectively can eliminate the interference that impurity detects PCB28, PCB52.This may be because N-propyl group ethylenediamine adsorbent effectively can remove the interference of carbohydrates, fatty acid, organic acid, phenols, carbohydrate and some the polarity pigments affecting object and detect, C18 adsorbent is mainly used in removing the nonpolar chaff interferences such as fat and ester class, and concentrated sulfuric acid purification has removed most pigment and fat, and no matter whether carry out concentrated sulfuric acid purification, PCB28, PCB52 go out peak position all can exist to a certain degree impurity interference.Then, N-propyl group ethylenediamine adsorbent content is investigated within the scope of 0 ~ 200mg on the impact of clean-up effect.Result shows, along with the increase of N-propyl group ethylenediamine adsorbent amount, clean-up effect increases to some extent, and after acquiring a certain degree, adsorbent increases, and recovery change is little.But because N-propyl group ethylenediamine adsorbent can adsorb certain normal hexane, PSA dosage increases, after centrifuging, supernatant reduces, if final sample selects 50 ~ 150mg when two steps purify (concentrated sulfuric acid purification+dispersive solid-phase extraction purification), if select 100 ~ 200mg when a step purification (only loose Solid phase extraction), now all can reach good clean-up effect, the higher recovery can be ensured again.
Step (6). gas chromatography-electron capture detector detects:
Sample introduction needle extracts above-mentioned supernatant, detects according to the gas chromatography-electron capture detector condition set.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 ﹪), and 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 keep 1min, and 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 DEG C with 15 DEG C/min, and keep 1min, total run time is 32min.
Described gas chromatographic column selects specification to be the CD-5MS capillary gas chromatographic column of 30m × 0.25mm × 0.25 μm, Stationary liquid is the mixed liquor of diphenyl and dimethyl polysiloxane, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 7 kinds of polychlorinated biphenyl.
Step (7). Specification Curve of Increasing: qualitative with retention time, quantified by external standard method.
When retention time is qualitative, get the polychlorinated biphenyl hybrid standard use liquid 100 μ L that concentration is PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L, 1mL is settled to normal hexane, obtain standard solution, obtain the standard solution that concentration is 10 μ g/L.Standard solution is carried out operating the gas chromatogram obtaining standard solution according to the requirement of above-mentioned steps (6), and carries out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of polychlorinated biphenyl; The retention time of these 7 kinds of polychlorinated biphenyl in order to during as quantified by external standard method, the foundation of 7 kinds of polychlorinated biphenyl chromatographic peaks identification.Accompanying drawing 1 is the gas chromatogram of standard solution.
During quantified by external standard method, get polychlorinated biphenyl hybrid standard use liquid 12.5,25,50,100,500, the 1000 μ L that concentration is 100 μ g/L respectively, be settled to 1mL with normal hexane, obtain the typical curve serial solution that six spiked levels scopes are 1.25 ~ 100 μ g/L.By the typical curve serial solution of six kinds of different spiked levels, according to the corresponding relation Criterion curve of the polychlorinated biphenyl concentration added and peak area.
Table 1 is the equation of linear regression of the inventive method, the range of linearity, related coefficient and detection limit.As shown in Table 1, each polychlorinated biphenyl, in the corresponding range of linearity, has good linear relationship, meets analytical approach requirement.
The equation of linear regression of table 1 the inventive method, the range of linearity, related coefficient and detection limit
Wherein, a:y and x represents the peak area and the theoretical concentration of analysis thing in 1mL normal hexane of analyzing thing respectively.
B: the concentration of thing in typical curve serial solution is analyzed in range of linearity representative;
Step (8). sample and determination of recovery rates:
Gather the actual sample (soil sample that Zhujiajian I., zhoushan Islands vegetable plot gathers and the mud sample that Dai Quyang enhancement releasing marine site, Zhoushan gathers) of two kinds of different substrates, operate according to the requirement of above-mentioned steps (1) ~ (6), and compare, by the content finally obtaining 7 kinds of polychlorinated biphenyl in testing sample that converts with the typical curve that above-mentioned steps (7) obtains.
Use above-mentioned actual sample, after requirement process according to (1) step, get 10.00g, add 12.5 respectively, 100, the 100 μ g/L polychlorinated biphenyl hybrid standards of 1000 μ L use liquid, be mixed with low (0.125 μ g/kg), in (1.00 μ g/kg) and high (10.0 μ g/kg) three kinds add the mark-on sample of concentration level, five operation repetitives are carried out respectively according to the requirement of above-mentioned steps (2) ~ (6), and compare with the typical curve that above-mentioned steps (7) obtains, the mensuration concentration finally obtaining 7 kinds of polychlorinated biphenyl in mark-on sample by converting, carry out recovery calculating according to the following formula:
In formula: R---the recovery, ﹪;
C
s---the mensuration concentration of 7 kinds of polychlorinated biphenyl in mark-on sample, μ g/kg;
C
0---the concentration of 7 kinds of polychlorinated biphenyl in actual sample, μ g/kg;
C---the theoretical spiked levels of 7 kinds of polychlorinated biphenyl in mark-on sample, μ g/kg;
After testing, in the mud sample of the soil sample that Zhujiajian I., zhoushan Islands vegetable plot gathers and the collection of Dai Quyang enhancement releasing marine site, Zhoushan, 7 kinds of polychlorinated biphenyl concentration are and do not detect, and in different substrates actual sample (soil sample that Zhujiajian I., zhoushan Islands vegetable plot gathers and the mud sample that Dai Quyang enhancement releasing marine site, Zhoushan gathers), the recovery testu of different spiked levels level the results are shown in Table 2.The gas chromatogram of the soil sample that Zhujiajian I., zhoushan Islands vegetable plot gathers and the soil sample that mark-on Zhujiajian I., zhoushan Islands vegetable plot gathers is shown in accompanying drawing 2, the gas chromatogram of the mud sample that Dai Quyang enhancement releasing marine site, Zhoushan gathers and the mud sample that Dai Quyang enhancement releasing marine site, mark-on Zhoushan gathers is shown in accompanying drawing 3, and whole sample analysis process flow diagram is shown in accompanying drawing 4.
The recovery of standard addition of 7 kinds of polychlorinated biphenyl and the precision (n=5) of method in the mud sample of the soil sample that table 3 Zhujiajian I., zhoushan Islands vegetable plot gathers and the collection of Dai Quyang enhancement releasing marine site, Zhoushan
The mud sample that Dai Quyang enhancement releasing marine site, Zhoushan gathers
Note: the unit of a. measured value is μ g/kg
The mensuration of 7 kinds of polychlorinated biphenyl in the soil sample that embodiment 2. Zhujiajian I., zhoushan Islands first vegetable plot gathers
(1) collection of sample and sample preparation: the soil sample that Zhujiajian I., zhoushan Islands first vegetable plot gathers, be sealed in polyethylene bags by the In Aluminium Foil Packing of cleaning, then laboratory is transported back with portable refrigerating box, sample is placed in the dry 24h of freeze drier again, took out 100 order stainless steel sifts, be placed in exsiccator to be measured.
The soil sample that mark-on Zhujiajian I., zhoushan Islands first vegetable plot gathers: the soil sample gathered to the Zhujiajian I., zhoushan Islands first vegetable plot that 10.00g handles well, the 100 μ g/L polychlorinated biphenyl hybrid standards adding 12.5,100,1000 μ L respectively use liquid, be mixed with low (0.125 μ g/kg), in the soil sample that gathers of (1.00 μ g/kg) and high (10.0 μ g/kg) the three kinds mark-on Zhujiajian I., zhoushan Islands first vegetable plot of adding concentration level.
(2) sampling and ultrasonic extraction: take the soil sample of the Zhujiajian I., zhoushan Islands first vegetable plot collection that 10.00g above-mentioned steps (1) is handled well or the soil sample of mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection, be placed in 50mL centrifuge tube, add 30mL normal hexane, vortex 2min, 30min is extracted in 30 DEG C of ultrasound waves with 480W power, add 1g copper powder ultrasound desulfurization, 6000r/m high speed centrifugation 5min; Extract color is more yellow, carries out two step purifications.
(3) concentrated sulfuric acid purification: add concentrated sulphuric acid 2mL in extract, vibration 2min, stratification, discards lower floor's concentrated sulphuric acid waste liquid, repeats said process 3 times, colourless to concentrated sulphuric acid layer, then with 30g/L aqueous sodium persulfate solution washing hexane extract to neutral.
(4) concentrated constant volume: after extract anhydrous sodium sulfate dehydration, pump vacuum degree 0.09MPa, bath temperature 35 DEG C, under rotating speed 80rpm, be evaporated to Rotary Evaporators dry, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid.
(5) dispersive solid-phase extraction purification: add 100mgN-propyl group ethylenediamine solid-phase adsorbent in 1mL n-hexane dissolution liquid, vortex 30s, 6000r/m high speed centrifugation 2min, gets supernatant.
(6) gas chromatography-electron capture detector detects: sample introduction needle extracts the supernatant 1 μ L that above-mentioned steps (5) obtains, and detects according to the gas chromatography-electron capture detector condition set.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 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 keep 1min, and 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 DEG C with 15 DEG C/min, and keep 1min, total run time is 32min.
Described gas chromatographic column selects specification to be the CD-5MS capillary gas chromatographic column of 30m × 0.25mm × 0.25 μm, Stationary liquid is the mixed liquor of diphenyl and dimethyl polysiloxane, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 7 kinds of polychlorinated biphenyl.
(7) Specification Curve of Increasing: qualitative with retention time, quantified by external standard method.When retention time is qualitative, get the polychlorinated biphenyl hybrid standard use liquid 100 μ L that concentration is PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L, 1mL is settled to normal hexane, obtain standard solution, obtain the standard solution that concentration is 10 μ g/L.Standard solution is carried out operating the gas chromatogram obtaining standard solution according to the requirement of above-mentioned steps (6), and carries out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of polychlorinated biphenyl; The retention time of these 7 kinds of polychlorinated biphenyl in order to during as quantified by external standard method, the foundation of 7 kinds of polychlorinated biphenyl chromatographic peaks identification.Accompanying drawing 1 is the gas chromatogram of standard solution.
During quantified by external standard method, get polychlorinated biphenyl hybrid standard use liquid 12.5,25,50,100,500, the 1000 μ L that concentration is 100 μ g/L respectively, be settled to 1mL with normal hexane, obtain the typical curve serial solution that six spiked levels scopes are 1.25 ~ 100 μ g/L.By the typical curve serial solution of six kinds of different spiked levels, according to the corresponding relation Criterion curve of the polychlorinated biphenyl concentration added and peak area.Table 1 is the equation of linear regression of the inventive method, the range of linearity, related coefficient and detection limit.As shown in Table 1, each polychlorinated biphenyl, in the corresponding range of linearity, has good linear relationship, meets analytical approach requirement.
(8) sample and determination of recovery rates: after the soil sample that Zhujiajian I., zhoushan Islands first vegetable plot gathers operates according to the requirement of above-mentioned steps (1) ~ (6), the typical curve obtained with above-mentioned steps (7) compares, and the mensuration concentration finally obtaining 7 kinds of polychlorinated biphenyl in the soil sample of Zhujiajian I., zhoushan Islands first vegetable plot collection by converting is and does not detect.The soil sample that mark-on Zhujiajian I., zhoushan Islands first vegetable plot gathers carries out five operation repetitives respectively according to the requirement of above-mentioned steps (1) ~ (6), and compare with the typical curve that above-mentioned steps (7) obtains, the mensuration concentration of 7 kinds of polychlorinated biphenyl in the soil sample of mark-on Zhujiajian I., zhoushan Islands first vegetable plot collection is finally obtained by converting, and calculate the recovery, the relative standard deviation of five replicate determinations.As shown in Table 2, the soil sample recovery that mark-on Zhujiajian I., zhoushan Islands first vegetable plot gathers is 72 ~ 107 ﹪, and relative standard deviation (n=5) is 3.5 ~ 5.8 ﹪, meets analytical approach to the recovery and reappearance requirement.
The mensuration of 7 kinds of polychlorinated biphenyl in the mud sample that Dai Quyang enhancement releasing marine site, embodiment 3. Zhoushan gathers
(1) collection of sample and sample preparation: the mud sample that Dai Quyang enhancement releasing marine site, Zhoushan gathers, be sealed in polyethylene bags by the In Aluminium Foil Packing of cleaning, then laboratory is transported back with portable refrigerating box, sample is placed in the dry 24h of freeze drier again, took out 100 order stainless steel sifts, be placed in exsiccator to be measured.
The mud sample that Dai Quyang enhancement releasing marine site, mark-on Zhoushan gathers: the mud sample gathered to the Dai Quyang enhancement releasing marine site, Zhoushan that 10.00g handles well, the 100 μ g/L polychlorinated biphenyl hybrid standards adding 12.5,100,1000 μ L respectively use liquid, be mixed with low (0.125 μ g/kg), in the mud sample that gathers of (1.00 μ g/kg) and high (10.0 μ g/kg) the three kinds Dai Quyang enhancement releasing marine site, mark-on Zhoushan of adding concentration level.
(2) sampling and ultrasonic extraction: take the mud sample of Dai Quyang enhancement releasing marine site, the Zhoushan collection that 10.00g above-mentioned steps (1) is handled well or the mud sample of Dai Quyang enhancement releasing marine site, mark-on Zhoushan collection, be placed in 50mL centrifuge tube, add 30mL normal hexane, vortex 2min, 30min, 6000r/m high speed centrifugation 5min is extracted in 30 DEG C of ultrasound waves with 480W power; The basic water white transparency of extract color, carries out a step purification.
(3) concentrated constant volume: after extract anhydrous sodium sulfate dehydration, pump vacuum degree 0.09MPa, bath temperature 35 DEG C, under rotating speed 80rpm, be evaporated to Rotary Evaporators dry, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid.
(4) dispersive solid-phase extraction purification: add 100mgN-propyl group ethylenediamine solid-phase adsorbent in 1mL n-hexane dissolution liquid, vortex 30s, 6000r/m high speed centrifugation 2min, gets supernatant.
(5) gas chromatography-electron capture detector detects: sample introduction needle extracts the supernatant 1 μ L that above-mentioned steps (5) obtains, and detects according to the gas chromatography-electron capture detector condition set.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 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 keep 1min, and 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 DEG C with 15 DEG C/min, and keep 1min, total run time is 32min.
Described gas chromatographic column selects specification to be the CD-5MS capillary gas chromatographic column of 30m × 0.25mm × 0.25 μm, Stationary liquid is the mixed liquor of diphenyl and dimethyl polysiloxane, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 7 kinds of polychlorinated biphenyl.
(6) Specification Curve of Increasing: qualitative with retention time, quantified by external standard method.When retention time is qualitative, get the polychlorinated biphenyl hybrid standard use liquid 100 μ L that concentration is PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L, 1mL is settled to normal hexane, obtain standard solution, obtain the standard solution that concentration is 10 μ g/L.Standard solution is carried out operating the gas chromatogram obtaining standard solution according to the requirement of above-mentioned steps (5), and carries out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of polychlorinated biphenyl; The retention time of these 7 kinds of polychlorinated biphenyl in order to during as quantified by external standard method, the foundation of 7 kinds of polychlorinated biphenyl chromatographic peaks identification.Accompanying drawing 1 is the gas chromatogram of standard solution.
During quantified by external standard method, get polychlorinated biphenyl hybrid standard use liquid 12.5,25,50,100,500, the 1000 μ L that concentration is 100 μ g/L respectively, be settled to 1mL with normal hexane, obtain the typical curve serial solution that six spiked levels scopes are 1.25 ~ 100 μ g/L.By the typical curve serial solution of six kinds of different spiked levels, according to the corresponding relation Criterion curve of the polychlorinated biphenyl concentration added and peak area.Table 1 is the equation of linear regression of the inventive method, the range of linearity, related coefficient and detection limit.As shown in Table 1, each polychlorinated biphenyl, in the corresponding range of linearity, has good linear relationship, meets analytical approach requirement.
(7) sample and determination of recovery rates: after the mud sample that Dai Quyang enhancement releasing marine site, Zhoushan gathers operates according to the requirement of above-mentioned steps (1) ~ (5), the typical curve obtained with above-mentioned steps (6) compares, and the mensuration concentration finally obtaining 7 kinds of polychlorinated biphenyl in the mud sample of Dai Quyang enhancement releasing marine site, Zhoushan collection by converting is and does not detect.The mud sample that Dai Quyang enhancement releasing marine site, mark-on Zhoushan gathers carries out five operation repetitives respectively according to the requirement of above-mentioned steps (1) ~ (5), and compare with the typical curve that above-mentioned steps (6) obtains, the mensuration concentration of 7 kinds of polychlorinated biphenyl in the mud sample of Dai Quyang enhancement releasing marine site, mark-on Zhoushan collection is finally obtained by converting, and calculate the recovery, the relative standard deviation of five replicate determinations.As shown in Table 2, the mud sample recovery that Dai Quyang enhancement releasing marine site, mark-on Zhoushan gathers is 88 ~ 115 ﹪, and relative standard deviation (n=5) is 3.7 ~ 6.9 ﹪, meets analytical approach to the recovery and reappearance requirement.
The mensuration of 7 kinds of polychlorinated biphenyl in the soil sample that embodiment 4. Zhujiajian I., zhoushan Islands second vegetable plot gathers
(1) collection of sample and sample preparation: the In Aluminium Foil Packing of the soil sample cleaning that Zhujiajian I., zhoushan Islands second vegetable plot gathers also is sealed in polyethylene bags, then laboratory is transported back with portable refrigerating box, sample is placed in the dry 12h of freeze drier again, took out 80 order stainless steel sifts, be placed in exsiccator to be measured.
The soil sample that mark-on Zhu family point second vegetable plot gathers: the soil sample gathered to Zhu family's point second vegetable plot that 10.00g handles well, the 100 μ g/L polychlorinated biphenyl hybrid standards adding 12.5,100,1000 μ L respectively use liquid, be mixed with low (0.125 μ g/kg), in the soil sample that gathers of (1.00 μ g/kg) and high (10.0 μ g/kg) the three kinds mark-on Zhu family point second vegetable plot of adding concentration level.
(2) sampling and ultrasonic extraction: take the soil sample of Zhu family's point second vegetable plot collection that 10.00g above-mentioned steps (1) is handled well or the soil sample of mark-on Zhu family point second vegetable plot collection, be placed in 50mL centrifuge tube, add 20mL normal hexane, vortex 1min, extracts 40min with 400W power in 35 DEG C of ultrasound waves; There is the background interference of sulfocompound, add 1g copper powder ultrasound desulfurization, 3000r/m high speed centrifugation 3min; Extract color is more yellow, carries out two step purifications.
(3) concentrated sulfuric acid purification: add concentrated sulphuric acid 1mL in extract, vibration 1min, stratification, discards lower floor's concentrated sulphuric acid waste liquid, repeats said process 2 times, colourless to concentrated sulphuric acid layer, then with 30g/L aqueous sodium persulfate solution washing hexane extract to neutral.
(4) concentrated constant volume: after extract anhydrous sodium sulfate dehydration, pump vacuum degree 0.08MPa, bath temperature 40 DEG C, under rotating speed 100rpm, be evaporated to dry with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid.
(5) dispersive solid-phase extraction purification: add 50mgN-propyl group ethylenediamine solid-phase adsorbent in 1mL n-hexane dissolution liquid, vortex 60s, 3000r/m high speed centrifugation 3min, gets supernatant.
(6) gas chromatography-electron capture detector detects: sample introduction needle extracts the supernatant 1 μ L that above-mentioned steps (5) obtains, and detects according to the gas chromatography-electron capture detector condition set.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 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 keep 1min, and 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 DEG C with 15 DEG C/min, and keep 1min, total run time is 32min.
Described gas chromatographic column selects specification to be the CD-5MS capillary gas chromatographic column of 30m × 0.25mm × 0.25 μm, Stationary liquid is the mixed liquor of diphenyl and dimethyl polysiloxane, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 7 kinds of polychlorinated biphenyl.
(7) Specification Curve of Increasing: qualitative with retention time, quantified by external standard method.When retention time is qualitative, get the polychlorinated biphenyl hybrid standard use liquid 100 μ L that concentration is PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L, 1mL is settled to normal hexane, obtain standard solution, obtain the standard solution that concentration is 10 μ g/L.Standard solution is carried out operating the gas chromatogram obtaining standard solution according to the requirement of above-mentioned steps (6), and carries out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of polychlorinated biphenyl; The retention time of these 7 kinds of polychlorinated biphenyl in order to during as quantified by external standard method, the foundation of 7 kinds of polychlorinated biphenyl chromatographic peaks identification.
During quantified by external standard method, get polychlorinated biphenyl hybrid standard use liquid 12.5,25,50,100,500, the 1000 μ L that concentration is 100 μ g/L respectively, be settled to 1mL with normal hexane, obtain the typical curve serial solution that six spiked levels scopes are 1.25 ~ 100 μ g/L.By the typical curve serial solution of six kinds of different spiked levels, according to the corresponding relation Criterion curve of the polychlorinated biphenyl concentration added and peak area.
(8) sample and determination of recovery rates: after the soil sample that Zhu family's point second vegetable plot gathers operates according to the requirement of above-mentioned steps (1) ~ (6), the typical curve obtained with above-mentioned steps (7) compares, and the mensuration concentration finally obtaining 7 kinds of polychlorinated biphenyl in the soil sample of Zhu family's point second vegetable plot collection by converting is and does not detect.The soil sample that mark-on Zhu family point second vegetable plot gathers carries out five operation repetitives respectively according to the requirement of above-mentioned steps (1) ~ (6), and compare with the typical curve that above-mentioned steps (7) obtains, the mensuration concentration of 7 kinds of polychlorinated biphenyl in the soil sample of mark-on Zhu family point second vegetable plot collection is finally obtained by converting, and calculate the recovery, the relative standard deviation of five replicate determinations.The soil sample recovery that mark-on Zhu family point second vegetable plot gathers is 76 ~ 110 ﹪, and relative standard deviation (n=5) is 3.9 ~ 6.4 ﹪, meets analytical approach to the recovery and reappearance requirement.
The mensuration of 7 kinds of polychlorinated biphenyl in the soil sample that embodiment 5. Zhujiajian I., zhoushan Islands third vegetable plot gathers
(1) collection of sample and sample preparation: the In Aluminium Foil Packing of the soil sample cleaning that Zhujiajian I., zhoushan Islands third vegetable plot gathers also is sealed in polyethylene bags, then laboratory is transported back with portable refrigerating box, sample is placed in the dry 20h of freeze drier again, took out 100 order stainless steel sifts, be placed in exsiccator to be measured.
The soil sample that mark-on Zhu family point second vegetable plot gathers: the soil sample gathered to Zhu family's point third vegetable plot that 10.00g handles well, the 100 μ g/L polychlorinated biphenyl hybrid standards adding 12.5,100,1000 μ L respectively use liquid, be mixed with low (0.125 μ g/kg), in the soil sample that gathers of (1.00 μ g/kg) and high (10.0 μ g/kg) three kinds mark-on Zhu family point third vegetable plot of adding concentration level.
(2) sampling and ultrasonic extraction: take the soil sample of Zhu family's point third vegetable plot collection that 10.00g above-mentioned steps (1) is handled well or the soil sample of mark-on Zhu family point third vegetable plot collection, be placed in 50mL centrifuge tube, add 40mL normal hexane, vortex 3min, extracts 20min with 500W power in 40 DEG C of ultrasound waves; There is the background interference of sulfocompound, add 3g copper powder ultrasound desulfurization, 3000r/m high speed centrifugation 5min; Extract color is substantially colourless, carries out two step purifications.
(3) concentrated sulfuric acid purification: add concentrated sulphuric acid 3mL in extract, vibration 3min, stratification, discards lower floor's concentrated sulphuric acid waste liquid, repeats said process 2 times, colourless to concentrated sulphuric acid layer, then with 30g/L aqueous sodium persulfate solution washing hexane extract to neutral.
(4) concentrated constant volume: after extract anhydrous sodium sulfate dehydration, pump vacuum degree 0.09MPa, bath temperature 40 DEG C, under rotating speed 50rpm, be evaporated to Rotary Evaporators dry, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid.
(5) dispersive solid-phase extraction purification: add 150mgN-propyl group ethylenediamine solid-phase adsorbent in 1mL n-hexane dissolution liquid, vortex 60s, 6000r/m high speed centrifugation 1min, gets supernatant.
(6) gas chromatography-electron capture detector detects: sample introduction needle extracts the supernatant 1 μ L that above-mentioned steps (5) obtains, and detects according to the gas chromatography-electron capture detector condition set.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 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 keep 1min, and 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 DEG C with 15 DEG C/min, and keep 1min, total run time is 32min.
Described gas chromatographic column selects specification to be the CD-5MS capillary gas chromatographic column of 30m × 0.25mm × 0.25 μm, Stationary liquid is the mixed liquor of diphenyl and dimethyl polysiloxane, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 7 kinds of polychlorinated biphenyl.
(7) Specification Curve of Increasing: qualitative with retention time, quantified by external standard method.When retention time is qualitative, get the polychlorinated biphenyl hybrid standard use liquid 100 μ L that concentration is PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L, 1mL is settled to normal hexane, obtain standard solution, obtain the standard solution that concentration is 10 μ g/L.Standard solution is carried out operating the gas chromatogram obtaining standard solution according to the requirement of above-mentioned steps (6), and carries out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of polychlorinated biphenyl; The retention time of these 7 kinds of polychlorinated biphenyl in order to during as quantified by external standard method, the foundation of 7 kinds of polychlorinated biphenyl chromatographic peaks identification.
During quantified by external standard method, get polychlorinated biphenyl hybrid standard use liquid 12.5,25,50,100,500, the 1000 μ L that concentration is 100 μ g/L respectively, be settled to 1mL with normal hexane, obtain the typical curve serial solution that six spiked levels scopes are 1.25 ~ 100 μ g/L.By the typical curve serial solution of six kinds of different spiked levels, according to the corresponding relation Criterion curve of the polychlorinated biphenyl concentration added and peak area.
(8) sample and determination of recovery rates: after the soil sample that Zhu family's point third vegetable plot gathers operates according to the requirement of above-mentioned steps (1) ~ (6), the typical curve obtained with above-mentioned steps (7) compares, and the mensuration concentration finally obtaining 7 kinds of polychlorinated biphenyl in the soil sample of Zhu family's point third vegetable plot collection by converting is and does not detect.The soil sample that mark-on Zhu family point third vegetable plot gathers carries out five operation repetitives respectively according to the requirement of above-mentioned steps (1) ~ (6), and compare with the typical curve that above-mentioned steps (7) obtains, the mensuration concentration of 7 kinds of polychlorinated biphenyl in the soil sample of mark-on Zhu family point third vegetable plot collection is finally obtained by converting, and calculate the recovery, the relative standard deviation of five replicate determinations.The soil sample recovery that mark-on Zhu family point third vegetable plot gathers is 73 ~ 105 ﹪, and relative standard deviation (n=5) is 3.2 ~ 6.3 ﹪, meets analytical approach to the recovery and reappearance requirement.
The mensuration of 7 kinds of polychlorinated biphenyl in the mud sample that Dai Quyang enhancement releasing marine site, embodiment 6. Zhoushan gathers
(1) collection of sample and sample preparation: the mud sample that Dai Quyang enhancement releasing marine site, Zhoushan gathers, be sealed in polyethylene bags by the In Aluminium Foil Packing of cleaning, then laboratory is transported back with portable refrigerating box, sample is placed in the dry 24h of freeze drier again, took out 100 order stainless steel sifts, be placed in exsiccator to be measured.
The mud sample that Dai Quyang enhancement releasing marine site, mark-on Zhoushan gathers: the mud sample gathered to the Dai Quyang enhancement releasing marine site, Zhoushan that 10.00g handles well, the 100 μ g/L polychlorinated biphenyl hybrid standards adding 12.5,100,1000 μ L respectively use liquid, be mixed with low (0.125 μ g/kg), in the mud sample that gathers of (1.00 μ g/kg) and high (10.0 μ g/kg) the three kinds Dai Quyang enhancement releasing marine site, mark-on Zhoushan of adding concentration level.
(2) sampling and ultrasonic extraction: take the mud sample of Dai Quyang enhancement releasing marine site, the Zhoushan collection that 10.00g above-mentioned steps (1) is handled well or the mud sample of Dai Quyang enhancement releasing marine site, mark-on Zhoushan collection, be placed in 50mL centrifuge tube, add 40mL normal hexane, vortex 2min, 20min, 6000r/m high speed centrifugation 5min is extracted in 40 DEG C of ultrasound waves with 400W power; The basic water white transparency of extract color, carries out a step purification.
(3) concentrated constant volume: after extract anhydrous sodium sulfate dehydration, pump vacuum degree 0.08MPa, bath temperature 40 DEG C, under rotating speed 80rpm, be evaporated to Rotary Evaporators dry, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid.
(4) dispersive solid-phase extraction purification: add 200mgN-propyl group ethylenediamine solid-phase adsorbent in 1mL n-hexane dissolution liquid, vortex 30s, 6000r/m high speed centrifugation 2min, gets supernatant.
(5) gas chromatography-electron capture detector detects: sample introduction needle extracts the supernatant 1 μ L that above-mentioned steps (5) obtains, and detects according to the gas chromatography-electron capture detector condition set.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 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 keep 1min, and 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 DEG C with 15 DEG C/min, and keep 1min, total run time is 32min.
Described gas chromatographic column selects specification to be the CD-5MS capillary gas chromatographic column of 30m × 0.25mm × 0.25 μm, Stationary liquid is the mixed liquor of diphenyl and dimethyl polysiloxane, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 7 kinds of polychlorinated biphenyl.
(6) Specification Curve of Increasing: qualitative with retention time, quantified by external standard method.When retention time is qualitative, get the polychlorinated biphenyl hybrid standard use liquid 100 μ L that concentration is PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180 of 100 μ g/L, 1mL is settled to normal hexane, obtain standard solution, obtain the standard solution that concentration is 10 μ g/L.Standard solution is carried out operating the gas chromatogram obtaining standard solution according to the requirement of above-mentioned steps (5), and carries out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of polychlorinated biphenyl; The retention time of these 7 kinds of polychlorinated biphenyl in order to during as quantified by external standard method, the foundation of 7 kinds of polychlorinated biphenyl chromatographic peaks identification.
During quantified by external standard method, get polychlorinated biphenyl hybrid standard use liquid 12.5,25,50,100,500, the 1000 μ L that concentration is 100 μ g/L respectively, be settled to 1mL with normal hexane, obtain the typical curve serial solution that six spiked levels scopes are 1.25 ~ 100 μ g/L.By the typical curve serial solution of six kinds of different spiked levels, according to the corresponding relation Criterion curve of the polychlorinated biphenyl concentration added and peak area.
(7) sample and determination of recovery rates: after the mud sample that Dai Quyang enhancement releasing marine site, Zhoushan gathers operates according to the requirement of above-mentioned steps (1) ~ (5), the typical curve obtained with above-mentioned steps (6) compares, and the mensuration concentration finally obtaining 7 kinds of polychlorinated biphenyl in the mud sample of Dai Quyang enhancement releasing marine site, Zhoushan collection by converting is and does not detect.The mud sample that Dai Quyang enhancement releasing marine site, mark-on Zhoushan gathers carries out five operation repetitives respectively according to the requirement of above-mentioned steps (1) ~ (5), and compare with the typical curve that above-mentioned steps (6) obtains, the mensuration concentration of 7 kinds of polychlorinated biphenyl in the mud sample of Dai Quyang enhancement releasing marine site, mark-on Zhoushan collection is finally obtained by converting, and calculate the recovery, the relative standard deviation of five replicate determinations.The mud sample recovery that Dai Quyang enhancement releasing marine site, mark-on Zhoushan gathers is 79 ~ 112 ﹪, and relative standard deviation (n=5) is 3.2 ~ 6.5 ﹪, meets analytical approach to the recovery and reappearance requirement.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet application claims, all belongs to protection scope of the present invention.
Claims (5)
1. the dispersive solid-phase extraction gas-chromatography detection method of polychlorinated biphenyl in soils and sediments, is characterized in that the method comprises the following steps:
Step (1). the collection of sample and sample preparation:
Soils and sediments sample to be detected is placed in the dry 12 ~ 24h of freeze drier, took out 80 ~ 100 order stainless steel sifts, and be placed in exsiccator to be measured;
Step (2). sampling and ultrasonic extraction:
Take 10.00g testing sample, add 20 ~ 40mL normal hexane, vortex 1 ~ 3min, extract 20 ~ 40min with 400 ~ 500W power in 30 ~ 40 DEG C of ultrasound waves; When the background interference of sulfocompound in sample, can add 1 ~ 3g copper powder ultrasound desulfurization, 3000 ~ 6000r/m high speed centrifugation, 3 ~ 5min, gets supernatant, is hexane extract; Observe extract color, if basic water white transparency, directly carry out the concentrated constant volume of step (4), namely only need a step purification, otherwise carry out step (3) concentrated sulfuric acid purification, namely need two step purifications;
Step (3). concentrated sulfuric acid purification:
Add the concentrated sulphuric acid 1 ~ 3mL in hexane extract, vibration 1 ~ 3min, stratification, discards lower floor's concentrated sulphuric acid waste liquid, as required, can repeatedly add concentrated sulfuric acid purification colourless to concentrated sulphuric acid layer, then with 30g/L aqueous sodium persulfate solution washing hexane extract to neutral;
Step (4). concentrated constant volume:
After hexane extract anhydrous sodium sulfate dehydration, pump vacuum degree 0.08 ~ 0.09MPa, bath temperature 35 ~ 40 DEG C, under rotating speed 50 ~ 100rpm, be evaporated to dry with Rotary Evaporators, add n-hexane dissolution, be settled to 1.0mL, obtain n-hexane dissolution liquid;
Step (5). dispersive solid-phase extraction purifies:
In 1mL n-hexane dissolution liquid, add 50 ~ 200mgN-propyl group ethylenediamine solid-phase adsorbent, vortex 30 ~ 60s, 3000 ~ 6000r/m high speed centrifugation 1 ~ 3min, gets supernatant;
Step (6). gas chromatography-electron capture detector detects:
Sample introduction needle extracts above-mentioned supernatant, detects according to the gas chromatography-electron capture detector condition set;
Step (7). Specification Curve of Increasing: qualitative with retention time, quantified by external standard method;
When retention time is qualitative, standard solution is carried out operating the gas chromatogram obtaining standard solution according to the requirement of above-mentioned steps (6), and carry out retention time with the gas chromatogram of single analyte and compare, determine the retention time of 7 kinds of polychlorinated biphenyl; The retention time of these 7 kinds of polychlorinated biphenyl in order to during as quantified by external standard method, the foundation of 7 kinds of polychlorinated biphenyl chromatographic peaks identification;
In described standard solution, solute is polychlorinated biphenyl, and solvent is normal hexane, and concentration is 10 μ g/L;
During quantified by external standard method, by the typical curve serial solution of different spiked levels, according to the corresponding relation Criterion curve of the polychlorinated biphenyl concentration added and peak area;
In described typical curve serial solution, solute is polychlorinated biphenyl, and solvent is normal hexane, and concentration range is 1.25 ~ 100 μ g/L;
Step (8). sample and determination of recovery rates:
By the actual sample collected, operate according to the requirement of above-mentioned steps (1) ~ (6), and compare, by the content finally obtaining 7 kinds of polychlorinated biphenyl in actual sample that converts with the typical curve that above-mentioned steps (7) obtains;
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 compare with the typical curve that above-mentioned steps (7) obtains, the mensuration concentration finally obtaining 7 kinds of polychlorinated biphenyl in mark-on sample by converting; Carry out recovery calculating according to the following formula:
In formula: R---the recovery, ﹪;
C
s---the mensuration concentration of 7 kinds of polychlorinated biphenyl in mark-on sample, μ g/kg;
C
0---the concentration of 7 kinds of polychlorinated biphenyl in actual sample, μ g/kg;
C---the theoretical spiked levels of 7 kinds of polychlorinated biphenyl in mark-on sample, μ g/kg;
Described mark-on sample is the sample after adding polychlorinated biphenyl in step (1) pretreated actual sample;
2. the dispersive solid-phase extraction gas-chromatography detection method of polychlorinated biphenyl in a kind of soils and sediments as claimed in claim 1, is characterized in that the chromatographic condition that step (6) gas chromatography-electron capture detector detects is: injector temperature is 260 DEG C; Electron capture detector temperature is 300 DEG C; Carrier gas is volume content 99.999 ﹪ high pure nitrogen, and 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 keep 1min, and 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 DEG C with 15 DEG C/min, and keep 1min, total run time is 32min;
Described gas chromatographic column selects specification to be the CD-5MS capillary gas chromatographic column of 30m × 0.25mm × 0.25 μm, Stationary liquid is the mixed liquor of diphenyl and dimethyl polysiloxane, wherein the massfraction of diphenyl is 5 ﹪, the massfraction of dimethyl polysiloxane is 95 ﹪, can realize effective separation of 7 kinds of polychlorinated biphenyl.
3. the dispersive solid-phase extraction gas-chromatography detection method of polychlorinated biphenyl in a kind of soils and sediments as claimed in claim 1 or 2, is characterized in that described polychlorinated biphenyl comprises PCB28, PCB52, PCB101, PCB118, PCB153, PCB138, PCB180.
4. the dispersive solid-phase extraction gas-chromatography detection method of polychlorinated biphenyl in a kind of soils and sediments as described in claim 1 or 2 or 3, when two step purifications, 50 ~ 150mgN-propyl group ethylenediamine solid-phase adsorbent is selected, if select 100 ~ 200mgN-propyl group ethylenediamine solid-phase adsorbent when a step purification if it is characterized in that.
5. the dispersive solid-phase extraction gas-chromatography detection method of polychlorinated biphenyl in a kind of soils and sediments as claimed in claim 1 or 2 or 3 or 4, it is characterized in that described copper powder use before first with watery hydrochloric acid process to remove its surface film oxide, a small amount of acid on its surface is attached to again with distilled water flushing removing, finally flow down with acetone rinsing and at volume content 99.999 ﹪ high pure nitrogen and dry up, in case copper powder again be oxidized.
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