CN110346472A - A kind of method of organic matter in Gas Chromatography-Mass Spectrometry deposit - Google Patents
A kind of method of organic matter in Gas Chromatography-Mass Spectrometry deposit Download PDFInfo
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- CN110346472A CN110346472A CN201910614696.XA CN201910614696A CN110346472A CN 110346472 A CN110346472 A CN 110346472A CN 201910614696 A CN201910614696 A CN 201910614696A CN 110346472 A CN110346472 A CN 110346472A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The present invention provides a kind of method of organic matter in Gas Chromatography-Mass Spectrometry deposit, the method specifically includes deposit is dehydrated after it is dry, be ground up, sieved, sample be made；It extracts: sample being subjected to ASE extraction, obtains extract liquor；Purification: extract liquor is concentrated, concentrate is separated using chromatographic column；Measurement: purified sample is subjected to qualitative and quantitative analysis with gas chromatography-mass spectrography.The present invention extracts object using accelerated solvent extraction method, and upper glass chromatography column carries out stage purification after extracting solution concentration, and the laggard GC-MS qualitative and quantitative analysis of constant volume is concentrated.Characteristic ion according to chromatographic peak retention time and object is qualitative, inner mark method ration.This method sample treatment of five kinds of organic matters, analysis test suitable for coastal waters, river mouth, bay, culture zone deposit.
Description
Technical field
The invention belongs to field of chemical detection, and in particular to organic matter in a kind of Gas Chromatography-Mass Spectrometry deposit
Method.
Background technique
It is deposited on water-bed various deposits, such as bed mud.Source has: (1) river, river, lake, the mud carried secretly in seawater body
The suspended matters such as sand；(2) remains and its decomposition product of aquatile；(3) water pollutant, especially mercury, cadmium, lead, zinc, nickel
The organic matter of equal heavy metals and strong adsorption.By the specificity analysis of physics, chemistry, biology to benthal deposit etc., and
The research of depositional environment, can find out over the type of pollutant in some time, determine pollution level, determine pollution sources position
It sets.
Summary of the invention
The object of the present invention is to provide a kind of methods of organic matter in Gas Chromatography-Mass Spectrometry deposit, by right
The comparisons of different extraction conditions selects suitable extraction conditions, select suitable method for concentration and purification pillar to sample into
Row thickening-purification technology classification processing, tests object different in sample using different analysis methods.
For achieving the above object, the present invention is achieved by the following scheme:
A kind of method of organic matter in Gas Chromatography-Mass Spectrometry deposit, the described method comprises the following steps:
(1) it prepares: deposit being dehydrated, ground 100~150 mesh, sample is made；
(2) it extracts: sample being subjected to ASE extraction, obtains extract liquor；
(3) it purifies: extract liquor being concentrated, concentrate is separated using chromatographic column, collects eluent respectively；
(4) it measures: the organic matter in eluent is subjected to qualitative and quantitative analysis with gas chromatography-mass spectrography, wherein
Characteristic ion according to chromatographic peak retention time and object is qualitative, inner mark method ration.
Further: the organic matter is polycyclic aromatic hydrocarbon, Polychlorinated biphenyls, six six six, DDT and n-alkane.
Further: the method dehydrated in the step (1) is to use freeze drier vacuum freeze drying.
Further: the solvent that ASE extraction uses in the step (2) is methylene chloride；Extraction conditions is system pressure
10~11MPa, 90~110 DEG C of extraction temperature, 3~7min of heating time, 5~10min of quiet hour, flush volume is extraction
The 60~70% of pond body product, recycle 2~3 times.
Further: after the step (2) further includes extraction, the copper powder that addition has activated is non-discolouring to copper powder, obtains
To extract liquor.
Further: the diameter of chromatographic column is 8mm, the fill method of the chromatographic column are as follows: under in the step (3)
To the upper deactivation neutral alumina for successively filling out 3~4cm, the deactivation neutral silica gel of 3~4cm, the anhydrous sodium sulfate of 1~2cm.
It is further: the specific steps separated in the step (3) are as follows:
Concentrate is added drop-wise in chromatographic column, successively with n-hexane, n-hexane and methylene chloride, methylene chloride and methanol
Chromatographic column is eluted, non-polar component, middle polarity component and polar compound are respectively obtained；
After rotary evaporation and nitrogen are blown, non-polar component adds inner mark solution PCNB and HMB, and middle polarity component adds internal standard
HMB, with n-hexane constant volume.
It is further: the condition of gas-chromatography in the step (4) are as follows:
Chromatographic column: column length 30m, diameter 0.25mm, 0.25 μm of film thickness；250~300 DEG C of temperature of vaporization chamber；Carrier gas is high-purity
He；0.9~1.2mL/min of flow velocity；1 μ L of sample volume；Input mode is Splitless injecting samples.
It is further: the temperature program of the condition of gas-chromatography in the step (4) are as follows:
Polycyclic aromatic hydrocarbon:, keeping 1~2min by 50~70 DEG C, rises to 250~300 DEG C with 5 DEG C/min, keeps 15~20min；
Polychlorinated biphenyls, six six six, DDT:, rising to 180~200 DEG C with 30 DEG C/min by 80~100 DEG C, then with 3 DEG C/
Min rises to 200~210 DEG C, keeps 2~5min, then rise to 250~300 DEG C with 5 DEG C/min, keeps 3~6min；
N-alkane:, keeping 1~2min by 50~80 DEG C, rises to 150~200 DEG C with 12 DEG C/min, keeps 1~2min,
270~310 DEG C are risen to 8 DEG C/min again, keeps 0.5~1min；300~350 DEG C are risen to again with 12 DEG C/min, keep 10~
15min。
It is further: Mass Spectrometry Conditions in the step (4) are as follows: electron impact ion source；Electron energy 70eV；Transmission line
280~300 DEG C of temperature；230~250 DEG C of ion source temperature；130~170 DEG C of quadrupole rod temperature；The solvent delay time 3~
6min。
Compared with prior art, advantages of the present invention and have the technical effect that five kinds of organic pollutants include petroleum hydrocarbon point
It analyses, five kinds of organic pollutants (PAHs, PCBs, HCHs, DDTs, n-alkanes) in deposit use accelerated solvent extraction side
Method is extracted, and upper glass chromatography column carries out stage purification after extracting solution concentration, and the laggard GC-MS qualitative and quantitative analysis of constant volume is concentrated.
Characteristic ion according to chromatographic peak retention time and object is qualitative, inner mark method ration.This method is suitable for coastal waters, river mouth, port
The sample treatment of five kinds of organic matters, analysis test in gulf, culture zone deposit.
Detailed description of the invention
Fig. 1 is the total ion chromatogram of polycyclic aromatic hydrocarbon；
Fig. 2 is Polychlorinated biphenyls, six six six, the total ion chromatogram of DDT；
Fig. 3 is the total ion chromatogram of n-alkane.
Specific embodiment
With reference to embodiments by the technical scheme of the present invention will be explained in further detail.
Embodiment 1
One, the scope of application
The organic matter of test is analyzed in the present embodiment are as follows: polycyclic aromatic hydrocarbon, Polychlorinated biphenyls, six six six, DDT and N-alkanes
Hydrocarbon.5 kinds of organic matters difference is as follows:
The polycyclic aromatic hydrocarbon (PAHs) include 16 kinds: naphthalene, acenaphthylene, acenaphthene, fluorenes, phenanthrene, anthracene, fluoranthene, pyrene, benzanthracene,Benzene
And (b) fluoranthene, benzo (k) pyrene, benzo (a) pyrene, indenes benzene (1,2,3, cd) pyrene, dibenzanthracene, benzo (ghi) pyrene.
The Polychlorinated biphenyls (PCBs) includes 28 kinds: CB-8, CB-18, CB-28, CB-52, CB-44, CB-66, CB-
101、CB-77、CB-81、CB-114、CB-118、CB-123、CB-153、CB-105、 CB-138、CB-126、CB-187、CB-
128、CB-167、CB-156、CB-157、CB-180、CB-169、 CB-170、CB-189、CB-195、CB-206、CB-209。
The six six six (HCHs) includes 4 kinds: α -666, γ -666, β -666, δ -666.
The DDT (DDTs) includes 4 kinds: PP '-DDE, OP '-DDT, PP '-DDD, PP '-DDT
The n-alkane (n-alkane) includes: nC10H22、nC11H24、nC12H26、nC13H28、nC14H30、 nC15H32、
nC16H34、nC17H36、Pristane、nC18H38、Phytane、nC19H40、nC20H42、nC21H44、 nC22H46、nC23H48、
nC24H50、nC25H52、nC26H54、nC27H56、nC28H58、nC29H60、nC30H62、 nC31H64、nC32H66、nC33H68、nC34H70、
nC35H72。
Two, reagent and its preparation
Unless otherwise indicated, chromatography pure reagent that meet national standards is used when analysis.Experimental water is super for Mili-Q
Pure water.
Acetone (C3H6O): chromatographically pure；N-hexane (C6H14): chromatographically pure；Methylene chloride (CH2Cl2): chromatographically pure；Methanol
(CH3OH): chromatographically pure；Hydrochloric acid (HCl): 1+1 is mixed with top grade pure hydrochloric acid according to 1: 1 volume ratio；N-hexane-methylene chloride is mixed
Bonding solvent: 1+1 n-hexane and methylene chloride are mixed by 1: 1 volume ratio；Methylene chloride-methanol mixed solution: 1+1 dichloro
Methane and methanol are mixed by 1: 1 volume ratio；
Anhydrous sodium sulfate: take appropriate anhydrous sodium sulfate in Muffle furnace in 450 DEG C of high temperature sintering 4h, after being cooled to room temperature
It is spare.
Silica gel/aluminium oxide: take proper silica gel/aluminium oxide (100-200 mesh) with methylene chloride in Accelerate solvent extraction instrument
Decontamination is rinsed, excessive organic solvent is extracted and is cooled to room temperature using preceding 130 DEG C of activation 4h in an oven, every 100g silica gel/
Aluminium oxide adds the ultrapure water of 3-5mL to deactivate.Be placed in tool plug bottle in it is spare, in 7 days effectively.
Copper powder (200 mesh, purity 99.8%): embathing half a minute with hydrochloric acid solution, and incline acid, is washed with water to neutrality, then use
Acetone cleans for several times, logical to be dried with nitrogen, and is stored in spare in the tool plug vial filled with nitrogen.
Silica wool: taking appropriate silica wool, in 450 DEG C of high temperature sintering 4h, to be cooled to room temperature in Muffle furnace, is stored in tool plug
It is spare in vial.
Polycyclic aromatic hydrocarbon Standard Stock solutions: 2000 μ g/mL are dissolved in benzene: dichlorotoleune (1: 1)
Polycyclic aromatic hydrocarbon standard intermediate solution: the hybrid standard stock solution of appropriate volume is accurately pipetted, is diluted with n-hexane
To required concentration, 2-8 DEG C is kept in dark place.
Polycyclic aromatic hydrocarbon internal standard stock solution: it is molten to accurately weigh 0.01g hexamethylbenzene (Hexamethylbenzene, HMB)
In 10mL n-hexane solvent, it is prepared as the stock solution that concentration is 1000 μ g/mL.
Polycyclic aromatic hydrocarbon internal standard uses solution: accurately pipetting the hybrid standard stock solution of appropriate volume, is diluted with n-hexane
To required concentration, 2-8 DEG C is kept in dark place.
The polycyclic aromatic hydrocarbon rate of recovery indicates standard solution: 2000mg/L is dissolved in methylene chloride, contains five kinds of deuterated polycyclic aromatic hydrocarbons
Compound: acenaphthene-d10, phenanthrene-d10,- d12 ,-d12, naphthalene-d8.
The polycyclic aromatic hydrocarbon rate of recovery indicates intermediate solution: accurately pipetting the polycyclic aromatic hydrocarbon rate of recovery instruction standard of appropriate volume
Solution is diluted to required concentration with n-hexane, is kept in dark place.
Polycyclic aromatic hydrocarbon hybrid standard working solution: appropriate mixing intermediate solution, rate of recovery instruction solution are accurately pipetted and is fitted
Amount internal standard be dissolved in suitable n-hexane solvent using solution be prepared into polycyclic aromatic hydrocarbon concentration be 0.05 μ g/mL, 0.1 μ g/mL,
0.5 μ g/mL, 1 μ g/mL, 2 μ g/mL, 5 μ g/mL and containing the internal standard object concentration be 1 μ g/mL hybrid standard working solution, 2-8 DEG C
It is kept in dark place.
Polychlorinated biphenyls Standard Stock solutions: 100 μ g/mL are dissolved in isooctane.
Polychlorinated biphenyls standard intermediate solution: the hybrid standard stock solution of appropriate volume is accurately pipetted, is diluted with isooctane
To required concentration, 2-8 DEG C is kept in dark place.
Polychlorinated biphenyls internal standard stock solution: accurately weigh 0.01g pentachloronitrobenzene (Pentachloronitrobenzene,
PCNB it) is dissolved in 10mL n-hexane solvent, is prepared as the stock solution that concentration is 1000 μ g/mL.
Polychlorinated biphenyls internal standard uses solution: accurately pipetting the hybrid standard stock solution of appropriate volume, is diluted with n-hexane
To required concentration, 2-8 DEG C is kept in dark place.
Six six six, DDT Standard Stock solutions: 100 μ g/mL are dissolved in toluene.
Six six six, DDT standard intermediate solution: accurately pipetting the hybrid standard stock solution of appropriate volume, use just oneself
Alkane is diluted to required concentration, and 2-8 DEG C is kept in dark place.
The chlorine-containing compound rate of recovery indicates that standard solution: 2,4,5,6- tetra- chloro-m-xylenes (TCmX), 1000 μ g/mL are molten
In n-hexane, ten chlordiphenyls (PCB-209), 100ng/ μ L is dissolved in hexamethylene.
The chlorine-containing compound rate of recovery indicates working solution: accurately pipetting the chlorine-containing compound rate of recovery instruction of appropriate volume
Standard solution is diluted to required concentration with n-hexane, is kept in dark place.
Polychlorinated biphenyls hybrid standard working solution: appropriate mixing intermediate solution, rate of recovery instruction solution are accurately pipetted and is fitted
Amount internal standard is dissolved in suitable n-hexane solvent using solution is prepared into Polychlorinated biphenyls concentration as 0.005 μ g/mL, 0.01 μ g/
The hybrid standard that mL, 0.05 μ g/mL, 0.1 μ g/mL, 0.2 μ g/mL, 0.5 μ g/mL and containing the internal standard object concentration are 1 μ g/mL works
Solution, 2-8 DEG C is kept in dark place.
N-alkane Standard Stock solutions: 500 μ g/mL are dissolved in toluene.
N-alkane standard intermediate solution: the hybrid standard stock solution of appropriate volume is accurately pipetted, is diluted with n-hexane
To required concentration, 2-8 DEG C is kept in dark place.
The n-alkane rate of recovery indicates stock solution: accurately weighing the deuterated n-tetracosane (nC of 0.01g24D50) be dissolved in
In 10mL n-hexane solvent, it is prepared as the stock solution that concentration is 1000 μ g/mL.
The n-alkane rate of recovery uses solution: the hybrid standard stock solution of appropriate volume is accurately pipetted, it is dilute with n-hexane
It releases to required concentration, 2-8 DEG C is kept in dark place.
N-alkane hybrid standard working solution: appropriate mixing intermediate solution, rate of recovery instruction solution are accurately pipetted and is fitted
Amount internal standard is dissolved in suitable n-hexane solvent using solution (HMB) is prepared into polycyclic aromatic hydrocarbon concentration as 0.05 μ g/mL, 0.1 μ
G/mL, 0.5 μ g/mL, 1 μ g/mL, 2 μ g/mL, 5 μ g/mL and containing the internal standard object concentration are the hybrid standard working solution of 1 μ g/mL,
2-8 DEG C is kept in dark place.
Three, instrument and equipment
Gas chromatography-mass spectrometry；Chromatographic column: J&WDB-5MS quartz capillary chromatograph (30m*0.25mm*0.25 μ
m)；Muffle furnace；Constant temperature oven；Rotary Evaporators；Glass chromatography column；Supersonic cleaning machine；Accelerate solvent extraction instrument；Nitrogen evaporator；It is cold
Lyophilizer；Ten thousand grades of balances；Common laboratory common instrument and equipment.
Four, in the Gas Chromatography-Mass Spectrometry deposit organic matter method the following steps are included:
1, sample preparation
Sample be placed in advance clean drying and 450 DEG C of calcination 4h wide-mouth sampling bottle in or with equally processed aluminium
Foil package, sample contain a large amount of moisture, to pay special attention to the sealing of container, refrigerate under the conditions of being placed in -20 DEG C to -40 DEG C.Sample
After being sent to laboratory after product acquisition, it should handle and analyze as early as possible.
Contain large quantity of moisture in deposit, it is necessary to be removed, be not directly exposed to the sun in the sun or high with method appropriate
Temperature drying, the method that vacuum freeze drying can be used, dry 3-7 days (depending on the sample size) in freeze drier.It will
Dry sample is after agate mortar is ground by spare after the sieve of 100 mesh after dehydration.
2, sample extraction
10g sample is weighed, rate of recovery indicator is added and is fitted into ASE abstraction pool by step, after installing sample, placed
Loading after night carries out ASE extraction, and solvent is methylene chloride, takes out receiving bottle after extraction, is added in receiving bottle appropriate
The copper powder sulphur removal activated is non-discolouring to copper powder, and the liquid in receiving bottle is transferred in pear shape bottle.
ASE condition:
System pressure 10.3MPa, 100 DEG C of extraction temperature, heating time 5min, quiet hour 5min, flush volume is extraction
The 60% of pond body product is taken, is recycled 2 times.
3, sample purification
Pending chromatography post separation is concentrated by Rotary Evaporators in liquid in pear shape bottle.It is chromatographed in the glass of 8mm internal diameter
Column successively fills out the deactivation neutral alumina of 3cm, the deactivation neutral silica gel of 3cm, the anhydrous sodium sulfate of 1cm from top to bottom.First with two
Chloromethanes is washed pillar 2 times (10mL), then is washed pillar 2 times (10mL) with n-hexane, just drops to anhydrous sodium sulfate circle to liquid level
When face, concentrate is added drop-wise in chromatographic column, fills the pear shape bottle of concentrate, rinse liquid three times with n-hexane/methylene chloride rinse
Also upper chromatographic column.When sample drops to anhydrous sodium sulfate interface, successively with 10mL n-hexane, 20mL n-hexane/methylene chloride,
10mL methylene chloride/methanol elutes extraction column, collects eluent respectively.N-hexane affords non-polar component (F1), just oneself
Alkane/dichloromethane eluent obtains middle polarity component (F2), and methylene chloride/methanol elutes to obtain polar compound (F3).Deposition
PCBs, HCHs, DDTs, n-alkane are present in F1 component in object, and PAHs is present in F2 component.Through rotary evaporation and nitrogen
After blowing, F1 component adds inner mark solution each 1000ng of PCNB and HMB, and F2 component adds internal standard HMB1000ng, fixed with n-hexane constant volume
Hold to 1ml, is placed in -20 DEG C of refrigerators and saves, it is to be analyzed.
4, sample measures
(1) GC condition:
J&W DB-5MS quartz capillary chromatograph (30m × 0.25mm × 0.25 μm)；280 DEG C of temperature of vaporization chamber；Carrier gas is
High-purity He (99.999%)；Flow velocity 1.0mL/min；1 μ L of sample volume；Splitless injecting samples.
Temperature program:
1) 60 DEG C (keeping 1min), 280 DEG C (keeping 15min) polycyclic aromatic hydrocarbon: are risen to 5 DEG C/min；
2) Polychlorinated biphenyls, six six six, DDT: 80 DEG C, 180 DEG C are risen to 30 DEG C/min, then rise to 205 with 3 DEG C/min
DEG C (keep 2min), then 290 DEG C (keeping 4min) are risen to 5 DEG C/min；
3) n-alkane: 60 DEG C (keeping 1min), 170 DEG C (keeping 1min) are risen to 12 DEG C/min, then with 8 DEG C/min
Rise to 300 DEG C (keeping 0.5min)；320 DEG C (keeping 10min) are risen to 12 DEG C/min again:
(2) MS condition:
Electron bombardment (EI) ion source；Electron energy 70eV；280 DEG C of transmission line temperature；230 DEG C of ion source temperature；Quadrupole
150 DEG C of bar temperature；Solvent delay time 4min；Quantitative analysis using Salbutamol Selected Ion Monitoring (SIM) type collection polycyclic aromatic hydrocarbon,
Polychlorinated biphenyls, six six six and DDT, using full scan type collection n-alkane.28 kinds of PCBs and 8 kinds of organo-chlorine pesticides
The quantitation curves dependent linearity coefficients R of HCHs, DDTs2It is 0.990~0.998；The quantitation curves phase of 16 kinds of PAHs
Close coefficients R2It is 0.995~0.999；The quantitation curves coefficient R of n-alkane2It is 0.992~0.999.
Five, record and calculating
1, qualitative analysis
(1) qualitative analysis of polycyclic aromatic hydrocarbon
It uses SIM method (table 1).Fig. 1 is the total ion chromatogram of polycyclic aromatic hydrocarbon.
1 SIM method characteristic ion in different time periods of table
Retention time refers to (table 2).
The different the retention time of the compound of table 2
(2) qualitative analysis of Polychlorinated biphenyls, six six six, DDT
It uses SIM method (table 3).Fig. 2 is Polychlorinated biphenyls, six six six, the total ion chromatogram of DDT.
3 SIM method characteristic ion in different time periods of table
Retention time refers to (table 4).
The different the retention time of the compound of table 4, characteristic ion and calibration curve
(3) qualitative analysis of n-alkane
Use full scan method, scanning range: (50-500) m/z.Fig. 3 is the total ion chromatogram of n-alkane.It protects
Stay time reference table 5.
The different the retention time of the compound of table 5, characteristic ion and calibration curve
2, the calculating of response factor
The relatively corresponding factor R Fi of standard series the i-th point target compound is calculated according to formula (1).
In formula: RFi-- the relative response factor of the i-th point target compound in standard series；
Ai-- the response of the i-th point target compound quota ion in standard series；
AISi-- the response of i-th point of internal standard quota ion corresponding with target compound in standard series；
cISi-- the mass concentration of internal standard compound in standard series, μ g/mL；
ci-- the mass concentration of the i-th point target compound, μ g/mL in standard series.
3, the result of sediment sample calculates
Target compound content w (mg/kg) in sediment sample dry sample, according to following calculation.
In formula: the object content in w-- sample, mg/kg；
Ax-- the peak area of target compound quota ion in test fluid；
AIS-- the peak area of internal standard compound quota ion in test fluid；
cIS-- interior target concentration, μ g/mL in test fluid；
RFi-- the average relative response factor of calibration curve；
Vx-- concentration constant volume, mL；
M-- sample size, g；
Six, precision and accuracy
1, precision
It is respectively 1 μ g/mL polycyclic aromatic hydrocarbon, 0.1 μ g/mL Polychlorinated biphenyls, six six six, DDT, 1 μ g/mL to spiked levels
The hybrid standard of n-alkane is unified sample and is determined.Relative standard deviation is respectively 0.9%-4.6%, 1.4%-
7.9% and 1.5%-7.1%.
2, accuracy
Recovery of standard addition measurement carried out to 10g sediment sample respectively, spiked levels are 1 μ g/mL polycyclic aromatic hydrocarbon, 0.1
μ g/mL Polychlorinated biphenyls, six six six, DDT, 1 μ g/mL n-alkane.Recovery of standard addition average value ranges are respectively as follows: polycyclic virtue
Hydrocarbon is 75-112%, Polychlorinated biphenyls, six six six, DDT 84%-105%, n-alkane 85-102%.
3, detection limit and quantitative limit
It is 2-5 times of the sample that estimation method detects limit value to concentration value or content according to the Overall Steps of sample analysis
N >=7 time are carried out to be measured in parallel.The standard deviation that n times are measured in parallel is calculated, method detection limit is calculated by formula.Detection limit difference
Are as follows: polycyclic aromatic hydrocarbon 0.06-0.76ng/g, Polychlorinated biphenyls, six six six, DDT 0.04-0.26ng/g, n-alkane are
0.04-0.82ng/g；It is 0.20-2.53ng/g that quantitative limit, which is respectively as follows: polycyclic aromatic hydrocarbon, and Polychlorinated biphenyls, six six six, DDT are
0.13-0.87ng/g, n-alkane 0.13-2.74ng/g.It is shown in Table 6.
The detection limit and quantitative limit of the different compounds of table 6
Seven, quality controls
1, solvent blank is tested
It after experiment solvent hexane and methylene chloride are concentrated 60 times, is detected into GC-MS, the blank result of analysis is answered
Lower than method detection limit.
2, analysis margin is tested
Every batch of sample (being no more than 20) must do a blank test, the target concentration side of being not to be exceeded in measurement result
Method detection limit.Otherwise, reagent blank, instrument system and pretreatment process should be checked.
3, mark-on reclaims
Standard is added in blank sample kind and uses solution, remaining step is executed according to 5, and one batch sample of every analysis is to whole
A analytic process carries out 10% recovery testu.The sample analysis rate of recovery is preferably controlled in 60-130%.
4, Duplicate Samples and Quality Control sample
Every 12 samples add a Duplicate Samples, and every 24 samples add a Quality Control sample.The test knot of Duplicate Samples and Quality Control sample
Fruit relative deviation should be less than 30%.
Eight, points for attention
Acquisition, storage and the transport of sample should meet the regulation of GBT12763.8-2007.
Reagent used in experiment and standard liquid have certain toxicity, Ying Caiyong safeguard procedures.
For the pollution for avoiding organic substance, sediment sample should be placed in the wide mouth glass bottle of calcination or calcination
Aluminium foil package.
All vessel used in experiment need rinse or calcination by organic reagent.
All waste liquids and waste (including the raffinate after detection) generated in test, which should be placed in closed container, to be saved, and is entrusted
Hold in the palm qualified processed in units.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than is limited；Although referring to aforementioned reality
Applying example, invention is explained in detail, for those of ordinary skill in the art, still can be to aforementioned implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these are modified or replace
It changes, the spirit and scope for claimed technical solution of the invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of method of organic matter in Gas Chromatography-Mass Spectrometry deposit, it is characterised in that: the method includes following
Step:
(1) it prepares: deposit being dehydrated, is ground up, sieved, sample is made；
(2) it extracts: sample is subjected to ASE extraction, the solvent used is methylene chloride, obtains extract liquor；
(3) it purifies: extract liquor being concentrated, concentrate is separated using chromatographic column, collects eluent respectively；The chromatographic column
Fill method are as follows: successively fill out the deactivation neutral alumina of 3 ~ 4cm from top to bottom, the deactivation neutral silica gel of 3 ~ 4cm, 1 ~ 2cm's
Anhydrous sodium sulfate；
(4) it measures: the organic matter in eluent being subjected to qualitative and quantitative analysis with gas chromatography-mass spectrography, wherein according to color
The characteristic ion of spectral peak retention time and object is qualitative, inner mark method ration.
2. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 1, it is characterised in that:
The organic matter is polycyclic aromatic hydrocarbon, Polychlorinated biphenyls, six six six, DDT and n-alkane.
3. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 1, it is characterised in that:
The method dehydrated in the step (1) is to use freeze drier vacuum freeze drying 3-7 days.
4. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 1, it is characterised in that:
ASE extraction conditions is 10 ~ 11MPa of system pressure in the step (2), and 90 ~ 110 DEG C of extraction temperature, 3 ~ 7min of heating time is quiet
5 ~ 10min of state time, flush volume are the 60 ~ 70% of abstraction pool volume, are recycled 2 ~ 3 times.
5. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 1, it is characterised in that:
After the step (2) further includes ASE extraction, the copper powder that addition has activated is non-discolouring to copper powder, obtains extract liquor.
6. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 1, it is characterised in that:
The diameter of chromatographic column is 8mm in the step (3).
7. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 1, it is characterised in that:
The specific steps separated in the step (3) are as follows:
Concentrate is added drop-wise in chromatographic column, successively elutes layer with n-hexane, n-hexane and methylene chloride, methylene chloride and methanol
Column is analysed, non-polar component, middle polarity component and polar compound are respectively obtained；
After rotary evaporation and nitrogen are blown, non-polar component adds inner mark solution PCNB and HMB, and middle polarity component adds internal standard HMB, uses
N-hexane constant volume.
8. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 1, it is characterised in that:
The condition of gas-chromatography in the step (4) are as follows:
Chromatographic column: column length 30m, diameter 0.25mm, 0.25 μm of film thickness；250 ~ 300 DEG C of temperature of vaporization chamber；Carrier gas is high-purity He；Stream
0.9 ~ 1.2mL/min of speed；1 μ L of sample volume；Input mode is Splitless injecting samples.
9. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 8, it is characterised in that:
The temperature program of the condition of gas-chromatography in the step (4) are as follows:
Polycyclic aromatic hydrocarbon:, keeping 1 ~ 2min by 50 ~ 70 DEG C, rises to 250 ~ 300 DEG C with 5 DEG C/min, keeps 15 ~ 20min；
Polychlorinated biphenyls, six six six, DDT: 80 ~ 100 DEG C, 180 ~ 200 DEG C are risen to 30 DEG C/min, then rise to 3 DEG C/min
200 ~ 210 DEG C, 2 ~ 5min is kept, then rise to 250 ~ 300 DEG C with 5 DEG C/min, keep 3 ~ 6min；
N-alkane:, keeping 1 ~ 2min by 50 ~ 80 DEG C, rises to 150 ~ 200 DEG C with 12 DEG C/min, keeps 1 ~ 2min, then with 8 DEG C/
Min rises to 270 ~ 310 DEG C, keeps 0.5 ~ 1min；300 ~ 350 DEG C are risen to 12 DEG C/min again, keeps 10 ~ 15min.
10. the method for organic matter in Gas Chromatography-Mass Spectrometry deposit according to claim 1, it is characterised in that:
Mass Spectrometry Conditions in the step (4) are as follows: electron impact ion source；Electron energy 70eV；280 ~ 300 DEG C of transmission line temperature；Ion
230 ~ 250 DEG C of source temperature；130 ~ 170 DEG C of quadrupole rod temperature；3 ~ 6min of solvent delay time.
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