CN101294938B - Method for analyzing and distinguishing sea surface excessive oil by ozone oxidization deriving liquid chromatogram coupling technique - Google Patents
Method for analyzing and distinguishing sea surface excessive oil by ozone oxidization deriving liquid chromatogram coupling technique Download PDFInfo
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- CN101294938B CN101294938B CN2008100168416A CN200810016841A CN101294938B CN 101294938 B CN101294938 B CN 101294938B CN 2008100168416 A CN2008100168416 A CN 2008100168416A CN 200810016841 A CN200810016841 A CN 200810016841A CN 101294938 B CN101294938 B CN 101294938B
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Abstract
The invention provides a method for analyzing and identifying the overflowing oil on the sea by using the ozone oxidation derivation liquid chromatographic coupling technology; the method adopts the pre-column derivatization technology, namely the ozone oxidation derivation process to lead the structural characteristic of an oil fingerprint unit to be obvious without being effected by weathering and biodegradation, and has identical unit information and high representation and high reliability; the liquid chromatography is characterized by high speed, high efficiency, high sensitivity, good repeatability and simple structure, etc.; then a differential refraction detector and a ultraviolet absorption detector are provided so as to obtain an oil fingerprint-chromatogram with detailed oil fingerprint unit information by separating analysis of the ozone oxidation derivation technology coupled with the liquid chromatographic technology; the analysis and identification for the types of the overflowing oil and the overflowing oil source can be carried out by comparing the oil fingerprint-chromatograms of the overflowing oil sample, the overflowing oil source and standard oil products.
Description
Technical field
The present invention relates to the environmental chemistry monitoring technical field, relate in particular to the method for ozone oxidization deriving liquid chromatography technology analyzing and distinguishing sea surface excessive oil.
Background technology
In recent years; continuous development along with marine petroleum exploitation and oil forwarding business waterborne; the marine oil overflow incident happens occasionally; the ecologic environment of ocean and land-based area in serious threat; for protecting the marine environment; must in time adopt the whole bag of tricks to administer the pollution that oil spilling causes, therefore the source of express-analysis identification oil spilling is differentiated the kind of offshore spilled oil and is understood fully that the pollution source of oil spilling are significant to the resource of protecting the marine environment.
The physical property of offshore spilled oil has uniqueness with chemical composition information as human fingerprint, being referred to as " oily fingerprint " compares to " the oily fingerprint " of offshore spilled oil and oil spilling source oil sample and standard oil and differentiates and to confirm oil spilling source and kind that i.e. oil spilling analysis is differentiated.
It is the important evidence obtaining means that oil spill accident is investigated that the oil spilling analysis is differentiated, " oily fingerprint " differentiates the main path of then differentiating as present oil spilling, and handling for oil spill accident by all kinds of oily finger print information of analyzing more suspicious oil spilling source and oil spilling sample provides very important scientific basis.It is complicated unusually that but crude oil (or oil product) is formed, can not analyze comparison to all information, just can represent the information of crude oil feature to be used, and the instability of many information also require will be allowed a choice when utilizing these data in the crude oil from the extracting data that is obtained.
Along with the development of analytical technology, utilize " oily fingerprint " to carry out oil spilling analysis authentication technique method and get more and more.According to " oily fingerprint " information feature that is detected, can be divided into 2 classes: non-characterization method and characterization method, traditional non-characterization method mainly contains vapor-phase chromatography (GC-FID), fluorescent spectrometry, infra-red sepectrometry (IR), high performance liquid chromatography (HPLC) and thin-layered chromatography (LC), exclusion chromatography, supercritical fluid chromatography (SFC), ultraviolet spectroscopy (UV), gravimetric method etc., also has the infrared fibre optics sensor method of rise recently etc.These method pre-service and analysis time are shorter, but complicacy in view of the oil composition, these methods are difficult to obtain detailed oil characteristic component information usually, therefore on oil spilling is differentiated, certain limitation is arranged, also do not have a kind of method the on-the-spot independent analysis that solves offshore spilled oil apace to differentiate problem at present; Characterization method mainly contains gas chromatography/mass spectrometry method (GCMS) and other distinguish the analytical technology of individual petroleum hydrocarbon component, can more easily obtain the details of component, especially can weatherproof compound information, as some palycyclic aromatics and biomarker etc., can carry out " oily fingerprint " more accurately and analyze discriminating, therefore more and more cause scientist's concern, but the shortcoming of these method maximums is to rest on the manual analysis basis, laboratory, in analytic process, the method longer duration, analytic process is numerous and diverse, the condition harshness, the equipment complexity, reagent consumption is big, produce secondary pollution etc., therefore use which kind of characterization method to carry out the oil spilling discriminating and all can not realize the scene, automatically analyze differential mode, for briny environment complicated and changeable, especially the oil spilling accuracy and the reliability that are subject to weathering and its result of biological degradation is under suspicion, and said method is difficult to satisfy on-the-spot, the needs of oil spilling are differentiated in real-time analysis.
In recent years, along with electronic technology, new material, new technology, the development of new optical device, especially computer technology makes rapid progress, adopt the corresponding appearance of on-the site analysis authentication equipment of developing on the classic method basis, but because the technical difficulty of some realization aspect is too big, though these methods have been broken away from some shortcomings of lab analysis, but the pattern from work on the spot also has a segment distance, big as reagent consumption, on-the-spot, the real time execution cycle is short, poor stability, sensitivity and resolution are low, the defective that equipment complexity etc. is difficult to overcome, the inreal on-the site analysis of realizing is differentiated the pattern of oil spilling.
Summary of the invention
The invention provides a kind of method of ozone oxidization deriving liquid chromatography coupling technique analyzing and distinguishing sea surface excessive oil, it can solve can not on-the-spot real-time analysis differentiating of existing method existence, analyze longer duration, analytic process is numerous and diverse, and condition harshness, equipment volume greatly, especially produce secondary pollution problems.
In order to reach the purpose that solves the problems of the technologies described above, technical scheme of the present invention is, a kind of method of ozone oxidization deriving liquid chromatography coupling technique analyzing and distinguishing sea surface excessive oil, described method adopt analyzes identification device, and described device comprises three parts,
First is column front derivation-ozone oxidization deriving device, and it comprises ozone generator, ozone discharge pump, ozone oxidization deriving reaction chamber, oil spilling sample extraction device, carries oil spilling sample and extraction back sample pump;
Second portion is a liquid chromatographic system, and it comprises high pressure pump, moving phase liquid reservoir, chromatographic column, dual-detector, and described dual-detector is differential refraction detector and ultraviolet absorption detector;
Third part is computer control and data handling system;
The threeway sampling valve is connected with high pressure pump and chromatographic column with the ozone oxidization deriving reaction chamber by pipeline, and described method is undertaken by following step by analyzing identification device:
(1) utilize ozone generator to produce ozone, the concentration of ozone is 2-4mg/L, and it is sent into the ozone oxidization deriving reaction chamber under the 100-200ml/min flow by the ozone discharge pump;
(2) the oil spilling sample is input to oil spilling sample extraction device through carrying the oil spilling sample pump, stops after the extraction;
(3) by extracting the back sample pump extract is transported to ozone oxidization deriving reaction chamber and ozone at ozone oxidization deriving reaction chamber mixing generation oxidative degradation;
(4) by micro pump the sample delivery after having reacted in the quantity tube of threeway sampling valve;
(5) after quantity tube is full of sample, the threeway sampling valve cuts out the sample delivery passage, open the moving phase passage, start high pressure pump simultaneously, moving phase is carried the quantity tube of sample by the threeway sampling valve and is entered chromatographic column under the effect of high pressure pump, the stationary phase of sample and chromatographic column interacts, and distributes between moving phase and the stationary phase, and each component in the sample is by its different chromatographic columns that successively flow out at two alternate partition factors;
(6) effluent from chromatographic column enters differential refraction detector and ultraviolet absorption detector respectively by the equivalent threeway, and alkane family is the shows signal peak on differential refraction detector, alkene, fragrant hydrocarbon system shows signal peak on UV-detector;
(7) computer control and data handling system to signal peak gather, quantification treatment obtains oily fingerprint-chromatogram, by oily fingerprint image and the comparison of target oil fingerprint image that obtains, can analyze the oil spilling source of differentiating, can obtain oil spill type by oily fingerprint image comparison with standard oil, and demonstration, printout.
Supplementary technology scheme of the present invention is as follows:
Be provided with filtrator in the ozone oxidization deriving reaction chamber, described filtrator is porosint-teflon, and ozone gas filters through porosint-teflon and enters in the ozone oxidization deriving reaction chamber.
The oil spilling sample extraction time is 3min-7min, stops after the extraction.
Quantity tube volume in the described threeway sampling valve is at 20 μ L-30 μ L.
Described moving phase is cyclohexane, and described chromatographic column is a bonding phase cyano group chromatographic column.
The flow range of described moving phase is 0.75-1.25ml/min.
Described high pressure pump is mechanical reciprocating pump, and all the other are peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
Utilize computer control, by the control of software programming realization to system, signal Processing and calculating; Utilize data handling system, carry out the oily fingerprint image comparison of oily fingerprint image and target oil fingerprint image and standard oil, and demonstration, printout.
Offshore spilled oil is by alkane substantially, alkene, the potpourri of the different compositions of structure such as aromatic hydrocarbons, the strand length of its component differs, the molecular weight ratio of component is bigger, because the some of them component is subject to weathering, biodegradable influence, therefore " oily fingerprint " characteristic that obtains by traditional compartment analysis means is not obvious, but the unit information of handling back " oily fingerprint " by the pre-column derivatization technology is very obvious, ozone is as a kind of strong oxidizer, because it in use has the secondary pollution of not producing, so in oxidative degradation oil spilling process, have very large application prospect, be a kind of very desirable pre-column derivatization reagent, can make long-chain oil spilling component be degraded to the short chain organism by the ozone oxidization deriving processing, larger molecular organics is degraded to small organic molecule, its cellular construction characteristics are obvious, identical oil spilling sample has identical unit information simultaneously, have very high representativeness and reliability, obtain very detailed " oily fingerprint " unit information, and be not subjected to weathering, biodegradable influence.Liquid chromatography has at a high speed, efficient, high sensitivity, good reproducibility, characteristics such as simple in structure, by being equipped with differential refraction detector and ultraviolet absorption detector, in analysis result, both can provide each hydrocarbon system's content in the oil spilling behind the compartment analysis, and can on " oily fingerprint "-spectrum peak, observe the change information of aromatic hydrocarbons group composition in the oil spilling again.Ozone oxidation column front derivation technology coupling liquid chromatography technology carries out compartment analysis and obtains " oily fingerprint "-chromatogram and have detailed unit information, can analyze discriminating oil spill type and oil spilling source by the comparison oil spilling sample and " oily the fingerprint "-chromatogram of oil spilling source and standard oil.
Therefore it is abundant to utilize the analysis of ozone oxidization deriving technology coupling chromatographic technique to differentiate that oil spilling has unit information, good reliability, characteristics such as method is simple, quick, being beneficial to on-the site analysis differentiates, avoid classic method Analysis of Complex, long, the not high problem of discriminating reliability of analytical cycle, belonged to the environmental protection method.
Description of drawings
Fig. 1 is the inventive method principle of work process flow diagram;
Fig. 2 is the analysis identification device structural representation that the inventive method adopts.
1. oil spilling sample; 2. peristaltic pump; 3. oil spilling sample extraction device; 4. peristaltic pump; 5. ozone oxidization deriving reaction chamber; 6. ozone generator; 7. peristaltic pump; 8. porosint-teflon; 9. pressure valve; 10. peristaltic pump; 11. moving phase-cyclohexane liquid reservoir; 12. high pressure pump; 13. threeway sampling valve; 14. chromatographic column; 15. differential refraction detector; 16. data handling system; 17. waste collection device; 18. ultraviolet absorption detector.
Embodiment
The inventive method is carried out according to the following steps by pick-up unit:
(1). utilize ozone generator 6 to produce ozone, the concentration of ozone is 2mg/L, and under the 100ml/min flow, it is sent into ozone oxidization deriving reaction chamber 5 by peristaltic pump 7, ozone gas disperses to enter in the ozone oxidization deriving reaction chamber 5 through porosint-teflon 8;
(2). oil spilling sample 1 is input to oil spilling sample extraction device 3 via peristaltic pump 2, stops behind the extraction 5min;
(3). by peristaltic pump 4 the good extract of extraction is transported to ozone oxidization deriving reaction chamber 5 and mixes the generation oxidative degradation at reaction chamber 5 with ozone, in order to guarantee fully to mix between ozone and the extract, utilize porosint-teflon 8, ozone gas is emerged from the micropore of porous material surface, in the extract around being mixed into, porosint-teflon 8 application targets are to increase the gas-liquid area that contacts, strengthen mass transfer power, mix fully, reaction efficiency is strengthened, and stops behind the reaction 10min;
(4). by micro pump 10 the sample delivery after having reacted in the quantity tube of threeway sampling valve 13, the volume of quantity tube is 25 μ L;
(5). after quantity tube is full of sample, threeway sampling valve 13 cuts out the sample delivery passage, open moving phase-cyclohexane passage, start high pressure pump 12 simultaneously, moving phase-cyclohexane carries the quantity tube of sample by threeway sampling valve 13 and enters bonding phase cyano group chromatographic column 14 under the effect of high pressure pump 12, the stationary phase of sample and chromatographic column 14 interacts, between moving phase and stationary phase, distribute, because each component physics in the sample, the chemical property difference, also different at two alternate partition factors, therefore each component flows out chromatographic columns 14, mobile phase flow rate 1.0ml/min by its different priorities at two alternate partition factors in the sample;
(6). the effluent from chromatographic column 14 enters dual-detector respectively by the equivalent threeway: differential refraction detector 15 (sensitivity of differential refraction detector 15 is 8X) and ultraviolet absorption detector 18 (absorbing wavelength 254nm), alkane family is the shows signal peak on differential refraction detector, alkene, fragrant hydrocarbon system shows signal peak on UV-detector.
(7). 16 pairs of signal peaks of computer control and data handling system are gathered, quantification treatment obtains oily fingerprint-chromatogram, oily fingerprint image and the comparison of target oil fingerprint image by obtaining again, can analyze the oil spilling source of differentiating, can obtain oil spill type by oily fingerprint image comparison with standard oil, and demonstration, printout.
Oil spilling sample extraction device 3 has agitating function, finishes the extraction work of oil spilling so at short notice, makes oil spilling extraction efficiency height.
Ozone oxidization deriving reaction chamber 5 carries out corrosion-resistant and preventing oil spill absorption design, because ozone has highly corrosive, so the ozone transfer pipeline adopts poly-PTFE, reaction chamber 5 adopts stainless steel material.
In order to guarantee ozone pressure and concentration stabilize, we are provided with pressure valve 9 and control below the ozone oxidization deriving reaction chamber.
Threeway sampling valve 13 has quantity tube, and volume is 25 μ L.
High pressure pump is mechanical reciprocating pump, and all the other are peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
Adopt dual-detector: differential refraction detector 15 (sensitivity 8X) and ultraviolet absorption detector 18 (absorbing wavelength 254nm), guaranteed that like this all components can both be embodied on oily fingerprint-chromatogram, information is detailed.
Utilize computer control by the control of software programming realization to system, signal Processing and calculating; Utilize data handling system, carry out the oily fingerprint image comparison of oily fingerprint image and target oil fingerprint image and standard oil, and demonstration, printout.
The present invention adopts pre-column derivatization technology-ozone oxidization deriving technology coupling liquid chromatography technology to analyze the method for discriminating, can make us obtain very detailed oily fingerprint unit information by the ozone oxidization deriving technology, liquid chromatography has at a high speed simultaneously, efficiently, high sensitivity, good reproducibility, characteristics such as simple in structure, therefore it is abundant to utilize the analysis of ozone oxidization deriving technology coupling chromatographic technique to differentiate that oil spilling has unit information, good reliability, method is simple, characteristics such as fast, being beneficial to on-the site analysis differentiates, avoided the classic method Analysis of Complex, analytical cycle is long, differentiate the not high problem of reliability, belong to the environmental protection method.The advantage that this method had can make this method developed and popularization in fields such as environmental analyses.
Claims (8)
1. the method for an ozone oxidization deriving liquid chromatography coupling technique analyzing and distinguishing sea surface excessive oil, described method adopt analyzes identification device, and described device comprises three parts,
First is column front derivation-ozone oxidization deriving device, and it comprises ozone generator, ozone discharge pump, ozone oxidization deriving reaction chamber, oil spilling sample extraction device, carries oil spilling sample and extraction back sample pump;
Second portion is a liquid chromatographic system, and it comprises high pressure pump, moving phase liquid reservoir, chromatographic column, dual-detector, and described dual-detector is differential refraction detector and ultraviolet absorption detector;
Third part is computer control and data handling system;
The threeway sampling valve is connected with high pressure pump and chromatographic column with the ozone oxidization deriving reaction chamber by pipeline, and described method is undertaken by following step by analyzing identification device:
(1) utilize ozone generator to produce ozone, the concentration of ozone is 2-4mg/L, and it is sent into the ozone oxidization deriving reaction chamber under the 100-200ml/min flow by the ozone discharge pump;
(2) the oil spilling sample is input to oil spilling sample extraction device through carrying the oil spilling sample pump, stops after the extraction;
(3) by after the extraction, sample pump is transported to ozone oxidization deriving reaction chamber and ozone to extract at ozone oxidization deriving reaction chamber mixing generation oxidative degradation;
(4) by micro pump the sample delivery after having reacted in the quantity tube of threeway sampling valve;
(5) after quantity tube is full of sample, the threeway sampling valve cuts out the sample delivery passage, open the moving phase passage, start high pressure pump simultaneously, moving phase is carried the quantity tube of sample by the threeway sampling valve and is entered chromatographic column under the effect of high pressure pump, the stationary phase of sample and chromatographic column interacts, and distributes between moving phase and the stationary phase, and each component in the sample is by its different chromatographic columns that successively flow out at two alternate partition factors;
(6) effluent from chromatographic column enters differential refraction detector and ultraviolet absorption detector respectively by the equivalent threeway, and alkane family is the shows signal peak on differential refraction detector, alkene, fragrant hydrocarbon system shows signal peak on UV-detector;
(7) computer control and data handling system to signal peak gather, quantification treatment obtains oily fingerprint-chromatogram, by oily fingerprint-chromatogram and the target oil fingerprint-chromatogram comparison that obtains, can analyze the oil spilling source of differentiating, by can obtaining oil spill type with the oily fingerprint of standard oil-chromatogram comparison, and demonstration, printout.
2. method according to claim 1 is characterized in that being provided with filtrator in the ozone oxidization deriving reaction chamber, and described filtrator is porosint-teflon, and ozone gas filters through porosint-teflon and enters in the ozone oxidization deriving reaction chamber.
3. method according to claim 2 is characterized in that the oil spilling sample extraction time is 3min-7min, stops after the extraction.
4. method according to claim 3 is characterized in that quantity tube volume in the described threeway sampling valve is at 20 μ L-30 μ L.
5. method according to claim 4 is characterized in that described moving phase is cyclohexane, and described chromatographic column is a bonding phase cyano group chromatographic column.
6. method according to claim 5, the flow range that it is characterized in that described moving phase is 0.75-1.25ml/min.
7. method according to claim 6 is characterized in that described high pressure pump is mechanical reciprocating pump, and all the other are peristaltic pump, and described pipeline adopts polytetrafluoroethylmaterial material to make.
8. according to any described method of claim in the claim 1 to 7, it is characterized in that utilizing computer control, by the control of software programming realization to system, signal Processing and calculating; Utilize data handling system, carry out oily fingerprint-chromatogram comparison of oily fingerprint-chromatogram and target oil fingerprint-chromatogram and standard oil, and demonstration, printout.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1053128A (en) * | 1990-01-04 | 1991-07-17 | 宜昌市药品检验所 | The high-efficient liquid phase chromatogram process measuring method of 18 compound amino-acids injection liq |
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| CN1053128A (en) * | 1990-01-04 | 1991-07-17 | 宜昌市药品检验所 | The high-efficient liquid phase chromatogram process measuring method of 18 compound amino-acids injection liq |
Non-Patent Citations (2)
| Title |
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| 周益奇等.柱前衍生-气相色谱/质谱法测定壬基酚方法研究.《分析化学（FENXIHUAXUE）研究报告》.2005,第33卷(第8期),全文. * |
| 张相年等.高效液相色谱柱前衍生技术在低浓度药物分析中的应用.《医药导报》.2008,第27卷(第1期),全文. * |
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