Application of 2-D gas chromatography for environmental analysis
The conventional one-dimensional gas chromatography (1D-GC) compared to a comprehensive two-dimensional gas chromatography (GC?GC) which provides the highest capacity, improved resolution and many of sensitivity. Additionally, it was create two-dimensional structure chromatogram, which is the proof of assistance in the composite class. Samples can often be minimized or even eliminated in some cases for the practice, as technology provides excellent separation power. All these benefits make GC?GC in the toxic compounds involved in the determination of trace level environmental analysis of a very good tool in complex matrices. This paper summarizes some of the environmental analysis and review and monitoring of the GC?GC applications
Many years of humans society development led to many of the world distribution of chemicals in the atmosphere, the Earth’s surface and land border. Many of these compounds are harmful to the world’s ecosystems and the people. Analysis of these compounds in the environment is important. When analytes have high vapor pressure, gas chromatography is the selection method. The main problem in the environmental analysis is to analyze the existence of material is usually very complex matrix trace. Result, a huge research work into the analysis of major environmental pollutants .
Methods used in environmental analysis is usually the same as in all aspects of practice. It includes sampling, sample preparation, separation and detection. All of these steps may benefit from change, it is usually the biggest limitations imposed by the separation step. In gas chromatography (GC) cases, the majority of environmental samples containing analyte and matrix components of many closely eluting peaks in a chromatographic dimension (1D) the maximum total capacity is greatly exceeded, and many coelutions and unresolved in the separation region was observed. This led to the analyte of interest and quantify the poor separation .
Poor resolution in the chromatographic analysis of sample preparation and detection of high demand for equipment placement. Expensive and labor-intensive sample preparation, and solvent waste may cause a lot of harmful to the environment. By microextraction method development, such as liquid-liquid microextraction (LLME) and solid phase microextraction (SPME) and non-dissolved sample introduction system (ie, direct thermal desorption), has the potential to greatly simplify the sample preparation process, without sacrificing sensitivity and selectivity [2-5]. On investigation, lack of resolution often means using mass spectrometry (MS), including high-resolution mass spectrometry (HRMS), in some cases, is necessary. Figure 1 illustrates the GC-MS encountered in the common problems . In the analysis of food extracts commonly 1D-GC clinch with insecticides (Fig. 1b), trace interest (in this case chlorfenvinphos) coelute analyte and sample matrix is ??more abundant components. Results obtained for such compounds, mass spectrometry (Figure 1e) frequently contains compounds derived from fragments of interference, leading to poor matching and library mass spectrometry (Fig. 1d). MS overlap algorithm may greatly improve the quality of the information of coeluting peak, but they are not always successful, when the number of coelutions is high. Figure 1a shows, full 2D-GC (GC?GC) to increase space and improve the chromatographic separation of the resolution, resulting in the separation of analytes of interest (chlorfenvinphos) from coeluting compounds and matrix components. Result, improved the quality of the analyte mass (Fig. 1c), taking into account the proof of a more confident analysis of material (Figure 1d). It is possible that some coelutions exist; these may often solve efficiently overlap with the MS, leading to better results, while reducing the number of components when the coeluting. GC?GC separation with the increased power resulting in a successful demonstration and quantification of analytes.
Fig. 1 GC?GC–TOF MS versus 1D-GC–TOF MS for the analysis of a carrot extract.
The highest-capacity problem in terms of conventional gas chromatography through multi-dimensional gas chromatography to cope (MDGC) implementation. In this method, one-dimensional (1D) chromatogram of a complex and unresolved part is subjected to the stationary phase coated with a second column separation of the other selectivity . Although this method increases the 1D chromatographic part of the choice of chromatographic resolutions, this method with automation challenging, and only a few sample components can be adequately addressed. However, the many applications is good for the PCBs, pesticides and toxaphene analysis, among other things, the report with different degrees of success [6-12]. Overall, however, is the exact number of separation will be beneficial, if the entire sample is subjected to a separation in two dimensions. This became possible a comprehensive two-dimensional gas chromatography (GC?GC) in the introduction.
Principle for Two-Dimensional Gas Chromatography (GC?GC)
2D-GC is a comprehensive method of fundamental solution to meet the highest capacity. A typical structure of GC?GC set in Figure 2. The basic structure of GC?GC using virtually is the same as the composition of 1D-GC. These include syringes, oven, columns and detectors. In a typical GC?GC system, using non-polar stationary phase coated with a thick coating of a long column was installed as the main column. The exports through a special interface or modem is connected to the entrance of the second dimension column coated with stationary phase of another selectivity. Modulator connected not only to primary and secondary column; its main role is repeated trapping of the effluent fractions from the first dimension and periodic injection of them to the form of narrow pulses separated into further chromatographic analysis. Because the operation of 2D-GC in the fast condition, the detector in the GC?GC selection is limited to those capable of fast data collection rate. For example, GC?GC detector can include flame ionization detector (FID), electron capture detector (ECD), single atomic emission detector (AED), sulfur compounds optical detector (SCD), nitrogen photodetector compounds (NCD) and time of flight mass spectrometer (TOF MS).
Fig. 2 A block diagram of a GC?GC system.
Modulator is the important part of the instrument, because it guarantees the separation is comprehensive and multidimensional . In 1991, the first implementation of the GC?GC, the field has witnessed a number of modulator design . Initially, the use of thermal adjustment of the heat modulator was implemented; however, the modular cryogenic liquid (liquid carbon dioxide or nitrogen) is currently the main use. Modulator at low temperatures within the system, each design has its own distinct advantages and limitations, making it suitable for analysis of the specific type. For example, the analysis of water pollutants has been developed an interface , when the buildings, and an in-house applications modulator in the quantitative analysis of PAHs and PCBs has been described . Then, the modulator of the different types of analyte in the analysis of organohalogenated been evaluated .
The implementation of GC?GC provides the following advantage to surpass the 1D separation method: improvement separation strength; improved sensitivities; and constructs or highly predetermined, stratography spectrum. In the environment analysis, GC?GC has the potential to improve the toxic compound through the separation from the coeluting analysis and the matrix component, increases the detection limit such chemical product and provides the ideal for the surveillance application the two-dimensional stratography spectrum which constructs. Finally, this possibly causes to reduce to the smallest sample preparation procedure, and reduces analysis time. Other applications are also possible. For example, recently, GC?GC the product estimate which divided into for the diesel oil hydrocarbon environment had used, was important affected many ecosystems  the oil leak.
Application of GC?GC in Environmental Analysis
Water and Sediment Analysis
The water is the most basic material to the life in planet. In order to estimate that the tap water safety for human consumption, the rapid, precise and the accurate method needs to analysis the water. The sediment is also important for river and the lake; The analysis of water pollutant is time-consuming sample preparation, follows by GC-MS analyzes. In the initial period realized that GC?GC has the great potential improvement to analysis water and sediment.
In its earliest applications in this region, GC?GC was explained possibly from the common matrix interference which is separating the BTEX (benzene, toluene, ethyl benzene and xylene) and methyl alcohol tert butyl ether (MTBE), when and SPME . The separation strength of GC?GC is improved; MTBE and the benzene are the foundation line solution in the 2nd chromatograph analysis space. This research showed GC?GC has the great potential for water pollutant analysis by combination this technology with microextraction (head space SPME).
Certain Earth’s freshwater body is polluted daily by petroleum and the oil contamination. In the 1970s, it is pays attention the petroleum sample stratography spectrum to exhibit a model, has not solved, foundation line which rises “hillock” . Chromatogram is the complex part, including compound many different kinds, refers to “unsolution complex mixture” at present . GC?GC-FID uses in analysis of two different freshwater sediments . Observed the conventional sample preparation procedure, the author has used the superior resolution, and has constructed the chromatogram of sediment for UCM different levele by GC?GC. The chromatogram obtained for two samples provides by clue direction contamination important source researcher. , The research showed GC?GC the potential importantly in the environment law, for an environmental chemistry basic tool, environmental audit.
The nonylphenol polyethylene ethoxides’ degenerated product, was possible feminine hormone splitter . Increases the concern, NPs from the urban district  the water and the deposition present are found. GC?GC-TOF MS is the NP isomer separation from technical mixture  used. 41 components are identified. Figure 3 explanation GC?GC-TOF MS application to NP isomer respective ion trace analysis from identical research. Two NP stave products were explained that m/z 135 (chart 3a) and m/z 149 (chart 3b). Two chromatogram exhibition group type separation, emphasizes by the connection compound peak maximum value in the identical homologous family incline line. It from as a result of various NP isomer structure similarity, the complete separation is the very difficult this chart is obvious. However, other resolution strength by GC?GC provided “cleanly” the mass spectrum to provide, made the analysis proof to be easier.
Fig. 3. Extracted ion GC?GC–TOF MS chromatograms of a technical nonylphenyl (NP) mixture
GC?GC for to the environment pollutant’s analysis was recently the application current in oceanic deposit . A qualitative method has developed, fast and is unified according to the tendency by the ultrasonic wave assistance’s extraction to the complex sample’s high resolution analysis provides to GC?GC-TOF UAE which is fast and high efficiency selective sampling pretreatment procedure is utilized solid sample . A high efficiency and has the selective sample preparation method, when the powerful separation method GC?GC combine with UAE can causes 1500 kind of more than several not aromatic hydrocarbon (PAHs) the compound and the certificate resolution, NPs and dialkylated benzene. Once more, GC?GC not only ability from each other isolation analysis, and has proven from the sample matrix priceless.
The carcinogen which and the mutagen suspected, PAHs is many industry activity by-product and the universal existence is distributed in the environment. Because it requests the hard sledding and has the selective sample preparation, they in the deposition sample’s trace determination are difficult. The improvement to complex matrix’s PAHs, the Cavagnino trace analysis with GC?GC-FID [large-volume splitless injection (LVSI) technology]. Sample complex which analyzes is many deposition sample representative who obtains from the river and the lake. Separated and investigates seven PAHs which diluted in the synthesis diesel oil to demonstrate the LVSI- GC?GC-FID potential achievement in the low ppb level for to trace amount analysis one powerful and the rapid tool in complex matrix PAHs.
While, Ong. and so on has developed a PAHs rapid surveillance method probably in the soil sample, utilizes liquid extraction (PLE) – GC?GC-FID . The current publishing work is merely GC?GC latent serviceable demonstration to deposition sample PAH analysis. In brief, with the resolution which improves, improvement many sensitivities and the stratography spectrum which orders, GC?GC may add on the result which effective and the rapid sample preparation method produces cannot be achieved by the routine analysis procedure.
Analysis of PCBs, PCDDs and PCDFs
Polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and some polychlorinated biphenyl (PCB) congeners is dominated by bioaccumulation and biomagnification in the environment and thus is a dangerous The wildlife and people. Many are suspected carcinogens and induced changes of . Of PCBs, dioxins and furans in the environment assessment of certain requirements of a method to isolate and quantify them in complex samples such as food, soil and water.
GC?GC provides one advantageous method in complex matrix’s PCDDs and the PCDFs analysis. In its one of early experiments, a liquid crystal main column and a limitless secondary column (according to steam pressure separation) uses in (according to the planarity separation) separates the tone – and from technical mixture  non-straight PCB congeners. The connection GC?GC microelectron captures investigates (MECD) is toxic PCBs, PCDDs and the PCDFs determination is the application in the cod liver sample . The analysis result showed all 12 priority PCB from liver sample congeners, and most toxic Dai Aoxin and fu nan the full separation and the proof nail fast with 90 PCBs and 17 contain poison PCDDs and PCDFs. Moreover, when compares with the standard sample preparation procedure, the liver sample pretreatment does not have the selectivity and reduces to is smallest. It has included the direct injection and fractionation followed cell degree of illness gradually draws back, the centrifuge process to enter GC?GC the system. Figure 4 showing from the 2nd stratography spectrum which obtains to the cod liver sample’s analysis. Recently, an item of multilaboratory research has been conducted in food sample, analyzes PCDD/Fs and World Health Organization PCBs through once more GC?GC-MECD and the GC-HRMS comparison and the explanation GC?GC great potential in the rapid surveillance application .
With the standard analysis method comparison GC?GC, GC?GC the performance is unified (GC?GC-ID-TOF MS) has to 13C mark isotopic dilution (ID) TOF MS conventional GC-HRMS to appraise . Quantification 17 PCDD/Fs and four PCBs nail fast in the soil and in the deposition sample are two methods are comparable. However, GC?GC implementation request only smallest sample preparation, and causes the signal improvement (factor 5-10), superior resolution, lower instrumentation expense, and improved TOF the MS data  the ghost overlaps legitimately. As highest capacity which and resolution result increases, the unknown compound’s proof is possible.
Fig. 4 GC?GC–ECD chromatogram of a cod liver sample spiked with 90 PCBs .
Forms the challenge to the pesticide analysis to analyze the chemist to prepare about the sample to make the law and the chromatography. Is similar other toxic compound, the pesticide is usually distributed in the trace amount environment. Moreover, they are extreme complex matrix part of for example foods, the soil and the water sample. Needs to be like today presses to the rapid high resolution analysis method.
GC?GC the application early showed the method potential regular implementation to the pesticide analysis in person’s organization in the future. Supercritical invariable extraction (SFE) with GC?GC-FID together utilizes the analysis in person’s blood serum  the pesticide. To were few from the sharp person’s blood serum extraction’s 15 pesticide’s foundation line segments achieve in four minutes. Later, GC?GC-FID to estimate that the child pesticide exposure has been utilized through the use urine and the blood serum  low-power. This special example in were few showed 16 pesticide complete separations in four minutes. Recently, has been demonstrated including PCBs and the organic chlorine pesticide 59 organization pollutant’s proof and the quantification . But GC?GC-ID-TOF MS completed the comparable result author who ran in standard routine analysis (GC-ID-TOFMS) to indicate that analyzed like this, three different injection needs. GC?GC the application early showed the method potential regular implementation to the pesticide analysis in person’s organization in the future. Supercritical invariable extraction (SFE) with GC?GC-FID together utilizes the analysis in person’s blood serum .
Pesticide determination in food extract is similarly important. Separated using GC?GC-TOF MS and identifies 58 pesticides to nail fast completely on the vegetable was explained . This completed with has been smallest and the non-selective sample preparation: The celery or the carrot sample and the sodium acetate and the ethyl acetate have chopped, mixed, was mixed, has been separated, and is dried. The extract is injected entered GC?GC .
Recently, separated 12 halogenate compound kind of groups five different GC?GC column combination to appraise, including PCBs, PCDDs, PCDFs, multi-chlorobenzene diphenyl ester (PCDEs), multi-chlorobenzene naphthalene (PCNs), multi-chlorobenzene dibenzothiophenes (PCDTs), multi-chlorobenzene terphenyl (PCTs), multi-chlorobenzene alkane (PCAs), toxaphene, multi-bromination biphenyl (PBBs), multi-bromination diphenyl ether (PBDEs) and organic chlorine pesticide (OCPs) . Although this article focal point is the different compound kind of major group separates, was also explained in the family separation. When the separation and proof all 28 OCPs are pure pesticide mixture has only been demonstrated that majority has been separated fully, since, when injects along other 11 compound kind of . Therefore, its as if that the column establishment which disposes appropriately with one, GC?GC may use takes mainly shields step for the environment sample contamination and along pollutant many other kind of pesticides, with smallest sample preparation.
Volatile organic compound (VOCs) in metropolis photochemical smog  the generation plays a strong character. The World Health Organization thought that possibly has to the air granular material’s exposition to the human health  the ill effect. But, uncertainty existence about from VOCs health effect in metropolis granular material (PM) . Therefore, requests rapid, reliable and information method guarantee in air pollutant successful surveillance, proof and discovery.
Many PAHs and PAHs (oxy-PAHs) which oxidizes is the carcinogen which and the mutagen suspected, with, therefore they are in the metropolis aerosol analysis profitable target analysis. GC?GC-FID and GC?GC four-pole MS (QMS) is applied permits from Finland about 1500 peaks goal PAHs  investigates in the metropolis air sample and the proof. But woman is unified the method for the compound proof and the quantification, used GC?GC-FID the combination to confirm the good reproducibility. 13 non-goal PAHs has been identified, and ten goal PAHs by quota. Found PAH centralism scope (0.5-5.5 ng/m3) with in Europe  other parts of standard methods obtained the result was comparable.
The cigarette smoke is estimate extreme complex mixture component  which has not recognized including about 4,700 kind of identification’s compound and 100,000. GC?GC-TOFMS utilizes the solution approximately from the cigarette smoke  30,000 peaks. After this, analyzes cigarette smoke condensate simpler sample determination neutrality score , basic score  and acidic score  chemical composition. Conventional GC-MS possible to separate 200 unknown peaks and identifies 115 hydrocarbons from the cigarette condensate limitless neutral scores; To identical sample GC?GC analysis, however, has achieved 4,000 kind of compound separations and 1,800 hydrocarbons  proved. In another research, GC?GC-TOF has identified 377 kind of nitrogen-containing compound to the cigarette condensate’s basic score’s MS analysis, in 155 is the pyridine derivative, 104 kinds kui lin or different kui lin derivative and 56 kind of pyrazine derivative .
GC?GC has achieved the condition rapidly for to the volatile organic compound analysis most powerful tool. It appoints oneself achievement to be suitable completely for in the complex sample surveillance analysis technology. In the environment analyzed area, this includes PCBs by the analysis many example testimony to the common environment pollutant, PCDDs, PCDFs, PAHs and the pesticide in the complex environment matrix. Moreover, GC?GC has the potential to simplify the sample preparation procedure (even completely to eliminate them), when simultaneously causes when the shorter overall analysis time high resolution stratography spectrum.
Regarding widely a new analysis method which adopts, not only it is certainly reliable and renewable, but it should also exhibit the significant advantage to surpass the method which accepts. The example reported the showing GC?GC method advantage in this review in the traditional 1DGC separation. In GC?GC historical first years period, the instrumentation development is the main focal point; However, from GC?GC system’s commercialization, the application quantity which reported greatly increases in the environment analysis and other scientific fields. Therefore, we may anticipate that the transition automation GC?GC is unified on-line sample which the correspondence uses to prepare gradually the equipment in the regular environmental monitoring.
1. Marriott PJ. Haglund P, Ong RCY. Clin Chim Acta. 2003, 328:1–19.
2. Pawliszyn J. Solid phase microextraction, theory and practice. Wiley, New York. 1997.
3. Pawliszyn J. (1999) Applications of solid phase microextraction. Royal Society of Chemistry, Cambridge.
4. Dettmer K, Engewald W. Anal Bioanal Chem. 2002, 373: 490–500.
5. Butrym E. LC-GC. 1999, 17:S19–S24.
6. de Geus H-J, Wester PG, Schelvis A, de Boer J, Brinkman UATh. J Environ Monit. 2000, 2:503–511.
7. Mrowetz SHJ. J Chromatogr A. 1983, 279:173–187.
8. Duinker JC, Schultz DE, Petrick G. Mar Pollut Bull. 1998, 19:19–25.
9. Storr-Hansen E. Int J Environ Anal Chem.1991, 43:253–266.
10. Silvis LD, Kapila S, Yan Q, Elseewi AA. J Chromatogr A.1994, 688:221–230.
11. Schurig V, Reich S. Chirality. 1998, 10:425–429.
12. Liem DAK. Trends Anal Chem. 1999, 18:499–507.
13. Giddings JC. Anal Chem. 1984, 6:1258A–1270A.
14. Liu Z, Phillips JB. J Chromatogr Sci.1991, 29:227–231.
15. Hyotylainen T, Kallio M, Hartonen K, Jussila M, Palonen S, Riekkola M-L. Anal Chem. 2002, 74:4441–4446.
16. Kristenson EM, Korytar P, Danielsson C, Kallio M, Brandt M, Makela J, Vreuls RJJ, Beens J, Brinkman UATh. J Chromatogr A. 2003, 1019:65–77.
17. Arey JS, Nelson RK, Xu L, Reddy CM. Anal Chem. 2005, 77:7172–7182.
18. Gaines RB, Ledford EB, Stuart JD. J Microcol Sep. 1998, 10:597–604.
19. Beens J, Dalluge J, Adahchour M, Vreuls JJR, Brinkman UATh. J Microcol Sep. 2001, 13:134–140.
20. Blumer M, Souza G, Sass J. Mar Biol. 1970, 5:195–202.
21. Frysinger GS, Gaines RB, Xu L, Reddy CM. Environ Sci Technol. 2003, 37:653–1662.
22. Mueller SO. Anal Bioanal Chem. 2004, 378:582–587.
23. Ieda T, Horii Y, Petrick G, Yamashita N, Ochiai N, Kannan K. Environ Sci Technol. 2005, 39:7202–7207.
24. Moeder M, Martin C, Schlosser D, Harynuk J, Gorecki T. J Chromatogr A. 2006, 1107:233–239.
25. Morales-Munoz S, Vreuls RJJ, Luque de Castro MD. J Chromatogr A. 2005, 1086:122–127.
26. Cavagnino D, Magni P, Zilioli G, Trestianu S. J Chromatogr A. 2003, 1019:211–220.
27. Ong R, Lundstedt S, Haglund P, Marriott P. J Chromatogr A. 2003, 1019:221–232.
28. Schwarzenbach RP, Gschwend PM, Imboden DM. Environmental organic chemistry, 2nd edn. Wiley-Interscience, Hoboken, NJ. 2003.
29. Korytar P, Leonards PEG, de Boer J, Brinkman UATh. J Chromatogr A. 2002, 958:203–218.
30. Haglund P, Harju M, Ong R, Marriott P. J Microcol Sep. 2001, 13:306–311.
31. Danielsson C, Wiberg K, Korytar P, Bergek S, Brinkman UATh, Haglund P. J Chromatogr A. 2005, 1086:61–70.
32. Focant J-F, Reiner EJ, MacPherson K, Kolic T, Sjodin A, Patterson DG Jr, Reese SL, Dorman FL, Cochran J. Talanta. 2004, 63:1231–1240.
33. Liu Z, Sirimanne SR, Patterson DG Jr, Needham LL. Anal Chem. 1994, 66:3086–3092.
34. Dimandja J-M, Grainger J, Patterson DG Jr, Turner WE, Needham LL. J Exp Anal Environ Epidem. 2000, 10:761–768.
35. Focant J-F, Sjodin A, Turner WE, Patterson DG Jr. Anal Chem. 2004, 76:6313–6320.
36. Dalluge J, van Rijn M, Beens J, Vreuls RJJ, Brinkman UATh. J Chromatogr A. 2002, 965:207–217.
37. Korytar P, Leonards PEG, de Boer J, Brinkman UATh. J Chromatogr A. 2005, 1086:29–44.
38. Fowler D, Coyle M, Ashmore MR, Bower J, Williams ML, Smith R, Dollard GJ, Lee DS, Jenkin M, Stedman JR, Cox RA, Derwent RG, Harrison RM, Hewitt CN, Maynard RL, Penkett SA, Weston KJ, Woods PJ, Burgess RA, Anderson R. Fourth Report of the Oxidants Review Group 75-104. UK Department of the Environment, Transport and Regions, London. 1997.
39. WHO. Health aspects of air pollution with particulate matter, ozone and nitrogen dioxide. World Health Organization, Bonn. 2003.
40. Welthagen W, Schnelle-Kreis J, Zimmermann R. J Chromatogr A. 2003, 1019:233–249.
41. Kallio M, Hyotilainen T, Lehtonen M, Jussila ML, Hartonen K, Shimmo M, Riekkola M-L. J Chromatogr A. 2003, 1019:251– 260.
42. Schnelle-Kreis J, Welthagen W, Sklorz M, Zimmermann R. J Sep Sci. 2005, 28:1648–1657.
43. Dalluge J, van Stee LLP, Xu X, Williams J, Beens J, Vreuls RJJ, Brinkman UATh. J Chromatogr A.2002, 974:169–184.
44. Lu X, Zhao M, Kong H, Cai J, Wu J, Wu M, Hua R, Liu J, Xu G. J Chromatogr A. 2004, 1043:265–273.
45. Lu X, Zhao M, Cai J, Kong H, Wu J, Wu M, Hua R, Liu J, Xu G. J Sep Sci. 2004, 27:101–109.
46. Lu X, Cai J, Zhao M, Kong H, Wu J, Wu M, Hua R, Liu J, Xu G. Anal Chem. 2004, 74:4441–4451.