1. The questions to be posed:
An Historic Perspective of Applications of Chromatography - Mass Spectrometry to Environmental Matrix Analysis Peter J Baugh, Leader, EFASIG, The BMSS, c/o 23, Priory Rd., Sale M33 2BU, Greater Manchester Abstract
The questions to be posed:
How did it all commence?
What has been achieved?
What does the future hold?
The applications of chromatography mass spectrometry to environmental matrix analysis are numerous. Although the origins of GC/MS can be traced back to 1959, the major thrust towards the utilization of GC/MS in environmental analysis was in 1976 when the USEPA proposed that the coupled instrumental technique should be the method of choice for analysis of priority pollutants in sludge. At that time, the chromatography employed packed columns with a jet separator. The first attempts were futile because one sample completely destroyed the chromatography and severely contaminated the ion source of the mass spectrometer leading to a total loss in sensitivity. Sample preparation became of prime importance and the methodology has become ever more sophisticated as has the resolution of the chromatography with the advent of fused-silica capillary columns and with a wide range of non-polar to polar stationary phases. A parallel increase in the capability and capacity of LC columns has enhanced LC/MS. The sophistication in mass spectrometry has been beyond expectation and almost beyond belief. In this short review, only a snapshot of the advances in the applications can be presented but it will be demonstrated that practioners with the instrument companies have succeeded in ensuring that chromatography mass spectrometry has a very bright and long future. 1

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Origins, Fundamentals and Foundation of MS and GC (LC), where to start?
Question: If m/e (z) for charged particles had not been discovered, which is a fundamental absolute, would mass spectrometry have evolved, as such, and if not, where would we now be without m over e??
To be discussed:
The origin of the relationships between matter and electricity: M. Faraday, Extrapolation ions and current ion current TIC (Mass Spec.) J J Thomson, mass/charge ratio (m/e), the basic ratio for all mass spectrometry.
Historical development of mass spectrometry instrumentation: Thomson/Aston
GC /GLC, early successes, 1960s, capillary column resolution capability.
The foundations of Chromatography Mass Spectrometry, GC/MS
Early advances in the applications of GC/MS
Upsurge in the environmental applications of chromatography mass spectrometry following USEPA initiative 1976
Ionisation methods and mass analysers for environmental applications, low cost /high cost.
Advances in sophistication in the chromatography- MDGC & GCxGC
Importance of sample preparation for environmental analysis
Bibliography
Conclusions
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3. 1 & 2. M/e to the development of first mass spectrograph
The first measurement of mass to charge ratio (m/e) for a charged particle can be traced back to J J Thomson, 1897, who used a combination of electric and magnetic fields to measure m/e leading to the discovery of electrons, the first subatomic particles, which were previously unidentified negatively charged particles, known as cathode rays. 
In 1912 Thomson with his assistant Aston channeled a stream of neon ions through a magnetic and an electric field and measured the deflection by placing a photographic plate in its path. They observed two patches of light on the photographic plate, which suggested two different parabolas of deflection, and concluded that neon is composed of atoms of two different atomic masses (neon-20 and neon-22)
The first sector instrument (E/B), mass spectrograph, was developed by Aston 100 years ago with which he detected the separation of isotopes from a large number of non-radioactive elements, and for which he was awarded the Nobel Prize in 1922.
Θ = F.e.l/mv2   ; φ = H.e.l/mv
When Θ = φ then m/e = H2.l/F.Θ
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3. GC /GLC 1950s, James and Martin, and early successes, 1960s
Capillary column resolution exhibited a unique capability but initially long retention times, with limited detectors, TCD, FID
High-resolution capillary GC chromatogram from This is a chromatogram of all 17 octane isomers, a separation that many thought was not possible, retention time range ~ 4 h. Taken from Harold McNair, LC-GC North America, 28, , 2010, A History of GC. My Early Experiences. Quote: Dr. Marcel Golay taught both myself and Carl Cramers (later Prof. Dr. C.C.) how to make capillary GC columns using both stainless steel and polymeric tubing. Later, Dennis Desty from British Petroleum installed a glass drawing machine and we began to (not easily) make glass capillary columns. Glass could be made more inert than stainless steel, but it was not easy to manufacture or deactivate.
The resolving potential of GLC was recognised almost from the advent. The progression of capillary column fabrication through the 1960s to 1980s was metal, polymer tubing, borosilicate and fused silica with an increased capability chemically bonded and range of stationary phases.
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4. The foundations of Chromatography Mass Spectrometry, GC/MS
In 1959, a GC was coupled with a TOF-MS, which appears to be the earliest recorded instrument in the development of GC/MS.  Gohlke, R. S. (1959). "Time-of-Flight Mass Spectrometry and Gas-Liquid Partition Chromatography". Analytical Chemistry. 31 (4): 535–541. doi: /ac50164a024. ISSN 
Direct combination of a BENDIX TOF-MS scanning from m/e 1 to 6000 at rate of 2000 times per sec. with a gas liquid partition chromatograph to characterise organic chemical mixtures with bpt below 350oC. Immediate application to environmental sample analysis.
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5. Early advances in GC/MS instrumentation and applications, 1960s to 1970s and the use of data systems, with some personal observations
An indication of the development of MS, by the 1960s, as an example, Finnigan alone had produced 500 MS instruments and there were many other developments of MS analysers, ionisers and detectors.
I recall through a personal contact that AEI had installed GC/MS facility at a location on the Eastern seaboard of the USA as early as 1965, using a tape recorder for data collection.
With the advent of borosilicate columns introduced and manufactured by Desty using capillary drawing machine, there was an increase in the applications of gas chromatography to complex mixture analysis and in the coupling to mass spectrometry.
Experts in both techniques combined their knowledge to enable the interfacing of capillary columns to large magnetic sector instruments. For example, in the 1974, I spent a month at the Max Planck Institute for Kohlenforschung, Mulheim, where Schomburg (GC specialist) and Henneberg (MS specialist), applied capillary GC/MS to analyse many multi-component systems using and utilised Atlas main-frame computers to analyse the data, offline (on the fly). Borosilicate capillary columns up to m in length were required for the separation of frequently closely similar analytes.
Reference: Computer Systems for Chemical Research
Dr. Engelbert Ziegler  Dr. Dieter Henneberg  Dr. Gerhard Schomburg
First published: May 1972 Angew. Chem., 11, 1972,  
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Advances in chromatographic column technology for interfacing to MS
Packed column GC required a jet separator for interfacing to MS.
Borosilicate open tubular columns were susceptible to breakage at the GLT interface and were superseded by:
Fused silica capillary columns in the late 1970s, which enhanced the capability from several standpoints:
Including ease of interfacing of GC to MS (thread through GLT for alignment in ion source), and
Facilitating chemically bonded, non-polar to semi-polar, stationary phases to be applied.
Data system advances
Incos provided the prime advancement in Data Systems in the 1970s and was acquired by Finnigan initially for quadupole mass filter instruments but subsequently also interfaced to sector instruments in the early 1980s (e.g., VG)
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6. Upsurge in the environmental applications of chromatography mass spectrometry
Prior to 1970 for drinking water about 100 compounds were known to be present.
Early references:
L H Keith was a pioneer and editor of the first book published on the subject of
Identification and Analysis of Organic Pollutants in Water.
Example reference from the book
Keith, L. H.; Garrison, A. W.; Allen, F. R.; Carter, M. H.; Floyd, T. L.; Pope, J. D.; Thruston, A. D., Jr. In Identification and Analysis of Organic Pollutants in Water; Keith, L. H., Ed.; Ann Arbor Science: Ann Arbor, MI, 1976; pp
B. For environmental applications, an important date also was 1976 when the USEPA selected GC/MS as the method of choice for environmental analysis for the monitoring of ca toxic pollutants out of which 122 were termed Priority Pollutants to which several metals and 2,3,7,8 TCDD have been subsequently added, to increase the total to 129.
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31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,3-dichloropropylene
34. 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. Ethylbenzene
39. Fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. Bis(2-chloroisopropyl) ether
43. Bis(2-chloroethoxy) methane
44. Methylene chloride
45. Methyl chloride
46. Methyl bromide
47. Bromoform
48. Dichlorobromomethane
49. (Removed)
50. (Removed)
51. Chlorodibromomethane
52. Hexachlorobutadiene
53. Hexachlorocyclopentadiene
54. Isophorone
55. Naphthalene
56. Nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
91. Chlordane
92. 4,4-DDT
93. 4,4-DDE
94. 4,4-DDD
95. Alpha-endosulfan
96. Beta-endosulfan
97. Endosulfan sulfate
98. Endrin
99. Endrin aldehyde
100. Heptachlor
101. Heptachlor epoxide
102. Alpha-BHC
103. Beta-BHC
104. Gamma-BHC
105. Delta-BHC
106. PCB-1242 (Arochlor 1242)
107. PCB-1254 (Arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
113. Toxaphene
114. Antimony
115. Arsenic
116. Asbestos
117. Beryllium
118. Cadmium
119. Chromium
120. Copper
1. Acenaphthene
2. Acrolein
3. Acrylonitrile
4. Benzene
5. Benzidine
6. Carbon tetrachloride
7. Chlorobenzene
8. 1,2,4-trichlorobenzene
9. Hexachlorobenzene
10. 1,2-dichloroethane
11. 1,1,1-trichloreothane
12. Hexachloroethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16. Chloroethane
17. (Removed)
18. Bis(2-chloroethyl) ether
19. 2-chloroethyl vinyl ethers
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. Parachlorometa cresol
23. Chloroform
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. Pentachlorophenol
65. Phenol
66. Bis(2-ethylhexyl) phthalate
67. Butyl benzyl phthalate
68. Di-N-Butyl Phthalate
69. Di-n-octyl phthalate
70. Diethyl Phthalate
71. Dimethyl phthalate
72. Benzo(a) anthracene
73. Benzo(a) pyrene
74. Benzo(b) fluoranthene
75. Benzo(k) fluoranthene
76. Chrysene
77. Acenaphthylene
78. Anthracene
79. Benzo(ghi) perylene
80. Fluorene
81. Phenanthrene
82. Dibenzo(,h) anthracene
83. Indeno (1,2,3-cd) pyrene
84. Pyrene
85. Tetrachloroethylene
86. Toluene
87. Trichloroethylene
88. Vinyl chloride
89. Aldrin
90. Dieldrin
121. Cyanide, Total 122. Lead 123. Mercury 124. Nickel 125. Selenium 126. Silver 127. Thallium 128. Zinc ,3,7,8-TCDD
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10. 6. Test methods and directives for pollutant monitoring in environmental matrices
The US-EPA methods are the hallmark for environmental analysis, which can be accessed via the website links:
EPA offices and laboratories, and outside organizations, have developed approved methods for measuring the concentration of a substance or pollutant.  Below are categories of methods:
Air and Radiation
Water
Prevention, Pesticides, and Toxic Substances
Research and Development - Not Approved
Solid Waste and Emergency Response
Index to EPA Test Methods
Drinking Water Inspectorate Drinking Water Inspectorate - GOV.UK
The Water Framework Directive 2000/60/EC is an EU directive which commits European Union member states to achieve good qualitative and quantitative status of all water bodies by 2015.
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7. Ionisation methods and mass analysers for environmental matrix analysis
Ionisation methods: EI (70 eV electrons) has been and is a primary mode of ionisation for environmental GC/MS because of the characteristic mass spectral fragmentation patterns generated. Molecular ions are most often in low abundance except for aromatic compounds, such as, PAHs. The mass spectral fragmentation patterns of the target analytes allow data base matching with standard mass spectra, NIST/Wiley, which enables positive identification in many instances for known targets.
EI/CI switching can be of advantage to verify the molecular ion for the analyte of interest.
Enhancement of the molecular ion using soft EI (12 eV electrons) has been made possible in recent years.
Mass Analysers: Almost all types of mass spectrometric instrumentation have been used for environmental analysis, although TOF, historically the first to be coupled chromatographically, did not find favour until more recently.
Low cost quadrupoles (Q) were introduced in the 1970s, which promoted their use in lieu of more expensive sector instruments. Ion traps (IT) also because of cost have been widely used as has MSD. Sift-MS has also been introduced in recent years. Scan modes are FS (ms data base matching) and SIM (specificity)
High cost tandem (QqQ) and hybrid MS (EBqQ) have advantages in that MRM provides a further level of selectivity for reactant ion to product ion specificity for target analytes.
The MS capability has been extended by the introduction of the QTOF (reflectron) orbitrap, ion mobility, and FTICR MS. The choice of MS also depends on the mass accuracy required to avoid false positives (dioxin/PCBs targeting).
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Mass Analysers
Triple Quadrupole Mass Analyser, TSQ
Single Quadrupole Mass Filter
Time of Flight Mass Analyser, TOF
TOF, Reflectron
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13. EB Dual Focus Sector (& reverse geometry BE)
Mass Analysers, continued
QTOF
EB Dual Focus Sector (& reverse geometry BE)
Orbitrap
IM MS Drift tube
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8. Advances in the sophistication of chromatography in recent years
Heart cutting has been well used for a number of decades
MDGC
GCxGC (LCxLC)
Not discussed here
Ion Chromatography, IC
EC CEC
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15. 8. Principle of Comprehensive 2D Chromatography
Normal Chromatography
Heart-cut 2D Chromatography
Multi-dimensional
techniques
Comprehensive 2D Chromatography
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16. 8. Colour plots and surface plots
Time in the second dimension is the modulation period
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17. Typical peak widths in 2D = <200 ms
8. 2D peak widths
1-methyl naphthalene
1-methyl naphthalene
0.16 s
Typical peak widths in 2D = <200 ms
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9. The Importance of Sample Preparation & Clean-up
Although with reasonably clean samples, sample preparation and clean up can be avoided. Here, direct sample introduction can be allowed using, for example, triple quadrupole via which MRM can be conducted to select reactant ions from the target analyte, which may undergo unique processes to generate product ions thus increasing the selectivity.
Generally though, it is advisable to clean-up and prepare samples prior to injection.
Sample preparation procedures are dependent on target analyte physical properties: RMM, volatility/vapour pressure, hydrophobicity, polarity, ionicity. A range of clean-up methods involve the following column based clean up technologies.
Protein precipitation
Phospholipid depletion
Non-selective SPE
LLE
C18 SPE C8 C2
IE SPE
Immunoaffinity techniques
Dirty Sample
Clean sample
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19. Microwave digestion/extraction
9. Sample extraction and preparation methods for water and solids
Sample preparation can be conducted off-line or on-line depending on the
nature of the matrix and the extent to which clean-up and concentration are
required.
Off-line or On-Line ?
Essentially, the extent to which sample preparation is necessary from
the raw matrix depends on the physical nature, liquid or solid (or gaseous
atmosphere).
Water as a matrix (river system/effluent) can be solvent (LLE) or solid phase
extracted (SPE) and the resulting sample pre-concentrated prior to analysis.
Large volume Injection (&headspace) is also possible for a water based matrix
(direct or on-line preconcentration injection)
SolidPhaseMicroExtraction can be conducted off-line or on-line. (VOCs & SVOCs)
Purge & trap for VOCs can be conducted on-line (lost in LLE).
Soil or fly ash as matrix may be solvent extracted (direct, soxhlet or microwave extraction)
but the resultant liquid will require extensive clean-up involving a number of
Steps (classic case- dioxins). PFE can replace soxhlet extraction
Note: Fauna & flora also will require a similar sample treatment
SPME Oct 1, 2012 By: John Hinshaw LCGC EUROPE Volume 25, Issue 10, pp
On-Line SPME
P urge& Trap
Microwave digestion/extraction
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9. Automated sample preparation and injection
AutoPrep GC-QQQ
Improved selectivity and lower detection limits for target compound analysis, with the benefits of automated sample preparation and injection.
AutoPrep GC-MSD
The AutoPrep GC-MSD extends the capability of the Agilent product by automating sample preparation and introduction - for volatiles and semi-volatiles.
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9. Automated and semi-automated sample preparation and clean-up instrumentation
Simple to Operate - 
Fast - 
High Throughput -
Green Technology - 
Quality Consumables - 
Low Solvent - 
Reliable - 
No Cross-Contamination - 
Economical - 
Affordable - 
High Fat removal capacity -
No Computer or Electronics
30 to 45 minutes
6 Samples in ParallelZero DCM
Guaranteed Certified Columns
As Low as 90 ml Per Sample
No Electronic or Mechanical Components to Fail
No Tubing
Column Kits to Meet Your Sample Matrix
No Capital Equipment Cost, Low cost consumables
Up to 10 grams
EconoPrep®
Sample Cleanup for Dioxin, PCB & PBDE Analysis
Fast Processes 8 Samples in 45 min
Green Technology    Zero DCM
Low Solvent              As low as 90ml Per Sample
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10. Bibiography
REVIEWS, BOOKS relating to environmental mass spectrometry
Early Gas Chromatography Mass Spectrometry
R S Gohlke and F W J McLafferty, J. Amer. Soc. Mass Spectrometry, 4, 367, 1993
The years from the 1970s to 2001 are reviewed in
Mass Spectrometry in Environmental Science
Susan D Richardson, Chem. Rev., 2001, 101, with 1145 references.
More than 60 reviews are cited alone.
History of Mass Spectrometry
Jennifer Griffiths, Anal. Chem., 80, , 2008.
Comprehensive Environmental Mass Spectrometry
Albert T Lebedev, ed., Advanced Topics in Environmental Science Series, 2012, (ILM Publications), pp 510, 21 authors.
Environmental Mass Spectrometry
A T Lebedev, Ann Rev. Anal Chem., 6, , 2013.
Encyclopedia of Mass Spectrometry, Volume 9: Historical Perspectives, Part A:
The Development of Mass Spectrometry
M L Gross, R M Caprioli eds., 2016.
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Typical Range of Applications, chapter titles from Lebedev (1)
GC/MS: A workhorse of modern environmental analysis
LC/MS- Qualitative/quantitative analysis of environmental pollutants
MS/MS Approaches for the analysis of environmental pollutants
Informatics & mass spectral data bases in evaluation of environmental mass spectral data
Advanced methods for GC/MS including GC/GC/MS
Ambient MS- environmental analysis without sample preparation.
Desorption electrospray MS
Miniaturised MS for environmental analysis
ICPMS in environmental analysis
MS- role in studies of VOPs
MS- ID & quantification of toxicologically important drinking water disinfection by-products
Emerging contaminants in the environment
Pesticide residue analysis by GC & LC/MS
Analysis of persistent halogenated compounds- DBDs & DBFs
MS of Atmospheric aerosols
MS in the study of interactions of environmental pollutants with DNA
Petroleomics- complex organic mixtures using FTICR MS
Ultrahigh resolution FTICR for the analysis of natural organic matter
MS Imaging in environmental science
ICR MS, e.g., earth sciences
(1) Comprehensive Environmental Mass Spectrometry, Advances Topics in Environmental Science, Albert T.
Lebedev, ed. (2012), ILM Publications (St Albans, England ; Glerndale, AZ, USA),
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FERA Mesocosm
Animation
By Jon Baugh
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25. Thank you for your attention!
11. Conclusions
It is without doubt that Chromatography coupled with MS has succeeded well beyond expectation and competes strongly with all other instrumental techniques to tackle a wide range of environmental applications. In many instances, it is the and one and only technique of choice.
It is clear that with the advances made to date that the future for Chomatography Mass Spectrometry is healthy and further refinements to the chromatography, the interfacing, the instrumentation and the data systems will be forthcoming because of the innovative and inventive capability of the community, the practitioners and MS high tech. organisations, acting in concert.
Thank you for your attention!
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