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Pyrolysis : Instrumentation and Application By: Ben King What is Pyrolysis? A technique that is used in the analysis of natural and artificial polymers or macromolecules

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slide2

What is Pyrolysis?

  • A technique that is used in the analysis of natural and artificial polymers or macromolecules
  • A sample is heated up (mainly in a inert atmosphere or vacuum) to decomposition to produce smaller units which are carried by a gas such as helium to the next instrument for characterization.
  • Pyrolyzer is usually linked to a GC and a detector such as MS or FTIR.

Reference 16, 2

slide3

Py-GC/MS

Auto sampler

Heated transfer line

MS

GC

Pyrolysis controller

pyrolyzer

http://www.csam.montclair.edu/earth/eesweb/imageU90.JPG

slide4

How Does it Work?

  • Use either one of three pyrolysis designs: Isothermal furnace, Curie Point filament (inductively heated), and resistively heated filament.
  • Sample heated to a pyrolysis temperature slowly or rapidly and held for a few seconds.
  • Cleavage of chemical bonds within the macromolecular structure producing low molecular weight, more volatile chemical moieties that are specific units of a particular macromolecule.

Reference 16,2

slide5

Sample Preparation

  • Normally no sample preparation is powdered or particulate materials
  • Some samples require an extraction with an organic solvent to remove any low molecular mass components.
  • Some solid samples need to be dissolved in solvents or ground up.
  • Amount of sample preparation depends on type of polymer and how homogeneous the sample is.
  • Methylating reagents, which increase the volatility of polar fragments, can be added to a sample before pyrolysis.
    • Tetramethylammonium hydroxide (TMAH) and trimethyl sulfonium hydroxide (TMSH)

Reference 16, 2

slide6

The Three Pyrolyzers

  • Each type can give reproducible results for small samples
  • Furnace and resistively heated filament pyrolyzers can be used for slow heating or rapid heating.
  • Curie Point is used only in rapid heating mode
  • Selectivity depends on personal preference, experimental requirements, budget, or availability

Reference 2

slide7

Furnace Pyrolyzer

  • Small mount on the inlet of GC
  • The metal or quartz sample tube is wrapped with heating wire and thermally insulated
  • The furnace pyrolyzer has a much larger sample chamber than the filament pyrolyzers as seen in the figure.

Reference 2

slide8

Furnace Pyrolyzer Design

  • Carrier gas enters from top or front to sweep past sample inlet (carrying of the pyrolyzate) before moving then directly into injection port of chromatograph
  • Temperature is stabilized to within ±10 °C of the desired temperature setpoint.
  • Thermocouple or resistance thermometer used to indicate wall temperature

Reference 2

slide9

Furnace Pyrolyzer

http://www.sge.com/uploads/lh/_0/lh_0zRR1NSHibbVkFiPo4A/pyrojector.jpg

slide10

Furnace Pyrolyzer Sample Introduction

  • Can’ t usually admit air during sample introduction due to GC
  • Heat rate dependent on sample material and composition of sample introduction device
  • Liquid samples are injected by a syringe.
  • Solids are dissolved and injected, or injected using a solid injecting syringe
  • A cool chamber is used to load samples into a crucible which is lowered into hot zone.

Reference 2

slide11

Furnace Pyrolyzer Temperature Control

  • Resistive heating element is around the central tube of furnace
  • Temperature is monitored by sensor with data feedback to the controller for adjustments of thermal energy.
  • Temperature control also depends on size and mass of sample, and residence time inside furnace.

Reference 2

slide12

Furnace Pyrolyzer Advantages

  • Inexpensive and relatively easy to use
  • Isothermal heating, with no heating ramp rate or pyrolyis time unless that is the intention.
  • Liquid and gas pyrolysis is more easily achieved than with filament type.

Reference 2

slide13

Furnace Pyrolyzer Disadvantages

  • Since the tube is considerably larger than sample, temperature control is more difficult to achieve
  • Large volume for sample to pass through to get to analytical device
  • Excessively low carrier gas flow may lead to secondary pyrolysis
  • Temperature stability depends on sample size, nature, and geometry

Reference 2

slide14

Furnace Pyrolyzer Disadvantages

  • Metal systems, initial pyrolysis may produce smaller organic fragments which encounter hot surface of tube and undergo secondary rxns
  • Generally necessitating split capillary analysis
  • Has longer retention times, broad peak shapes, and interference peaks.

Reference 2, 13

slide15

Heated Filament Pyrolyzer

  • Sample placed directly onto cold heater then rapidly heated to pyrolysis temperature
  • Two Methods:
    • resistance-controlled current is passed through heating filament
    • Inductive- current is induced into heating filament which is made of ferromagnetic metal
  • Sample size limited to an amount compatible with mass of filament. (low to high microgram range)
  • A sample must also be compatible for the analytical devices that are linked up to the pyrolyzers.
    • GC, FTIR, ICP, MS, etc.

Reference 2

slide16

Filament Pyrolyzer Examples

Fischer America

Curie Point Pyrolyzer

Analytix Ltd

Resistively Heated Filament Pyrolyzer

slide17

Inductively Heated Filament: Curie-pt Pyrolyzer

  • Electrical current induced onto a wire made of ferromagnetic metal by use of magnet or high frequency coil
  • Continual induction of current wire will begin to heat until it reaches a temperature at which it is no longer ferromagnetic
  • Becomes paramagnetic, no further current may be induced in it.
  • Heated to pyrolysis temperature in milliseconds

Reference 2

slide19

Curie-pt Design

  • Insertion:
  • Pyrolysis chamber which is surrounded by coil, is opened and sample wire is dropped or place inside
  • Sample wire is attached to a probe which is inserted through a septum into the chamber which is surrounded by the coil

Reference 2, 13

slide20

Curie-pt Pyrolyzer Design

  • Chamber can be attached directly to part of GC or isolated from GC by valve
  • Allows for autosampling and for loading wires into glass tubes for sampling and inserting into coil zone.
  • Controls for parameters of pyrolysis wire and also temp selection for interface chamber housing the wire.

Reference 2, 13

slide21

Curie-pt Pyrolyzer Sample Introduction

  • Sample and wire kept to low mass
  • Samples either coated onto filament as very thin layer
  • Soluble materials dissolved in appropriate solvent and wire dipped into.
    • Solvent dries and leaves thin deposit
  • Non-soluble:
    • finely ground samples maybe deposited onto wire from a suspension which is dried to leave coating of particles
    • Applied as melt
    • Create a trough with wire
    • Bend or crimp wire around material
    • Encapsulate sample with foil of ferromagnetic material and dropped into high frequency cell chamber.

Reference 2

slide22

Curie-pt Pyrolzer: Temperature Control

  • Pyrolysis temperature is determined by the composition of the ferromagnetic material
  • Reproducible and accurate temp control depends on accuracy of wire alloy, power of coil, and placement of wire into system
  • Use the same manufacturer, same sample loading, and placement to minimize variation of sample results

Reference 2, 13

slide23

Curie-pt Advantages

  • Self-limiting temperature
  • Rapid heating
  • No temperature calibration to perform
  • Can prepare several samples and store
  • Can be automated b/c no connections to wire- simple insertion
  • Can either clean and reuse wire or discard
  • Gives sharper characteristic peaks than furnace type
  • Demonstrates constant pyrolysis product composition yield even with sample weight increases
  • Good heat transfer

Reference 2, 13

slide24

Curie-pt Disadvantages

  • Limited temperatures to choose
  • Harder to optimize pyrolysis temperature
  • Concerns of catalytic effect of metals on very small samples.
  • Range of temps 350 - 1000°C (10 - 20 specific alloys )
  • Can’t have linear heating

Reference 2

slide25

Resistively Heated Filament Pyrolysis

  • Heat from ambient to pyrolysis temperature quickly also with small samples
  • Current supplied is connected directly to filament
  • A filament made of material with high electrical resistance and wide operating range. (Ex: Fe, platinum, and nichrome

Reference 2

slide26

Resistively Heated Filament: Design

  • Sample placed onto pyrolysis filament which is then inserted into the interface housing and sealed to insure flow to column.
  • Flat strip, foil, wire, grooved strip, or coil.
  • Coil- tube or boat inserted into filament, like very small rapidly heating furnace
  • Must be connected to controller capable of supplying enough current to heat filament rapidly with some control or limit
  • Temperature measured by resistance of material or by external measure such as optical pyrometry or thermocouple.

Reference 2

slide28

Resistively Heated Filament: Sample Preparation

  • Solution applied to filament by syringe
  • Powder solids use small quartz tubes which is inserted into coiled filament
  • Place in tube, held in position using plugs of quartz wool, weighed, and inserted into coiled element.
  • Rise and final temp different then directly on filament
  • Not used for soils, ground rock, textiles, and small fragments of paint
  • Viscous liquid applied on surface of filament or suspended on surface of filler material.

Reference 2

slide29

Resistively Heated Filament: Interfacing

  • Can be easily interfaced with other analytical devices as long the filament is positioned right and the probe is sealed off from air.
  • Need a heated interface between pyrolyzer and column
  • Interface has its own heater to prevent condensation of pyrolyzate compounds and should have minimal volume
  • Valve needed between pyrolyzer and column so insertion or removal of filament can be done.

Reference 2

slide30

Resistively Heated Filament: Temperature Control

  • Temperature is related to current passing through it
  • Conditions have to be very similar for good reproducibility
  • Computers control and monitor filament temp, control voltage used and adjusted for changes in resistance
  • Use photodiode to read actual temp of filament
  • Can select any final pyrolysis temp and any desired rate
  • Can heat as slow as .01 °C/min and as rapidly as 30000 °C/sec

Reference 2

slide31

Resistively Heated Filament: Advantages

  • Can measure how materials are affected by slow heating (TGA)
  • Permits interface of spectroscopic techniques with constant scanning for 3d, time-resolved thermal processing.
  • Can be inserted directly into ion source of MS or light path of FTIR
  • Products monitored in real time throughout heat process.

Reference 2

slide32

Resistively Heated Filament: Disadvantages

  • Can’t automate process since multiple samples need same filament and multiple filaments need same instrument
  • Any damage or alteration to the resistance of part of the loop will have an effect on actual temp produced by controller.
  • Introduction of some samples into heated chamber before pyrolysis may produce volatilization or denaturation, altering nature of sample before degradation.
  • Not good heat transfer
  • Yields can decrease as sample weight increases

Reference 2

slide33

Slow-rate Pyrolysis

  • Related to TGA, multiple step degradation
  • Gives time-resolved picture of production of specific products
  • Programmable furnace and resistively heated filament
  • 50-100 °C/min to extract organics

Reference 2

slide34

Direct/Indirect Transfer of Pyrolyzate to Detectors

  • Direct
    • Collection directly onto GC, at ambient or subambient conditions
    • Direct to MS or FTIR
    • Pyrolyzer inserted into an expansion chamber, which flushed or leaked into spectrometer, or the pyrolyzer is inserted directly into instrument
  • Indirect
    • A trap is connected to pyrolyzer and is later connected to analytical device

Reference 2

slide35

Reproducibility of Pyrolysis

  • Sources of error- size and shape, homogeneity, and contamination of sample
  • For polymers, need to make same size and shape samples
  • Overloading affects rate at which sample heats (thickness of material- thermal gradient)
  • 10-50 microgram samples desirable for direct pyrolysis to GC and twice that for FTIR

Reference 2

slide36

Increasing Reproducibility by Homogeneity

  • Ground up material under cryogenic conditions
  • Chop sample finely using scalpel and then analyze small fragments together
  • Made into solution
  • Bigger samples of .1mg
  • Use a split mode GC injection with a large split ratio to avoid signal saturations
  • Pass pyrolyzate in carrier gas through small sample loop attached to a valve which is interfaced to analytical unit. (clean run to run)

Reference 2

slide37

Accuracy of Pyrolysis

  • Study of compositional determination of styrene-methacrylate using Py-GC and H NMR
    • Standard deviation: 1-2% compared to 1% for NMR
  • Accuracy effected by pyrolysis temp rise time, sample size, sample surface area, and sample thickness
  • Small sample size, little sample prep, rapid turnaround time, relatively inexpensive, easily operable, and can be automated

Reference 8

slide38

Accuracy of Pyrolysis

  • 550-650 °C yielded reproducible fragmentation
  • Difference between NMR and GC pyrolysis results are in the range of 0-4% and 0-4.8% for styrene/n-butyl methacrylate and styrene/methyl methacrylate
  • Standard deviation for py-GC was from 1.2 to 2.1 %

Reference 8

slide39

Precision of Pyrolysis

  • Evaluating Emission of various materials for PAH’s released (Py-GC/MS)
    • Pyrolyzed at 1000 °C for 60 sec (resistively heated)
    • RSD from 7.5% (1-methyl naphthalene) to 18% (acenaphtene)
    • Most abundant species RSD less than or equal to 15% , less abundant much higher
  • Increase of precision and repeatability if using offline system
  • Shows good repeatability, limit of quantification, and linearity
  • Reasonably good for properly evaluating the quantity of PAHs emitted from different kinds of materials.

Reference 9

slide40

Precision of Pyrolysis

  • Investigation of Food Stuffs (Py-Elemental Analysis)
    • 65 Foods analyzed
    • RSD from 1 to 13% for Carbohydrates in each one of the samples that also contained protein, fats, and dietary fibers

Reference 7

slide41

Sample Amount and Selectivity

  • Sample amount
    • Milligrams or micrograms
  • Selectivity
    • Cellulose
      • Altering heating conditions improve selectivity
    • Sample vs Standards of PVC, PS, SB, PMMA, and PC mixture
      • All main marker compounds very similar
      • Naphthalene peak of polymer mixture 96% recovered relative to standards

Reference 15

slide42

Sensitivity of Pyrolysis

  • Volatile elements
    • Slurries- high sensitivity for pyrolysis temp < 400 °C, decrease from 400-800 °C
    • Aqueous and digested standards sensitivity plateaus across temps
    • Digested better sensitivity than aqueous 15% (As) & 65% (Pb)
    • High sensitivity obtained for As is obviously related to the presence of carbon in the plasma and increase sensitivity at low pyrolysis temp is in agreement with above-discussed charge-transfer mechanism.
    • Using modifiers Pd/Mg or raising concentrations of organics raises sensitivity at low temps.
    • Sensitivity changes due to differences in analyte transport from the ETV to the ICP produced by carrier effects and/or changes in analyte ionization in the plasma.

Reference 14

slide43

Detection Limit and Quantification Limit of Pyrolysis

  • Detection Limit is dependent on analytical device it is attached to
  • GC’ s detection limit
  • Can be as low as ng or pg
  • Analysis of polymer mixture Py - ETV - ICP - MS
  • Limit of Quantification
  • 500ng, 10 mg / kg dry mass
  • Limit of Detection
  • 150ng,
  • S / N = 3
  • Linearity in a range from .5 to 100 microgram

Reference 15

slide44

Application of Pyrolysis

  • Pyrolysis can be applied to the analysis of many natural and artificial macromolecules
  • Natural: lignin, cellulose, chitin, etc
  • Artificial: PVC, acrylics, varnishes, etc
  • Can be used for applications similar to TGA
  • Used in several specific areas as well
slide45

Presence of 5-hydroxyguaicyl as Unit Native in Lignin

  • Lignin content was estimated by the Klasan method
  • Curie-pt pyrolyzer, pyrolysis temp- 610 °C
  • Fibers were finely ground to sawdust
  • In samples of eucalypt, abaca, and kenaf, compounds 3-methoxycatechol, 5-vinyl-3-methoxycatechol, and 5-propenyl-3-methoxycatechol were detected.
  • Compounds arise from the pyrolysis of 5-hydroxyguaiacyl lignin moieties
  • Only the first one ever really detected, the other two rarely until using pyrolysis-GC/MS technique

Reference 6

slide46

Determination of Abaca Fiber Composition for Paper Pulping

  • Nonwoody source for paper for developing countries
  • Curie-pt pyrolyzer, pyrolysis temp-610 °C
  • Pyrolysis in presence of tetramethylammonium hydroxide (prevents decarboxylation)
  • Abaca fiber is 13.2% lignin
  • Main compounds of lignin are p-hydroxyphenyl (H), guaiacyl (G),and syringyl (S)
  • Reference 4
slide47

Determination of Abaca Fiber Composition for Paper Pulping

syringyl

guaiacyl

  • S/G-4.9
  • Efficiency of pulping directly proportional to amount of syringyl units in lignin due to easy delignification of S-lignin
    • S-lignin is mainly linked by a more labile ether bond
    • S-lignin is relatively unbranched
    • S-lignin is lower condensation degree than the G lignin

Reference 4

slide51

Determination of Kenaf Fiber Composition for Paper Pulping

  • Kenaf alternative raw material for pulp b/c renewable, inexpensive, and grown easily
  • Pyrolysis-GC/MS in presence of TMAH
  • Curie-pt pyrolyzer, pyrolyzed at 500 °C for 4 sec
  • Tried offline pyrolysis and low-temp pyrolysis 250 °C for 30 min
  • Chinpi-3: core 1.53 S/G and bast 3.42 S/G
  • Similar results of wet chemical method core 1.87 S/G and bast 4.71 S/G

Reference 11

slide52

Early Detection of Fungal Attack on Industrial Pine Lignin

  • Double-shot pyrolyzer, pyrolysis at 500 °C
  • Samples treated with laccase and others with laccase-mediator system
  • Py-GC/MS showed a decrease in phenolic and methoxy-bearing pyrolysis products during the onset of incubation.
  • Immediately, a 22% decrease in the total phenolic lignin content, increase in aldehyde (64%), ketone (50%), and acid groups (.21%).
  • After 48 hrs, 10% decrease in lignin, 10% guaiacyl units, 1% syringyl units, 10% decrease in ethyl phenolic derivatives
  • Klason Lignin (KL) recovered from the laccase-mediator system (LMS) after 48hrs of incubation shows high degree of oxidation and depolymerization
    • Desirable for industrial applications
  • KL recovered from the laccase shows a lower degree of oxidation, accompanied by a substantial polymerization.
    • Used for commodity and specialty markets

Reference 3

slide53

Determination of Grass Fiber Composition for Bio-oil Application

  • 15 Lolium and Festuca grasses
  • Speculated by researchers that reduce lignin content will produce a more stable bio-oil by reducing the chances of phase separation by improving solubility, stability, and homogeneity
  • Pyrolysis by inductive heated coil, pyrolysis at 600 °C, .4 °C/ms
  • Wet chemistry- grass leaves contained 2.14 to 3.72% lignin
  • Abundances of key markers of lignin added up by py-GC/MS were correlated to the amount of Klason Lignin in each grass.

Reference 10

slide54

Determination of Tagasaste Fiber Composition for Paper Pulping

  • Found in Canary islands, Australia, and New Zealand
  • Usefulness for paper pulp production
  • Microfurnace pyrolyzer, pyrolysis temp- 500 °C, 20 °C/min
  • 18.9% lignin
  • S/G 1.6

Reference 12

slide55

Determination of Lignin Contribution in soil-HA by Pyrolysis

  • Lignin contribution to the soil Humic Acid (HA) from maize plants
  • Curie-pt pyrolyzer, 600 °C for 5 sec
  • Pyrolysate of maize plant was dominated by lignin-derived products
  • Py-GC/MS determined HA derived from plants was composed of aromatic compound derived mainly for lignin had a high S/G ratio.
  •  Hemp and flax showed a predominance of guaiacyl
  • Jute, sisal, and abaca showed a predominance of syringyl
  • P-hydroxycinnamic acids, namely p-coumaric and ferulic acids, are also found in isolated lignin

Reference 1

slide56

Early Detection of Wood Decay by Lignin Composition

  • Furnace pyrolyzer
  • Characterization of internal wood degradation of London-plane tree (early detection of white rot fungal infection by lignin degradation before cavity formation)
  • Use pyrolysis product composition -syringyl/guaiacyl ratio
  • Samples from sound wood, extensively degraded wood, and R-zone (phenol-enriched barrier between infected and living).

Reference 17

conclusion
Conclusion
  • Pyrolysis is a technique that has endless possibilities for polymer or macromolecule analysis.
  • It can give reproducible results with good precision and with short amount of time
  • Py-GC/MS can be used extensively for analysis of lignins in the composition of plants and can be a great tool for the paper industry and biofuel industry.
references
References

[1]Adani, Fabrizio; Spagnol, Manuela; Nierop, Klaas G. J. Biochemical Origin and Refractory Properties of Humic Acid Extracted From Maize Plants: the Contribution of Lignin. Biochem. 2007, 82, 55-65.

[2]Applied Pyrolysis Handbook, Wampler Thomas P., Ed. ; M. Dekker: New York, 1995.

[3]Arzola, K. Gonzalez; Polvillo, O.; Arias, M. E.; Perestelo, F.; Carnicero, A.; Gonzalez-Vila, F. J. ; Falcon, M. A. Early Attack and Subsequent Changes Produced in an Industrial Lignin by a Fungal Laccase and a Laccase-mediator System: an Analytical Approach. Appl. Microbiol. Biotechnol. 2006, 73, 141-150.

[4]Del Rio, Jose C. ; Gutierrez, Ana. Chemical Composition of Abaca (Musa textilis) Leaf Fibers Used for Manufacturing of High Quality Paper Pulps. J. Agric. Food Chem. 2006, 54, 4600-4610.

[5]Del Rio, Jose C. ; Gutierrez, Ana; Rodriguez, Isabel M.; Ibarra, David; Martinez, Angel T. Composition of Non-woody Plant Lignins and Cinnamic Acids by Py-GC/MS, Py/TMAH and FTIR. J. Anal. Appl. Pyrolysis 2007, 79, 39-46.

[6]Del Rio, Jose C. ; Martinez, Angel T. ; Gutierrez, Ana. Presence of 5-hyroxyguaiacyl Units as Native Lignin Constituents in Plants as Seen by Py-GC/MS. J. Anal. Appl. Pyrolysis2007, 79, 33-38.

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[7] Dennis, M. J.; Heaton K.; Rhodes, C.; Kelly, S.D.; Hird, S.; Brereton, P.A. Investigation Into The Use of Pyrolysis-elemental Analysis for the Measurement of Carbohydrates in Food Stuffs. Analytica Chimica Acta 2006, 555, 175-180.

[8]Evans, Donald L.; Weaver, Judith L.; Mukherji, Anil K.; Beatty, Charles L. Compositional Determination of Styrene-Methacrylate Copolymers by Pyrolysis Gas Chromatography, Proton-Nuclear Magnetic Resonance Spectrometry, and Carbon Analysis. Anal.Chem.1978, 50, 857-860.

[9]Fabbri, Daniele; Vassura, Ivano. Evaluating Emission Levels of Polycyclic Aromatic Hydrocarbons From Organic Materials by Analytical Pyrolysis. J. Anal. Appl. Pyrolysis 2006, 75, 150-158.

[10]Fahmi, R.; Bridgwater, A.V.; Thain, S.C.; Donnison, I. S.; Morris P. M.; Yates N. Prediction of Klason Lignin and Lignin Thermal Degradation Products by Py-GC/MS in a Collection of Lolium and Festuca Grasses. J. Anal. Appl. Pyrolysis, 2007, 80, 16-23.

[11]Kuroda, Ken-ichi; Izumi, Akiko; Mazumder, Bibhuti B.; Ohtani, Yoshito; Sameshima, Kazuhiko. Characterization of Kenaf (Hibiscus Cannabinus) Lignin by Pyrolysis-Gas Chromatography-Mass Spectometry in the Presence of Tetramethylammonium Hydroxide. J. Anal. Appl. Pyrolysis 2002, 64, 453-463.

[12]Marques, Gisela; Gutierrez, Ana; Del Rio, Jose C. Chemical Composition of Lignin and Lipids from Tagasaste (Chamaecytisus Proliferus Spp. Palmensis). Indust. Crops Prod. 2008, 28, 29-36

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[13] Oguri, Naoki; Kirn, Poongzag. Design and Applications of a Curie Point Pirolyzer.

[14] Silva, A. F.; Welz, B.; De Loos-Vollebregt, M.T.C. Evaluation of Pyrolysis Curves for Volatile Elements in Aqueous Standards and Carbon-Containing Matrices in Electrochemical Vaporization Inductively Coupled Plasma Mass Spectrometry. Spectrochimica Acta B.2008, 63, 755-762.

[15] Tienpont, Bart; David Frank; Vanwalleghem, Freddy; Sandra, Pat. Pyrolysis-capillary Gas Chromatography-Mass Spectometry for the Determination of Polyvinyl Chloride Traces in Solid Environmental Samples. J. Chromatography A.2001, 911, 235-247.

[16] University of Bristol. Pyrolysis Gas Chromatography Mass Spectrometry. http://www.bris.ac.uk/nerclsmsf/techniques/pyro.html (Accessed Apr. 27, 2005)

[17] Vinciguerra, Vitterio; Napoli, Aldo; Bistoni, Angela; Petrucci, Gianluca; Sgherzi, Rocco. Wood Decay Characterization of a Naturally Infected London Plane-tree in Urban Environment Using Py-GC/MS. J. Anal. Appl. Pyrolysis 2007, 78, 228-231.