Micro-thermal analysis employs a scanning probe microscope fitted with a mi
niature resistive heater/thermometer to obtain images of the surface of mat
erials and then perform localised thermoanalytical measurements. We have de
monstrated that it is possible to use the same configuration to pyrolyse se
lected areas of the specimen by rapidly heating the probe to 600-800 degree
sC. This generates a plume of evolved gases which can be trapped using a sa
mpling tube containing a suitable sorbent placed close to the heated tip. T
hermal desorption-gas chromatogaphy/mass spectrometry can then be used to s
eparate and identify the evolved gases. This capability extends the normal
visualisation and characterisation by micro-thermal analysis to include the
possibility of localised chemical analysis of the sample (or a domain, fea
ture or contaminant). The isolation and identification of natural products
from a plant leaf are given as an example to illustrate this approach. Prel
iminary results from direct sampling of pyrolysis products by mass spectrom
etry are also presented.