Int. J. Appl. Radiat. Isot. Vol. 36, No. 12, pp. 95%960, 1985 0020-708X/85 $3.00 +0.

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Printed in Great Britain. All rights reserved Copyright ~ 1985 Pergamon Press Ltd

Dual Collector Cycloidal Mass Spectrometer

for Precision Analysis of Hydrogen Isotopes
STANISLAW HALAS

Institute of Physics, Mafia Curie-Sklodowoska University, 20-031 Lublin, Poland

(Recewed28May 1985)

The cycloidal mass spectrometer design of Andrewm has been adapted to dual ion collection for
hydrogen isotope analysis. Difficulties experienced by Andrew with thermal expansion of the wire used
to produce uniform electric fields were overcome by using 0.05 mm diameter tungsten wire. The focal
lengths for ion beams M/e ---2 and 3, are 2 and 3 cm respectively. The sensitivity is about two orders of
magnitude higher than for magnetic sector mass spectrometers of similar size. Under normal operating
conditions the H~ production is 10% of the total ion current HD + and H~', and the reproducibility of
6D measurements is better than + 0.5 per rail. Increase of the resolving power to 600 for separation of
3He÷ from HD ÷ and H~" ions appears feasible.

Introduction described by Halas. (3) The fine tungsten wire retains

its rigidity despite considerable ohmic heating during
The perfect focussing property of crossed uniform
normal operation.
electric and magnetic fields was first discovered and
Construction details are shown in Fig. 1. Focal
applied to mass spectrometry by Bleakney and
lengths (i.e. the distance between the narrow entrance
Hipple. (2) The usual method of producing a uniform
slit and two collector slits) were chosen as 2 and 3 era
electric field in a given space has been to build a stack
for M/e beams of 2 and 3, respectively. The width of
of conducting frames precisely separated by ceramic.
the entrance slit is 0.2 mm whereas those of the H,+
This system contains many components which have
and H D + + H~" collector slits are 0.8 and 1.5 mm
to be electrically connected and outgassed.
respectively.
A simplified design which overcomes these disad-
A magnetic field of 0.125 T was produced by an
vantages, was used in the cycioidal mass spectrometer
external permanent magnet removed from a dis-
described by Andrew. °) He used a fine resistance wire
carded high vacuum ion pump. The mass spec-
wound in a hefix around four threaded insulating
trometer chamber was evacuated through a I cm i.d.
corner posts to form a potentiometer between the
bellows valve. The system was pumped down to
centre plate and two other side-plates. A disadvan-
2 x 10 -7 torr by a l0 L/s mercury diffusion pump
tage of this design is the limitation of the voltage
with a liquid nitrogen trap. The mass spectrometer
across the winding, which in turn limits the mag-
assembly was mounted on a 10 crn flange having 8
nitude of the electric field and the mass range. This
electrical feedthroughs and a 6.0mm o.d. stainless
limitation, however, is of no consequence for an
steel tube for introducing H2 gas. Four feedthroughs
instrument designed for isotope analysis of a single
were used for the two filaments positioned against the
element like hydrogen, helium, etc.
electron entrance slits in the ion source. (One filament
This paper describes the construction of a cycloidal
is heated during operation while the other, a spare,
mass spectrometer of Andrew's design, which is ideal
may be used for the electron trap). The other four
for D/H analysis.
feedthroughs were used to obtain the potential distri-
bution on the electrodes as shown in Fig. 2.
Consmlction The - 1 0 V plate was connected to the ground
The following modifications were made to the inside the vacuum chamber through a tungsten wire
original design described by Andrew: °) (i) An addi- resistor, of the same diameter as that used for pro-
tional plate was added to shield the ion source cage, ducing the homogeneous electric field.
(ii) The resistive wire helix was constructed with The collectors were made from molybdenum sheet
0.05 mm diameter tungsten wire which possesses both and supported with ceramic washers. Each collector
strength and low thermal expansion, (iii) A dual ion was shielded with a stainless steel box.
collector was built, (iv) H~ gas was introduced to the In order to overcome problems with expansion of
ion source cage from an inlet system similar to that the wire, Andrew o) used techniques such as notching
957
958 STANISLAWHALAS

the ceramic support pillars and loading springs to

keep the winding under slight tension. Such devices
were not required with the 0.05 mm tungsten wire.
The two tungsten coils are approximately the same
length and therefore differ in their turn density
(2.5/mm in the large coil and 3.3/ram in the small
coil). In this way, the electric fields produced in both
regions were approximately the same. Precision ad-
justment of these electric fields was possible with an
external potentiometer with the slider connected to
the - I 0 V plate. The coils were wound in opposite
directions to partially cancel their magnetic fields
during operation.
The electronics system of this mass spectrometer
included (i) an electron emission supply, stabilized to
4-0. 1% modified from an ionization gauge control-
ler, (2) adjustable voltage (100 V max) for ion accel-
eration, which was coincidentally available from the
ionization guage controller, (3) a stabilized power
supply for the electric fields (200 V, 150 mA max.), (4)
two d.c. electrometers with digital voltmeters for ion
current measurement.

Performance
Figure 3 shows part of the mass spectrum of
hydrogen. The mass-2 (H~) and mass-3 (HD + +
H;') peaks are collected simultaneously with about
120V potential difference between the side-plates,
which correspond to E ~ 2450 V/m. The electric field
intensities in both regions of mass spectrometer were
adjusted slightly for maximum resolving power.
The mass-2 and mass-3 ion beam intensities are
5 x I0 -~ and I0-~2A under the following operating
conditions:
Fig. I. Constructional details of cycloidal mass spectrometer (I) electron emission current m 50/~A,
(explanation in text). (2) gas flow rate about I0 nmol/s,
-70V

E ~B ® ,

-10v .==_.-

_1_
Jco)lectors [~

*50 V
Fig. 2. Typical electrode potentials for cycloidal mass spectrometer.
 Precision analysis of hydrogen isotopes 959

H2 HD+(r~IH; Table 1. Long term reproduce-

ability of 6D measurements on H:
gas prepared separately from a dis-
tilled Lublin tapwater sample
1.0
Date 6D* Standard
(1984) (~) error
Oct. 30 -70.3 0.5
Nov. 8 -70.2 0.7
- 70.3 0.6
-69.3 0.5
Nov. 13 -70.6 0.7
Nov. 21 -70.1 0.5
- 70.2 0.6
Nov. 27 -69.0 0.7

Fig. 3. Partial mass spectrum of H 2 used in D/H analysis
(the vertical scale of the second peak is multiplied by factor
of 3 x 103).
(3) electron accelerating voltage ~ 70 V,
(4) ion accelerating voltage ~, 80 V.
To simplify the construction of the ion source, an ion
repeller was not used. Although many factors are
involved, the ion yield would appear to be about two
orders of magnitude greater than that of a typical
Nier-type mass spectrometer~4) with similar electron
emission and gas flow. The high sensitivity of this
spectrometer arises from the wide aperture ( - 2 0 " to
+ 20 °) which was designed by choosing appropriate
dimensions of windows in the internal plates.
The resolving power of the mass spectrometer can
be estimated from the fact that at 50% height, the
peak width is about 4.0 V, thus
M 120
" 30
AM 4.0
in agreement with the value theoretically predicted by
t h e f o r m u l a (2)
M d
a M = a-d '
where d is the focal length, and Ad is the sum of
entrance and collector slit widths.
Results of ~D measurements for Lublin tapwater
over a period of one month are given in Table I.
These measurements were performed on H2 gas pre-
pared from H20 by the zinc reduction method of
Coleman. (~) Because the standard gas was prepared
from V-SMOW water, the results are expressed in
terms of this standard after two multiplicative cor-
rections as follows:
(1) Background correction, Co, defined as the ratio
of the major beam intensity after closing the capillar-
ies (no gas is admitted to the ion source) to that
intensity when one capillary is open to the ion source.
This correction is usually about 1.02.
(2) The H~" correction, Ct,(° defined as the ratio of
mass-3 to mass-2 ion beam intensities to that of
extrapolated value when the mass-2 ion beam inten-
sity approaches zero. This correction ranged from
1.10 to 1.20.
= (. R sample 1)
* 6D \ R standard
× IOJxCoxCI,
where R denotes mass-3 to mass-2
ion beam intensity ratio, C a and C t
are "'instrumental" corrections, see
tex t.
The average 6 D value calculated from Table 1
agrees well with two independent calibrations made
in other laboratories:
-70.59/00 (Cluj, Romania), and
-70.09/00 (Calgary, Canada).
The accuracy of 6D measurements was further
confirmed by using the SLAP standard water distrib-
uted by IAEA, Vienna. The corrected 6D value
agreed to within + 2%0 of the assigned value of
- - 4 2 8 % 0 . (7) This suggests that instrumental correc-
tions ca) apart from Co and G , are not necessary.
Thus is its concluded that the cycloidal mass
spectrometer is highly suitable for D/H analysis.
It has the distinct advantage that a high voltage
supply (of a few kV), is not required as is the case
for the Nier type instrument. It is anticipated that
some improvement in precision of cSD determinations
would result if an electron current integrating
device(gJ°) were used.
Possibility of Tritium Content Determinations
It is exciting to consider the possibility of using the
cycloidal mass spectrometer to determine the tritium
content of natural waters. Clarke et al. (t') first applied
high resolution static mass spectrometry for tritium
determinations by measurement of 3He accumulated
over a certain period from tritium decay. A resolution
of 600-1000 is normally used for the 3He+ collector
in order to separate 3He+ from interfering HD + or
H~" ions. A single focussing magnetic sector mass
spectrometer must be relatively large (r = 30 cm). A
large volume is undesirable because this decreases the
sensitivity of the instrument during static operation.
The cycloidal mass spectrometer described in this
paper has small dimensions. On the basis of our
experience, it should be possible to increase its reso-
lution significantly by narrowing the entrance and
3He-collector slits. Since the sensitivity is high, the ion
960 STANISLAW HALAS
currents at the required resolution should be quite
adequate. Thus the cycloidal mass spectrometer
might prove to be ideal for determining 3He at
natural levels or radiogenic 3He from environmental
3H decay.
Acknowledgements--This work was supported by MR 1.5
Program (University of Warsaw). It thank Professor H. Roy
Krouse, The University of Calgary, for critical reading of
this manuscript. Thanks are also due to S. Bronisz, T.
Kopysc and D. Pulinski for their patience during mechani-
cal construction of the mass spectrometer, and to J. Sikora
for modification of a PW-12 ionization gauge controller for
stabilizing the electron emission.
References
1. Andrew D. (1967), Trans. 3rd Int. Vac. Congr., Vol. 2,
p. 527 (Pergamon Press, New York, 1967).
2. Bleakney W. and Hippie T. A. Phys. Rev. 53, 521
(1938).
3. Halas S. I. Phys. E: Sci. Instrum. 12, 418 (1979).
4. Nier A. O. Rev. Sci. Instrum. 18, 398 (1947).
5. Coleman M. Anal. Chem. 54, 993 (1982).
6. Friedman I. Geochim. Cosmochim. Acta 4, 89 (1953).
7. Gonfantini R. Nature 271, 534 (1978).
8. Deines P. Int. J. Mass Spectr. Ion Phys. 4, 283.
9. Halas S. and Skorzynski Z. J. Phys. E: Sci. Instrum. 13,
346 (1980).
I0. Halas S. and Skorzynski Z. J. Phys. E: Sci. Instrum. 14,
509 (1981).
11. Clarke W. B., Jenkins W. J. and Top Z. Int. J. Appl.
Radiat. Isot. 27, 515 (1976).