of polonium-210 in the tellurium precipitation. Because po-
Four measurements by direct
lonium-210 emits alpha particles having energies only 20 keV
lower than those of uranium-232, any polonium-210 not re-
moved will add to the uranium-232 peak and make the re-
covery of tracer appear to be higher than it really is, giving low
results. For example, the solutions can be centrifuged rather
than filtered if desired, but about 1%of the polonium-tellu-
rium precipitate will be decanted with the supernate because
of a scum at the surface that is not pulled down by centrifu-
gation. A considerably larger error, and one that is not readily
apparent, is produced in the presence of hydrochloric acid. If
5 mL of concentrated hydrochloric acid is used instead of the
2 mL of concentrated sulfuric acid specified, the reduction of
the tellurous acid and subsequent agglomeration of the ele-
mental tellurium takes place so much more rapidly that much
of the polonium will not have been precipitated and/or in-
cluded in the tellurium carrier by the time the available sur-
face of the carrier has been reduced to negligible proportions.
The results will be 5 to 10%low.
The accuracy of the procedure for determination of the
three main thorium isotopes in thorium ores was verified by
comparing the results obtained for thorium-232 by the present
alpha spectrometric procedure with those obtained for natural
thorium by a fluorometric procedure of previously demon-
strated accuracy (B), and by direct measurement of the lead-
212 daughter by gamma spectrometry. On 24 measurements
of 8 different solid aliquots of a standard monazite ore, the
fluorometric procedure gave a mean of 1.404 f 0.017
(f0.004)% thorium, where the first uncertainty is that of an
individual about the mean and the one in parentheses is that
of the mean itself. Using a value of 2428 f 21 dpm/g of tho-
rium-232 per percent natural thorium, the percentage values
convert to 3409 f 51 ( f 3 1 ) dpm/g of thorium-232. On 20
measurements on the same 8 aliquots of the sample by the
present alpha spectrometric procedure, a mean of 3421 f 74
(f16) dpm/g was obtained, in excellent statistical agreement
Separation and Determination of Nanogram Amounts of Inorganic
Arsenic and Methylarsenic Compounds
Robert S. Braman,* David L. Johnson,' Craig C. Foreback,2 James M. Ammons, and Joseph L. Bricker
Department of Chemistry, University of South Florida, Tampa, Fla. 33620
Arsenate and arsenite ions, methylarsonlcacid, and dimeth-
ylarslnic acid in aqueous solutions are reduced to arslne and
the corresponding methylarslnes respectlvely at pH 1-2 by
sodlum borohydrlde In a reaction chamber. Entrained by He
carrier gas the arsines are frozen out In a liquid nltrogen cooled
U-trap. Their separation Is accompllshed by volatlilzatlon upon
warming the U-tube trap. Arslnes carried out of the trap by the
carrler gas are passed through a direct current electrlcai
dlscharge. Arsenic atomic emlsslon lines produced in the
discharge are detected by a recording, scannlng monochro-
mator system. Llmlts of detectionfor arsenic are approximately
1 ng for each of the arsines.
Present address, State University of New York, College of Envi-
ronmental Science and Forestry. Syracuse, N.Y. 13210.
* Present address, Chemistry Division, Henry Ford Hospital, De-
troit, Mich. 48202.
with the chemical values.
gamma spectrometry gave a mean of 1.444 f 0.018 (f0.009)%
thorium, also in acceptable agreement. In addition, the mean
ratio of thorium-228 to thorium-232 for the 20 measurements
was 0.996 f 0.024 (f0.005),showing that the measurement
of thorium-228 is no less exact and that the system is in
equilibrium so that the gamma spectrometric measurements
can be related unequivocally to the thorium-232 concentra-
tion. Although no independent method was available to check
the thorium-230 result in thorium ores, there is no reason to
believe that its determination will be any less accurate than
the other two isotopes.
ACKNOWLEDGMENT
The author wishes to express his appreciation for the as-
sistance of his associates, particularly to F. D. Hindman for
the thorium and uranium separations, to R. L. Williams for
the electrodepositions and alpha spectrometry, and to J. S.
Morton for the gamma spectrometry.
LITERATURE CITED
(1)J. N. Rosholt, A. P. Butler, E. L. Garner, and W. R. Shlelds, con. Geol., 60,
199 (1965).
(2)J. N.Rosholt, E.N. Harshman, W. R. Shlelds, and E.L. Garner, con. GeoL,
59, 570 (1964).
(3)J. Kronfeld, Nucl. Sci. Abstr., 26, 2982 (1969),Abstract No. 31018.
(4)C.W. Sill, "Simultaneous Determlnation of U-238.U-234,Th-230, Ra-226
and Pb-210 in Uranium Ores, Dusts and Mill Tailings, U. S. Energy Research
and Development Administration, Health Services Laboratory, Idaho Falls,
Idaho.
(5) C. W. Sill, K. W. Puphal, and F. D. Hlndman, Anal. Chem., 46, 1725
(1974).
(6)C.W. Sill, Anal. Chem., 46, 1426 (1974).
(7)C.W. Sill and R. L. Williams, Anal. Chem., 41, 1624 (1969).
(8)C.W. Slll and C. P. Willis, Anal. Chem., 34,954 (1962).
(9)C. W. Sill and F. D. Hlndman, Anal. Chem., 46, 113 (1974).
(10)D. R. Perclval and D. 8. Martin, Anal. Chem., 46, 1742 (1974).
(11)C.W. Silland C. P. Willis, Anal. Chem., 37, 1661 (1965).
RECEIVED
for review October 29,1976. Accepted January 14,
1977.
Considerable interest in the environmental chemistry of
arsenic stems from the toxicity of its compounds and their use
as silvicides or pesticides. An extensive annotated bibliogra-
phy on arsenic in the environment has been prepared (1).
Nearly all of this referenced work used analytical methods for
total arsenic with no differentiation of arsenic by chemical
form except for thin-layer and paper chromatography sepa-
ration methods reported by Sachs, Anastasia, and Wells ( 2 ) .
Methylarsenic acids are important compounds of arsenic
produced by biomethylation and could play an important role
in its environmental chemistry. Concentrations of arsenic
found in the environment are generally small, several parts
per billion in sea water to less than 1ppb in many fresh waters
and parts per million in soil.
Prior to the work of Braman and Foreback (3) little had
been available for the determination of the arsenic forms in
environmental samples. Johnson and Pilson ( 4 ) developed a
spectrophotometric method for differentiation of arsenic(II1)
ANALYTICAL CHEMISTRY, VOL. 49, NO. 4, APRIL 1977 621
Table I. Reduction of Arsenic Compounds
agb at
Molecular form PKa
As(III), Arsenous acid, HAsOz 9.23
As(V), Arsenic acid, H3As04 2.25 (pK1)
Methylarsonic acid, CH3AsO(OH)2 2.60
Dimethylarsenic acid, (CH3)2AsO(OH) 6.19
Trimethylamine," (CH3)3As ...
Phenylarsonic acid, C6HsAsO(OH)z 3.59
Or its oxidized form presumed t o be (CH3)sAsO. cy0 is the fraction of the acid in the undissociated form.
1 ElDiSC'
Figure 1. Sample reaction chamber, U-trap, and detector arrange-
ment
and arsenic(V) anions. Peoples, Lakso, and Lais (5) reported
a method to some extent capable of distinguishing between
inorganic arsenic and organic arsenic acids in aqueous samples
containing more than 2 pg of arsenic.
Gas chromatography of methyliodide-treated dimeth-
ylarsinic acid has been reported (6)but this technique has not
been applied to the other arsenic compounds.
Braman, Justin, and Foreback (7)have reported a method
for inorganic arsenic based upon continuous detection of vo-
latilized arsine. The low limits of detection served as a basis
of the method reported here.
T a l m i and Bostick (8) have recently reported based upon
gas chromatographic separation of sodium borohydride re-
duced arsenic compounds with detection by a microwave
discharge emission type detector. Talmi and Norvell(9) have
reported a method for inorganic As and Sb based upon gas
chromatographic separation after preparation of triphenyl
derivatives. E d m o n d s and Francesconi (10) have recently
reported a separation similar to the one reported here; t h e y
used a flame type atomic absorption spectrometer as t h e de-
tection unit.
This paper reports i n detail on the analytical method of
B r a m a n and Foreback (3) including improvements since its
first use in their environmental studies. The method has been
adapted to air analysis i n environmental studies ( 3 , l l ) .
EXPERIMENTAL
Reduction Chemistry of Arsenic Compounds. Development of
this method proceeded from our finding that the several arsenic acid
compounds may be reduced to arsine or corresponding methylarsines
in aqueous solution by sodium borohydride. Further, the reduction
reaction was found to be pH dependent, and related to the pK, of the
arsenic acids, a fact which aids the identification of arsenic compounds
found in samples. Table I shows the reduction conditions now used
622 ANALYTICAL CHEMISTRY, VOL. 49, NO. 4, APRIL 1977
(YO a t Reduction Reduction
PH 1 PH 4 PH product bP
1.00 1.00 4 ASH^ -55
0.948 0.017 1-2 ASH^ -55
0.975 0.038 1-2 CH3AsH2 2
1.00 1.00 1-2 (CW2AsH 35.6
... ... 1-4 (CH~)~AS 70
1.00 0.280 1-2 CsH&Hz 148
for analysis and gives the pKa data and (YO, fraction of arsenic acids
in the undissociated form present at analysis pH conditions.
Arsenous acid or arsenic(II1) ions, dimethylarsinic acid, and oxi-
dized forms of trimethylarsine are partially reduced above pH 4, even
though, considering the reduction potential for sodium borohydride
(-1.24 V), one might predict that inorganic arsenic(V) ions and
methylarsonic acid would also be reduced. A pH 3.5-4.0 condition was
selected for determination of arsenic(II1) ions in the analysis proce-
dure because arsenic(V) was not reduced in this pH range and because
reduction of arsenic(II1) was more rapid than a t higher pH values.
The reduction of arsenic(V) noted in earlier work (7) was found to
be due to a partial reduction observed when strongly acidic solutions
of arsenic(V) were injected into sodium borohydride solutions or vice
versa. Therefore, it is necessary to buffer samples to the appropriate
pH prior to addition of NaBH4 when arsenic(II1) is to be deter-
mined.
Reduction of arsenic(V) by sodium cyanoborohydride in a pre-
reduction step prior to analysis proved less convenient than using
several treatments with 2% aqueous NaBH4 a t pH 1-1.5. The cya-
noborohydride ion decomposes and produces hydrogen cyanide which
obscures the methylarsine and the dimethylarsine peaks, thus pre-
venting their analysis in the same sample and at the same time as total
inorganic arsenic. Sodium cyanoborohydride was also unsuitable as
a prereducing agent for seawater analyses.
Although sodium borohydride rapidly hydrolyzes at pH 1-1.5, it
apparently has sufficient life to effect reduction of arsenic compounds.
Completeness of arsenic(V) reduction was studied. Results indicated
that over 95% of arsenic(V) was reduced after 4 to 5 additions of 2 mL
each of 2% NaBH4 in both seawater and distilled water. Reduction
of all other arsenic compounds was over 99% complete by the analysis
procedure.
Oxalic acid was found to be the best acid for pH control a t pH 1-1.5.
The use of sulfuric acid to produce pH 1or lower was tried but found
to cause approximately a 2-5% disproportionation in analysis of di-
methylarsinic acid. This type of effect was not observed with the
procedures reported here. The analysis process by itself did not cause
the methylation of inorganic arsenic either in standard mixes or in
natural water samples to which inorganic arsenic has been added.
Methylarsenic compounds were not demethylated.
Zinc and hydrochloric acid were also found to reduce methylarsonic
acid and dimethylarsinic acid but were not as rapid or as convenient
to use as sodium borohydride.
Apparatus. The apparatus arrangement used and characteristics
of the detector and the scanning monochromator system have been
reported previously (12,13).
Arsines are generated in a reaction chamber, trapped out in the
U-trap, and carried through the detector by helium carrier gas in the
apparatus shown in Figure 1.All glassware was constructed locally.
Quartz tubing, 6-mm 0.d. was used to construct the detector chamber.
Polytetrafluoroethylene (PTFE) tubing, 0.25 inch 0.d. was used to
connect parts of the glassware system. The tubing connectors fit
tightly over 6-mm 0.d. glass tubing, yet could be easily disconnected
to facilitate disassembly of the apparatus. The detector was attached
to the monochromator by means of a linen-filled Bakelite mounting
board.
The reaction chamber was constructed from a ground glass joint
size 34/35 and could be used with samples up to approximately 70-mL
volume. A side arm injection port was constructed with a 0.25-inch
Swagelok nut fitting sealed to the 6-mm 0.d. tube by epoxy cement.
Medium or coarse frits were used. Heavy hooks were used to secure
the top and bottom parts of the chamber by means of rubber bands.
Ball joints and O-ring joints have also been successfully used in similar
reaction chamber designs.
The U-trap, 8 inches long each arm, was half-filled with 60-80 mesh
glass beads.
Table 11. Reproducibility of Volatilization Timesa
Standards in H2O
Methylarsine 9.2 s f 1.2 s.d. N =5
Dimethylarsine 23.2 s f 2.0 s.d. N =7
Lake water analyses
Methylarsine 13.0 s f 0.8 s.d. N =3
Dimethylarsine 24.1 s f 0.9 s.d. N =3
Trimethylamine 34.2 s f 1.3 s.d. N =3
0 Appearance of peak maximum after starting t o heat t h e U-
trap.
The addition of a carbon dioxide absorber with a bypass, a 2- to
3-inch long column packed with small sodium hydroxide beads, was
a major improvement removing carbon dioxide interference with
arsine detection. These beads used were not the usual larger pellets
but were approximately 2-mm 0.d. obtained from Fisher Scientific
Co., NaOH No. S612. The carbon dioxide absorber occasionally needs
replacement and must be protected from water vapor. The bypass
directs methylamines around the sodium hydroxide trap so as to avoid
small losses of the methylamines.
Characteristics of the Separation Method. Differences in boiling
points of the arsines suggested separation by a gas chromato-
graphic-like procedure.
Water vapor, arsines, carbon dioxide, and any other vapors from
the sample or generated in the reduction process are frozen out in the
U-trap. After removal of the liquid nitrogen flask and upon warming,
all trapped compounds are evolved from the U-trap generally in order
of their boiling points. Reasonably good separation of the arsines is
obtained. The carrier gas is then passed through the detector cell
where an arsenic atomic emission line intensity is observed and re-
corded to provide a higher degree of selectivity.
The separation is carried out under non-isothermic conditions. The
liquid nitrogen is removed from the U-tube which is at first allowed
to warm up without heating. Any low boiling gases volatilize out of
the trap in 10-30 s. Arsine volatilizes out just prior to carbon dioxide
which is always present, at least in small amounts, as an impurity in
sodium borohydride. After the carbon dioxide has been vaporized out
of the U-tube, the wire heater is turned on with the heating rate
controlled by a laboratory autotransformer.
A slow heating rate is optimum; U-tubes wound with approximately
48 inches of B & S gauge 24 Chrome1 A wire, approximately 1.65 R per
foot, were heated by an impressed voltage of 12-20 V from the auto-
transformer. The optimum heater voltage for each U-tube is deter-
mined by experiment with standards. Generally, the more rapid the
heating rate, the more rapidly do the methylamines volatilize out of
the U-tube, but the separation can become poorer a t high heating
rates. The response of the arsines was found to be uninfluenced by
heating rate with the exception of dimethylarsine. At high heating
rates, a 2040% decrease in signal was noted for dimethylarsine at-
tributable to thermal decomposition. After removal of the arsines,
water finally starts to volatilize out of the trap, quenches the dis-
charge, and ends the analysis.
The U-trap volatilization separation could be considered to be a
programmed temperature gas chromatographic effect on a solid phase
with a rapid heating rate. The heating rate is greater than 100 "C per
minute since the U-trap is heated from -195 to approximately 60 "C
in 1-2 min.
The half-packed U-trap is an interesting feature. A fully-packed
U-trap did not function well nor did an empty open U-tube. Water
vapor condenses and freezes in the up-stream end of the U-tube while
the lower boiling arsines and other gases apparently freeze out further
down stream. During the volatilization and analysis step, the lighter
gases pass through or out of the packed section before water. Water
vapor apparently is kept from volatilizing out of the U-tube at the
same times as the arsines by the still-cold glass beads. Nevertheless,
the gas velocity through a fully packed column may be sufficient to
distribute water vapor almost throughout the entire column. Water
vapor then emerges in time to quench the dimethylarsine and tri-
methylarsine peaks.
The effect of carrier gas flow rate on separation of peaks was found
to be important. A flow rate of 300 mL per min was optimum for
analysis. Considerably lower values gave poorer separation of the alkyl
arsines. Table I1 gives typical retention time reproducibility data
under optimum operating conditions and with the same liquid ni-
T a b l e 111. Calibration C u r v e s f o r Arsenic Compounds
As(II1) (sodium arsenite)
y (cm2) = 0.172 f 0.010 ng (as As) - 0.25 f 0.16
n=5
As(V) (sodium arsenate)
y (cm2) = 0.164 f 0.005 ng (as As) - 0.23 f 0.11
n=7
Sodium methylarsonate
y (cm2) = 0.172 f 0.0017 ng (as As) - 0.26 f 0.051
n=6
Dimethylarsinic acid
y (cm2) = 0.165 i 0.0033 ng (as As) - 0.40 f 0.11
n = 5
trogen level. Retention time reproducibility is not critical to the
analysis.
Reagents. Powdered sodium borohydride and sodium methylar-
sonate were obtained from Ventron Corp., Beverly, Mass. Dimeth-
ylarsinic acid was obtained from Research Organic/Inorganic Chemi-
cal Corp., Sun Valley, Calif. Oxalic acid and other reagent grade
chemicals used were obtained from Matheson, Coleman and Bell
Corp., East Rutherford, N.J. Sodium arsenate and sodium arsenite
were Baker Analyzed Reagents grade. All non-arsenic reagents must
be analyzed for the presence of traces of the various arsenic com-
pounds. Methylarsenic acid compounds were analyzed for purity by
acidimetric titration. Airco laboratory grade helium has been used
with no purification.
Sodium borohydride used for reductions should be low in carbonate
ion content. Commercial aqueous solutions of sodium borohydride
have been found to contain much larger amounts of carbonate ion
than the powders. Although the carbon dioxide trap prevents inter-
ference in arsine detection, large amounts of carbon dioxide can in-
terfere in methylarsine detection. Prepared solutions of 2% sodium
borohydride in distilled water were kept in a closed plastic dispenser
bottle to avoid absorption of carbon dioxide from air.
Standards. Stock solutions of from 500 to 1000 ppm of the several
arsenic compounds were prepared in distilled water. These were
reasonably stable for several days to approximately one week. Serial
dilutions, usually 1 : l O O of the stock solutions were made. Diluted
solutions had to be prepared fresh each time a calibration sample was
needed; their arsenic content decreased perceptibly in 15-30 min.
Microliter range syringes (1-10) were used to sample the diluted
standard solutions.
Instrument Parameters. The 228.81 nm or 234.98 nm atomic
emission lines for arsenic are the most sensitive (7) but the former was
used in most work. Each has approximately the same sensitivity if a
1P28 photomultiplier (PM) tube is used. Slit widths used were from
100 to 200 pm. Photomultiplier voltages used ranged from 900 to 1050
V. The slit width and P M tube voltage may be adjusted to whatever
voltage range is desired to meet sensitivity. At these settings and with
a 40-mA discharge current, output currents of the photomultiplier
module were in the 1 X 10-8-1 X A range. A chart speed of 4
inchedmin was used.
Procedure for Inorganic Arsenic(II1). Samples containing from
0 to 100 ng of arsenic in up to 70 mL of solution are neutralized, if
necessary, and placed in a clean bubbler. To this is added 1-3 mL of
5% potassium biphthalate. The sample should now be approximately
pH 3.5-4. Carrier gas is then allowed to pass through the system at
300-350 mL/min for 1-2 min to flush out air. The U-trap is then
connected and cooled by the liquid nitrogen trap. Two milliliters of
2% sodium borohydride is then added and the system is allowed to
stand with the carrier gas passing through it for 5 min. The discharge
is turned on 1 min prior to analysis and allowed to warm up. The liquid
nitrogen flask is removed and arsine passes through the carbon
dioxide trap into the detector. A small fraction of dimethylarsine and
trimethylamine may also be detected. The system is then prepared
for the next analysis. The U-trap is disconnected from the system and
heated while passing carrier gas through it to remove water prior to
reuse.
Procedure for Arsenic(V). A sample just analyzed for arsenic(II1)
according to the previous procedure may be further analyzed for ar-
senic(V). The sample is buffered to pH 1-1.5 by adding 5 mL of a
saturated solution (approximately 10% wt/vol) of oxalic acid in water.
After assembling the trapping system, four additions of 2 mL of 2%
ANALYTICAL CHEMISTRY, VOL. 49, NO. 4, APRIL 1977 623
Table IV.Reproducibility of Water Analyses
Golf Course Pond (10-mL samples)
Arsenic compound
+
As(II1 V)
Methylarsenic acid
Dimethylarsenic acid
Trimethylarsine
Lake Carroll (25-mL samples)
+
As(I1 V)
Methylarsonic acid
Dimethylarsenic acid
Trimethylarsine compounds
DMAA Standard in distilled water, replicates, (25-mL Samples)
20.0 f 0.49 ng (s.d.), 2.5% rel, N = 5
sodium borohydride each are made at 30-8intervals. Carrier gas is
passed through the system for 6 min. Arsine in the U-trap is measured
as in the prior procedure. The balance of dimethylarsine and tri-
methylamine and all of the methylamine produced will also be de-
tected.
Procedure for Total Inorganic Arsenic and Alkylarsenic
Compounds. It is most convenient to analyze samples for total in-
organic arsenic compounds and alkylarsenic compounds in a single
procedure. Samples are neutralized, if necessary, and are buffered by
addition of 5 mL of oxalic acid reagent. Four 2-mL additions of 2%
sodium borohydride are made 30 s apart. After collectionof the arsines
for 6-8 min, the liquid nitrogen trap is removed. Arsine is passed
through the carbon dioxide trap. The methylarsines bypassed around
it while heating the U-trap.
RESULTS AND DISCUSSION
Response a n d Limits of Detection. Response curves for
the four arsenic compounds studied were found to be linear
from the limit of detection near 1 ng to the upper limit of
sample sizes studied, 100 ng (as As). Table I11 gives typical
calibration curves for four arsenic compounds. The four ar-
senic compounds give approximately the same calibration
curve based upon response as arsenic.
The uncertainty in detecting small amounts of the arsenic
compounds in the 1-10 ng range as measured by the noise level
of the discharge response was found to be: 0.2 ng for arse-
nic(II1) and (V), 0.2 ng for methylarsonic acid, and 1 ng for
dimethylarsinic acid and trimethylamine. Dimethylarsinic
acid has a poorer limit of detection, likely because it is evolved
from the cold trap more slowly than the other arsines and
background noise is integrated over a larger time period.
Concentration limits of detection calculated using 50-mL
samples range from 0.004 to 0.02 ppb (as arsenic).
Interferences. Any volatile compounds which are scrubbed
out of the reaction chamber and which are evolved out of the
U-trap prior to water can be an interference if present in
sufficient amounts to increase the background emission, or
if they quench arsenic emission. I t is possible by wavelength
scanning to determine if detected peaks are arsenic line
emission or background or band emission. Fortunately, few
compounds encountered in environmental samples have the
requisite volatility. None have been observed in any appli-
cation of the method.
A number of metal ions were tested for interference in the
method for inorganic arsenic. The following ions were not an
interference a t 20 ppm: A13+, Cd2+, C r ~ 0 7 ~ Fe3+,
-, Mn2+,
Ni2+,Pb2+,Zn2+,NO3-, Br-, and HP0d2-. The ions Ag+ and
Cu2+ at 20 ppm partially inhibit arsine evolution, but had no
effect at 2 ppm. Seawater and a number of fresh waters had
no effect on evolution of the arsines.
624 ANALYTICAL CHEMISTRY, VOL. 49, NO. 4, APRIL 1977
Total found, as As
64 f 4.2 (s.d.) ng, 6.5% rel, N = 4
74 f 4.4 (s.d.) ng, 5.9% rel, N = 4
trace
not detected
50 f 5.5 (s.d.) ng, 11%rel, N = 3
4.39 f 0.23 (sad.)ng, 5.2%rel, N = 3
6.31 f 0.38 (s.d.) ng, 5% rel, N = 4
5.31 f 0.44 (sod.)ng, 8.4%rel, N = 3
Silver and copper in interferences were removable by
passing sample solutions through a cation exchange column
in the ammonium ion form. The Amberlite IR124 (Rohm and
Haas) exchange resin had no arsenic blank background.
Samples which contain large amounts of surface active
materials may foam excessively. T o prevent this, 1-3 mL of
a 0.1% (wt/vol) solution of Anti-Foam B (Technicon product)
may be added to the sample.
Antimony does not interfere in the arsenic analysis in a ratio
of up to at least 1001, despite the fact that it is reduced to
stibine under the same conditions. If comparatively large
samples of arsenic, over 1 pg, are run through the detector,
small amounts may deposit in the chamber. This arsenic is
removed by the stibine vapor and can lead to a positive arsenic
signal. Deposition of arsenic in the discharge can also decrease
the signal response by blocking the light path. Removal of
deposited arsenic was done by injection of air or ammonia
vapors into the discharge while it was operating. Samples
containing up to a t least 100 ng of arsenic did not deposit ar-
senic in the detector chamber a t an appreciable rate.
Identification of Arsenic Compounds. Comparison of
retention times for detected compounds to that of methylar-
senic standards is useful for identification. The disappearance
of arsenic peaks (by analysis of samples a few angstroms off
of the arsenic emission line) indicates the presence of arsenic
compounds. The pH effect on reduction of arsenic compounds
may also be used. Analysis at pH 4-5 will eliminate signals of
inorganic arsenic(V) ions, methylarsonic acid and most of the
dimethylarsinic acid present. Thus, disappearance of these
peaks by pH effect is also positive evidence of the presence of
arsenic acids. GC-mass spectroscopy has also been used to
positively identify the methyl arsines.
Applications. The analytical procedures have been used
for the analysis of a variety of samples in environmental
chemistry studies. Lakes and rivers in the Tampa Bay, Florida
area, seawater, human urine, and various types of biological
materials (3, 14, 15) have been analyzed.
Analysis of air particulate and of filtered air for the arsines
(11, 16) has been successfully carried out. Air particulate on
glass wool is analyzed after tearing apart the filter pad in a
small amount of 0.05 N NaOH. Inorganic arsenic appears to
be completely trapped by the Gelman Instrument Co. type
A glass fiber filters used. No apparent volatility of AS203 was
observed in the air analysis work reported (11)as none was
ever observed on the silvered bead column used under each
filter pad to pick up alkyl arsines.
Reproducibility of the procedures for the replicate analyses
of water samples is given in Table IV. The standard error of
the technique which is approximately f10% relative is likely
satisfactory for most trace analysis applications.
 LITERATURE CITED
(1) "Arsenic in the Environment-An Annotated Bibliography", Oak Ridge
National Laboratory, Oak Ridge, Tenn., ORN-2-EIS-73-16 (1973).
(2) R. M. Sachs, F. 8. Anastasia, and W. A. Wells, Proc. Northeast. Weed
Control Conf., 24, 316 (1970).
(3) R. S. Braman and C. C. Foreback, Science, 182, 1247 (1973).
(4) D. L. Johnson and M. E. Q. Pilson, Anal. Chim. Acta, 58, 289 (1972).
(5) S. A. Peoples, J. Lakso, and T. Lais, Proc. West. Pharmacol. Soc.,14, 178
(1971).
(6) C. J. Sonderquist, D. G. Crosby, and J. B. Bowers, Anal. Chem., 46, 155
(1974).
(7) R. S. Braman. L. L. Justen, and C. C. Foreback, Anal. Chem., 44, 2195
(1972).
(8) Y. Talmi hnd D. T. Bostick, Anal. Chem., 47, 2145 (1975).
(9) Y. Talmi and V . Norvell, Anal. Chem., 47, 1510 (1975).
(10) J. S.Edmonds and K. A. Francesconi,Anal. Chem., 48, 2019 (1976).
Band Broadening Studies Using Parameters for an Exponentially
Modified Gaussian
R. E. Pads1 and L. B. Rogers*
Department of Chemistry, University of Georgia, Athens, Ga. 30602
The effects on chromatographic peak shape of dead volume
and flow rate have been examined using the standard devlatlon
of the Gaussian component of the peak and the exponential
decay constant. For a nonretalned solute, addltlon of dead
volume led to an increase in the standard devlation that was
Independent of flow rate while the decay constant was ln-
versely proportional to the flow. Smaller changes were ob-
served for a retalned species.
A gas chromatographic column is normally assumed to act
as a Gaussian operator, broadening the 6 input into a Gaussian
distribution as it passes through the column. However, pure
Gaussian peaks are not found experimentally. This is because
noncolumn factors such as dead volume, detector time-con-
stants, and injection profile convolute the Gaussian distri-
bution. Schmauch ( I ) , as well as Johnson and Stross ( 2 ) ,have
shown that detector dead-volume will exponentially modify
a chromatographic peak. McWilliam and Bolton (3) have also
shown that time constants of detector-amplifier systems will
exponentially convolute a Gaussian input profile. For these
reasons, an exponentially modified Gaussian has been widely
used as a model for chromatographic peak shapes.
Several workers (4-6) have applied an exponentially
modified Gaussian as a model in the least-square fitting and
deconvolution of chromatographic peaks. An exponentially
modified Gaussian is generated by the following integral:
N Reagents. Helium (Selox, Inc.) was used as the carrier gas after it
f(t) = --
r u v z
where N is the peak amplitude, t~ is the center of gravity of
the Gaussian component, u is the standard deviation of the
Gaussian, r is the time constant of the exponential decay and
t' is a dummy variable of integration. The width of an expo-
nentially modified Gaussian has two components: u, a sym-
metrical component due to the original Gaussian distribution
Present address, Amoco Research Center, P.O. Box 400, Naper-
ville, Ill. 60540.
(1 1)D. L. Johnson and R. S.Braman, Chemosphere, 6, 333 (1975).
(12) R. S. Braman and A. Dynako, Anal. Chem., 40, 95 (1968).
(13) R. S.Braman, Anal. Chem., 43, 1462 (1971).
(14) D. L. Johnson and R. S.Braman, Deep-sea Res., 22,503 (1975).
(15) C. C. Foreback, Ph.D. Thesis, University of South Florida, Tampa, Fla.,
1973.
(16) R. S. Braman, "Arsenic in the Environment" in "Arsenical Pesticides",
E. A. Woolson, Ed., American Chemical Society, Washington, D.C.,
1975.
RECEIVEDfor review October 1, 1976. Accepted December
23,1976. The support of this research by the National Science
Foundation, RANN program, under grants No. GI-43753, and
AEN 74-14598 A01 is gratefully acknowledged.
and, r, a nonsymmetrical contribution due to the exponential
decay. These two width terms are additive to give the second
moment or peak variance.
Mz = u2 + r2 (2)
Sternberg (7)has published a comprehensive review of
extra-column broadening and discussed the contributions to
the peak variance of input profile, connecting tubing, and
detector time Constants. He distinguished contributions from
mixing chambers, diffusion chambers, and tubing-diameter
expansions. Several workers ( I , 2, 8, 9) have published on
extra-column factors, especially on the effects on column ef-
ficiency of dead volume, such as connecting tubing, fittings,
and detector volume. Perhaps the most extensive experi-
mental study on the effects of dead volume on column effi-
ciency has been that by Maynard and Grushka (IO).In that
work they showed that pre-column dead volume degraded
column efficiency more than post-column dead volume. They
also showed that dead-volume effects were much larger for
nonretained species, and that expansions in tubing diameter
seriously affected column performance even if the expansion
occurred after the column.
The purpose of this study was to briefly examine the effect
of pre-column dead volume on the values of c and r for a
chromatographic peak. Post-column effects were not exam-
ined because they were reported to be small (10).
EXPERIMENTAL
had been purified by passage over a molecular sieve. Methane and
n-pentane (spectrophotometric grade, Aldrich Corp., East Ruther-
ford, N.J.) were used as solutes. Chromosorb W, 100/120 mesh, and
SE-30 silicone stationary phase were obtained from Alltech Associates
(Arlington Heights, Ill.).
Apparatus. A large chromatographic oven described earlier (11)
was used in this study. The temperature in the oven was controlled
by a Thermatrol proportional controller (Hallikainen Instrument Co.,
Richmond, Calif.). The oven temperature was measured using a
platinum resistance thermometer (Omega Engineering Inc., Stamford,
Conn.) in conjunction with a digital multimeter (Keithley Instru-
ments, Cleveland, Ohio).
Carrier gas was fed to the sampling valve through 1.5 m of capillary
tubing so that back-diffusion of the sample into the gas supply would
be negligible. Carrier gas flow was controlled by a Millaflow pressure
regulator (Veriflow Corp., Richmond, Calif.) and a manual flow
ANALYTICAL CHEMISTRY, VOL. 49, NO. 4, APRIL 1977 625