Fresenius' Joumal of
Fresenius J Anal Chem (1990) 337:721 -728
Applications of ICP-MS in marine analytical chemistry
J. W. McLaren, K. W. M. Siu, J. W. Lam, S. N. Willie, P. S. Maxwell, A. Palepu*, M. Koether**, and S. S. Berman
Analytical Chemistry Section, Chemistry Division, National Research Council of Canada, Ottawa, Ontario K1A OR9, Canada
Summary. The versatility of ICP-MS in marine analytical
chemistry is illustrated with applications to the multielement
trace analysis of two recently released marine reference mate-
rials, the coastal seawater CASS-2 and the non-defatted
lobster hepatopancreas tissue LUTS-I, and to the determina-
tion of tributyltin and dibutyltin in the harbour sediment
reference material PACS-I by HPLC-ICP-MS. Seawater
analyses were performed after separation of the trace
elements either by adsorption on immobilized 8-hydroxy-
quinoline or by reductive coprecipitation with iron and pal-
ladium. Simultaneous determination of seven trace elements
in LUTS-1, including mercury, by isotope dilution ICP-MS,
was achieved after dissolution by microwave digestion with
nitric acid and hydrogen peroxide. Butyltin species in PACS-
1 were separated by cation exchange HPLC of an extract of
the sediment; method detection limits for tributyltin and
dibutyltin in sediment samples are estimated to be 5 ng Sn/
g and 12 ng Sn/g, respectively.
Introduction
Since the inception of the National Research Council of
Canada (NRCC) Marine Analytical Chemistry Standards
Program (MACSP) in 1976, a major portion of the research
capacity of our laboratory has been devoted to the develop-
ment of methods for the determination of trace elements in
marine samples, and the production of a family of marine
reference materials including both fresh and saline natural
waters, marine sediments, and biological tissues. The addi-
tion of inductively coupled plasma mass spectrometry (ICP-
MS) to our existing array of techniques for inorganic trace
analysis in 1984 has made a considerable impact on MACSP.
In some cases, the effect has been the replacement of a
formerly used method by virtue of the superior performance
of ICP-MS. For example, ICP-MS has largely supplanted
inductively coupled plasma atomic emission spectrometry
(ICP-AES) for the determination of trace elements in natural
water samples because of its much superior detection power.
The capability of ICP-MS for isotope ratio determinations
has also been heavily exploited in our laboratory in the
performance of isotope dilution analyses formerly carried
out by spark source mass spectrometry (SSMS). In other
cases, ICP-MS has complemented other techniques in
Offprint requests to. J. W. McLaren
* Summer assistant 1988
** Summer assistant 1989
@ Springer-Verlag 1990
enabling the certification of additional elements for which
there were previously an insufficient number of independent
methods of adequate sensitivity. For example, ICP-MS data
have been combined with results obtained by graphite
furnace atomic absorption spectrometry to permit the certifi-
cation of tin concentrations in a number of marine sediments
and biological tissues [1]. Another complementary effect has
been the use of ICP-MS as a very sensitive and selective
detection technique for high performance liquid chromatog-
raphy (HPLC) to address questions of chemical speciation,
for selected elements such as arsenic and tin, as, for example,
in the determination of arsenic speciation in a dogfish muscle
reference material [2].
In this paper the versatility of ICP-MS in marine analyti-
cal chemistry is illustrated with three applications carried
out in the past year: the determination of 11 trace elements
in the coastal seawater reference material CASS-2 after sepa-
ration by two preconcentration techniques, the multielement
analysis of the non-defatted lobster hepatopancreas tissue
LUTS-I, and the quantitation of tributyltin and dibutyltin in
the harbour sediment reference material PACS-1 by HPLC-
ICP-MS.
Experimental
Instrumentation
A Perkin-Elmer SCIEX (Thornhill, Ont., Canada) in-
ductively coupled plasma mass spectrometer was used for
all of the work. Samplers and skimmers were either the all-
nickel or Pt-tipped nickel type provided by the manufac-
turer; sampler and skimmer orifice sizes in either case were
1A4mm and 0.89 ram, respectively. Standard operating
conditions for aqueous sample introduction were as follows:
plasma Ar, 12 1 rain-l; auxiliary Ar, 2 1 rain-l; nebulizer
Ar, 0.9 1 rain-l; R. F. forward power, 1.2 kW; sampling
depth, 15 mm from the top of the load coil. Thermal mass
flow controllers were used for both the nebulizer and auxili-
ary gas flows. The instrument has been fitted with the
"organics kit" (offered as an accessory by the manufacturer),
which includes a thermostatted nebulizer spray chamber. A
glass concentric nebulizer (Model TR-30-C2, J. E. Meinhard
Associates, Santa Ana, CA, USA) was used throughout this
work.
The HPLC system used for the tin speciation work
consisted of two dual-piston reciprocating pumps (Waters
Model 6000), a gradient controller (Waters Model 680), a
valve injector (Rheodyne Model 7125) with either a 100 gl
or 200 gl loop, and a 10 ~tm strong cation exchange column
722
(Whatman SCX, 2 5 0 m m x 4 . 6 m m ) . A second valve
(Rheodyne Model 7010), installed immediately after the
column, allowed passage of the column effluent either to
waste or to the nebulizer of the inductively coupled plasma
mass spectrometer via a 0.5 m length of 0.25 mm I.D. Teflon
tubing. Standard operating conditions for HPLC-ICP-MS
were as follows: plasma Ar, 14 1/min; auxiliary Ar, 2 l/rain;
nebulizer Ar, 0.75 l/rain; RF forward power, 1.4 kW. The
recirculating bath for thermostatting of the spray chamber
was set at 0 °C.
Reagents
All acids were purified by subboiling distillation of reagent
grade feedstocks in quartz or Teflon stills. "Tin-free" hy-
drogen peroxide (Perone 30EG) was obtained from DuPont
Chemicals and Pigment Dept. (Wilmington DE, USA).
High purity water is obtained by passing laboratory
distilled water through a deionization system. Enriched
stable isotopes were purchased from either the Oak Ridge
National Laboratory (Oak Ridge, TN, USA) or US Services
Inc. (Summit, NJ, USA). Stock solutions of these isotopes
were prepared as previously described [3].
The purity of butyltin compounds purchased from
commercial sources (Alfa Inorganics or Aldrich Chemical)
was confirmed by HPLC-ICP-MS. Solutions of these were
usually made up in methanol and refrigerated when not in
use. Solution concentrations were standardized against an
inorganic tin standard using flow injection ICP-MS.
Solvents were "distilled-in-glass" grade (Caledon Scientific).
Ammonium dibasic citrate was Fisher reagent grade.
The reference materials CASS-2, LUTS-I, and PACS-I
are members of a family of marine reference materials avail-
able from the NRCC Marine Analytical Chemistry
Standards Program. Detailed information on the prepara-
tion, composition and procurement of these materials is
available from Dr. S. S. Berman.
Separation/preconcentration procedures for seawater analysis
All sample preparations were performed in a clean labora-
tory with laminar air-flow benches and fume cupboards pro-
viding a class 10 working environment. For both the pre-
concentration procedures described below, 900 ml seawater
samples were used.
The use of a method involving preconcentration by
adsorption on silica-immobilized 8-hydroxyquinoline (I-8-
HOQ) in combination with ICP-MS has been described in
detail in two previous publications [4, 5]. For 900 ml samples,
it yields a concentration factor of 90. It involves separation
of trace elements by passage of the sample through a small
column of I-8-HOQ at a rate of 10 - 20 ml min- l, followed
by elution with about 10 ml of a 1 mol/1 hydrochloric acid/
0.1 mol/1 nitric acid mixture. This solution is evaporated to
dryness to remove HC1, and the "residue" is redissolved in
10 ml of 0.1 tool/1 HNO3.
A second preconcentration method, involving reductive
coprecipitation of trace elements, reported by Nakashima et
al. [6], was found to be suitable for use with ICP-MS with
only a slight modification to eliminate the use of hydro-
chloric acid. After the addition of 2 mg each of iron and
palladium (as aliquots of concentrated stock solutions) to
the CASS-2 sample (filtered and acidified to pH 1.6 at the
time of sampling) the pH was adjusted to 8 . 5 - 9 . 0 with
ammonium hydroxide solution. Precipitation was induced
by addition of 6 ml of a 6% sodium borohydride solution.
After 15 h standing, the mixture was passed through a
25 mm diameter, acid washed, acid resistant cellulose nitrate
0.45 gm membrane filter (Sartorius). The precipitate was
washed with deionized distilled water, then dissolved by
passage of 3 ml of nitric acid and subsequent water washings
through the filter. The final volume of the solution was
15 ml; thus, the procedure affords a nominal concentration
factor of 60.
Chromium, nickel, copper, zinc, molybdenum, cadmium,
lead and uranium were determined in CASS-2 by isotope
dilution ICP-MS, using the following reference/spike isotope
pairs: 52Cr/53Cr, 6°Ni/62Ni; 63CH/65Cu; 66Zn/68Zn; 98M0/
l°°Mo; ll4Cd/iilCd; 2°Spb/2°Tpb; and 238U/235U. The
isotopic spikes were added to selected bottles of CASS-2 at
least 24 h prior to removing aliquots for processing. The
ICP-MS methodology has been described in detail in two
previous publications [4, 5]. Cobalt, manganese and arsenic
were determined by the method of standard additions.
Dissolution and analysis of lobster hepatopancreas LUTS-1
The non-defatted lobster hepatopancreas reference material
LUTS-1 is supplied as a stabilized suspension containing
85% water [7]. Although aliquots of up to 3 g of this
suspension have been subjected to the following microwave
digestion procedure, an aliquot of 1.5 g is recommended for
routine use. Microwave digestions were performed with a
commercially available oven (Model MDS 81, CEM Corp.,
Indian Trail, NC, USA), with a maximum rated power of
600 W, equipped with a model PM pressure transducer for
monitoring the internal pressure of one of the digestion
vessels. The use of this equipment in our laboratory for
dissolution of biological tissues with mixtures of nitric and
perchloric acids [8] and with mixtures of nitric acid and
hydrogen peroxide [9] has been previously reported. All
digestions in this work were performed with the standard
120 ml Teflon PFA pressure relief type vessels. The proce-
dure differed from that described in Ref. [9] in that hydrogen
peroxide was not added until maximum power was first used
to raise the pressure to about 3.5 atm, after which reduced
power was used to maintain this pressure for 10 rain. A
second digestion was carried out after cooling of the vessels,
controlled release of excess pressure, and addition of I ml of
"tin-free" hydrogen peroxide. (Most commercially available
reagent grade H20 2 contains part-per-million levels of tin
added as a stabilizer. The presence of a high level of tin not
only precludes the determination of trace tin in biological
materials, but can also degrade the accuracy of cadmium
determinations because of the tin isobaric interferences on
several of the most abundant Cd isotopes). The second
microwave digestion, of 5 min duration, was also initiated
with maximum power heating, with power reduction as re-
quired to avoid exceeding an internal pressure of 4 arm.
After cooling and uncapping, the contents of the vessels were
gently evaporated to dryness on a 130°C hot plate. The
residues were redissolved in deionized distilled water after
the addition of 0.5 ml HNO3, and diluted to a final volume
of 10 ml.
Nickel, copper, zinc, strontium, cadmium, mercury and
lead were determined by isotope dilution ICP-MS using the
following reference/spike isotope pairs: 6°Ni/62Ni; 63Cu/
65Cu; 66Zn/68Zn; 88Sr/S6Sr; ll4Cd/lilCd; 2O2Hg/Z°lHg;

and 2°Spb/2°7pb. The isotopic spikes were added to the
samples prior to the first digestion. The methodology has
been previously described in detail [10, 11]. The mono-
isotopic elements manganese and cobalt were determined by
the method of standard additions.
Extraction procedures for determination of butyltin species
in the marine harbour sediment reference material PACS-1
by HPLC-ICP-MS
Two procedures which had previously been shown to be
suitable for the extraction of butyltins from marine sedi-
ments [12] were evaluated for use with HPLC-ICP-MS. Pro-
cedure A is effective for tributyltin (TBT) and dibutyltin
(DBT), but not monobutyltin (MBT), while Procedure B
can be used for the extraction of all three species.
Procedure A. A mixture of 4 ml methanol and 8 ml hydro-
chloric acid was added to a 4 g subsample of sediment
(spiked with appropriate quantities of butyltins if desired)
in a 50 ml borosilicate glass centrifuge tube. The mixture
was agitated in an ultrasonic bath for 1 h, after which 4 ml
of a mixture of hexane and isobutyl acetate (80: 20 v: v) were
added. The sample was then shaken mechanically for 45 rain.
A known volume (usually 0.4 ml) of the hexane/isobutyl
acetate layer was drawn off the mixture and evaporated to
dryness under a stream of nitrogen. (It was difficult to re-
move more than this amount without disturbing a "plug" of
solid organic matter from PACS-I suspended at the interface
between the two liquid phases.) The dry residue was ex-
tracted with a few ml of a 0.18 tool/1 solution of ammonium
citrate in a methanol/water mixture (60:40, v:v). This ex-
tract was then diluted to 25 ml with the ammonium citrate
solution.
Procedure B. This procedure was almost identical to Proce-
dure A with the exception that a mixture of toluene/isobutyl
acetate (80:20, v:v) containing 1.5% (w:v) tropolone
(2-hydroxy-2,4,6-cycloheptatrien-l-one) was substituted for
the hexane/isobutyl acetate mixture in the second extrac-
tion step.
Chromatographic procedure for the separation
of butyltin species
The separation of all three species involved a gradient elution
with 0.3 tool/1 ammonium citrate in a methanol/water
mixture (60: 40, v: v) with a step pH change from 6 to 3 after
the first minute. This pH change was necessary to elute
the presumably triply-charged, and hence strongly-bound,
monobutyltin species from the column. The flow rate was
1 ml/min.
All of the PACS-1 analyses reported here involved the
determination of only TBT and DBT (see next Section). For
this purpose, it was possible to use a simplified chromato-
graphic procedure involving ±socratic elution with a mobile
phase of 0.18 tool/1 ammonium citrate in methanol/water
(60: 40, v: v) at pH 6, at a flow rate of 1 ml/min.
Determination of tributyltin and dibutyltin in PACS-1
The concentrations of tributyltin and dibutyltin in PACS-I
were determined by the method of standard additions. For
each analysis, extracts were prepared from one or more
723
Table 1. Precision and accuracy of isotope ratios determined by ICP-
MS for a 100 ggl i multielement solution
Ratio Expected value" Found b
53Cr/S2Cr 0.1134 0.1196 ± 0.0017
6SCu/63Cu 0.4457 0.4641 ± 0.0013
6aZn/66Zn 0.6738 0.6899 ± 0.0043
67Zn/66Zn 0.147 0.1478 ± 0.0016
111Cd/114Cd 0.4455 0.4466 ± 0.0014
2°6pb/2°SPb 0.4612 0.4763 _+0.0028
2°TPb/2°SPb 0.4218 0.4284 ± 0.0034
2°4pb/2°aPb 0.0272 0.0287 ± 0.0003
Based on IUPAC recommended natural abundances except for
Pb, for which data are for NIST SRM 981
b Means of 6 determinations; precision expressed as the standard
deviation
unspiked 4 g samples ofPACS-1, one or more samples spiked
with 4 gg (as Sn) of tributyl- and dibutyltin, and one or
more samples spiked with twice this amount. Each of these
solutions was run at least twice, so that the minimum number
of data points in the standard additions calculation was 6,
and the usual number was 1 0 - 1 6 .
The HPLC-ICP-MS chromatograms were recorded with
the ELAN "multiple elements display" software configured
for single ion monitoring at m/z 120. Data acquisition was
manually triggered immediately after the sample injection.
Subsequently, the data were transferred via the printer port
to an off-line computer for further processing with custom
software which yields both peak height and peak area data.
Throughout this study, results obtained by using peak height
and peak area measurements were almost identical.
Results and discussion
Precision and accuracy of isotope ratio measurements
The isotope ratio data presented in Table I are typical of the
precision and accuracy that can be routinely achieved with
ICP-MS. The results are mean values of six determinations
of selected isotope ratios for a 100 ggl-1 multielement stan-
dard. Each determination comprised 200 cycles of repetitive
"peak-hopping" through the list of selected isotopes, with
dwell times as short as 25 ms for the more abundant isotopes,
and required 200 s. It can be seen that the precision of the
ratios, expressed as % R.S.D., ranges from 0.28% (for 65Cu/
63Cu) to 1.4% (for 53Cr/52Cr) but that, in general, a pre-
cision of 1% R.S.D. or better can be routinely achieved for
ratios likely to be measured in isotope dilution analyses. The
relatively poor precision for the 53Cr/S ZCr ratio is probably a
result of the relatively large correction for isobaric in-
terference at m/z 52 from 36ArO, which contributed more
than 10% of the total signal for 100 ggl- ~ Cr in this exper-
iment. The expected values for the isotope ratios are based on
invariant natural isotopic abundances for all of the elements
except lead, for which the N.I.S.T. (formerly N.B.S.) SRM
981 isotopic standard was used in the solution preparation.
Significant mass discrimination, for which a correction must
be applied to ratios measured for isotope dilution analyses,
is observed for some elements. Fortunately, these effects are
quite reproducible from day to day provided that major
changes are not made to the lens voltages of the mass
724

Table 2. Analysis of coastal seawater CASS-2 by isotope dilution Table 4. Analysis of coastal seawater CASS-2 by standard additions
ICP-MS. Preconcentration by I-8-HOQ adsorption. Results in ICP-MS. Results in ggl 1
ggl- 1
I-8-HOQ a BH4" Certified value b
Found a Certified value b
Co 0.039 ± 0.004 0.029 ± 0.002 0.025 ± 0.006
Cr 0.108 ± 0.005 0.121 ± 0.016 Mn 2.13 +_0.12 - 1.99 ±0.15
Ni 0.295 ± 0.010 0.298 ± 0.036 As - 1.03 ± 0.06 1.01 ± 0.07
Cu 0.669 ± 0.014 0.675 ± 0.039
Zn 1.96 ±0.05 1.97 ±0.12 a Mean values based on 6 replicates; precision expressed as the
Cd 0.021 ± 0.001 0.019 ± 0.004 standard deviation
Pb 0.030 ± 0.003 0.019 ± 0.006 b Precision expressed as the 95% confidence interval
U 2.78 _+0.02 -

" Mean values based on 8 replicates; precision expressed as the Table 5. ICP-MS analysis of lobster hepatopancreas LUTS-1 by
standard deviation isotope dilution and standard additions. Results in gg/g (wet weight)
b Precision expressed as the 95% confidence interval
Found Certified value

Table 3. Analysis of coastal seawater CASS-2 by isotope dilution Ni 0.235 ± 0.011 0.200 ± 0.034
ICP-MS. Preconcentration by BH4 reductive coprecipitation. Re- Cu 15.9 ± 0.2 15.9 ± t.2
sults in ggl- 1 Zn 12.4 ± 0.2 12.4 + 0.8
Sr 2.24 ± 0.04 2.46 ±0.28
Found a Certified value b Cd 2.18 __0.04 2.12 ___0.15
Hg 0.017 ± 0.002 0.0167 ± 0.0022
Cr 0.129 ± 0.003 0.121 ± 0.016 Pb 0.010 + 0.001 0.010 ± 0.002
Ni 0.328 ± 0.007 0.298 _+0.036 Mn 1.20 ±0.04 1.20 ±0.13
Cu 0.66 + 0.04 0.675 ± 0.039 Co 0.065 ± 0.008 0.051 ± 0.008
Zn 1.89 ±0.16 1.97 ±0.12
Mo 9.19 _ 0.08 9.01 ± 0.28
Cd 0.016 ± 0.001 0.019 -t- 0.004
U 2.76 ± 0.02 -
here for the first time. The latter procedure complements
a Mean values based on 8 replicates; precision expressed as the the I - 8 - H O Q m e t h o d in permitting the determination o f
standard deviation m o l y b d e n u m and arsenic, b o t h o f which are presumably
b Precision expressed as the 95 % confidence interval present in CASS-2 as oxy anions. Both methods tend to
give high results for cobalt, p r o b a b l y because o f isobaric
interference by 42CaOH on 59C0. The retention o f even a
spectrometer. Our general rule is to apply a correction for small fraction o f the calcium present in the seawater would
mass discrimination if the effect exceeds -L-_2 % ; thus for be sufficient to pose a problem, in view o f the very low cobalt
example the d a t a o f Table 1 would indicate that such cor- concentration.
rections were necessary for Cr and Cu, and possibly also for Both methods also yielded high results for lead, perhaps
Zn and Pb, depending u p o n the choice o f spike isotope. because of an underestimation of the blank. N o such
difficulty was encountered in the application o f the I - 8 - H O Q
procedure to the determination of Pb in the open ocean
Analysis of the coastal seawater reference material CASS-2 seawater reference material N A S S - 2 [5], at a level of
I C P - M S is now routinely applied to multielement analysis 0.039 ~tgl-2, nor in the analysis of the St. Lawrence River
o f fresh [ 1 3 - 1 6 ] and saline [4, 5] n a t u r a l waters. A l t h o u g h water reference material SLRS-1 [13].
the direct determination o f a considerable n u m b e r o f trace A l t h o u g h either of the separation/concentration meth-
elements in freshwater samples is feasible, seawater analysis ods used in our l a b o r a t o r y requires several hours, the ICP-
still requires a separation/preconcentration step which in our MS analysis time for each concentrate is well under 10 rain.
l a b o r a t o r y is accomplished either by a d s o r p t i o n on silica- A concentration factor o f 5 0 - 1 0 0 is more than adequate
immobilized 8-hydroxyquinoline (I-8-HOQ) or by reductive for the determination o f most o f the trace elements o f interest
coprecipitation with iron and palladium. The m u c h superior at levels as low as 1 0 - 2 0 ng1-1. In most cases, the power
detection power of I C P - M S over I C P - A E S for most of the of detection is limited by the procedural blank rather than
elements of interest permits the simultaneous determination by the determination step.
o f m o r e elements with far better precision and accuracy. Finally, it is noteworthy that b o t h procedures yield d a t a
Results obtained during the recent certification analysis for u r a n i u m which are in excellent agreement. A certified
o f the coastal seawater reference material CASS-2, presented value for U is unfortunately not available for CASS-2, but
in Tables 2 - 4 , illustrate the current performance o f ICP- the validity of the I - 8 - H O Q procedure has been demon-
M S for seawater analysis. A total o f eight elements (Cr, Ni, strated in previous analyses o f S L R S - I [13] and N A S S - 2 [5].
Cu, Zn, M o , Cd, Pb, and V) were determined by isotope
dilution I C P - M S , while an additional three m o n o i s o t o p i c
Analysis of the non-defatted lobster hepatopancreas reference
elements (Co, Mn, and As) were determined by the m e t h o d
material LUTS-I
of s t a n d a r d additions. While the use o f the I - 8 - H O Q proce-
dure in c o m b i n a t i o n with I C P - M S for seawater analysis has Isotope dilution I C P - M S results obtained for seven elements
been previously described [4, 5], I C P - M S results o b t a i n e d (Ni, Cu, Zn, Sr, Cd, Hg, and Pb) in the non-defatted lobster
after b o r o h y d r i d e reductive coprecipitation are reported h e p a t o p a n c r e a s reference material LUTS-1, plus s t a n d a r d

additions data for two monoisotopic elements (Mn and Co)
are presented in Table 5. It is noteworthy that the mercury
determinations were achieved simultaneously with those for
the other elements; although the complete retention of
mercury during the digestion procedure has not been demon-
strated, it appears that, if partial loss occurs, it must occur
after equilibration of the 2°1rig isotopic spike has been
achieved. Immunity to partial loss of the analyte after
isotopic equilibration has been attained is a particularly
significant advantage of isotope dilution methodology in the
case of mercury. Certainly, the simultaneous determination
of lead and mercury at levels below 20 ng/g in a biological
material, with a precision of about 10% R.S.D., with no
sample preparation other t h a n a straightforward dissolu-
tion, is an impressive example of the capability of ICP-MS
for the trace analysis of biological materials. The results for
manganese and cobalt add to previous evidence that good
data can be obtained by standard additions [10] or even a
simple external calibration [11, 17] in cases in which isotope
dilution is not applicable. The discrepancy between the ICP-
MS result for cobalt and the certified value may be the result
of isobaric interference by 42CaOH on 59Co.
The isotope dilution results shown in Table 5 are based
on 9 replicates prepared simultaneously by microwave diges-
tion. The total ICP-MS analysis time for each solution was
about 5 min, including a i min flushing time prior to data
acquisition. The simultaneous determination of copper, at a
solution concentration of about 1.6 mg1-1, and lead, at a
solution concentration of about 1 gg1-1, would not have
been possible without the use of the "Omnirange" feature
recently added to the Perkin-Elmer SCIEX ICP mass
spectrometer. This feature permits a reduction of the
sensitivity for selected elements in an element list, while
retaining full sensitivity for the others, by application of
appropriate d.c. offset voltages to the quadrupole rods. In
this work, an offset of 1.5 V was applied for ~3Cu, 65Cu,
86Sr, and 88Sr to reduce sensitivity for these elements in
order not to exceed the dynamic range of the detector. It was
demonstrated that application of this voltage caused only
small and reproducible changes in the 63Cu/65Cuand 88Sr/
86Sr isotope ratios measured at full sensitivity, and that
isotope dilution results for copper and strontium obtained
in this way were indistinguishable from data obtained in a
separate analysis in which overall instrumental sensitivity
was reduced by operating at a nebulizer gas flow rate of
0.7 1 min -1 rather than the usual 0.9 1 m i n - L It was also
confirmed that the application of rod offset voltages for the
copper and strontium isotopes had no effect on the results
obtained for any of the other elements, including zinc,
positioned between Cu and Sr in the peak-hopping routine
in which our normal procedure is to arrange the elements in
order of ascending mass. Although the manufacturer advises
caution in the use of Omnirange in applications involving
the measurement of isotope ratios (rather than simple ion
intensities), it appears from our results that this feature can
be used to extend the dynamic range in multielement isotope
dilution ICP-MS analyses.
A capability for performing isotope dilution mass spec-
trometric (IDMS) analyses is a very important component
of any reference materials program. The majority of IDMS
analyses to date have been accomplished by thermal ioniza-
tion mass spectrometry (TIMS); other techniques which
have been used are spark source mass spectrometry (SSMS),
electron impact ionization, field desorption mass spectro-
725
metry, and recently, ICP-MS [18]. It seems clear from our
own work and that of others [14, 19-26] that ICP-MS will
quickly become the dominant method for IDMS.
Prior to the advent of ICP-MS, all IDMS determinations
in our laboratory were achieved by SSMS [27]. ICP-MS
offers a number of advantages over SSMS, including greatly
reduced sample preparation and analysis time, better pre-
cision, and lower blanks because of the reduced sample
manipulation. The major advantage of ICP-MS over TIMS
for IDMS is its capability for rapid multielement analyses
without separations, which results in greatly reduced sample
preparation time. While TIMS is definitely capable of
superior precision in the measurement of isotope ratios, the
limiting factor with respect to precision in IDMS is usually
not the mass spectrometer, but rather the chemical treatment
of the sample, the blank problem and sample homogeneity
[18].
Application of HPLC-ICP-MS to trace element speciation
Several recent reports [2, 2 8 - 3 4 ] have demonstrated the
practical utility of inductively coupled plasma mass
spectrometry (ICP-MS) as a sensitive and selective on-line
detection method for HPLC in trace element speciation stud-
ies. Compatibility of the instrumentation with a range of
mobile phases typically used in ion pairing, ion exchange,
and size exclusion HPLC has been established. Reported
applications include the study of cadmium speciation in
cooked and uncooked pig kidney [31], the determination of
methylmercury in an albacore tuna research material and
of thimerosal in contact lens sterilizing solutions [32], the
identification and quantitation of arsenic species in a dogfish
muscle reference material [2], and the determination of gold
drug metabolites and related metals in human blood [34]. A
recent report by Suyani et al. [33] indicated the potential of
HPLC-ICP-MS for the determination of trialkyl and triaryl
tin compounds including tributyltin in environmental
samples. The compatibility of the ICP-MS instrumentation
with both ion pairing and ion exchange chromatography
was demonstrated and absolute detection limits in the range
of 0 . 4 - 1 . 0 ng were achieved. Our objective in this work was
to develop an HPLC-ICP-MS procedure suitable for the
simultaneous quantitation of tributyltin and its potential
breakdown products, dibutyltin and monobutyltin, and to
apply it to the determination of these species in PACS-I, a
relatively contaminated harbour sediment containing 41 ~g/g
total tin.
Optimization of lCP-MS operating conditions
for methanol/water mixtures
Prior to coupling of the HPLC apparatus to the ICP mass
spectrometer, solutions of proposed methanol/water mobile
phases containing 100 Ixg/1 of Sn were introduced into the
plasma in the normal manner to establish optimal operating
conditions. No problems of plasma instability were en-
countered with methanol/water mixtures containing up to
70% methanol if the plasma was operated at a forward
power of at least 1.4 kW, with the nebulizer gas flow rate at
0.75 l/rain and the sample solution delivery rate at 1 ml/min.
In fact, stable operation could be achieved with a forward
power as low as 1.2 kW, but a higher power was desirable
in order to achieve optimal sensitivity. The addition of oxy-
gen to the nebulizer gas stream, as reported by Suyani et al.
726

40000 40000-

BuSn 3+

,0000 Bu3so + 30000-

C
° 0- -

20000- 20000-

,.+-.

10000 - 10000- / ~

0 . . . . . . . . . . . . . . . . . . . . . . . . 0 .... i .... i .... ~ .... i .... n ....

0.0 2.0 4.0 6.0 8.0 10.0 12.0 0.0 2.0 4.0 6.0 8.0 10.0 12.0

time (rain) time (min)

Fig. 1. HPLC-ICP-MS chromatogram for a 200 ttl injection of a Fig. 2. HPLC-ICP-MS blank chromatogram obtained for the
standard containing 20 ng Sn/ml of each of TBT, DBT, and MBT gradient elution program for separation of TBT, DBT, and MBT
as shown in Fig. 1

[33], did not seem to be necessary. Although there was a very 40000-

noticeable envelope of blue-green emission (from molecular

carbon species) around the plasma, there was no observable Bu3Sn +
deposition of soot on the sampler after several hours of
30000-
continuous aspiration of a 70:30 methanol/water mixture.
Furthermore, a solution of 0.3 mol/1 ammonium citrate in
60 : 40 methanol/water could be run for long periods with no
2+
observable deposition. This solution, chosen as the mobile 2oooo- ~UzlSn
phase for separation of the 3 butyltin species by cation-
exchange HPLC, contains about 7% total dissolved solids,
well above the normal limit assumed for continuous sample
10000 -
introduction to an ICP mass spectrometer. The very high
tolerance of the instrument for ammonium citrate would
appear to be a serendipitous effect related to the relatively
high volatility of this particular salt and/or its breakdown 0 . . . . i . . . . i . . . . i . . . . i . . . . ~ . . . .
products. o.o 2.0 ~.o 8.o 8.0 ~o.o ~o
As expected for the instrument used in this work, the ti~ (mio)
changes in the plasma operating conditions to accommodate Fig. 3. HPLC-ICP-MS chromatogram for a 200 gl injection of an
a non-aqueous solvent did not necessitate any changes to extract of the marine sediment reference material PACS-1
the mass spectrometer lens voltage settings.

The chromatogram of an extract of the harbour sediment

Optimization of the chromatography for separation PACS-1 obtained by Procedure A run under the same
of butyltin species conditions is shown in Fig. 3. It is evident that this material
Initially it was assumed that quantifiable amounts of tri- contains easily quantifiable concentrations of TBT and
butyl-, dibutyl-, and monobutyltin would be extracted from DBT. Unfortunately, this cation exchange separation was
PACS-1, so a chromatographic procedure permitting the not compatible with extraction Procedure B; it appeared
separation of all three species was developed. The chromato- that the tropolone complexation of the butyltin species
gram obained from an injection of a mixture containing 4 ng interfered with their separation by this method. Since
(as Sn) of each species is shown in Fig. 1. The separation Procedure A was known not to be effective for the extraction
was achieved by a step gradient elution with 0.3 mol/1 ammo- of MBT, the chromatographic procedure was required to
nium citrate in 60:40 methanol/water in which the pH was separate only TBT and DBT. This was readily achieved by
changed from 6 to 3 after the first minute of elution. The isocratic elution with 0.18 mol/1 ammonium citrate in 60: 40
monobutyltin peak is superimposed on a background peak methanol/water at a flow rate of 1 ml/min.
which was always observed with this chromatographic pro-
gram, as can be seen from the blank chromatogram il-
Determination of TBT and DBT in PACS-1
lustrated in Fig. 2. This broad peak most likely arises from
the elution of inorganic tin scavenged from the mobile phase Results for TBT and DBT in PACS-1 obtained by HPLC-
and retained on the column at higher pH. During the 10 min ICP-MS are compared in Table 6 with data obtained by gas
re-equilibration of the column at pH 6 prior to the next chromatography with flame photometric detection and by
injection, the elevated background signal gradually returned ionspray MS/MS, and with the certified values. The certified
to a level of 300 - 500 counts/s. values were obtained from a database which includes all the

Table 6. Determination of dibutyltin and tributyltin in PACS-1
Technique Dibutyltin Tributyltin
ttg Sn/g dry weight
HPLC-ICP-MS 1.19 _+0.14(7) a 1.18 _+0.15(7)
GC-FPD b
Extraction procedure A 1.07 ± 0.31(8) 1.14 _+0.27(8)
Extraction procedure B 1.08 _+0.31(6) 1.11 _+0.33(7)
ISMS/MS c t.29 ± 0.07(5)
Certified value 1.16 ± 0.18 d 1.27 ± 0.22 d
a Precision expressed as standard deviation; number of replicate
analyses in parentheses
b Gas chromatography - flame photometric detection (Ref. [12])
c lonspray mass spectrometry/mass spectrometry (Ref. [36])
d Uncertainty of the certified values is expressed as a 95% confi-
dence interval
results obtained by the three methodologies developed in
this laboratory plus results from five external laboratories
which collaborated in the certification process, using their
own methods. (The same database yielded a certified value
of 0.28 + 0.17 gg/g for MBT). The TBT and D B T values
obtained by H P L C - I C P - M S are in excellent agreement with
the certified value.
An experiment was carried out .to assess the limitation
imposed on the precision of the results by the flow injection
mode of sample introduction. Sixteen 100 ~tl injections of a
20 p.g/1 solution of tin in the chromatographic mobile phase
(0.3 tool/1 a m m o n i u m citrate in 60:40 methanol/water) were
performed with the column temporarily removed from the
system. The relative standard deviation of the peak height
data was approximately 10%. The precision of data from
injections of separately prepared extracts subjected to chro-
matography cannot be better than this 10% value. It should
also be kept in mind that, while the flow injection replicates
could be obtained in only a few minutes, acquisition o f
the chromatographic data for a typical standard additions
analysis required several hours. A n y drift in the instrumental
sensitivity which occurred during this period would of course
add to the imprecision of the data. Also adding to the
variability for real samples will be any variation among the
spiked and unspiked samples in the recovery of the alkyltin
species in the extraction procedure.
Detecfion limits for T B T and D B T
The normal background signal observed during ±socratic
elution of TBT and D B T with 0.18 tool/1 a m m o n i u m citrate
in 60 : 40 methanol/water at p H 6 was 3 0 0 - 500 counts/s. If
it is assumed that the standard deviation of this signal is
roughly equal to its square root (i.e., that Poisson statistics
are obeyed), the estimated solution detection limits (based
on the usual 3 sigma criterion) for a 100 ~tl injection are
about 0.2 ng Sn/ml and 0.4 ng Sn/ml, respectively, for TBT
and DBT, i.e., 0.02 ng Sn and 0.04 ng Sn absolute. A detec-
tion limit was not calculated for MBT, but would be con-
siderably higher because of the much higher background
singal during the elution of this species at p H 3, as shown
in Fig. 2. The detection limit for TBT compares very
favourably with H P L C - L E I data recently reported by Epler
727
et al. [35] and with the H P L C - I C P - M S data of Suyani et al.
[331.
Detection limits for TBT and D B T in sediment samples,
estimated using mean sensitivity values from several sets of
standard additions data, were estimated at 5 ng Sn/g and
12 ng Sn/g, respectively.
Conclusion
In the five years since installation of one of the first
commercially available instruments in our laboratory, ICP-
MS has proven itself to be a very powerful and versatile
technique. Its impact on the N R C C Marine Analytical
Chemistry Standards Program can be summarized as
follows:
1. Use of ICP-AES for the determination of trace
elements in natural water reference materials has been
greatly reduced. Because of the far superior detection power
of ICP-MS, a much larger number of trace elements can be
directly determined in freshwater samples, and in
concentrates prepared from seawater samples.
2. ICP-MS has replaced SSMS for the performance of
isotope dilution analyses, an important component of any
reference materials program. The major advantages are
greatly reduced sample preparation and analysis time, and
improved precision.
3. ICP-MS is complementing other sensitive techniques
such as graphite furnace atomic absorption spectrometry in
permitting the certification of new elements for which there
were previously an insufficient number of independent meth-
ods of determination.
4. The use of ICP-MS in combination with H P L C offers
a powerful new approach to the determination of trace ele-
ment speciation which has been applied to arsenic speciation
in a fish tissue and to tin speciation in a harbour sediment.
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Received September 1, 1989