CHAPTER 14.
THE USE OF LASER ABLATION-ICP-MS IN THE ENVIRONMENTAL
SCIENCES
Geoff Veinott
Environmental Sciences Section; Science, Oceans, and Environment Branch,
Fisheries and Oceans Canada,
St. John’s, NF, A1C 5X1, Canada
INTRODUCTION
The joining of high powered lasers to
inductively coupled plasma-mass spectrometers
in the 1980’s produced an analytical tool that
could sample, in situ, ηg quantities of solid
materials and produce information on the isotopic
composition of the sampled material (Jackson et
al. 1992; Longerich et al. 1991; Moenke-
Blankenburg 1989). Geologists and metallurgical
scientists were the first to apply this technique,
now known as LA-ICP-MS (laser ablation-induct-
ively coupled plasma-mass spectrometry), to the
analyses of micro-structures. However, over the
past 10 years LA-ICP-MS has moved into the
field of environmental science. The technique has
been applied to the analysis of a variety of
biological structures (e.g. tree rings, mollusk
shells, otoliths, fin rays, and fish scales), which
can act as archives of environmental exposure.
Environmental scientists have been
drawn to LA-ICP-MS for the same reasons that
have attracted earth scientists; minimal sample
preparation, spatial resolution at the ηm scale,
and the reduction of spectral interferences offered
by a dry plasma. Unfortunately, the main chal-
lenge, that of fully quantitative analyses, has yet
to be achieved for many environmental matrices.
This chapter will review the application
of LA-ICP-MS in the environmental sciences,
discuss the strategies used to quantify the data,
and suggest future directions for this relatively
new analytical tool.
INCREMENTAL GROWTH STRUCTURES
Many plants and animals contain struct-
ures that are produced incrementally. That is, a
new layer of material is added to the structure
over some fixed time interval (annually, daily,
seasonally, etc.). Tree rings are the best known
example of an incremental growth structure. Each
year a tree produces two optically distinct layers
of woody material which can be counted to
determine the age of the tree.
Other, perhaps less well known,
213
incremental growth structures include mollusk
shells, bone, teeth, fish scales, and fish otoliths
(ear stones) (Figure 14.1). Each structure
produces optically distinct layers of material
which have been used to estimate age and growth
rates, and have been analyzed to determine their
chemical composition (see Outridge et al. 1995
for a review). The attraction of these structures to
environmental scientists is the possibility that the
growth structures would accumulate and preserve
information about an organisms environment at
the time of their formation. If a relationship could
be established between the composition of a layer
of shell, for example, and the ambient water
composition, then the shell chemistry would
become a predictor of the water chemistry. If the
shell material is not altered or resorbed after
deposition, the shell then would become a
permanent archive of the water chemistry.
Shells and otoliths are the two biological
structures most commonly analyzed by LA-ICP-
MS. Both are hard calcified structures that are
preserved after death and the incremental layers
are not resorbed after formation. Coutant (1990)
suggested that chemical information contained in
otoliths may provide information on habitat use
and selection, timing of exposure to a pollutant,
timing of migrations from fresh to salt waters, or
temporal changes in water chemistry.
Outridge et al. (1995) published a review
of the application of LA-ICP-MS to incremental
structures including a discussion on how various
structures are formed. As well, Durrant (1999)
published a general review of LA-ICP-MS with
excellent discussions of the principles of lasers,
types of lasers, and laser-solid interactions, which
are also covered in other chapters in this volume.
Therefore, the remainder of this chapter will focus
on recent applications in environmental sciences,
calibration strategies, and the future of LA-ICP-
MS in environmental sciences.
LA-ICP-MS OF BIOLOGICAL MATERIALS
Otoliths and mollusk shells have
 A B

C D

Figure 14.1. Examples of incremental growth structures. A. Otolith, B. Fin Ray, C. Fish Scale, D.
Bivalve Shell. The fin ray (B) is reprinted from the Canadian Journal of Fisheries and Aquatic
Sciences, Vol. 56, Veinott, G. Northcote, T., Rosenau, M., and Evans, R.D. Concentrations of
strontium in the pectoral fin ray of the white sturgeon (Acipenser transmontanus) by laser
ablation sampling – inductively coupled plasma – mass spectrometry as an indicator of marine
migrations, pp. 1981-1990, Copyright (1999), with permission from NRC Research Press.

received the most attention from researchers using
LA-ICP-MS in the environmental sciences. The
reasons, as was mentioned above, are that these
structures are believed to reflect environmental
conditions, and they are not resorbed after
deposition. Also, shells and otoliths degrade very
slowly after the death of an organism. Shells have
been retrieved from ancient sediments and used
as indicators of past environmental conditions
(e.g. Von Grafenstein et al. 1994; Abell &
Williams 1989). The structures, therefore, have
tremendous potential for preserving information
about the environment in which an organism
lived.
In fisheries research LA-ICP-MS
analyses of various regions of the otolith,
corresponding to different life stages of a fish,
have led to some interesting discoveries. For
example, Milton et al. (1997) showed that the
variation in the chemistry of otolith nuclei from
tropical shad could not be explained by the
differences in water chemistry from the only two

214
 known spawning sites. They hypothesised that
other spawning sites must exist. Thorrold et al.
(1997), on the other hand, found no difference in
the chemistry of the otolith nuclei in Atlantic
croaker from different sites. However, they did
find a difference in the chemistry of the outer
edge of the otoliths. This was explained by a
movement of the fish from oceanic to estuarine
habitats prior to capture.
In a laboratory experiment Geffen et al.
(1998) exposed sand gobies, place, and sole to Pb
and Hg. They then analyzed, using LA-ICP-MS,
points on the otoliths corresponding to pre-
treatment, start of exposure, mid-way through
exposure, and at termination of exposure. The
sand gobies and the sole otoliths showed
significant increases in metal accumulation (Fig.
14.2), but the place did not. This type of
experiment simulates exposure that might occur
from an accidental spill and demonstrates the
ability of LA-ICP-MS to detect such exposure.
The Geffen et al. (1998) study also demonstrated
that there is not a simple relationship between
otolith composition and environmental
concentrations of metals. Growth rate,
physiology, and species all play a role in
determining the final otolith metal concentration.
As well, there is still some concern over
the accuracy and precision of LA-ICP-MS when
analyzing otoliths. For example, the otolith
studies mentioned above used frequency-
quadrupled (266nm) Nd:YAG lasers coupled to a
quadrapole ICP-MS (Q-ICP-MS) to determine
total metal concentrations. Yet, Thorrold and
Shuttleworth (2000) demonstrated that a sector
field-ICP-MS (SF-ICP-MS) might be better suited
for analyzing otoliths using laser ablation than a
Q-ICP-MS. By using the instrument in medium
resolution they were able to show that 48Ca2+ and
potassium oxide (39K16O) in otoliths were
interfering with 24Mg and 55Mn respectively.
Since these interferences are caused by the
sample matrix they can not be corrected for by
running an Ar blank. Therefore, Q-ICP-MS using
an Ar blank would overestimate the abundance of
Mg and Mn in otoliths.
Bivalves have been used extensively to
monitor the environment because of their ability
to concentrate metals (see Rainbow & Phillips
1993 for a review). Generally the soft tissue is
sampled, but soft tissue provides a time integrated
concentration value only. In other words, the
concentration of metals in the soft tissue reflects
accumulation of the metal over the entire life of
the organism or from the time of exposure
onward. Growth can dilute the metal
concentration and many organisms are capable of
regulating certain metals or releasing metals from
their tissue. Therefore, extensive sampling, which
is usually expensive, is the only way to obtain
data on temporal trends of contaminants in the
environment using bivalve soft tissue.

7 8
Otolith metal concentration
Otolith metal concentration

Lead levels in sole otoliths Lead levels in gobie otoliths

6 7
control 6 control
5
low dosage low dosage
5
4
(ug/g)
(ug/g)

high dosage high dosage

4
3
3
2
2
1 1
0 0
core mark midtreatment edge core mark midtreatment edge

Position on otolith Position on otolith

Figure 14.2. Lead levels in otoliths determined by LA-ICP-MS. Modified and reprinted
from Marine Ecology Progress Series, Vol. 165, Geffen, A.J., Pearce, N.J.G., and Perkins,
W.T., Metal concentrations in fish otoliths in relation to body composition after laboratory
exposure to mercury and lead, pp. 235-245, Copyright (1998), with permission from Inter-
Research Science Publisher.

215
 Bivalve shells, however, grow incre-
mentally. Once a shell layer is buried beneath
subsequent layers of shell, there is little evidence
that any active resorption of the early-formed
shell layers takes place. The shell therefore,
becomes a somewhat permanent record of the
composition of the individual layers at the time of
their formation. If a relationship between external
environmental conditions and shell composition
exists then a single shell would contain many
years of environmental data.
Quite a few studies have applied LA-
ICP-MS to the individual growth rings on
bivalves (see Outridge et al 1995). A few of the
more recent examples include Price & Pearce
(1997) who reported spikes (high concentrations
over short time periods) of Pb, Cu, and Zn in
cockle shells. They believed the spikes were
caused by short-term extreme pollution events,
such as storm events or spring melt which washed
metal contaminated sediment into the water. They
also believed that whole shell analysis would
mask or dilute such spikes and limit the
usefulness of shells as monitoring tools.
Bellotto and Miekeley (2000) reported
similar findings for mussel shells. Transplanted
and laboratory reared animals both incorporated
increased concentrations of Cu, Cd, Pb, and Zn in
their shells when exposed to higher concentration
of the metals in their environment. However,
there is rarely a simple relationship between
environmental metal concentrations and the
concentrations found in shells.
In an effort to better understand the
effect environmental parameters have on shell
composition, Putten et al. (2000) compared water
temperature and salinity, along with shell δ13C
and δ18O to Mg, Mn, Sr, Ba, and Pb concentra-
tions in the shells of the common blue mussel
(Mytilus edulis). They maintained mussels in the
field for 2-3 years and then analyzed the annual
growth layers by ICP-MS. In each case the
elements exhibited annual cyclic variations. The
observed metal cycles could not be explained by
seasonal changes in the water composition. The
Putten et al. (2000) study suggested that the shell
Ba cycle was related to the spring phytoplankton
bloom, and that the Mn maximums may be
related to the mussel’s respiration rate. Stecher et
al. (1996) found similar seasonal patterns for Sr
in Mercenaria mercenaria and Spisula
solidissima shells. They concluded that growth
rate was more important than temperature in
determining Sr shell concentrations (Fig. 14.3).
Shells, therefore, are not only recording inform-
ation about environmental conditions but the
physiology of the animal as well.
Bone also offers the possibility of
obtaining information on an animal’s environ-
ment and physiology. Bone is precipitated from
material carried by the blood and the ionic
composition of fish blood or blood plasma has
been shown to change during periods of stress
(e.g. spawning, increased temperature, physical

2800 1985
1984
1992
1988
1989

1991
1990
Sr/Ca (umol/mol)

1987
2400 1986

2000

1600

1200
Decreasing Growth Rate

Figure 14.3. An example of the effect of growth rate on Sr concentrations in a bivalve shell. Note the
decrease in Sr concentrations as sampling proceeds from left to right over 9 years of growth.
Modified and reprinted from Geochimica et Cosmochimica Acta, Vol. 60, Stecher III, H.A., Krantz,
D.E., Lord III, C.J., Luther III, G.W., and Bock, K.W., Profiles of strontium and barium in
Mercenaria mercenaria and Spisula solidissima shells, pp. 3445-3456, Copyright (1996), with
permission from Elsevier Science.

216
exertion), or when exposed to toxins (e.g. Roche
& Bogé 1996). In humans, bone material is
produced and resorbed as we age and grow.
However, many fish species produce acellular
bone, containing no osteoclasts (cells associated
with bone dissolution), which may not change in
composition after deposition.
Veinott and Evans (1999) demonstrated
the stability of the elemental composition of a
fish’s bone by analyzing fin rays from white
sturgeon. The fin ray (a boney structure in the
pectoral fin) grows incrementally and can be
sampled without sacrificing the fish. By sampling
the same fish at two different times Veinott and
Evans (1999) were able to show that for Sr, Mn,
Mg, and Ba there was a strong linear relationship
between the fin ray concentrations from the two
sampling periods (Fig 14.4). Furthermore, the
absolute change in concentration for the above
elements was quite small suggesting little change
in the fin ray composition for these elements.
Veinott et al. (1999) exploited the
stability of Sr in sturgeon fin rays to test the
hypothesis that white sturgeon from the Fraser
River make regular marine migrations. The Sr:Ca
ratio in fresh water is approximately four times
lower than in the marine environment. Fish
migrating to a marine environment would be
expected to deposit layers of bone in their fins
enriched in Sr (Fig. 14.5). However, Veinott et al.
(1999) found few growth zones enriched in Sr and
no growth zones enriched in Sr after about 40
years of age. They concluded that Fraser River
white sturgeon spent most of their life in the river

25
300
20
Second Capture
Second Capture

260
15
220
10
180 5

140 0
140 180 220 260 300 0 5 10 15 20 25
First capture First capture

2600 -0.86
2400 -0.88
Second Capture
Second Capture

2200 -0.9
2000
-0.92
1800
-0.94
1600
1400 -0.96
1200 -0.98
1200 1400 1600 1800 2000 2200 2400 2600 -0.98 -0.96 -0.94 -0.92 -0.9 -0.88 -0.86
First capture First capture

Figure 14.4. Relationship between elemental concentrations in the annual growth zones of
white sturgeon fin rays from first and second captures. Concentrations are in parts per
million except Ba which is presented as a ratio to Ca. Solid line has a slope of 1. Reprinted
from Transactions of the Americal Fisheries Society, Vol. 128, Veinott, G.I. and Evans,
R.D., An examination of elemental stability in the finray of the white sturgeon with laser
ablation sampling-inductively coupled plasma-mass spectrometry (LAS-ICP-MS), pp.352-
361, Copyright (1999), with permission from the American Fisheries Society.

217
 600
500

Sr (ppm)
400
300
200
100
0
0 10 20 30 40
Age (years)

Figure 14.5. Relationship between the age of a white sturgeon at the time of production of
an annual growth band and the Sr concentration in the growth band. This sturgeon is
believed to have made one marine migration around age 9. Reprinted from the Canadian
Journal of Fisheries and Aquatic Sciences, Vol. 56, Veinott, G., Northcote, T., Rosenau,
M., and Evans, R.D. Concentrations of strontium in the pectoral fin ray of the white
sturgeon (Acipenser transmontanus) by laser ablation sampling – inductively coupled
plasma – mass spectrometry as an indicator of marine migrations, pp. 1981-1990,
Copyright (1999), with permission from NRC Research Press.

and did not make regular migrations to the ocean.
This information has important implications for
the management of the Fraser River white
sturgeon stock which is considered endangered.
Other recent applications of LA-ICP-MS
in the aquatic sciences include a study on corals
and a study on the gut contents of the opossum
shrimp. In the coral study Sinclair et al.(1998)
analyzed the growth zones in sections of coral
using an argon-fluoride excimer laser operating
with a wavelength of 193 nm. This is one of the
few environmental studies that did not use a
Nd:YAG laser. As well, they scanned across the
surface of the coral with their laser beam rather
than analyzing a single point. This produced a
larger volume of material for analysis and a more
stable signal at the ICP-MS.
Sinclair et al. (1998) found that the
composition of the coral varied seasonally. In this
case sea surface temperature was a good predictor
of the B, Mg, Sr, and U concentrations in the
coral. This is different from the results of the
Putten et al. (2000) and Stecher et al. (1996)
studies which found seasonal trends in the
composition of bivalve shells but did not find a
strong correlation with water temperature.
In a rather unique application of LA-
ICP-MS, Lasenby and Veinott (1998) examined
the gut contents of the freshwater shrimp Mysis
relicta. The specimens were fed either sediment
or zooplankton, both of which are common foods
for the shrimp. LA-ICP-MS was then used to
ablate individual gut sacs in an attempt to identify
the food source. Normally, individual guts are too
small to analyze separately and have to be pooled
which limits estimates of individual variability.
Although the variability within a gut was high,
Lasenby and Veinott (1998) reported significant
difference in V, Pb, and Ca concentrations
between the two groups. Identifying the source of
food in omnivorous invertebrates can be used to
model trophic transfer of contaminants in aquatic
ecosystems.
Outside of aquatic research, the primary
application of LA-ICP-MS in the environmental
field has been the analyses of plant material (tree
rings, bark, leaves). As with other incremental
growth structures the notion that the growth rings
of a single tree may contain information on
hundreds of years of environmental change is
quite appealing to researchers.
Hoffmann et al. (1994) produced some
of the first data on tree rings analyzed by LA-
ICP-MS. However, Garbe-Schönberg et al.
(1997) were very critical of the technique. They
suggested that single trees behaved very

218
individualistically in terms of the heavy metal
content of their growth rings. No consistent
relationship was found in pine and birch trees
between the metal concentration of the growth
rings and the pollution history of the area. Also,
no correlation was found between the pollution
levels in the soil and the metal content of the tree
rings.
Nevertheless, in a study using sycamore
tree rings from Britan, Watmough et al. (1997)
concluded that the decline in Pb in the growth
rings formed after 1975 was a result of the decline
in atmospheric Pb levels. They also showed that
Cd concentrations in tree rings declined with
distance from a Cu-Cd refinery. Furthermore,
Hutchingson et al (1998) were able to
demonstrate that there was minimal lateral
movement of metals across the growth rings in
sugar maple. Metals that were mobilized in the
soil following deliberate acidification were
detected in the growth rings at a later date and
were restricted to the growth rings that formed
during acidification. This suggests that some tree
species are better suited for pollution studies than
others.
In a study using material from oak trees,
Hoffmann et al. (2000) applied LA-ICP-MS to
investigate the spatial distribution of elements in
single leaves. A NdYAG laser was used but the
more traditional 4th harmonic (266nm) used in
most studies of biological tissue was found to be
less efficient at ablating the green leaf material
that the 3rd harmonic (355nm). This was attributed
to the chlorophyl content of the leaves which is
very efficient at absorbing radiation with a
0.5
Pb
Instrument Response
0.4
0.3
0.2
0.1
0
0 20
S ta nda rd Conce ntra tion (ppb)
Figure 14.6. Typical calibration curve for solution nebulization ICP-MS.
wavelength of approximately 400nm (Hoffmann
et al. 2000).
The Hoffmann et al. (2000) study
reported a pattern of increasing concentrations of
Mg, Pb, Al, Mn, Cu, Ni towards the tip of the
leaf. Calcium displayed the opposite pattern.
Also, the concentrations of Ni, Pb, and Al were
higher in June in trees considered “damaged” due
to forest decline compared with healthy trees. No
explanation was given for the difference.
The success of many researchers to link chemical
changes in the environment to changes observed
in incremental growth structures by LA-ICP-MS
provides reason to be optimistic about this
technique. However, the single greatest limitation
for LA-ICP-MS of biological materials is the
difficulty researchers have in quantifying the data.
CALIBRATION STRATEGIES
Regardless of the instrument used or the
analytical technique employed, calibration
involves correlating the output signal from an
instrument to the input of some material of known
composition (Fig. 14.6). An ideal instrument and
technique would provide a straight line
relationship, over a large range of concentrations
and varying matrices, between the composition of
the known material and the output from the
instrument.
For LA-ICP-MS the simplest calibration
strategy involves ablating a material of known
composition (a standard reference material), then
ablating an unknown and comparing the count
rates from the two. If the counts per second
measured by the ICP-MS are the same on both
40 60 80 100 120
219
materials for Pb, for example, then it can be
assumed that the unknown contains the same
concentration of Pb as the standard. Unfortunately
this only seems to work consistently for precisely
matched (chemically and physically) environ-
mental materials. This simple approach also does
not correct for variations in ablation efficiencies
nor allow for any drift of the output signal over
time, which is common in LA-ICP-MS.
Arrowsmith (1987) and then Hager
(1989) suggested a more robust way of obtaining
quantitative data by LA-ICP-MS based on
determining “element response factors”.
Basically, the ratio of the response of the analyte
to a matrix element (internal standard) in the
unknown is compared to the response of the same
elements in a standard of known composition. For
example, the ratio of Pb to Ca can be compared in
a standard and unknown if one is analyzing an
otolith. In this case Ca is acting as the internal
standard. This assumes that as the matrix varies
and the signals drift, the analyte and the internal
standard will both react in the same way.
Suppose, for example, that there is a difference in
the amount of material ablated in a summer
growth band of a bivalve shell compared to a
winter growth band (Fig. 14.7A). Without some
sort of correction for the amount of material
ablated, the logical conclusion from the unknown
and standard signals would be that there is higher
element concentrations in one season compared to
the other. However, the ratio of analyte to Ca may
not have changed as a result of additional material
being ablated (Fig. 14.7B). The conclusion when
comparing ratios would be that there was no
difference in the concentrations of trace elements
between seasons.
The “element response” approach, or

25000

20000 A
Pb (cps)

15000

10000

5000

0
0 10 20 30 40 50
Time (sec)

1.6
1.4
B
1.2
Pb/Ca (cps)

1
0.8
0.6
0.4
0.2
0
0 10 20 30 40 50
Time (sec)

Figure 14.7. An Example of a transient Pb signal generated by LA-ICP-MS during the

analyses of summer (squares) and winter (circles) growth zones in a bivalve shell. (A)
Raw Pb counts per second (cps) over time. (B) Calcium normalized Pb cps over time.

220
some variation of it, has been used in most of the
environmental studies mentioned above with
glass or pressed pellets used as standards. How-
ever, even this more robust calibration strategy is
accurate only for elements whose fractionation is
similar to that of the element chosen as an internal
standard (Chen 1999). Selecting an internal
standard then, becomes critical to the accuracy of
the results. With environmental matrices few
elements meet the criteria for an internal standard.
That is, the internal standard must be present in a
high enough concentration so that the signal is
well above background, it must be
homogeneously distributed, and the true
concentration must be known. It is the first and
second requirements that are often lacking in
biological materials. Otoliths, for example, are
approximately 96% calcium carbonate, 3% org-
anic material, and 1% trace impurities (Campana
et al.1997). Calcium then becomes a good candid-
ate for an internal standard. However, normaliz-
ing to Ca provides accurate results for Ba and Sr
in otoliths but not for Cu and Ni (Campana et al.
1997). Few if any other elements are present at
high enough concentrations or evenly distributed
throughout the otolith, especially at the spatial
scale of a finely focused laser beam, to be used as
internal standards. Carbon-13 has been used as an
internal standard in plant studies (Hoffmann et al.
2000; Garbe-Schönberg et al. 1997; Watmough et
al. 1997), but C13 as an internal standard suffers
from the same problems as Ca.
To overcome the problems of an internal
standard, Scholze et al. (1996) spiked their leaf
samples with an enriched isotope solution.
However, this required pulverizing of their
specimens to obtain a homogeneous mixture.
Pulverizing shells or otoliths to add an intenal
standard would nullify what is perhaps the
greatest attraction of LA-ICP-MS, the ability to
analyze individual growth zones in situ.
Therefore, other approaches are necessary to
obtain accurate results in incremental growth
structures over a wide mass range.
One solution is to return to the simpler
approach of closely matching the standard and
unknown. Durrant (1999) noted numerous
difficulties with this approach: 1. samples and
standards must be matrix matched, 2. the
standards must be well characterized and contain
all the elements of interest, 3. the standards must
be easy to make or commercially available, 4. a
221
full set of standards covering a wide con-
centration range is required.
Well characterized matrix matched
standards suitable for the LA-ICP-MS analyses of
biogenic materials are not commercially avail-
able. Researchers, therefore, generally use com-
mercially available glass standards or produce
their own standards (e.g. Veinott et al. 1999;
Perkins et al. 1991). The primary problem with
in-house standard production is the heterogeneity
of the final product. However, Bellotto and
Miekeley (2000) appear to have overcome this
problem by producing powders from the co-
precipitation of trace elements into a CaCO3
matrix. The resulting powder is then pressed into
a pellet and used as a standard. Bellotto and
Miekeley (2000) have reported excellent
calibration curves (R>0.99) for Cr, Mn, Co, Cu,
Zn, As, Cd, Sn, Ba, Hg, and Pb over a wide range
of concentrations. Furthermore, they produced
very good results when analyzing the limestone
reference material JLs-1 (Geological Survey of
Japan) as an unknown. This technique holds a lot
of promise and should be explored further.
THE FUTURE OF LA-ICP-MS IN
ENVIRONMENTAL SCIENCES
Despite some of the problems with
accuracy noted by many authors and demon-
strated in the Campana et al.(1997) study there is
still tremendous potential for LA-ICP-MS in
environmental sciences. As was mentioned, the
notion that large numbers of plants and animals
may be recording and preserving information
about the environment in which they grew is
extremely enticing.
Work is clearly required in two areas.
First, additional controlled laboratory studies are
needed to better understand the relationship
between environmental concentrations of trace
elements and their subsequent concentration in
growth structures. The Putten et al. (2000), and
Stecher et al. (1996) studies have clearly shown
that there is a complex relationship between
environmental conditions, growth rate and shell
chemistry. As well, the Geffen et al. (1998) study
is an excellent example of how species will have
a significant effect on metal uptake in otoliths.
Given these recent results it is obvious that there
are still many unknowns with respect to the
factors that control the final trace element
composition of many growth structures. A
concerted effort is required to determine the
structures and elements that are best suited for
LA-ICP-MS. For example, the world mussel
watch program has selected Mytilus edulis, the
common blue mussel, as its organism of choice
for monitoring pollution globally. However, it is
known that blue mussels can regulate Cu.
Therefore, it is understood, within the program,
that soft tissue Cu values are not a good indicator
of Cu pollution in the environment. This sort of
effort among LA-ICP-MS researchers in the
environmental sciences would allow for greater
comparability among studies.
The second area that requires further
attention is the production and use of standard
reference materials. Many LA-ICP-MS studies
analyzing biological materials used commercially
available glass beads as standards. However, it is
known that glass beads will not produce accurate
results, for all the elements of interest, due to
fractionation effects (Chen 1999). Furthermore,
despite the good results obtained using
“homemade” standards (Bellotto & Miekeley
2000; Narewski et al. 2000; Watmough et
al.1998; ) there is still no agreed upon formula for
producing matrix matched standards. This adds to
the difficulty in making comparisons among
studies. Agreed upon recipes for producing
standards are required or matrix matched
standards need to be produced in bulk and made
readily available to the LA-ICP-MS community
as with solution analyses. A series of standards
for different materials (bone, shell, wood,
otoliths) would be required. For example,
Watmough et al. (1998) used single rings from a
series of trees as their standards. They used trees
varying in distance from a smelter to obtain rings
with varying concentrations of metals. As well,
Narewski et al. (2000) produced good calibration
curves from pressed pellets made from bark. They
used bark of variable elemental concentrations
from different sections of the tree to make
standards of varying concentrations. These
studies suggest that trees grown in controlled
conditions could provide a source of wood to be
used as standards. It is necessary to determine the
most appropriate species to use for standard-
ization and then use that species for tracking
historical changes in tree ring chemistry.
Similarly, fish and bivalves could be
raised under controlled conditions. However,
Campana et al. (1997) assayed otoliths from fish
222
raised under controlled conditions and found that,
among various laboratories and instruments, there
was little difference in the accuracy and precision
of natural otoliths compared with artificial
otoliths produced from powders. Given the results
from the Bellotto and Miekeley study (2000),
producing shell and otolith standards from
powders may be the better option.
Once the types and method of production
for standards is agreed on all studies could refer
their analyses to these universal standards. This is
not unlike how stable isotope data are reported.
Standard Mean Ocean Water, for example, is one
of the accepted standards against which oxygen
and carbon isotopes in water are compared. A
similar approach may work for LA-ICP-MS.
CONCLUSION
There is potentially a vast amount of
environmental data stored within the incremental
growth structures produced by plants and animals.
LA-ICP-MS is one means of extracting this
information. The spatial resolution and sensitivity
of LA-ICP-MS systems makes the method
competitive with other microbeam techniques.
With improvements in high resolution
instruments and collision cell technology the
applications of LA-ICP-MS will only expand.
The greatest challenge facing LA-ICP-
MS in environmental sciences is quantification of
the data. Until standards are made widely
available and researchers report their data relative
to a well-accepted set of protocols it will be very
difficult to make comparisons between studies.
Nevertheless the technique has far too much
potential to be ignored and it is expected to
continue to grow in popularity among
environmental scientists.
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