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Laser-based Elemental Assays
Beam-based elemental assays target a particular age or date range in
the sectioned otolith, and thus take advantage of the chronological
growth sequence recorded in the otolith. These types of targeted assays
have proven to be popular among those reconstructing migration
histories and identifying nursery areas, as well as those using Sr:Ca
ratios to infer temperature history. The advantages of an age-structured
approach are obvious, particularly since the beam sizes of the current
generation of instruments approach the width of a typical daily
increment. As a result, the assay can be limited to the time scale of
interest, whether it is weekly, annual or at an intermediate scale.
Disadvantages of the approach include the requirement for sectioning
to expose the growth sequence, the potential for contamination from
the sectioning and polishing procedure, and some degree of beam
penetration into underlying growth layers. However, the most
significant disadvantage is the reduced sensitivity and precision of
beam-based assays compared to their solution-based counterparts.
There are a wide variety of sophisticated instruments available for
probed assays of the otolith, but the most frequently used include
the energy-dispersive (ED-EM) and wavelength-dispersive (WD-EM) electron microprobes, proton-induced X-ray emission
(PIXE),
and laser ablation ICPMS (LA-ICPMS). No one instrument type is
sensitive to each element, nor is any one instrument preferred for
use in all assays. In general however, the minor elements such as
Na and K can only be measured accurately with an electron
microprobe, while the trace elements require PIXE or LA-ICPMS.
Reconstruction of migration histories using the elemental composition
along an otolith growth sequence is similar in many respects to stock
discrimination based on analysis of the otolith core, and shares many of
the same assumptions. However, migration analysis expands the scope
of the interpretation, by linking a series of elemental assays along an
otolith transect to the growth chronology recorded in the otolith, thus
allowing the reconstruction of migration pathways structured by age or
date. In principle, migration analysis is one of the most powerful
applications of otolith microchemistry, although its successes to date
have been largely limited to the detection of anadromy. Subtler
migration patterns are now being detected with LA-ICPMS, which is
more sensitive to non-physiologically regulated trace elements.
Previously reported difficulties in interpreting migration histories may
have been due to the use of the electron microprobe, which is more
suited to assays of physiologically-regulated elements.
Several forms of migration analysis have been reported. One of the
most successful has been the comparison of elemental trajectories
among fish in search of a common history, or alternatively, the
determination of the age or date at divergence. This is a particularly
robust application, since it requires no knowledge of the fish's past
environment, and is relatively insensitive to any ontogenetic shifts
in otolith elemental composition which may have occurred. In
many respects, this comparative approach is analogous to the use of
elemental fingerprints as biological tracers, as described earlier. A
potentially more powerful approach is one in which the otolith
elemental trajectory is linked to shifts in temperature and water
chemistry along possible migratory routes. Such an approach is the
basis for the detection of anadromy using Sr:Ca ratios, in which the
shift between freshwater and saltwater environments is so marked in
the otolith as to be virtually unambiguous. Similar interpretations in
more homogeneous environments appear possible, but are
complicated by the assumption that a given elemental concentration
at any point along an otolith transect reflects the environment in the
same way. In other words, ontogenetic changes in otolith elemental
composition are assumed not to exist. Yet such changes have been
clearly documented, even in fish held under constant environmental
conditions. As a result, observed trends in concentration across an
otolith could reflect either a shift in the fish's environment, an
age-related change in incorporation rate independent of the environment,
or both. With further experimentation, it should be possible to
factor out ontogenetic shifts in elemental composition, thus
simplifying the interpretation of possible migration pathways. To
date however, it is not always clear from published reports whether
reconstructed distributions have been adjusted for ontogenetic
effects.
Recent work in our laboratory which describes the use of laser-based elemental
assays include Campana et al. (1997), Thorrold et
al. (1997), Fowler et al. (1995b) and
Campana et al.
(1994). A more complete review of
the field is provided in Campana
(1999).
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