|
RESEARCH
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Screening
& Diagnosis
A
BRIEF REVIEW OF THE LEAD ISOTOPE FINGERPRINTING METHOD
Dr.
Brian L. Gulson
Introduction
Identifying the
correct sources and pathways of lead in the environment and humans is
fundamental to the implementation of the most cost-effective remedial
actions. In the past, the main approach to identifying sources and pathways
has been the statistical analysis of large databases of environmental
samples and human subjects using lead concentrations. In concert with
its main application in the earth sciences (isotope geochemistry), the
technique of lead isotope fingerprinting has been commonly applied in
environmental situations to problems focussed on establishing sources
of lead in for example air, water, ice, soils, dust and paint (see references
in section "Environmental Investigations"). Application of
lead isotope fingerprinting has recently been applied in animal studies
(references in "Animal Investigations") whereas the application
to human studies is limited ("Human Investigations").
The form of
this review will be to present an introduction to the lead isotope method
and then briefly summarise some of the projects that we have undertaken
mainly over the past 8 years at CSIRO/Macquarie University. The reference
list for investigations using lead isotopes as a tracer, although comprehensive,
is not exhaustive and excludes most papers in which the isotopic ratios
have been measured by Inductively Coupled Plasma Mass Spectrometry,
the reasons for which are given in the following section.
Lead Isotope
Method
The lead isotope
method makes use of the variations in isotopic abundance arising from
radioactive decay over geological time of 238U, 235U
and 232Th to 206Pb, 207Pb and 208Pb.
204Pb has no parent and has remained essentially constant
in abundance since the time of formation of the Earth. Isotopic abundance
is expressed as ratios such as 206Pb/204Pb, 207Pb/206Pb
and 208Pb/206Pb or as the 204-based ratios 206Pb/204Pb,
207Pb/204Pb and 208Pb/204Pb.
The isotopic ratios are presented in this report as 206Pb/204Pb.
For geologically old (~1700 million years) lead deposits such as Broken
Hill and Mount Isa in Australia, the 206Pb/204Pb
ratio is 16.00 and 16.10 respectively, whereas for geologically young
(~400 million years) deposits on the same continent (such as Woodlawn
or Elura), the 206Pb/204Pb ratio is ~18.1. These
differences are very large as it is possible with our techniques to
distinguish between the Broken Hill and Mount Isa deposits. The lead
isotopic composition observed in the different sources depends on the
geological source of the lead and its fate thereafter. For example,
the 206Pb/204Pb ratio used in gasoline in Sydney
over the last 10 years ranged from 16.4 - 17.0. Hence, the tetraethyl
lead is a mixture of geologically old lead such as from the Broken Hill
and/or Mount Isa mines in Australia with a small component of geologically
younger lead.
Analytical Methods
All sample preparation
is performed in purpose-built low contamination laboratories (‘clean
rooms’) incorporating features such as filtered air intake and laminar
flow hoods. Almost any sample can be analysed. Biological samples include:
blood, urine, teeth, food, breast milk. Environmental samples include:
air, soil, dust, water, paint, gasoline.
Samples are leached
or dissolved using ultra pure reagents, with or without microwave digestion.
Lead is separated from interfering elements, such as Fe and Zn, by anion-exchange
chromatography in a hydrobromic acid medium. Fractions of the purified
lead samples are loaded onto a rhenium filament using the silica gel
technique and analysed for high precision lead isotopic composition
on a thermal ionisation mass spectrometer (or TIMS) run in fully automatic
mode. Isotopic ratios are measured as 208Pb/206Pb,207Pb/206Pb
and 206Pb/204Pb. Data are normalised to the accepted
values of the international standard NBS SRM 981, by applying a correction
factor of +0.08% a.m.u. to allow comparisons between laboratories.
Four individual
isotopes are measured - 208Pb, 207Pb, 206Pb
and 204Pb. Each isotope is measured as it passes through
a magnetic field in the mass spectrometer, and the isotopes detected
are conventionally reported as the ratios mentioned above. These three
ratios provide three independent measurements from which to evaluate
each sample, accompanying the measurement of lead concentration in ppm.
Because of the diagnostic potential of the isotopic ratios and interdependence
between them as 206Pb is common to all three variables, only
one or two ratios are commonly reported. Furthermore, the 206Pb/204Pb
ratio is often not reported because of difficulties in measuring the
low abundance 204Pb isotope. In many cases, it is also possible
to recognise contaminated samples using an isotope-based method, as
such samples exhibit a distinct signature.
The TIMS method
allows isotopic ratios to be measured with a high degree of precision.
Our current research has shown that the isotopic techniques employed
can easily detect very small differences in isotopic ratios that are
essential for valid data interpretation. This cannot be achieved using
the current generation of Inductively Coupled Plasma Mass Spectrometers
(ICP-MS) in which precision is an order of magnitude, or more, worse
than TIMS, and accuracy may be questionable. The TIMS method is also
superior to using lead concentrations alone, as these require large
databases and sophisticated statistics to provide results that may be
equivocal due to poor correlation between variables. The other advantage
that lead isotopes has over lead concentrations is the fact that the
isotopic abundance (and thus isotopic ratios) are not changed by physiological
processes because of their high atomic weights. Justification of the
number of samples:
The lead isotope
method is sometimes criticised because of the relatively small numbers
of samples used in such investigations. This criticism may be due to
a lack of understanding of isotope studies, to which the concept of
analysis numbers does not translate to one result for each sample. This
misunderstanding is common as the use of the lead isotope technique
in health and environmental research has only really come to the forefront
over the past decade and it is a highly specialised field. (There are
only four laboratories in the world in which high precision lead isotopic
measurements of biological materials are regularly performed).
In validation and
later testing for a major study (Biokinetics of Lead in Human Pregnancy),
we demonstrated that it is possible to measure samples of blood and
urine collected from the same person over several months, and water
from same tap with the following precision (2 standard deviations):
|
Sample
|
208Pb/206Pb
|
207Pb/206Pb
|
206Pb/204Pb
|
Pb (ppb)
|
n
|
|
Blood
|
2.1759 ±
0.0028
|
0.9225 ±
0.0011
|
16.756 ±
0.044
|
7.7 ± 0.2
|
15
|
|
Urine
|
2.1748 ±
0.0024
|
0.9233 ±
0.0005
|
16.752 ±
0.026
|
2.2 ± 0.1
|
12
|
|
Water
|
2.2099 ±
0.0014
|
0.9489 ±
0.0005
|
16.223 ±
0.025
|
3.1 ± 0.1
|
11
|
For the 207Pb/206Pb
ratio this means that numbers in the fourth decimal place can be significant.
Thus the high precision
measurements of isotopic ratios allow for a high discriminatory power
with minimal statistical manipulation, and it is possible to provide
definitive answers from a small number of samples. This compensates
for the drawbacks of the method (lead isotopic measurements are costly
as they are extremely labour-intensive, require expensive equipment
and ultra-clean laboratories). Low sample numbers are also advantageous
if blood samples are taken from children (or adults), as sampling methods
involve a degree of personal invasion on them.
Examples of the
Use of Lead Isotope Fingerprinting
Endogenous
versus Exogenous sources of lead (Biokinetics of Lead in Human Pregnancy)
This major international
longitudinal study supported by the U.S. National Institute of Environmental
Health Sciences using the lead isotope method has determined that lead
is mobilised from the maternal skeleton during pregnancy and lactation,
with a higher amount mobilised during lactation (Papers 69, 74, 77,
80, 81, 84, 86 in reference list).
Smelter communities
(Port Pirie, Port Kembla, Hobart, Boolaroo)
Environmental samples
(soil, house dust, house air, ambient air) and blood and urine from
adult females and some children were analysed as part of the study of
Biokinetics of Lead in Human Pregnancy (Paper 74). Sources and pathways
were established of lead contained in ceiling dust and historical sources
of lead contamination in sediments from Lake Illawarra especially arising
from the Port Kembla smelter (Paper 31).
Mining Communities
(Broken Hill, Mount Isa, Woodlawn)
The Broken Hill
investigation established that paint and petrol were significant contributors
to blood lead in some children. In addition, it demonstrated the importance
of monitoring family members as a pathway for "take-home"
lead. This was also the testing ground for development of the tooth
method and the petri dish method. (Papers 25, 27, 63, 64, 65, 66, 71,
72, 73, 75, 76, 85). The Woodlawn study showed that the blood in workers
contained lead dominantly from mining activities and "take home"
mine dust which contaminated their residences (Paper 76).
Urban Areas
(Sydney, Brisbane, Adelaide)
In Sydney, studies
demonstrated that paint from renovating houses could contaminate neighbourhoods
and was also a test of the petri dish method (Papers 26, 27).
The majority of
the subjects (n>80) in the Biokinetics of Lead in Human Pregnancy
study are in Sydney. Petri dish dust, tap water, 6-day duplicate diet,
and blood and urine are monitored in these subjects and their children
and new-born infants.
Air and petrol are
monitored on a monthly basis with high volume air filters supplied by
the NSW EPA and Queensland Department of Conservation and the Environment.
(Papers 22, 29, 74). Ceiling dust and soils from houses around a former
lead paint factory have been analysed for a company to establish their
potential liability.
"Take
Home" Lead
On the clothes of
workers, it was convincingly demonstrated using the lead isotope method
in Broken Hill (Paper 75 ), Woodlawn mine (Paper 76), and potentially
from engine reconditioning shops (Paper 32).
Lead Paint
Removal from Bridges
The lead isotope
method has been used to monitor removal of lead paint from bridges in
several Australian states. Environmental samples were used for the monitoring
and in one case, blood samples of the workers were also collected as
a control measure in case of lead poisoning.
Advantages of
Lead Isotopes
- Often diagnostic
for sources and pathways
- Allows distinction
of skeletal Vs environmental exposures compared with indirect measures
(e.g. statistics, bone XRF)
- Small numbers
of samples can provide a definitive answer
- Low sample numbers
are also advantageous if blood samples are taken from children (or
adults), as sampling methods involve some degree of personal invasion
on them.
Disadvantages
of Lead Isotopes
- Expensive (equipment,
ultra clean labs, trained technical staff) - new model mass spectrometers
may lower costs
- Equivocal at
very low blood lead concentrations (<5 m g/dl)
- No use if ambient
isotopic signatures are similar (e.g. air+paint+water+blood) as in
U.S.
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