Journal of Analytical Toxicology,Vol.
31, June 2007
Determinationof Mercury in Whole Bloodand Urine by
InductivelyCoupledPlasmaMassSpectrometry
Bonnie Mei Wah Fong, Tak Shing Siu, Joseph Sai Kit tee, and Sidney Tam*
Division of Clinical Biochemistry,QueenMary Hospital, Hong Kong, China
[ Abstract J
The conventional method for the determination of mercury in
clinical samples is cold vapor atomic absorption spectrometry.
Sample digestion or pretreatment require large sample volume and
long sample preparation time. The inductively coupled plasma
mass spectrometry (ICP-MS) method developed in this study
requires only 100 pt of sample with practically no preparation,
except for dilution with diluent. Significant savings in sample
volumes, reagents, technician time, and analysis time are realized.
Among different types of diluents, the one containing acid,
tert-butanol, and potassium dichromate gave the best results to
remove the mercury memory effect. The interassay precisions for
whole blood and urine were < 5% and < 8%, respectively, and the
intra-assay precisions were < 3% and < 7%, respectively. The
lower limits of detection were 0.13, 0.17, and 0.26 pg/L for
aqueous standard, urine, and whole blood, respectively. The
developed ICP-MS method correlated well with the atomic
absorption method and can offer an alternative to the atomic
absorption method for mercury analysis with less sample volume
requirement as well as shorter analysis time.
Introduction
Mercury is widelydistributed in nature, circulating among
several media, and is found in different states (gas, liquid, and
solid) and different chemical forms (mineral, organic), ex-
hibiting various degrees of toxicity. Mercury may cause kidney
injury, central nervous system disorders, intellectual deterio-
ration, and even death (1). Therefore, efficient assessment of
suspected mercury intoxication through determination of mer-
cury levels in various biological matrices, particularly blood
and urine, is vitally important. Various methods for the deter-
mination of total mercury have been reported, including
atomic fluorescence spectrometry (2), atomic absorption
spectrometry (3), inductively coupled plasma (ICP)-atomic
* Author to whom correspondence should be addressed: LG 131, Block K, Division of Clinical
Biochemistry, Queen Mary Hospital, 102 Pokfulam Road, Hong Kong, China.
E-maih sidneytam@hku.hk.
Reproduction(photocopying)of editorialcontentof thisjournal is prohibitedwithoutpublisher'spermission.
emission spectrometry (4), and ICP-mass spectrometry (MS)
(5-10).
The conventional method for the determination of mercury
in clinical samples is cold vapor atomic absorption spectrom-
etry (CVAAS)(11-15). Sample digestion or pretreatment is re-
quired to decompose organic mercury compounds, and then
total mercury can be determined by stannous chloride reduc-
tion (15,16). This method requires large sample volume and
time consuming sample preparation. Because copious amounts
of strong acids and strong oxidants are used to assure the
complete decomposition of organic mercury, it is also haz-
ardous. In the last decade, there has been a rapid growth in the
use of ICP-MS because of its strong detection power and the
possibility of multi-element analysis in a single run. The ver-
satility of the ICP-MStechnique makes it a multi-disciplinary
analytical tool. It can be used in geological and environmental
sciences (17), nuclear and semi-conductor industries (18), ma-
terials science, medicine (19), agriculture (20), food, and bio-
logical sciences (21). Recently, there has been a growing in-
terest in the use of the ICP-MS for metal analysis in laboratory
medicine. This study investigated the application of ICP-MS on
clinical analysis utilizing simple dilution techniques. The ICP-
MS method developed requires only 100 IJL of sample with
practically no preparation, except for dilution with diluent
containing acid, tert-butanol, and potassium dichromate. Sig-
nificant savings in sample volumes, reagents, technician time,
and analysis time are realized.
The well known "mercury memory effect" is the major ob-
stacle in mercury quantitation by ICP-MS.Long after a sample
containing mercury has been nebulized into a conventional
spray chamber, a significant residual mercury signal can be de-
tected indicating its failure to return to baseline. The persis-
tence of residual mercury in spray chambers and long acid
washout times has been observed (22). Mercury adheres to the
spray chamber walls and/or remains as vapor in the spray
chamber. Limiting the solution to acid only prevents mercury
adsorption onto the spray chamber walls, but mercury volatility
persists (23). This problem is overcome through the addition
of gold or dichromate, which prevents mercury volatilization
and adsorption losses (23). Use of a direct injection nebulizer
281

(24) may also overcome these problems. However,its operation
is so complex that it precludes its routine applications (22).
This paper describes the use of 60 mg/L potassium dichro-
mate in 2% HCI and 5% tert-butanol as a diluent for mercury
analysis of whole blood and urine. As an alternative to the
combination of dichromate with acid, gold was also evaluated
as it has been used in mercury analysis for decades. The
common use of dichromate as a modifier-oxidant for CVAAS
(25), for graphite furnace mercury determination (26), and
also as an effective preservative for mercury standard solu-
tions (23) led to our consideration of its use in this test. Be-
cause dichromate is a strong oxidant, compounds such as mer-
curous sulfide (cinnabar) are completely solubilized and
remain in solution (25). In order to reduce the mercury
memory effect further, a smaller size cyclonic spray chamber
was used, and the nebulizer flow rate was lowered. This ap-
proach is a hybrid of conventional sample introduction systems
and a direct injection nebulizer.
Materials and Methods
The analysis was performed on a PerkinElmer Sciex ELAN
DRCrlu~ 6100 ICP-MS (PerkinElmer Sciex, Thornhill, ON,
Canada) equipped with an autosampler (AS 93 plus,
PerkinElmer) and a Meinhard concentric quartz nebulizer. A
reduced-size (25-mL) cinnabar spray chamber (Glass Expan-
sion, West Melbourne, Australia) was used to minimize the
mercury memory effect. Nickel sampler and skimmer cones
were used. Nebulizer gas flow and the lens voltage were ad-
justed daily to give minimum count for oxide level and doubly
charged ions and maximum count for USindium. Running
conditions for ICP-MS are summarized in Table I.
Reagents and standards
Stock solutions of mercury (Hg) with a concentration of
1000 mg/L and germanium (Ge) with a concentration of 1000
mg/L were purchased from Chem Service (West Chester, PA).
For the preparation of all solutions and reagents, ultra-pure
water (18.2 M-ohm) from a MilliQ-Element A10 system (Mil-
Table I. Optimized Operating Conditions for the ICP-MS
Plasma Conditions
RF-power 1300 W
NebulizerGas Flow 1.04 L/rain
AuxiliaryGas Flow 1.02 L/min
PlasmaGas Flow 15 L/min
DRC Parameters
LensVoltage 6.75 V
Autolens On
MassSpectrometerSettings
Dwell Time 100 ms
Sweeps/Reading 20
Readings/Replicate 3 first measured as a blank. The sample probe was inserted into
Replicates 3 the test solution containing only the testing diluent. The mea-
282
Journal of AnalyticalToxicology,Vol. 31, June2007
lipore, Milford, MA)was used. To compensate for instrumental
drift, 72Gewas used as internal standard with a final working
concentration of 2 IJg/L. Hydrochloric acid (HCI, 2%) from
TEDIA (trace metal grade, Fairfield, OH), tert-butanol (5%)
from BDH (AR grade, BDH Laboratory Supplies, Poole, Eng-
land), and potassium dichromate (60 rag/L) from Sigma (St.
Louis, MO) were used.
Certified controls
Quality control materials were purchased from Seronorm
(Trace Elements whole blood control, SERO, Billingstad,
Norway) and Bio-Rad (Lyphochek urine metals control, Bio-
Rad Laboratories, Diagnostic Group, Hercules, CA).Proficiency
testing whole blood and urine samples were obtained by par-
ticipation in Trace Elements External Quality Assessment
Scheme (NEQAS, Centre for Clinical Science and Measure-
ment, University of Surrey, Guildford, Surrey, U.K.).
Patient samples
Urine samples were collected in an acid-washed plastic
bottle. Total volume excreted was measured and recorded for
each 24-h urine specimen. All whole blood samples were col-
lected using the standard phlebotomy technique in vacu-
tainer tubes containing sodium heparin anticoagulant (Vac-
uette, Greiner Bio-One, Kremsmfinster, Austria). Specimens
were stored at 4~ and analysis was performed within two
weeks. Both urine and whole blood samples were mixed thor-
oughly before taking aliquots. Patient samples kept for
method comparison were randomly selected from routine
requests for mercury analysis.
Sample preparation and calibrators
Working aqueous standards were prepared in 2% HC1 at
concentrations of 20-1000 l~g/Lfrom a stock solution of 1000
mg/L Hg. Calibrators were prepared at Hg concentrations of 0,
2, 5, 10, 30, 60, 80, and 100 IJg/Lby either dilution with water
(aqueous calibrators) or spiking into whole blood or urine
(matrix matched calibrators) from a non-exposed subject. The
ratio of 2~ to 72Gewas plotted against the prepared mercury
concentrations. The endogenous Hg concentration was de-
rived from the blank specimen and subtracted from the cali-
bration points.
A 100 tJL of a standard, whole blood, or urine sample was di-
luted with 1.7 mL diluent (as later described), and 200 IJL in-
ternal standard (Ge, 2 IJg/L) was added and thoroughly mixed.
The final mix was then ready for Hg determination.
Memory effect experiment
The effectiveness of dichromate, gold, HCI, and tert-butanol
in reducing the memory effects was determined on 50 IJg/LHg
in 2% HCI by taking readings at 2-s intervals with a dwell time
of 100 ms and 20 sweeps for the sampling sequences. Ultra-
pure water was first measured to ensure that no mercury was
present. To test equilibrium and washout, the trial diluent was
surement sequence was initiated as the liquid sample entered
Journal of Anal,/tical Toxicology, Vol. 31, June 2007

the nebulizer. Measurements at 2-s intervals were accumu-
lated until a steady state signal was observed. The number of
counts was recorded. The probe was then inserted into the
testing solution containing mercury plus the testing diluent.
Once again, measurements were taken at 2-s intervals and the
number of counts was recorded. The probe was then rein-
serted into the diluent and the washout time measured. Data
was collected throughout the blank diluent, sample, and
washout sequences. Five different kinds of diluents were tested:
2% HC1;2% HCI with 5% tert-butanol; 2 mg/L gold in 2% HCI
and 5% tert-butanol; 60 mg/L dichromate in 2% HCl and 5%
tert-butanol; and 60 mg/L dichromate and 2 mg/L gold in 2%
HC1 and 5% tert-butanol.
HCI was chosen because of its effectiveness in organic mer-
cury solubilization (6,27). The addition of gold or dichromate
is well known for preventing mercury volatilization (23,25).
The physiochemical properties of a nebulized solution are al-
tered by the introduction of small amounts of some organic
solvents, improvingdesolvation of the aerosol, and thus, an en-
hanced signal (28).
After the "analysis time" and the '~vashout time" were known
and the suitable diluent selected, the 's~vashouttime" study
was repeated in both urine and whole blood.
Validation
For validation of the method, the following parameters were
determined: range of linearity, intra- and interassay precision,
accuracy, recovery, detection limit, and correlation.
Linearity
The Hg aqueous calibration curve ranged from 0 to 100
IJg/Land was prepared fresh daily from serial dilution from the
Hg stock standard with a concentration of 1000 mg/L with
water. Matrix matched calibration curves for urine and whole

A B

2.000 - 2,000- WashSolution

1,500- ~. 1,500-
(3 WashSolution (..1
1,090- 1.000-

500- 500-

8s Time Is) eo Time (e)

C D
2,~" Wash Solution 2,000- WashSolution
1,5~-

I,!
1,000-
1,01~-

I"q
6s
I' 6s
118s I' 80s '1
Time (s) Time (e)

E
2,00oi Wash Solution

1,000-

6s
I, ,I
Thne (el

Figure 1. Wash-outcharacteristicsof different diluent/rinsesolution for 50 p~/L Hg in 2% HCI. The graphsrepresent2% HCI (A); 2% HCI with 5% ten-butanol
(B); 2 mg/kgold in 2% HCI and 5% tort-butanol(C);60 mg/k dichromate in 2% HCl and 5% tert-butanol(D); and 60 mg/Ldichromateand 2 mg/Lgold in 2%
HCl and 5% tert-butanol(E).

283
 Journal of Analytical Toxicology, Vol. 31, June 2007

blood were prepared by spiking non-exposed subject's urine and urine to final concentrations of 2 to 100 pg/L and by mea-
whole blood with known quantities of mercury. suring the Hg concentrations before and after the additions.

Precision and accuracy Detection limit

To study the intra- and interassay precision, urine and whole The limit of detection is defined as the mercury concentra-
blood from non-exposed and exposed subjects were used. Intra- tion that produces a signal of 3 times the standard deviation
assay precision was calculated based on repeat analysis of the (SD) of the reagent blank readings. In this experiment, 20
same sample within the same batch for 20 times. For inter- blank readings were taken to calculate the SD. The matrix ef-
assay precision, samples were analyzed once a day for 2 weeks. fect on detection limit was studied for water, urine, and whole
Accuracy is determined by replicate analysis of urine and blood.
whole blood control samples containing known concentra-
tions of mercury. Proficiency testing whole blood and urine Correlation
samples were also analyzed. Unused portions of 21 whole blood specimens and a group of
63 urine specimens routinely analyzed by CVAASwere retested
Recovery using the new ICP-MS method.
Recoveries were evaluated by adding Hg to whole blood and
CVAAS facility and method
The AASused was the VarianAA-400 (Varian Techtron, Mul-
Wash SolutJo41 ~ grade, Australia) with vapor generation accessory (VGA 76
2.000 - ~, UI~II from Varian Techtron). The sample digestion method (29) is de-
"'" ..... ~IOhl scribed briefly as follows. Aliquots of 0.5 mL of concentrated
sulfuric acid were added to a 0.5-mL standard or sample in a di-
gestion tube and allowed to stand for 30 min at room temper-
1,000 - ~ ature. A total volume of 4 mL KMnO 4 was then added to each
tube, 1 mL at a time at 15-min intervals while standing in a dry
block heater set at 95~ The samples were digested at this tem-
perature for 4 h with occasional mixing. A persistent dark
t
color indicates complete digestion (29,30). Two milliliters of
Time (s) 20% hydroxylamine/HC1was added, followedby 20 pL octanol.
I" sos 'l The mixture was diluted to a final volume of 8 mL with ultra-
e2s --"1 pure water. Standard CVAASanalysis was performed on these
I~ . . . . . . . . . . . . . . . -e~~. . . . . . . . . . --I samples (31,32).
Figure 2. Matrix effect on washout time.

Results and Discussion

Table II. Precision in the ICP-MS Analysis of Hg on Patient Samples

Intra-assay (N = 20) Interassay (N = 10) The traditional CVAASmethod for the

determination of mercury required
Mean • SD CV Mean _+SD CV sample digestion prior to analysis. Such
(pg/L) (%) (pg/L) (%)
digestion step at high temperatures may
cause losses of mercury, which would re-
Whole Blood (Non-exposed) 5.2 _+0.177 3.4 5.1 + 0.255 5.0
Whole Blood (Exposed) 18.8 + 0.526 2.8 19.2 _+0.595 3.1
sult in a falsely low value. In addition,
Urine (Non-exposed) 1.19 + 0.080 6.7 1.24 _+0.091 7.3 the detection limit of traditional CVAAS
Urine (Exposed) 58.5 -+ 1.755 3.0 56.9 _+2.390 4.2 method for Hg determination is about
0.5 pg/L, which is not low enough for
non-exposed subjects. In order to improve
Table III. Accuracy in the ICP-MS Analysis of Hg the detection limit, several modifications
had been applied, such as on-line mi-
~r~t Interassay (N = 10) crowave sample pretreatment (16) and
on-line digestion with flow injection (2).
Value Mean • SD CV
Although a better detection limit can be
(pg/t) Range (pg/L) (%)
achieved, the physical set up is rather
Seronorm Whole Blood 1 2.06 1.72-2.40 2.21 _+0.197 8.9 complicated, which limits its use in rou-
Seronorm Whole Blood 2 7.7 6.8-8.5 8.02 _+0.385 4.8 tine clinical laboratory. Recent develop-
Seronorm Whole Blood 3 14.4 13.2-15.6 13.57 + 0.584 4.3 ments on ICP-MS for Hg determination
Lyphochek Urine Control 1 48 38-58 49.6 + 2.579 5.2 provide better sensitivity and precision,
and the detection limit can be achieved

284
Journal o f Analytical T o x i c o l o g y , Vol. 31, June 2 0 0 7

down to 0.01 pg/L (5). The improved assay performance relied effects. The cyclonic form prevented the sample from building
on sophisticated interface technique, such as anodic stripping up around the spray chamber wherein it could possibly be re-
voltammetry (24), direct-injection high-efficiency nebulizer nebulized. Slight tilting of the spray chamber ensured that all
(24), time-based on-line pre-concentration (5), or expensive Hg droplets thrown against its wall would run away from the tan-
isotope (10). The complexity and cost involved practically pre- gential nebulizer inlet and run out through the central drain.
clude their application in clinical laboratories in general. Five different kinds of diluent/wash solution were tested
(Figure 1). With HCl (Figure 1A) alone, the signal fails to re-
W a s h o u t characteristics turn to baseline level following the analysis of the standard and
Signal recovery time is an important analytical parameter as 30 min of washing. The addition of tert-butanol (Figure 1B) re-
it provides a reference point for analyzing the next sample in sulted in an increase in Hg signal's intensity due to improved
the queue, and thus indicates the rate of analysis. Significant Hg transport efficiency and its desolvation. For the wash-out
variables determining the signal decay time for potentially time, the addition of tert-butanol did not make any improve-
volatile analytes, like mercury, in an acidic medium are the ment compared with HC1 alone. For the diluent containing
volume and the surface area of a spray chamber. The small gold, HCI, and tert-butanol (Figure 1C), the washout time was
volume (25 mL) of the cinnabar spray chamber and the con- approximately 118 s. For the diluent containing dichromate in-
stant washing of its surfaces by the sample aerosol resulted in stead of gold (Figure 1D), the washout time was significantly
its rather rapid wash-out. The cinnabar spray chamber's small improved. It took only 80 s for the signal to return to baseline
surface area and appropriate shape also helped reduce memory level. Diluent with both dichromate and gold in HC1 and tert-
butanol (Figure 1E) had no additional improvement in washout
8 84
Blood H g time observed compared with only dichromate in HCI and
tert-butanol. Dichromate in HCI and tert-butanoi (Figure 1D)
6
was therefore chosen as the diluent for the analysis of mercury
9 +2SD = 4.04
4' m by ICP-MS. Matrix effect on washout time was shown in Figure
i

i 9 o ~
2, which indicated that there was only 5 s difference in washout
time with different matrix. As a result, a washout time of 85 s
t ~ qjt. . . . . . . . . . . . . ~ . . . . . . . . . . . . . . was used for the study.
9 9 Me~ = -0.68
coo
8 Linearity
The calibration curves, which covered the range of Hg con-
-2SD = -5.41
centrations in aqueous standard, whole blood, or urine, were
-8 consistently reproducible. We monitored between-day precision
I0 20 30 40 50 (x') 70 80 of the calibration curves on five days over a period of two
Average ot'this w o r k & N E Q A S consensus value (pig/L) weeks. The mean slope, intercept, and coefficient of linear re-
Figure 3. Biand-Altmanplot:comparisonof the ICP-MSmethodwiththe
gression (r2) in aqueous standard were 0.0888, 0, and 0.9999,
NEQAS consensusvalues in whole blood specimens. Linear regressionfor respectively. For whole blood they were 0.0767, 0.125, and
all samples (n = 21) in the comparison produced the following equation: 0.9989, respectively. For urine they were 0.0905, 0, and 0.9999,
y = 0.969x + 0.103 (r = 0.991 ). respectively. Calibration curves of the aqueous solution and
urine have practically the same slopes and intercepts, which
confirms that there is no matrix effect in urine sample. For
Urine H g whole blood sample, different slope and intercept were ob-
6'
served when compared with the aqueous solution. Therefore,
+ 2 S D = 3.56 a standard addition procedure should be used.

~i 2'_ "" =.
I glR
," 9
9 ."
9
Precision and accuracy
The intra- and interassay precisions are reported in Table II
f %. 9 .
O'JJ emr -o . . . . o- 9 . . . . . . . . . . . . . . . . . . . for the whole blood and urine samples. The method was found
9 9 9 9 9 09 ~ : -0.2?

-2' ~ 9
i . ,. . 9
. Table IV. Recovery (%) of Hg in ICP-MS (n = 3)
-4 . . . . . . . 9 9 9 -2SD : -4.09

-6
AddedHg
10 2O .3O 4O 5O 6O 70 80 9O (pg/L) Whole Blood Urine
A v e r q l e a r t h i s w o r k & NEQAS c e m e m m value (Itg/L)
2 107.4 95.6
Figure4. Bland-Altman plot: comparison of the ICP-MSmethod with the 10 99.4 103.0
NEQAS consensus values in urine specimens. Linear regression for all 50 103.7 104.1
samples (n = 63) in the comparison produced the following equation: y = 80 96.3 105.0
0.987x + 0.112 (r = 0.995). 100 105.2 101.7

285

to be highly precise with intra-assay coefficient variations (CVs)
< 4% and interassay CVs < 5.0% for whole blood. For urine
samples, intra-assay CVswere < 7% and interassay CVswere <
8%.
Results of the quality controls (QCs) studied in Table III in-
dicate the ICP-MS method for mercury has good performance
in accuracy. The performance of the ICP-MS method was also
tested using proficiency test samples from NEQAS (Centre for
Clinical Science and Measurement, University of Surrey, UK)
that covered a wide range of mercury levels in whole blood
(Figure 3) and urine (Figure 4). The obtained values agree
closely with the reported values at the 95% confidence in-
terval.
Recovery
Mean recoveries for five different Hg concentrations (Table
IV) ranged from 96.3% to 107.4% and from 95.6% to 105.0%
for whole blood and urine, respectively.
Limitof detection
The detection limits obtained were 0.13, 0.17, and 0.26 lag/L
for aqueous solution, urine, and whole blood, respectively.
Correlation
The correlations between the ICP-MS method and the
CVAASmethod were y = 0.93x + 0.56 (n = 22; r = 0.940) for
whole blood and y = 1.20x - 1.66 (n = 8; r = 0.989) for urine.
A Bland-Altman plot indicated equivalence of Hg results over
the concentration range found in routine specimen analysis
(Figure 5).
Conclusions
It has been shown that acidification of solutions prevents loss
of mercury by adsorption, and the addition of gold or dichro-
mate helps prevent mercury volatilization; however, in this
it
2t . ~
O I~
O O O
O ]~[E I !
9 0
O 9 0
-4 -
D 7. D. Beauchemin, K.W.M. Siu, and S.S. Berman. Determination of
-6
0 5 lO 15 20
A'~rqle oflwo mell~h ~ g / L )
Figure 5. Bland-Altman plot of the difference versus the mean of paired Hg
values between the ICPMS method and CVAAS method. Open-circles
and closed-circles denote whole blood and urine specimens, respectively.
286
Journal of Analytical Toxicology,Vol. 31, June2007
study dichromate is much more effective than gold in re-
moving residual mercury and reducing the mercury memory
effect. The approach of using a spray chamber of reduced
volume and a low-uptake neublizer demonstrates a significant
improvement in the determination of mercury by ICP-MS.
The total amount of sample being consumed and processed is
reduced to a minimum. Therefore, this approach offers the
advantages of simplicity and ease of use as no pre-analytical
steps, such as digestion, extraction, and chemical modifica-
tions, such as hydride generation, are required.
This study demonstrated that ICP-MScan be effectivelyused
for the determination of mercury in whole blood and urine. Re-
quiring only 100 laL of sample, determination of mercury by
ICP-MS yields accurate results compared to the traditional
CVAASmethod. This fast and simple method is suitable for rou-
tine use in a clinical laboratory setting where short turnaround
time is needed for proper management of patients suspected of
mercury exposure. The small sample size makes it particu-
larly suitable for micro-volume testing in the pediatric popu-
lation.
Acknowledgment
The authors thank Mr. Wu KW for helping with the atomic
absorption spectrometry assay.
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