Atomic fluorescence spectrometry and its

applications in As, Hg and Se analysis

Dr. Bin Chen

bc@psanalytical.com
Senior Application Specialist, P S Analytical Ltd.
Orpington, United Kingdom
 Recent Publications
Methylmercury in water samples at the pg/L level by online preconcentration liquid chromatography cold vapor-atomic
fluorescence spectrometry
Christoph-Cornelius Brombach, Bin Chen, Warren T. Corns, Jrg Feldmann, Eva M. Krupp
Spectrochimica Acta Part B: Atomic Spectroscopy, Volume 105, 1 March 2015, Pages 103-108

Direct online HPLC-CV-AFS method for traces of methylmercury without derivatisation: a matrix-independent method for
urine, sediment and biological tissue samples
Christoph-Cornelius Brombach, Zuzana Gajdosechova, Bin Chen, Andrew Brownlow, Warren T. Corns,
Jrg Feldmann, Eva M. Krupp
Analytical and Bioanalytical Chemistry, January 2015, Volume 407, Issue 3, pp 973-981

Quick and robust method for trace determination of MeHg in rice and rice products without derivatisation
Christoph-Cornelius Brombach, Mohamed Farouk Ezzeldin,Warren T. Corns, Bin Chen, Jrg Feldmann, Eva M. Krupp
Submitted to Journal of Analytical Atomic Spectrometry, April 2015

Trace Levels of Neurotoxic Methylmercury in commercial baby-food rice and other rice products vary by more than an order
of magnitude
Christoph-Cornelius Brombach, Bin Chen, Warren T. Corns, Jrg Feldmann, Eva M. Krupp
Submitted to Environmental Science and Technology, April 2015
Accurate fast screening for total and inorganic arsenic in rice grains using hydride generation atomic fluorescence
spectrometry (HG-AFS)
Bin Chen, Warren T. Corns, Peter B. Stockwell and Jen-How Huang
Anal. Methods, 2014,6, 7554-7558

Atomic Fluorescence Spectrometers Used in

SCI Publications
Why Speciation?
Why Speciation?
Modular Interface (10.820-1000)

Online
digestion
Hg
speciation
10.820 with Millennium Excalibur
10.820 Modular Interface
BEFORE

10.820 with Millennium Excalibur

10.820 with Millennium Merlin
Online Preparation Examples
Online Preparation Chemistry
As Speciation in Natural Water without

LOD (ng/ml, 3s)

As(III) 0.06
As(V) 0.22
HPLC pump
As(III) DMA
MMA
As(V)
Ammonium carbonate gradient elution
12.5 mM Ammonium carbonate at pH 9(A) and 60 mM Ammonium carbonate at pH 9 (B) in a gradient program at a flow-rate of 1
mL/min:
T= 0 min: 100% A, 0 % B
T=2min: 0 % A, 100 % B
T=10 min:100% A, 0% B
1200 Figure 1: Overlaid Chromatograms of
As(III), DMA, MMA and As(V). Blank, 0.5, 1,
1000 5, 10 and 20 g L-1.
Blank

800 0.5 g/L

1 g/L
600 5 g/L
10 g/L
400 20 g/L

200

0
0 5 time / min 10 15
Correlation coefficient Linear plot

As(III) 1.0000 1414.5x+31.408

DMA 1.0000 780.72x+87.67
MMA 0.9994 1258.1x+235.39
As(V) 0.9999 1416.1x+407.47
a c

b
d
Figure: Calibration of As(III) (a), DMA )(b), MMA (c) and As(V) (d) in the range of 0 to 20 g L-1 (lowest standard: 0.5 g L-1);
error bars represent one standard deviation (n=3). The equation gives the linear trendline for the calibration points and the
correlation coefficient R2.

Hydrogen as a support for the flame

Advantages
(1) Less NaBH4 consumption
(2) Lower baseline and less noise
(3) Better sensitivity and stability
(4) Flexible reagent concentrations and flow rates
800

700

600

500 Blank
0.5 ppb
400 1 ppb
5 ppb
300
10 ppb
20 ppb
200

100

0
0 2 4 6 8 10 12 14
time / min

50 L injection loop
As in Wastewater
Small shifts of peaks
because of ions in
matrix
Peak identification
can always be done
with spiking of the
species into the real
sample.
Se Species HPLC Column Mobile Phase
 5 mM Citric Acid, 2%
SeCys, SeIV,VI and SeMet Hamilton PRP-X100 200 Methanol, pH 5.9, 0.8
10 ppb each ul injection ml/min

Selenium in Yeast
Se-cystine Se(IV)
SeMet

SeMet Se(VI)

Se-cystine
Se(VI)
Se(IV)

Se(IV)
SeMet
Se-cystine Se(VI)
Se in FGD Wastewater
1600 120

FGD-Europe
1400
100
FGD-Europe Spike
1200
FGD-USA
80
1000

800 60

600
40

400

20
200

0
0

Se 1 ppb
 Methylmercury in Sediment
450

400
Hg(II)

350

300

250

200
Et-Hg (IS)
150 Me-Hg

100

50

0
0 1000 2000 3000 4000
Time (s)
Inorganic mercury partially dissolves in organic solvent
Hg Speciation (2 ppb MeHg,
EtHg and Hg2+)
Methylmercury Pre-concentration in Water/Food
Preconcentration-column

oxidant reductant

waste Detector
sample
HPLC HPLC CV-AFS
pump 1 pump 2
UV GLS
sample Mobile phase
cooler

Preconcentration Separation Detection

Oxidant: 10 % 0.1 N bromide/bromate solution, 3.7 % (v/v) hydrochloric acid
Reductant: 2 % SnCl2 in 3.7 % (v/v) hydrochloric acid
Mobile phase: 1.5 mM ammonium pyrrolidine dithiocarbamate in 78 % methanol
Methylmercury in the low-ppt range
700

y = 108,6x + 34,817 5
600
R = 0,9993

500 4

400
3

300 2

200
1

0,5
100
0

0
0 0,5 1 1,5 2 2,5 3 3,5 4 4,5 5
Methylmercury / ng L-1
 Sample preparation for rice
1. 300 mg rice + 3 mL TMAH
2. Microwave digestion (20 min at 55 C + 20 min at 60 C)
3. Addition of 2 mL HCl and ultrasonication for 10 min
4. Ultracentrifugation at 13000 rpm
5. Dilution of the supernatant to 50 mL for preconcentration
 MeHg in rice

y = 1,0318x + 0,0003
R = 0,9663 9 rice samples from local
3 supermarkets and stores
were analysed with prec.
HPLC-CV-AFS and ID-GC-
2 ICP-MS

0
0 1 2 3 4
c(MeHg) in g kg-1 --> prec HPLC-CV-AFS
 Conclusions
Accurate and precise results can be obtained with
AFS.
Compact design of 10.820 aim to reduce cost and
save lab space
Sample preparation simplified to almost zero for
some total analysis.
Conversion to the correct oxidation state can be
easily achieved.
PSA have developed methodologies and
international standards for numerous sample
types and applications.
 PSA offer first class assistance for applications and
technical support.