FIELD APPLICATION REPORT

ICP-OPTICAL EMISSION

Continuous Flow Hydride Generation

Using the Optima ICP

Authors:
Cynthia P. Bosnak, Leon Davidowski

PerkinElmer Life and Analytical Sciences

710 Bridgeport Avenue
Shelton, CT 06484

In tr od uct io n

Hydride generation techniques have been combined with ICP optical emission spectrometry for the routine determination of
trace concentrations of As, Sb, Bi, Ge, Se and Te since 1978 1. More recently, several statements of work (SOW) for the
U.S. EPA's contract lab program (CLP) have been published which call for "Hydride Generation Inductively Coupled Argon
Plasma Optical Emission Spectroscopic Analysis" (HY-ICP) using a continuous flow system 2.

In a continuous flow system, the acidified sample, blank or standard is continuously pumped and mixed with a pumped
stream of reductant, usually sodium borohydride, to produce the gaseous hydrides. At the point of reaction, hydrogen gas is
produced as a by-product. A flow of argon is added to this mixture and the hydrides are "stripped" into the gas phase. A
gas/liquid separator allows the gaseous, hydride-containing phase to enter the ICP for analysis, and allows the remaining
liquids to be pumped to waste. Limits of detection can generally be improved by about two orders of magnitude over simple
solution nebulization using hydride generation.

Work was done in an ICP Application Study 4, which detailed the construction and application of a simple and inexpensive
continuous flow hydride generator for ICP-OES analyses using the Optima™ 3000 ICP system. In this study, experimental
conditions were further optimized for the determination of As and Sb using the Optima 4300 DV ICP system.

Ex pe riment al

Instrumentation
All emission data were acquired on an Optima 4300 DV ICP spectrometer. Instrumental operating conditions and parameters
are listed in Table 1.
The built-in three-channel peristaltic pump used for the hydride generator is a standard, software-controlled part of the ICP
spectrometer system. The ICP spectrometer's mass-flow controlled "nebulizer argon" is used as the source of the hydride
stripping argon.

w ww .per k in e l me r.com
T ab l e 1 . In st ru me nta l Ope rat in g C o nd it io ns an d Pa ra me t er s
ICP RF Power 1450 W
Plasma Gas 17 L/min
Auxiliary Gas 0.2 L/min
Nebulizer Gas 0.50 L/min
Viewing Type Axial
Integration 2 / 20 seconds
Read Delay 30 seconds
Replicates 3

Continuous Flow Apparatus

The continuous flow hydride generator (Figure 1) consisted of inexpensive, readily available components. A parts list is
given in Table 2 (including the PerkinElmer part numbers). Two mixing T's (Chemifold Assembly) were used to combine
the sample and reductant streams and to add the stripping argon (Figure 2). The chemically resistant plastic gas/liquid
separator provided a very small volume, low sample dispersion and very fast rinse-out times. The gaseous hydrides were
transported by the stripping argon flow directly into the base of the Optima 4300 ICP torch. The standard 2 mm i.d. alumina
sample injector tube was used.

To ICP

Argon
Reductant

Waste

Sample

Figure 1. Chemifold apparatus Figure 2. Tubing diagram

Reagent Preparation for As and Sb Determination

5% KI/Ascorbic Acid Solution
Weigh 5 g potassium iodide and 5 g ascorbic acid into a 100 mL polypropylene bottle. Dilute to 100 mL with deionized
water.
0.5% Sodium Borohydride in 0.05% Sodium Hydroxide
Weigh 0.25 g of NaOH into a 500 mL polypropylene bottle. Add approximately 100 mL deionized water and swirl to
dissolve the NaOH. Weigh 2.5 g NaBH4 and add to the NaOH/deionized water mixture. Dilute to 500 mL volume with
deionized water. Prepare fresh daily.

Procedures
For this work, sodium borohydride (NaBH4) was used as the reducing agent to generate the gas phase hydride. An example
of the hydride generation reaction is given below:

NaBH4 + 3H2O + HCl Æ H3BO4 + NaCl + 8H + E Æ EHn + H2

where E is the analyte element.

Sodium borohydride was used at a concentration of 0.5% (w/v). This solution was stabilized with the addition of sodium
hydroxide to a final concentration of 0.05%. The flow rate used was 2.2 mL/min.

2
T ab le 2 . Co nt inuo us F low Sys t e m C o mpon ent s
Quantity Item Part Number
1 Chemifold Assembly B0507957
1 Gas line with quick connect N0770336
1 110 mm PTFE Tubing B0191058
2 300 mm PTFE Tubing B0198097
1 700 mm PTFE Tubing and Sinker B0191059
1 Injector Adapter N0695426
1 PTFE Membrane (pkg. of 50) B0508306
1 Adapter C B0196850
1 Adapter E B0196857
1 Adapter A B0193342
1 Adapter K B0507918
2 Connector 1B B0196882
1 Silicone Tubing B0018283
1 PVC Tubing B0048139
1 1.14 mm id peristaltic pump tubing, PVC, red/red N0680375
1 1.52 mm id peristaltic pump tubing, PVC, blue/yellow B0193161*
1 3.18 mm id peristaltic pump tubing, PVC, black/white B0508310*
* Remove the center tab of peristaltic pump tubing

The efficiency of the hydride generation reduction reaction is dependent on the oxidation state of the analyte; usually the
reaction proceeds best from the lower oxidation states. To ensure that the analyte is in the lower oxidation state, a pre-
reduction reaction is carried out before the hydride generation step.

Table 3 lists the typical oxidation states likely to be found in samples and the reagents and procedures utilized for pre-
reduction. The KI/ascorbic acid mixture used for a reducing agent for As and Sb cannot be used on samples in which Se or
Te are to be determined because Se and Te will be reduced all the way to their elemental forms and will therefore not be
available for the hydride formation reaction. It is therefore necessary to carry-out two separate pre-reduction procedures on
samples for which As or Sb and Se or Te are to be determined. Bismuth could be pre-reduced by either method.

Standards and blanks were treated in the same manner as the samples, and a flow rate of 3.6 mL/min was used for the sample
flow.

T ab l e 3 . A n a l yt e Ox id at io n Stat es a nd Pre - re du ct ion

Element Oxidation State Pre-Reduction Conditions
Sb V → III 0.2% KI/Ascorbic Acid + wait > 20 minutes
As V → III 0.2% KI/Ascorbic Acid + wait > 20 minutes
Bi V → III 0.2% KI/Ascorbic Acid + wait > 20 minutes // 7M HCl + 90 °C Heat
Se VI → IV 7M HCl + 90 °C Heat
Te VI → IV 7M HCl + 90 °C Heat

Pre-Reduction Step
For the pre-reduction of Sb and As, 20 mL of sample was placed in a 50 mL polypropylene autosampler tube. To this, 2 mL
of a 5% solution of KI and ascorbic acid was added. Six mL of concentrated HCl was also added, and the mixture was
allowed to sit for at least 20 minutes. The tube was brought to the 50 mL mark with deionized water and the sample was
ready to run.

3 www.perkinelmer.com
For the pre-reduction of Se and Te, 20 mL of sample was placed in a clean 125 mL beaker and 20 mL of concentrated HCl
was slowly added. The mixture was then heated on a hot plate just to a boil and then allowed to cool. The solution was then
transferred to a 50 mL polypropylene autosampler tube which was diluted to the 50 mL mark with deionized water.

Result s

Method detection limits were calculated by the three sigma method from the standard deviations of replicate measurements
in the multi-element determinations of Sb, As, Bi, Se, and Te using blank solutions 4. Two-point background correction was
used for the analyses. The results are listed in Table IV. The detection limits listed are on average at least 100x lower than
those attainable by normal pneumatic nebulization 3 and well within environmental requirements 2. Very high sensitivities
are attainable with this vapor generation technique and the hydride generation reactions and the sample transfer step are very
efficient. In addition, there are no losses or carry-over problems of the type associated with spray-chamber based sample
introduction systems.

T ab l e 4 . M et h od D et ect io n L im i t s (µg/L)

Element Wavelength (nm) Detection Limit (3*SD)

Sb 206.833 0.1
As 188.979 0.1
Bi 232.061 0.5
Se 196.026 0.4
Te 214.281 1.5

Co nc lus ion

This report shows that a very simple continuous flow hydride generator can be constructed for use with standard ICP-OES
instrument and applied to the determination of hydride forming elements at very low concentration levels. In addition,
multiple elements can be determined simultaneously using the Optima 4300 DV ICP.

Pre-reduction can be used to lower the oxidation state of the hydride-forming elements to insure more efficient vapor
generation. Improvements in sensitivity of approximately 2 orders of magnitude can be obtained by hydride generation over
standard typical pneumatic nebulization.

Re fer en ces

1. M. Thompson, B. Pahlavanpour, S. J. Walton, G. F. Kirkbright, Analyst, 103, 703 (1978).

2. U.S. EPA CLP Statement of Work for Inorganic Analyses (HCIN), October 1990.

3. "Guide to Techniques and Applications of Atomic Spectroscopy", The Perkin-Elmer Corporation (1991).

4. PerkinElmer ICP Application Study Number 67, L. Davidowski, March 1993.

Perkin Elmer Life and

Analytical Sciences
710 Bridgeport Avenue
Shelton, CT 06484-4794 USA
Phone: (800) 762-4000 or
(+1) 203-925-4602
www.perkinelmer.com

For a complete listing of our global offices, visit www.perkinelmer.com/lasoffices

©2004 PerkinElmer, Inc. All rights reserved. The PerkinElmer logo and design are registered trademarks of PerkinElmer, Inc. Optima is a trademark of PerkinElmer, Inc. or its
subsidiaries, in the United States and other countries. All other trademarks not owned by PerkinElmer, Inc. or its subsidiaries that are depicted herein are the property of their
respective owners. PerkinElmer reserves the right to change this document at any time and disclaims liability for editorial, pictorial or typographical errors.

The data presented in this Field Application Report are not guaranteed. Actual performance and results are dependent upon the exact methodology used and laboratory conditions.
This data should only be used to demonstrate the applicability of an instrument for a particular analysis and is not intended to serve as a guarantee of performance.

007062_01