AS Techniques

for the Analysis of

Environmental Samples
Novj Sad 2008, January 30th
Riccardo Magarini
ICPMS /ICPOES /AAS specialist
riccardo.magarini@perkinelmer.com

Summary
Poredenje razliitih spektroskopskih medoda u analizi
metala
Comparison of Atomic Spectroscopy Techniques and
P f
Performances
Flame-AAS, GF-AAS, ICP-OES, ICP-MS
DLs, speed, interferences, easy of use

A l ti l Factors
Analytical
F t
Sample preparation, pre-analytical factors, official methods

The analysis process

Method development
Calibration
Performances evaluation
Interferences
QC

Which Technique ?
At i Ab
Atomic
Absorption
ti

ICP OES
ICP-OES

Sample Preparation

ICP-MS
ICP
MS

Atomic spectroscopy techniques

A quick review

The evaluation parameters scheme

Detection
Limits ?

Sample
consumption ?

Analytical speed
and productivity ?

Which / how
many elements ?

M ti ?
Matrix

Concentration
range ?

? Official
methods ?

Operator
skill issues ?

Financial
resources

Detection Limits (ug/L)

AA
ICP-OES
GF- AA
ICP-MS
0 001 0.01
0.001
0 01

01
0.1

1
g/L

10

100 1000

Detection Limits (ug/L)

Linear Dynamic Range

Orderrs of Ma
agnitude
e

8
7
6
5
4
3
2
1
0

FL-AAS

GF-AAS

ICP-OES (DV) ICP-MS

Technique

Comparison of the Techniques

Radial ICP-OES set as average

Factor

Flame AA

GFAAS

Radial
R
di l
ICP-OES

Axial
A
i l
ICP-OES

-Poorer

-Much poorer

ICP-MS

Detection Limits
Accuracy/Precision
Concentration Range
Sample Volume
Elements per sample
Operator Expertise
Purchase price

-Much better

-Better

-Average

Definitions
Detection Limits
Accuracy
Precision

Detection Limits

0.06 mg/L
g
3x

noise
Detection Limit = 0.06 mg/L
Detection Limit can be defined in many ways
Most often it is approximated as the concentration of an
analyte that produces a signal that is 3x the standard
deviation of the noise level
It is often calculated using 3x the standard deviation of a
blank or a suitable low-level standard

Detection Limits: Environmental Analyses

Instrument Detection Limit (IDL)
Defined as the concentration of analyte which equals
three
h
times
i
the
h standard
d d deviation
d i i
off ten replicates
li
off the
h
calibration blank

Method Detection Limit (MDL)

(
)
The minimum concentration of analyte determined to be
different from the blank at a confidence level of 99%.
Error of carrying a sample through the entire analysis
process is built into the calculation.

Practical Quantitation Limit (PQL)

Lowest level that can reliably be achieved within specified
limits of precision and accuracy during routine operating
conditions;; often defined as 5 or 10x the standard
deviation of the noise level; from: SW846, 1986.

Calculation of MDL: From EPA Method 200.9 (1 of 2)

1. Prepare a suitable amount of sample spiked with

the element(s) of interest at a level two to three
times the IDL.
2. Split the sample into a minimum of seven
aliquots and process through the entire
analytical procedure (e.g., reagent addition,
digestion,
g
, replicates,
p
, etc.).
)
3. Perform all calculations as described in the
method and calculate the standard deviation of
th results
the
lt off the
th seven aliquots.
li
t

Calculation of MDL: From EPA Method 200.9 (2 of 2)

4. Calculate the MDL according to this

formula:
MDL = t s
where:
t = students t value at the 99%
confidence level using n-1
d
degrees
off freedom
f d
(t = 3.14
3 14 (f
(for
seven replicates)
s = standard deviation of the results
of the prepared aliquots

Calculation of Rugged MDL: From SW-846

1. Repeat steps 1-3 as in 200.9 over three nonconsecutive days

2. Average the daily MDL values to obtain the
rugged MDL

Precision and Accuracy

Accuracy
The difference between an average
g value and the
true value when the latter is known (from EPA)

Precision
The degree of mutual agreement among individual
measurements made under p
prescribed conditions
(from EPA)

Precision and Accuracy

Precise, Not accurate

Not Precise, Not Accurate

Precise,, Accurate

Accurate,, Not Precise

Flame Atomic Absorption

Fast
3 - 5 a determination

Low analytical
y
costs
Easy to use
Single element technique

M*

M+ + e_

Ionization

Mo

M*

Excitation

MA

Mo + Ao

Atomization

Solution

Page 18

Solid

Vaporization

Flame-AAS Method Development

Selecting the correct instrument parameters

Determining
g the range
g of analysis
y
for each element
Working Ranges
Sensitivity and Detection Limits

Setup and Optimization

Flame
Burner and Nebulizer Adjustments
Integration times

Interferences
Non spectral and spectral

Quality Control

Page 19

Recommended Conditions from AAWinLab

Page 20

Beers Law is Valid at only Low Absorbances

1.2

08
A 0.8
b
s
0.4

Non-linear Range
0

Linear Range
g

io

Conc

io = initial lamp intensity

i = final lamp intensity

ABSORBANCE: A = log (io /i)

Flame Sensitivity

C
r

Abs

Au

Cu

Lea
n

Ric
h

Choosing Integration Time

% CV

3
In general:

Time ((sec))

10

use 3-5 sec. for air-acetylene

y
use 5-10 sec. for nitrous oxide-acetylene

Interferences in Flame AA

Nonspectral
Any interference which affects the sample
signal in a manner which is different from the
calibrating materials
(M i Chemical;
(Matrix;
Ch i l Ionization)
I i i )

Spectral
Occur when the measured absorption in a
sample is erroneous due to the presence of
another species which is also absorbing
light at that wavelength
(Non Specific Absorption, more common in GF-AAS)

Matrix Interference (Non-Spectral)

Uptake Rate

Nebulizer

Droplet Size

1% HNO3
5% H2SO4

.................

MIBK

Viscosity and surface tension effect

Uptake
Uptake rate
Droplet size
Sensitivity

Matrix Interference

Chemical Interference
Example: Certain samples may contain components
that form thermally
y stable compounds
p
that will not
decompose with the typical energy available in the
flame
Temperature of air-C
air C2H2 flame: 2100 - 2400oC
Temperature of N2O-C2H2 flame: 2650 - 2800oC

Interference in air-C2H2
flame:
CaCl2

Cao

Ca3(PO4)2

Cao

Correcting for Chemical Interferences

Add releasing
g agent
g
to all solutions
Example: Add Lanthanum to combine with the
phosphate and allow the free Ca atoms to be
produced
d
d in
i the
th flame
fl
In this example, 0.2-0.5% La is usually added

Ca3(PO4)2

LaCl3

CaCl2

air-C2H2

Cao

Correcting for Matrix Interferences

Matrix match all samples, standards, and blanks
Analyze using Method of Standard Additions (MSA)
03
0.3

Abs
0.15

0
-0.82

1
Concentration

Spectral Interference

A
A
A
A

Background

BG

Background Correction: Continuum Source

Continuum
Source
Monochromator

Detector
Hollow
Cathode Lamp

Background Correction: Continuum Source

In
ntensity

AA

BG

BG

HCL

AA

BG

BG

Cont.
Source

HCL

Cont.
Source

Sample Preservation

Dissolved
Filtered through 0.45 m membrane filter
Acidified to pH < 2

Total recoverable
Acid preserved drinking water with turbidity < 1 NTU
no digestion necessary (unfiltered)

Others, acid digestion

SW-846 Sample Prep Procedures for FL-AAS

Method 3005A
Acid digestion of waters for total recoverable or
dissolved metals for analysis by FLAA or ICP
Spectroscopy
p
py

Method 3010A
Acid digestion of aqueous samples and extracts for
total metals for analysis by FLAA or ICP Spectroscopy

SW-846 Sample Prep Procedures for FL-AAS

Method 3015
Microwave assisted
Mi
i t d digestion
di
ti
off aqueous sample
l and
d
extracts

Method 3031
Acid digestion of oils for metals analysis by atomic
absorption or ICP spectrometry

Method 3040A
Di
Dissolution
l ti
procedure
d
for
f oils,
il greases, or waxes

SW-846 Sample Prep Procedures for FL-AAS

Method 3050B
Acid digestion of sediments, sludges, and soils

Method 3051
Microwave assisted acid digestion of
sediments sludges,
sediments,
sludges soils,
soils and oils

Method 3052
Microwave assisted acid digestion of siliceous
and organically based matrices

SW-846 Methods for Flame AAS

Element
Aluminum
Antimony
y
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper

Method Est. Range

mg/L *
7020
7040
7080A
7090
7130
7140
7190
7200
7210

* Based on 0.0044 absorbance

>1
> 0.5
> 0.4
> 0.025
> 0.025
0 025
> 0.08
> 0.25
> 0.2
> 0.1

Oxidant
Nitrous oxide
Air
Nitrous oxide
Nitrous oxide
Air
Nitrous oxide
Nitrous oxide
Air
Air

Bkg. Corr.
Not required
Required
q
Not required
Required
Required
Not required
Not required
q
Required
Recommend

Environmental Analysis: Flame AA

Barium
Numerous chemical interferences in air-C2H2 which are
virtually eliminated using N2O-C2H2
Strong emission of the N2O-C2H2 flame can lead to
excessive noise; try increasing the lamp current and/or
reducing the slit
Barium is ionized 80-90% in a N2O-C2H2 flame; add 0
0.2-0.5%
2-0 5%
of an easily ionizable metal (e.g., K as Cl-)
Char. conc. at 553.6 is approx.. 0.4 mg/L; can be improved
by concentrating sample and/or changing impact device

Environmental Analysis: Flame AA

Cadmium
At the primary wavelength of 228.8 nm, Cd is easily
determined in an air-C2H2 flame with a detection limit of
about 0.8 ug/L
g
Samples with high dissolved solids, such as wastewater,
often require background correction

Environmental Analysis: Flame AA

Chromium
For flame AA, most sensitive using a fuel-rich, air-C2H2
flame , but is extremely prone to interferences from Fe, Ni,
and other metals; 0.2% Na2SO4 and/or 2% NH4Cl have been
shown
h
to
t reduce
d
the
th effects
ff t
Cr(III) exhibits a higher sensitivity than Cr(VI) in the rich, airC2H2 flame; a lean flame flame or a N2O-C2H2 flame will
reduce the interference,
interference but also the sensitivity
For determinations of Cr(VI), EPA Methods 218.3 & 7197
chelate the Cr(VI) with ammonium pyrrolidine
dithiocarbamate ((APDC)) and subsequent extraction with
methyl isobutyl ketone (MIBK); extract can be determined by
flame or furnace; MDL by flame is approx. 1 ug/L

Environmental Analysis: Flame AA

Chromium (cont.)
(
)
For determination of Cr(VI), EPA Method 7195 involves the
coprecipitation of Cr(VI) as lead chromate with lead sulfate
in an acetic acid solution. The supernate
p
is drawn off and
the precipitate is resolubilized. Quantification can be by
flame or furnace AA.

Copper
Few interferences in an air-C2H2 flame at 324.8 nm
Sensitivity not affected by many instrument conditions so
frequently used as a test for instrument/method

Environmental Analysis: Flame AA

Lead
The resonance line at 217.0 nm is 2.5X more sensitive than
the 283.3 nm line, but the DL is slightly degraded because of
significantly
g
y higher
g
noise
The 217.0 nm line also suffers from additional background
effects
To improve sensitivity,
sensitivity an extraction procedure can be
performed; in EPA 600/4-79-020, Section 9.2 an extraction
with APDC in MIBK is recommended for flame
determinations where Pb levels are below 200 ug/L
g

Wastewater Analysis (ERA Wastewater Reference)

Many metals limits are of sufficient concentration for flame AA
determination
Wastewater standard from ERA Corporation, prepared with
EPA H
Hotplate
t l t method
th d 200.2
200 2

Element
Ba
Cd
Cr
Cu
Mn
Ni
Zn

Result
(mg/L)
0.464
0.147
0.790
0.218
0.185
0 351
0.351
0.108

True Value Spike Added

(mg/L)
(mg/L)
0.469
5.00
0.148
0.50
0.801
0.50
0.221
0.50
0.188
0.50
0 346
0.346
0 50
0.50
0.0995
0.50

Recovery
%
98.9
99.3
98.6
98.4
98.1
101
108

Spikes and comparison to the true values verify method performance

for a representative matrix
Page 43

Graphite Furnace -Atomic Absorption

Low DLs (g/L) for many elements
Slower than flame (45-90)
Little sample consumption (L)
Single element technique
Some experience is needed

Ab so rb an ce
A

0.06
AA-BG
BG

0.04
0.02
0.00
0

Time / s

Chromium, 10 L of 1 g/L
Page 44

Selecting Element Parameters

Page 45

GF-AAS typical thermal program (Pb)

HGA program for 20 uL sample and 5 uL modifier
Step

Temp
(oC)

Ramp
(sec)

Hold
(sec)

Gas Flow
(mL/min)

Dry 1

90

300

Dry 2

130

10

20

300

Pyrolysis

700

20

300

Atomization

1600

Clean-out

2650

300

Read

Teemp

Clean
At i ti
Atomization

P l i
Pyrolysis
Dry 1

Dry
2
Time

Page 46

Effect of Atomization Temperature (Pb, HGA)

0.610

2200oC

1800oC
1600oC

1400oC

Page 47

Time (sec)

5 00
5.00

Optimize the Atomization Temperature

Page 48

Stabilised Temperature Platform Furnace (STPF)

Parameter/Feature
Platform atomization
Integrated platforms
THGA (with & without
endcaps)
Integrated platform HGA
tubes
Uniform pyrolytic graphite
coatings

Benefit
Isothermal atomization
Ease of use (no changing
platforms)
Reproducible & reliable data
All elements from platform
Longer tube lifetimes (corrosive
samples)

Proof Statements
Gas-phase temperature
measurements (CARS)
Reduced or eliminated chemical
interferences
Characteristic mass (m0) stability
Lifetime studies
Scientific publications

Rapid, controlled furnace heating

Reliable day-to-day performance
Independent of line voltage, tube
parameters (i.e., resistance)
True Temperature Control (TTC)

Temperature measurements
Refractory element performance
with different voltages

Integrated Absorbance
(peak area) measurements

More robust measurements

Reliable day-to-day performance
Independent of matrix changes

Peak area vs peak height studies

Zeeman-effect
Z
ff t B
Background
k
d
Correction

No user selection
N
l ti required
i d
Wavelength independent method
Better detection limits

IInterference
t f
studies
t di
Scientific publications

Universal Chemical Modifier

Palladium/Magnesium nitrate

Faster, simpler method

development
Reproducible & reliable data

Interference studies
Recovery measurements
Scientific publications

Page 49

Cadmium Pyrolysis Curves

Page 50

Zeeman and D2 correction

Se in fish tissue

Continuum
BG

Abs

AA

Abs

Zeema
Bn
G

AA

Page 51

Deuterium bkgd. correction problems

(over / under correction)

As std. at 30 ug/L

As 30 ug/L + Al 100 mg/L

Interfering lines in slit band-width with D2 bkgd. correction

Page 52

Zeeman correction (PE THGA)

As 1 ug/L

Page 53

As 1 ug/L + Al 200 mg/L

EPA Method 200.9

From EPA Monitoring Systems Laboratory (EMSL) in

Ci i
Cincinnati
ti
Revision 1.2 published in 1991
Revision 2.2 published in 1994
Designed primarily for the analysis of waters including:
drinking, surface, ground, and wastewaters
Principles
p
of analysis
y
may
y also be applied
pp
for the analysis
y
of sediments, sludges, and soils

Page 54

EPA Method 200.9 Sample Preparation

Drinking water samples where the turbidity is < 1
NTU the sample are analyzed directly
Total Recoverable Metals in aqueous samples
require digestion

Sample preparation for total recoverable elements in water

or waste water
1 100 mL sample + 1 mL HNO3 + 0.5
1.
0 5 mL HCl
into a 250 mL beaker
2. Heat at 85 oC until the volume is reduced to
20 mL
3. Cover and reflux for 30 minutes
4. Cool; transfer to a 50 mL volumetric flask and
dil t to
dilute
t volume
l

Page 55

EPA Method 200.9 Sample Preparation

Sample preparation for total recoverable elements in solid

samples
1. 1 g of well homogenized sample + 4 mL
(1+1) HNO3 + 10 mL (1+4) HCl into a 250 mL
beaker
2. Cover and reflux for 30 minutes
3. Cool; transfer to a 100 mL volumetric flask
and dilute to volume
4. Allow to stand overnight before analysis

Page 56

Method 200.9 for GFAAS

STPF conditions
Pl tf
Platform
atomization
t i ti
Background correction
Where sample digestion is required a mixed acid digestion
using HCl and HNO3 is used
Palladium/magnesium nitrate modifier [0.015mg Pd +
0.01mg Mg(NO3)2]
A mixture of 95%Ar/ 5% H2 is used as the internal gas
during the dry and pyrolysis steps

Page 57

GF-AAS analysis
As in mineral waters (AAnalyst 6/800 EDL lamp)

AA and Bkgd.
signals for As in
a drinking water
sample
(3.3 g L-1)

Ab
bsorbancce

0 03
0.03
AA-BG
BG

0 02
0.02

0 01
0.01

0.00
0

3
Time / s

Page 58

GF-AAS analysis
As and Pb in drinking waters

Arsenic
Water

Conc.

+Spike

Sample

g/L

50 g/L Recovery g/L

Nist SRM 1643c 77.2

Page 59

Lead
%

Conc.

94

35.3

+Spike

25 g/L Recovery
100

Drinking

<DL

54.5

109

2.5

29.2

107

Ground

<DL

56 2
56.2

112

98
9.8

37 1
37.1

109

Stream

<DL

57.0

114

3.1

31.1

112

Pond

1.2

55.3

108

<DL

26.8

107

River

<DL

57.4

115

2.5

29.9

110

Atomic Absorption
CV / Hydrides
V
Very
low
l
DLs
DL (g/L),
( /L) but
b t
only useful for Hg; As; Sb; Se; Te; Bi; Sn

Slower than flame

Chemistry dependent

Page 60

CV / Hydrides

Examples of Prereduction:
Element

Page 61

Reduction

Method

As

+5

+3

As
Sb

+5
+5

+3
+3

Bi
Se
Te

+5
+6
+6

+3
+4
+4

10% KI +
5% Ascorbic Acid
L-cysteine
10% KI +
5% Ascorbic Acid
6M HCl
6M HCl, 90 oC
6M HCl,
HCl 100 oC

Time
30 min
min.
Immediate
Immediate
Immediate
20 min.
2 min
min.

GF-AAS
Data Verification

How Do You Know If The Sample Data is Good?

Use furnace conditions optimized for the sample matrices

U good
Use
d QA/QC
Examine the peak profiles

Page 63

Checking the Sample Matrix

Make sure the furnace temperatures are OK

Observe the peaks

Is the background peak high or complex?

Do either of the peaks go below the baseline?
Does the analyte peak come off too fast?
D
Does
th
the analyte
l t peak
k come off
ff ttoo slow?
l ?
Is there a BOC error?

If necessary, spike the sample to see an analyte peak

Page 64

Recovery Studies

Run the sample

Run the spiked (fortified) sample
Determine the spike recovery
conc. of fortified sample
- conc. off unfortified
f tifi d sample
l
= conc. of addition?

Page 65

Sample Spikes

Post-digestion Spikes
Sample is spiked the day of analysis
Checks for matrix interferences

Pre-digestion spikes
Sample is spiked prior to digestion
Checks for analyte contamination during the
sample preparation procedure
Checks for analyte losses during sample
preparation
ti
May not pick up volatile compound losses
(sample analyte is volatile, spike analyte is
stable)

Page 66

Checking the Sample Matrix

Spike recoveries are good (85-115%)

Proceed with the analysis

Spike recoveries are poor

Make sure the spike concentrations are
not within the precision levels
Further method development

Page 67

ICP--OES
ICP

Sample
Introduction
System

Environmental analysis
This multi-element analysis is usually performed
by ICP-OES due to its speed and robustness
National or supra-national regulations are
usually applied:
EPA 200.7 in USA ( ! As withdrawal !))
Determination of Metals and Trace Elements in Water and
Wastes by ICP-AES

Method 6010B from SW846

ASTM; APHA /AWWA
DIN 38 406 E 22 in Germany
EN ISO 11885:1998 Europe and global scale
Water quality. Determination of 33 elements by ICP-AES

Method Editor/Spectrometer/Define Elements

Periodic Table

Results for Drinking Water Sample

Element (nm)
Al
309
As
193
Ba
233
Be
234
Cd
214
Co
238
Mn
257
Mo
203
Ni
231
Pb
220
Sb
217
Se
196
V
309
Zn
206

found
125.3
56.6
506
12 4
12.4
6.4
24.6
37.8
113.
57.4
17.8
52 5
52.5
10.9
36.4
72.4

NIST 1643d (g/L)

S.D. certified
4
127.60
0.9
56.02
4
506.50
0.03
0 03 12.53
12 53
0.2
6.47
0.2
25.00
0.3
37.66
0.95 112.90
0.3
58.10
0.15 18.15
1.4
14
54 10
54.10
0.8
11.43
0.4
35.10
0.3
72.48

S.D.
3.5
0.73
8.9
0 28
0.28
0.37
0.59
0.83
1.7
2.7
0.64
11
1.1
0.17
1.4
0.65

NIST 1643d,
Trace elements
in water

Optima 2100 detection limits (axial)

Elem.
Al
As
B
Be
Cd
Co
Cr
Cu
Fe
Mn
Mo
Ni
Pb
Sb
Se
Tl
V
Zn

Wavelength
396.152
193.696
249 772
249.772
313.107
214.440
238.892
267.716
224.700
259.939
257.610
202.031
231.604
220.353
206 836
206.836
196.026
190.801
309.310
206.200

D.L.
0.9
3.6
0 25
0.25
0.017
0.07
0.25
0.25
0.9
0.2
0.03
2
0.4
1.4
4
4.5
3.5
0.15
0.2

Acquired using
10 seconds
d iintegration
t
ti titimes
Cyclonic spray chamber
Low-flow GemCone neb.
3 x Blank SD, ug/L

Ultrasonic Nebulizer (Cetac USN-5000AT+)

Vibrating piezoelectric crystal to

generate aerosol
Would result in introduction off
too high amounts of mass into
plasma

Removal of solvent through

vaporization (heating) and
condensation (cooling)

Cannot tolerate high TDS

Not for HF solutions
Usually increases sensitivity 5
5-15
15
fold
Can have washout problems due
to cooled transfer line
It is expensive

Ultrasonic Nebulizer DLs (ug/L, Optima 4x00DV, XL)

Optima 2100 environmental analysis

CRM W
Waste-Water
t W t CWW-TM-G
CWW TM G
Trace Metals in Certified Wastewater
(High Purity Standards, Charleston, SC USA)
Element
Al
As
Ba
Cd
Co
C
Cr
Cu
Fe
Mn
Mo
Ni
Pb
V
Zn

Meas.

SD

RSD

Certif.

Accuracy

[mg/L]

[mg/L]

[%]

[mg/L]

[%]

1.047
0 258
0.258
0.0241
0.255
1.036
0 0249
0.0249
0.0250
1.019
1.035
0.980
0.259
0.0252
1 00
1.00
0.0249

0.005
0 006
0.006
0.0001
0.004
0.002
0 00005
0.00005
0.0005
0.006
0.003
0.004
0.001
0.0001
0 007
0.007
0.0003

0.51
22
2.2
0.52
1.4
0.23
0 20
0.20
1.8
0.56
0.29
0.38
0.29
0.40
0 71
0.71
1.2

1.00
0 25
0.25
0.025
0.25
1.00
0 025
0.025
0.025
1.00
1.00
1.00
0.25
0.025
1 00
1.00
0.025

4.7
32
3.2
-3.6
2.0
3.6
-0.4
04
0.0
1.9
3.5
-2.0
3.6
0.8
00
0.0
-0.4

Optima 2100 and sludges

Method and instrument performances verified with
reference materials (Community Bureau of
R f
Reference,
B
Brussels,
l B
Belgium)
l i )
BCR 145 Trace Elements in Sewage Sludge
BCR 146 Trace Elements in Sewage Sludge of mainly
Industrial Origin

Sample preparation (as per DIN S7 method)

3 g dried sample and 28 mL of aqua regia were heated under
reflux for three hours and diluted to 100 mL. Two digestions
were done of each material

Optima 2100 and sludges

CRM Sewage Sludge BCR 145
(results are aqua regia soluble, while Hg is total)
Digest 1
Meas.
As
Ba
Be
Cd
C
Co
Cr
Cu
Hg
g
Ni
Pb
V
Zn

SD

Digest 2
Meas.

SD

[mg/kg] [mg/kg] [mg/kg]

[mg/kg]

3.5
3
5
295
0.203
17.7
77
7.7
76.2
403
10.65
38.6
364
13.5
2835

0.2
0
2
2
0.002
0.1
0 02
0.02
1
1
0.06
0.2
1
0.1
11

0.2
0
2
3
0.001
0.1
01
0.1
0.2
1
0.08
0.1
0.5
0.1
5

3.1
3
1
332
0.201
17.4
7 09
7.09
79
401
10.43
39.0
350
13.5
2799

CRM
Certif. Confidence
[mg/kg]
Interval
16.8
1.6
68
6.8
10
1.0
85.2
16.3
415.9
23.5
8.82
0.88
38.5
3.6
332
22
2772
209

ICP Interferences

Physical
Spectral
Chemical
Ionization

Physical

Internal Standardization

Corrects for p
physical
y
interferences
viscosity variations
surface tension variations

U
Uses
a non-analyte
l t element
l
t

Internal Standardization
Use element not in
samples
Add precisely
i l to
t all
ll
solutions
Calibration is on internal
standard to analyte ratio
as function of analyte
concentration
Software makes
correction
Consider solubility and
spectral characteristics

Spectral Interferences

Any
y unwanted light
g that reaches the detector
Approaches on dealing with spectral interferences
Choose another wavelength or use higher resolution, if
available
Simple background correction
Other correction techniques
Multicomponent Spectral Fitting (MSF)
Inter Element Correction (IEC)

Components of an Emission Spectrum

Emission Spectrum = sum of n contributions

+
A l t
Analyte

+
Bl k
Blank

=
Measured Spectrum

M ti
Matrix

Simple Background Shift

W Standard
Al 1000mg/L
g

W Standard

Al 1000mg/L

Blank

Sloping Background

Pb Standard
Al 1000mg/L

Pb Standard

Al 1000mg/L

Blank

Examine Spectra & Setting Background Points

Keep b
K
background
k
d points
i t away from
f
interferences
i t f
Setting points on interferences could result in large
negative IECs

Spectral Summation
The Observed Emission is the Sum of the Emission
from the Analyte, the Interfering Element and the
Background

Correcting for Interferences (MSF) Cd Corrected for As

Unknown
sample with
Arsenic
interference

Raw Signal

Cd signal
corrected

Method Editor/Spectrometer/ Define Elements

Wavelength Table

Continuous flow hydrides kit on ICP

to ICP
Sample

NaBH4
Argon

Waste

ICP-MS
It is an analytical technique for the
Determination of
Elements
El
t using
i
Mass Spectrometry of
Ions generated by an
Inductively Coupled Plasma

350000

300000

Fe

Cr

Ti

I
n 250000
t
e 200000
n
s 150000
i
t 100000
y

Co

Ni/Fe
Cu

Ni

50000

Zn Cu

Zn

Fe

0
45

50

55

60

65

70

Mass

ICP

Mass Spectrometer

Detector
Interface
.

sample

. ..

.. . .
.. .

ICP-MS as a routine analytical tool

ICPApplication Areas (Elan Database)

Environmental Applications
U.S. EPA approved methods

EPA Method 200.8 - approved for drinking water

and
d waste
t water
t

Approved December 5, 1994 (FR 59 (232) p. 62546)

12 metal contaminants approved, including Hg
Na, K, Ca, Ba going through approval process

EPA Method 6020 - approved for solid waste

Approved January 13, 1995 (FR 60 (009) p.3089)

15 metal contaminants approved

Sample Preparation Guidelines

Waters for EPA 200.8 - no dilution

exception for some waters
Method 3050 digests for EPA 6020
1:10 dilution
some samples require 1:20 dilution
TCLP samples
1:20
1 20 dil
dilution
ti
needed to reduce carbon buildup on cones

Page 95

US EPA ICP-MS Method 200.8

NIST 1643 Drinking Water

mg/L

g/L

Ca
Mg
g
Na
K
Be
Co
Pb

Measured
37.1
9.82
12.55
2.4
19.4
22.0
34 1
34.1

Certificate
36.8 1.4
9.45 0.27
12.19 0.36
(2.3)
23.2 2.2
23.5 0.8
35 3 0
35.3
0.9
9

US EPA ICP
ICP--MS Method 6020
NIST 2711 - Contaminated Soil

El
Element
t
Al
Sb
As
Ba
Be
Cd
Cr
Co
Cu
Pb
Mn
Ni
Ag
Tl
Zn

Sample
Conc.
(
(mg/kg)
/k )
20,070
3.9
94.0
192.2
1.1
40.0
23 7
23.7
8.1
104.1
1087
493
17.1
4.3
1.2
315.8

% Rec.
Spike % Recovery
Spike
Certified Amount
of
Recovery
V l
Value
(
(mg/L)
/L)
Spike
S
ik
Li it (%)
Limits
111
104
96
100
118
99
104
99
101
107
108
n/a
102

100
100
100
100
100
100
100
100
100
100
100
100
100
100
100

n/a
198
103
98
104
102
97
98
99
n/a
110
96
102
105
98.2

75-125
75-125
75-125
75
125
75-125
75-125
75-125
75 125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125
75-125

Uranium and Thorium determination by ICP-MS

Elan IDL for U: 0.02 ng/L

Elan IDL for Th: 0.03 ng/L

Isotopic ratio for

235U

/ 238U (10 ug/L)

Natural Uranium (U3O8)

Reading
-1
-2
-3
-4
-5
-6

ratio
0 00710
0.00710
0.00707
0.00708
0.00713
0.00708
0.00712

RSD
0 99
0.99
0.63
0.69
0.43
1.22
1.03

Depleted Uranium (Aldrich std)

Reading
-1
-2
-3
-4
-5
-6

ratio
0 00318
0.00318
0.00318
0.00318
0.00316
0.00316
0.00318
238U

99 27%
99.27%

235U

0.72%

RSD
1 21
1.21
1.25
1.03
0.98
1.08
1.36

Effect of Acids on Background

Page 100

Spectroscopic interferences correction equations

Page 101

Spectroscopic interferences Dynamic Reaction Cell

Page 102

Dynamic Reaction Cell DRC Operating Principle

Page 103

Sources of Contamination in ICP-MS

Acids
Water (use 18 M or better)
Pipettes and pipette tips
Do not use glass pipettes!
Use mechanical pipettes (Eppendorf, etc.)
Use only plastic, metal-free tips
S
Sample
l containers
t i
Plastic is preferred (see Spex information)
Use pre-cleaned when possible
NO lid liners allowed except Teflon!

Page 104

Sources of Contamination in ICP-MS

Volumetric ware
Glass flasks should be eliminated
Use
U Pl
Plastic
ti Volumetrics
V l
t i if necessary
Your lab environment
Dust
Paper
Rusty hoods
YOU!!! (Na, Ti, K, Fe, Cu, Zn, Co, Si, etc....)
Your skin in general (Na, Ca, K)
Lotions
Make-up
Make p
Hair sprays, gels
Deodorant, ....

Page 105

Procedures to avoid contamination

Use good clean lab techniques

Limit contact with extra devices, containers, etc.
Wear gloves and lint free labcoat
Keep any area where samples prepared or opened clean!
Hoods, benches, instrument
Pre-clean vessels for lowest level work
Clean
Cl
in
i dilute
dil t nitric
it i acid
id and
d keep
k
in
i closed
l
d containers
t i
Limit access to clean lab areas

Page 106

Procedures to avoid contamination

Determine Laboratory MDL with normal acids, procedures

If good enough no changes are necessary
If improvement needed (lower MDLs) need to work on
limiting
g contamination.
Use superior acids: Ultrex, Optima, etc..
Buy ICP or ICP-MS grade standards
AA standards contain too many impurities
Should not be used for multi-element standards

Purchase multi-element standards

All elements
l
certified
ifi d

Page 107

General Sample Preparation

Method 200.8 - Contained in Method

Method 6020 - Use any preparation procedure
3005
3010
3015 microwave (preferred for lowest level work)
3020
3050 (AA)
3050 (ICP)
3051 microwave (preferred for lowest level work)
YOU must decide upon sample preparation procedures to meet
requirements of ICP-MS (avoid HCl if possible) AND satisfy the
regulatory agency you report to.

Page 108

Other Sources of Contamination

Material

Page 109

Major Impurties

Glass test tubes

Si, B, Na

Polypropylene tubes

Cl Mg,
Cl,
Mg Ca (Cr
(Cr, Zn,
Zn Ni)

LDPE

Ca, Cl, K

HDPE

Ca, Zn, Si

TCLP Filters

Ba, Si, B

Speciation
Speciation
Allows separation and measurement of forms of an element
Oxidation state
Organic molecules bound to the element

Enviro and toxicology important elements:

Chromium ((Cr3 and Cr6))

Arsenic (As3; As6; organo-As)
Selenium
Mercury
Platinum, Gold

LC-ICPMS system diagram

Solvents
Reservoir

Vacuum
Degasser

LC P
Pump

Column Oven
Autosampler

HPLC Column

ICP

Computer

ICP-MS (DRC)

Neb /Sprayy
Chamber

Switching
S
it hi
Valve
Waste

Simultaneous As-Cr Speciation in Waters

Cr+3

Cr+6
As+3

As+5

seconds

1 g/L Mixed Standard on ELAN DRC

GC-ICPMS experimental setup

GC-ICPMS Sn in Sediments
Sn species of concern in marine waters and sediments
____ Sediment
____ 2.6 ppb std

Tri-butyl-Sn
Di-butyl-Sn

Mono-butyl-Sn

Tetra-butyl-Sn

Hvala
Grazie

Thank you