Trace Element Analysis of Industrial

Wastewater and Sewage with TXRF

and ICP-MS
Bruker AXS – Madison, WI
Bruker CAD – Fremont, CA
Welcome

Today’s Topics Speakers

• Introduction to TXRF Mike Beauchaine

Business Development TXRF
• Why wait for sample prep Madison, Wisconsin
• Application studies
• Sewage Analysis
• Industrial Wastewater
• Introduction to ICP-MS
• Operation of Bruker ICP-MS
• Wastewater analysis
• Interactive Q & A

Andrew Toms
ICP-MS Specialist
Milton, Ontario

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Introduction to TXRF

Mike Beauchaine
Principles X-ray fluorescence (XRF)
spectroscopy

1. An X-ray quantum hits an

inner shell electron in a
(sample) atom. The electron is
removed leaving the atom in
an excited state
2. The missing inner shell
electron is replaced by an
electron from an outer shell
3. The energy difference between
the inner and outer shell is
balanced by the emission of a
photon (fluorescence radiation)

12/13/2010 4
Principles X-ray fluorescence (XRF)
spectroscopy

• The energy, and therefore the wavelength, of the X-ray

fluorescence radiation is characteristic for the different chemical
elements.
QUALITATIVE ANALYSIS

• The intensity of the X-ray fluorescence radiation is, in first

approximation, proportional to the element concentration.
QUANTITATIVE ANALYSIS

Low Z High Z

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Principles X-ray fluorescence (XRF)
spectroscopy

“Common” XRF optics

Detector

X-ray tube

Sample

o o
Beam angle: 45 / 45

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Principles of total reflection
X-ray fluorescence (TXRF) spectroscopy

Typical instrument design of a TXRF spectrometer

Detector

Monochromator

X-ray tube

Sample carrier

Beam angle: 0o / 90o

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Principles of total reflection
X-ray fluorescence spectroscopy

Features and benefits of TXRF

• No scattering Detection limits down

monochromated X-rays to 0.1 ppb

• Versatile with regard Measurement of liquids

to sample type suspension, powders
etc.

• Sample amount Low µg or µl range

• Prepared as thin films Matrix effect are

inconsequential

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Principles of total reflection
X-ray fluorescence spectroscopy

• The S2 PICOFOX detects elements Element sensitivity

from Na(11) to U(92)
• The element sensitivities depend on K-lines L-lines
the atomic number
• The sensitivity factors are calibrated
ex works
• Sensitivities will differ based on the
tube

Atomic number

12/13/2010 9
The TXRF spectrometer
S2 PICOFOX

Benchtop TXRF spectrometer:

S2 PICOFOX
• Metal-ceramic X-ray tube
• Mo anode
• air-cooled
• optionally other tubes available

• Multilayer monochromator
• XFlash® Silicon Drift Detector
• thermoelectrically cooled
• ≤149 eV @ MnKα 100 kcps
• Automatic version
• 25-sample magazine

12/13/2010 10
Audience Poll

Please use your mouse to answer the question to

the right of your screen:

What would you most like to improve upon regarding your

current analysis?
 Speed of measurement
 Accuracy
 Sensitivity
 Sample prep
 Cost-of-ownership
 Ease-of-use

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Application studies
Sewage Analysis
Application studies
Sewage Analysis

• Control of threshold values of heavy metals

in sewage per 40 CFR 503.13:
• Dried sewage samples
• Sample prep
• Dilution (raw sewage sludge)
• Filtration and separate analysis of filtrate
possible
• Internal standardization
• Preparation – homogenization
• Apply 10 µl of sample to carrier
• Vacuum dry or heat
• Measurement
• Measurement time of 1000 s

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Application studies
Sample preparation for rapid screening

Sample preparation of Solid materials are ground to fine particle size and
filtrates, soils, and resuspended for direct analysis without digestion
solids

• fill powder in mortar

• grind carefully
• weigh about 20-50 mg
• transfer to vial

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Application studies
Sample preparation for rapid screening

• suspend in detergent solution

• add standard
• homogenize
• pipette on carrier

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 Application studies
Sewage Analysis

• Calculated detection limits in mg/l of

common elements measured at 1000 s
at 3σ in control solution, sewage, and raw
sewage.

• Exceeds threshold values for Cr, Mn, Fe,

Co, Ni, Cu, Zn, Se, Ba, and Pb

• Good correspondence with ICP-OES with

the added benefits of TXRF

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Application studies
Industrial Effluents

• Effluent analysis of heavy metals from

tanning leather process:
• Raw sewage samples
• Sample prep
• Internal standardization (Yttrium)
• Preparation – homogenization
• Apply 10 µl of sample to carrier
• Vacuum dry or heat
• Measurement
• Measurement time of 1000 s

12/15/2010 17
Sample preparation
Liquid samples

You‘ll need just a few steps for the preparation of liquid samples

• fill sample in micro tube

• add internal standard
• homogenize
• pipette on carrier

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Sample preparation
Final steps

• dry by heat / vacuum

• load the instrument
• start data acquisition

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 Application studies
Industrial Effluents

• Level of Detection was

well below limit value

• Level of Detection only

showed slight
improvement with
Microwave Digestion

• Analyzed using W tube

for 1000 s

• Little required sample

prep and low cost of
ownership • Concentrations expressed as mg/L
• Concentration limits for heavy metals in industrial wastewater
effluents according to the regulation from the Catalonia Water Agency
• Complementary tool to (Spain) and calculated detection limits from the analysis of the waste-
digestion techniques water reference material SPS-WW2 by TXRF
such as ICP-MS for * Acknowledgments to E. Margui – Institute of Earth Sciences
industrial treatment Barcelona, Spain
plants
12/15/2010 20
Application studies
Sewage Analysis

When applied to trace element analysis of fresh water and

sewage samples, TXRF offers the following benefits:
• Flexibility with regard to sample type
• Raw sewage
• Industrial wastewater and effluents
• Contaminated soils
• Filtered sewage
• Fresh water
• Sewage filtrates

• Easy multi-element analysis without external calibration – Allows for

prescreening of unknown samples prior to ICP-MS
• Low maintenance costs
• Small size of the system (mobile use)

12/13/2010 21
Conclusion
TXRF vs. AAS/ICP-OES
TXRF AAS / ICP-OES
• Small footprint/portable
• Microgram sample size
• % to ppb levels
• Single std. calibration
• Low maintenance
• Non-destructive
• Short learning curve
• Fast sample prep
12/13/2010
• Large, fixed installation
• Milligram sample size
• ppm to sub-ppb levels
• Multi-standard calibration
• High maintenance
• Destructive
• Long learning curve
• Laborious sample prep
22
Summary
Introduction to ICP-MS

Andrew Toms

12/15/2010 24
ICP-MS Overview

• Very high sensitivity and low background

• Low DLs <1 ppt for some elements in solution

• Large linear dynamic range (9 orders)

• Few spectral interferences

• Simple spectra produced

• Isotopic analysis capability

• Routine trace element analysis

• (ppb and below)

• Rapid multi-element analysis

• Wide range of elements (>75)

• Analysis of a wide variety of sample types

• Simple sample preparation

• Wide variety of sample introduction options

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Elemental Analysis by Mass
Spectrometry

Atomic Number Mass Number - common ICP-MS

The number of protons in the nucleus of
the atom
Also the number of electrons in a ground
state (electrically neutral) atom
Isotopes
Atoms of elements which have the same
number of electrons and protons but
different numbers of neutrons
terminology
The total number of protons and neutrons
in the nucleus of a particular isotope
AMU
Atomic Mass Unit - the mass of a proton or
neutron
The two isotopes of boron shown here will
have different masses but will otherwise be
essentially identical in their chemical
properties

Mass Number 11 10

5
B 5
B
Atomic Number

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Element Isotopes in ICP-MS

Example: Nickel
58 60 61 62 64
Ni Ni Ni Ni Ni
No. of protons (p+) 28 28 28 28 28
No. of electrons (e-) 28 28 28 28 28
No. of neutrons (n) 30 32 33 34 36
Atomic mass (p+ + n) 58 60 61 62 63
Atomic number (p+) 28 28 28 28 28
Natural abundance 68.1% 26.2% 1.14% 3.63% 0.93%
Atomic weight 58.69

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ICP-ES Spectrum for Ni

Many emission lines for Ni

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ICP-MS Spectrum for Ni

Five stable isotopes of Ni

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 Extent of Ionization in Argon Plasma

H >80% 50-10% He
Li Be 80-50% <10% B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw

Calculated values of degree of ionization of M+ and M+2 (T=7500K, ne = 1e15cm-3 )

* Houk 1986
12/15/2010 30
ICP-MS System Summary

• Sample nebulized (aerosol) in spray chamber

• Argon transports sample and sustains plasma
• RF generator supplies energy to induction coil
• Sample atomized and ionized in the plasma
• Ions are transmitted through the interface, most of the
gas removed
• Collision/reaction technology applied to minimize
interferences (some instruments)
• Ions are focused into mass analyzer
• Quadrupole filters the ions by mass
• Detector counts the ions

12/15/2010 31
 The Inductively Coupled Plasma

Auxiliary Gas

ICP-MS Sampling Plasma Gas

Position
Plasma Tail

Preheating Zone Nebulizer

Distance from Gas +
Initial Radiation Zone Sample
load coil
Induction Zone Aerosol

12/15/2010 32
Processes in the Plasma

MO+ M+ MX MX MXn M(H20)+ X-

Oxides Ions Atoms Gas Solid Liquid

Sample
aerosol

Recombination Ionization Atomization Vaporization

12/15/2010 33
 Plasma RF System

Solid state 27‐MHz RF generator

Microprocessor‐controlled 
impedance matching network

Interlaced Load Coils 
• High coupling efficiency for 
the utmost in plasma 
stability
• Allows unshielded cool 
plasma operation
Computer‐controlled XYZ 
alignment

12/15/2010 34
The ICP in operation

• RF-induced plasma operating at

~5000K

• Hot enough to ionize almost

every element in the periodic
table

• Argon used because of suitable

ionization properties

12/15/2010 35
Interface and Ion Mirror

12/15/2010 36
Common ICP-MS analytes
and their common interferences

Analyte Interferences Bruker’s Answer?

40Ca 40Ar The Collision/Reaction

Interface (CRI)
51V 35Cl16O

52Cr 40Ar12C, 35Cl16O1H, 36Ar16O H2 gas injected to react

53Cr 40Ar13C, 37Cl16O with Ar+ and ArX+
molecular ions
56Fe 40Ar16O, 40Ca16O

75As 40Ar35Cl He gas used to separate

78Se 40Ar38Ar
other interferences using
Kinetic Energy
80Se 40Ar40Ar
Discrimination (KED)

12/15/2010 37
Implementation of the CRI

The best conditions (high plasma density and high temperature) 
for collisions and reactions are found in the aperture of the 
skimmer .   

12/15/2010 38
The Quadrupole in operation

Ions are more affected by the alternating RF field.

Will drift until it finds itself in stronger and stronger
Too Light - regions of field. It will quickly collide with an
electrode and disappear.

Not affected much by the alternating field, but will

gradually drift in the constant (DC) part of the field. The
Too Heavy - alternating field is not strong enough to drag it back as it
wanders, so it also collides with an electrode, and is lost.

An ion of the correct mass/charge ratio is stable in the

Just “Right” - quadrupole field and reaches the end, where it can be
detected.

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Extended Dynamic Range Detector

Gain
Quadrupole Control

e- e- e-
+ e- e-
Signal
Output

Ion to e- Amplification
Conversion
Control
Section

Adjustment of gain applied to control dynode provides attenuation of

final output signal

12/15/2010 40
109 Linear Range

10 ppt -> 1000 ppm Tl205

R2 = 0.999999

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Trace Elements:
0.01 – 5 ppb Selenium

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Major elements:
0.1 ppb – 100 ppm Mg

12/15/2010 43
Sewage and Wastewater
Analysis by ICP-MS

• ICP-MS is less tolerant of samples with

high dissolved solids.
• Cloudy/murky solutions should be
dissolved/digested/filtered.
• Highly concentrated solutions can also be
diluted – automated online dilution is
optional
• ICP-MS is highly automated, and can run
100’s to 1000’s of samples unattended,
every day

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Application Notes ready to go

12/15/2010 45
Q&A

Any Questions?

Please type in questions you may have for

either of our speakers in the Q&A panel
and then click Send.

12/15/2010 46
Visit Us At

American Academy of Forensic Science

February 21 – 26, 2011
Chicago, IL

PITTCON
March 13 – 18, 2011
Atlanta, GA

American Chemical Society

March 27 – 31, 2011
Anaheim, CA

12/15/2010 47
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