CEN/TR 16176:2011

Characterization of waste - Screening methods for elemental composition by X-ray fluorescence spectrometry for on-site verification

In the framework of the EU Directive 99/31/EC on the landfill of waste and the EU Directive 2000/76/EC on the incineration of waste there is a growing need for fast, easy-to-handle screening tools. In this respect, low costs, fast analyses, control of truck loads and yes/no-acceptance decisions are relevant criteria. The X-ray fluorescence (XRF) technique meets these requirements as a screening tool for on-site verification on the landfill and for entrance control on the incineration plants.
Recent developments of the XRF technology have made this technique a method of choice for on-site analysis, namely miniaturisation of the XRF system (X-ray tube), the optimisation of the calibration programmes and the improvement of the detectors. Therefore, a state-of-the-art document on the current progress of the XRF technology and instruments available for on-site analysis shall support the key arguments, dealing with the pro’s and contra’s, and the performance of these systems to be expected.
The XRF standard EN 15309, is validated for Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, Sn, Sb, Te, I, Cs, Ba, Ta, W, Hg, Tl, Pb, Bi, Th and U, and describes in the informative annex the procedures for hand-held XRF systems together with the portable/transportable systems (placed in mobile labs). Although XRF can analyse a broad range of elements, the main focus of this document is on the series of elements that is also being covered by EN 15309. Of that series the following elements are related to the landfill directive: As, Ba, Cd, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Zn.
The information in this document will be useful in all cases in which on-site determination of the elemental compositions of waste is needed and hand-held instrumentation is therefore used. These cases may include, beside landfills and incineration plant, also waste treatment plants, contaminations soil sites and controls of transports of waste.

Charakterisierung von Abfällen - Anwendung von Screening-Verfahren bei der Vor-Ort-Prüfung - Bestimmung der elementaren Zusammmensetzung mittels Röntgenfluoreszenzspektrometrie

Im Rahmen der EU-Richtlinie 99/31/EG über Abfalldeponien und der EU-Richtlinie 2000/76/EG über die Verbrennung von Abfällen besteht ein wachsender Bedarf an schnellen, leicht zu handhabenden Screening-geräten. In diesem Zusammenhang sind geringe Kosten, schnelle Analysen, Kontrolle von LKW-Ladungen und Ja/Nein-Annahmeentscheide wichtige Kriterien. Die Röntgenfluoreszenztechnik erfüllt diese Anforderungen als Screeninginstrument bei der Vor-Ort-Prüfung auf Deponien und bei der Eingangskontrolle an Verbrennungsanlagen. Jüngste Entwicklungen der RFA-Technologie, insbesondere die Miniaturisierung des RFA-Systems (Röntgenröhre), die Optimierung der Kalibrierungsprogramme und die Verbesserung der Detektoren, haben diese Technik zum Verfahren der Wahl für die Vor-Ort-Analyse gemacht. Deshalb muss ein Dokument zum neusten Stand der Technik, über den aktuellen Fortschritt der für die Vor-Ort-Analyse zur Verfügung stehenden RFA-Technologie und -Geräte, die entscheidenden Argumente, die sich mit den Pros und Kontras und der zu erwartende Leistung dieser Systeme befassen, unterstützen. Die RFA-Norm EN 15309 ist für Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, Sn, Sb, Te, I, Cs, Ba, Ta, W, Hg, Tl, Pb, Bi, Th und U validiert und im informativen Anhang sind Verfahren für RFA-Handsysteme zusammen mit tragbaren/transportierbaren Systemen (untergebracht in mobilen Laboratorien) beschrieben. Obwohl mit der RFA ein breites Spektrum von Elementen analysiert werden kann, liegt der Schwerpunkt dieses Dokuments auf der Reihe von Elementen, die auch von EN 15309 erfasst werden. Aus dieser Reihe haben folgende Elemente einen Bezug zur Deponierichtlinie: As, Ba, Cd, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Zn. Die im vorliegenden Dokument enthaltenen Angaben sind in allen Fällen nützlich, bei denen eine Vor-Ort-Bestimmung der elementaren Zusammensetzung von Abfall benötigt wird und Handgeräte dafür eingesetzt werden. Diese Fälle können neben Deponien und Verbrennungsanlagen auch Abfallbehandlungsanlagen, Standorte mit verunreinigtem Boden (Altlasten) und Kontrollen des Transports von Abfall einschließen.

Caractérisation des déchets - Méthodes de dépistage pour la détermination de la composition élémentaire par spectrométrie à fluorescence de rayons X pour les vérifications in situ

Karakterizacija odpadkov - Rešetalne metode za elementno sestavo z rentgensko fluorescenčno spektrometrijo na kraju samem

V okviru Direktive Sveta 1999/31/ES o odlaganju odpadkov na odlagališčih in Direktive 000/76/ES Evropskega parlamenta in Sveta o sežiganju odpadkov obstaja rastoča potreba po hitrih rešetalnih orodjih, enostavnih za uporabo. Ustrezna merila v zvezi s tem so nizki stroški, hitre analize, nadzor nad tovori tovornjakov in odločitve o odobritvi, sprejete z odgovorom da/ne. Tehnika rentgenske fluorescence (XRF) kot presejalni test za preverjanje na odlagališču in nadzor pri dostavi v obrat za sežiganje ustreza tem zahtevam. Ta metoda je zaradi nedavnih dosežkov na področju tehnologije rentgenske fluorescence, zlasti zmanjšanja velikosti sistema rentgenske fluorescence (rentgenske cevi), optimizacije programov za kalibracijo in izboljšanja detektorja, najprimernejša za analizo na kraju samem. Zato mora dokument stanja tehnike o sedanjem napredku na področju tehnologije in instrumentov za rentgensko fluorescenco, ki so na voljo za analizo na kraju samem, utemeljiti ključne argumente, pri čemer morajo biti navedene dobre in slabe strani, in oceniti pričakovano zmogljivost teh sistemov. Standard za rentgensko fluorescenco EN 15309 je potrjen za Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, Sn, Sb, Te, I, Cs, Ba, Ta, W, Hg, Tl, Pb, Bi, Th in U ter v informativnem dodatku opisuje postopke za ročne sisteme za rentgensko fluorescenco in prenosne/prevozne sisteme (nameščene v mobilnih laboratorijih). Čeprav se z rentgensko fluorescenco lahko analizirajo številni elementi, se ta standard osredotoča na serijo elementov, ki jih zajema tudi EN 15309. Med elementi iz te serije so z direktivo o odpadkih povezani: As, Ba, Cd, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Zn. Informacije iz tega dokumenta so uporabne za vse primere, ko je treba določiti elementarno sestavo odpadkov in zato se uporabijo ročni instrumenti. Ti primeri lahko poleg odlagališč in obratov za sežiganje vključujejo tudi obrate za obdelavo odpadkov, območja s kontaminirano zemljino in nadzor prevoza odpadkov.

General Information

• Status: Published
• Publication Date: 08-Nov-2011
• ICS: 13.030.01 - Wastes in general
• Technical Committee: CEN/TC 444 - Environmental characterization
• Drafting Committee: CEN/TC 444/WG 3 - Inorganic analysis
• Current Stage: 6060 - Definitive text made available (DAV) - Publishing
• Start Date: 09-Nov-2011
• Due Date: 28-May-2012
• Completion Date: 09-Nov-2011
• Directive: 2000/76/EC - Directive 2000/76/EC of the European Parliament and of the Council of 4 December 2000 on the incineration of waste
• Directive: 99/31/EC - Landfill of waste
• Ref Project: SIST-TP CEN/TR 16176:2012 - Characterization of waste - Screening methods for elemental composition by X-ray fluorescence spectrometry for on-site verification

Standards Content (Sample)

SLOVENSKI STANDARD
01-februar-2012
.DUDNWHUL]DFLMDRGSDGNRY5HãHWDOQHPHWRGH]DHOHPHQWQRVHVWDYR]UHQWJHQVNR
IOXRUHVFHQþQRVSHNWURPHWULMRQDNUDMXVDPHP
Characterization of waste - Screening methods for elemental composition by X-ray
fluorescence spectrometry for on-site verification
Charakterisierung von Abfällen - Anwendung von Screening-Verfahren bei der Vor-Ort-
Prüfung - Bestimmung der elementaren Zusammmensetzung mittels
Röntgenfluoreszenzspektrometrie
Caractérisation des déchets - Méthodes de dépistage pour la détermination de la
composition élémentaire par spectrométrie à fluorescence de rayons X pour les
vérifications in-situ
Ta slovenski standard je istoveten z: CEN/TR 16176:2011
ICS:
13.030.01 Odpadki na splošno Wastes in general
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN/TR 16176
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
November 2011
ICS 13.030.01
English Version
Characterization of waste - Screening methods for elemental
composition by X-ray fluorescence spectrometry for on-site
verification
Caractérisation des déchets - Méthodes de dépistage pour Charakterisierung von Abfällen - Anwendung von
la détermination de la composition élémentaire par Screening-Verfahren bei der Vor-Ort-Prüfung - Bestimmung
spectrométrie à fluorescence de rayons X pour les der elementaren Zusammmensetzung mittels
vérifications in situ Röntgenfluoreszenzspektrometrie

This Technical Report was approved by CEN on 3 October 2011. It has been drawn up by the Technical Committee CEN/TC 292.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2011 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 16176:2011: E
worldwide for CEN national Members.

Contents Page
Foreword .3
Introduction .4
1 Purpose .5
2 Description of the XRF technique .5
2.1 General .5
2.2 Principle of XRF .5
2.3 Interferences .6
2.4 Measurement .7
2.5 Calibration/evaluation .7
2.6 Validation .8
3 Overview XRF applications .9
4 Influence of the sample preparation on the result .9
5 Evaluation of the XRF screening technique . 13
6 Robustness study: description and results . 15
6.1 General . 15
6.2 Technical description of the instruments . 15
6.3 Description of the selected samples and their characterisation . 16
6.4 Results of the field trial . 17
6.4.1 Defining performance criteria . 17
6.4.2 Evaluation of the repeatability, reproducibility and accuracy . 18
6.4.3 Influence of the sample pretreatment . 19
6.4.4 Evaluation of false positive / false negative results. 22
6.4.5 Limit of detection . 22
6.4.6 General evaluation of the portable XRF instruments. 22
6.4.7 Conclusions of the robustness study . 22
7 Conclusions . 23
Annex A (informative) Pre-normative robustness study . 24
Annex B (informative) Summary of EPA report on XRF technologies for measuring trace elements
in soil and sediment . 38
Bibliography . 42

Foreword
This document (CEN/TR 16176:2011) has been prepared by Technical Committee CEN/TC 292
“Characterization of Waste”, the secretariat of which is held by NEN.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
Introduction
Although bench-top instruments generally provide much more conclusive results, hand-held XRF instruments
are becoming an interesting screening tool for a wide range of applications. Their portability and their ability to
identify, characterise and also analyse a wide range of elements rapidly, along with the fact that little technical
expertise is needed to operate them, make the hand-held XRF instruments very useful. The recent
developments in the XRF technology tends to create hand-held instruments with performance levels
approaching bench top equipment. Some years ago, hand-held instruments required the use of radioactive
materials to provide a source of X-rays, resulting in very stringent regulatory demands. The development of
miniaturised low-power X-ray tubes overcomes these problems and provides new opportunities for the hand-
held instruments. Recent advances in the improvement of the detector efficiency led to a significant decrease
in the detection limits for hand-held systems compared to the older ones. Due to the required compact
configuration for hand-held XRF systems only energy dispersive X-ray fluorescence (EDXRF) are on the
market. On the other hand wavelength dispersive XRFs (WDXRF) are generally more laborious.
The use of the XRF technique in field screening trials can provide a number of benefits compared to the
traditional laboratory techniques. On-site analyses ensure a fast turnaround between the measurement itself
and the availability of data results. Sample preparation is frequently unnecessary or will be limited. Screening
can gain a large sample data set on a short time frame, but that can be at the expense of the accuracy and
precision. When better accuracy is required confirmative analysis has to be performed. This approach will
surely result in a significant reduction of analysis time and costs.
This report focuses on hand-held XRF instruments, although portable bench-top instruments are also on the
market for this type of application. Whenever portable instruments are specifically addressed in this report,
both types of instruments can be considered.
1 Purpose
In the framework of the EU Directive 99/31/EC on the landfill of waste and the EU Directive 2000/76/EC on the
incineration of waste there is a growing need for fast, easy-to-handle screening tools. In this respect, low
costs, fast analyses, control of truck loads and yes/no-acceptance decisions are relevant criteria. The X-ray
fluorescence (XRF) technique meets these requirements as a screening tool for on-site verification on the
landfill and for entrance control on the incineration plants.
Recent developments of the XRF technology have made this technique a method of choice for on-site
analysis, namely miniaturisation of the XRF system (X-ray tube), the optimisation of the calibration
programmes and the improvement of the detectors. Therefore, a state-of-the-art document on the current
progress of the XRF technology and instruments available for on-site analysis shall support the key
arguments, dealing with the pro‟s and contra‟s, and the performance of these systems to be expected.
The XRF standard EN 15309, is validated for Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn,
As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ag, Cd, Sn, Sb, Te, I, Cs, Ba, Ta, W, Hg, Tl, Pb, Bi, Th and U, and
describes in the informative annex the procedures for hand-held XRF systems together with the
portable/transportable systems (placed in mobile labs). Although XRF can analyse a broad range of elements,
the main focus of this document is on the series of elements that is also being covered by EN 15309. Of that
series the following elements are related to the landfill directive: As, Ba, Cd, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se,
Zn.
The information in this document will be useful in all cases in which on-site determination of the elemental
compositions of waste is needed and hand-held instrumentation is therefore used. These cases may include,
beside landfills and incineration plant, also waste treatment plants, contaminations soil sites and controls of
transports of waste.
2 Description of the XRF technique
2.1 General
X-ray fluorescence spectrometry is a fast and reliable method for the analysis of the total content of certain
elements within different matrices. The quality of the results obtained depends very closely on the type of
instrument used, e.g. hand-held, bench top. When selecting a specific instrument several factors have to be
considered, such as the matrices to be analysed, elements to be determined, detection limits required and the
measuring time. The quality of the results depends on the element to be determined and on the surrounding
matrix, together with the applied sample preparation method, and the heterogeneity of the test sample.
2.2 Principle of XRF
An electron can be ejected from its atomic orbital by the absorption of a light wave (photon) of sufficient
energy [1]. The energy of the photon (h ) must be greater than the energy with which the electron is bound to
the nucleus of the atom. When an inner orbital electron is ejected from an atom, an electron from a higher
energy level orbital will be transferred to the lower energy level orbital. During this transition a photon maybe
emitted from the atom. This fluorescent light is called the characteristic X-ray of the element (Figure 1). The
energy of the emitted photon will be equal to the difference in energies between the two orbitals occupied by
the electron making the transition. Because the energy difference between two specific orbital shells, in a
given element, is always the same (i.e. characteristic of a particular element), the photon emitted when an
electron moves between these two levels, will always have the same energy. Therefore, by determining the
energy (wavelength) of the X-rays (photon) emitted by a particular element, it is possible to determine the
identity of that element.
For a particular energy (wavelength) of fluorescent light emitted by an element, the number of photons per unit
time (generally referred to as peak intensity or count rate) is related to the amount of that analyte in the
sample. The counting rates for all detectable elements within a sample are usually calculated by counting, for
a set amount of time, the number of photons that are detected for the various analytes‟ characteristic X-ray
energy lines. It is important to note that these fluorescent lines are actually observed as peaks with a
semi-Gaussian distribution depending on the resolution of modern detector technology. Therefore, by
determining the energy of the X-ray peaks in a sample‟s spectrum, and by calculating the count rate of the
various elemental peaks, it is possible to qualitatively establish the elemental composition of the samples and
to quantitatively measure the concentration of these elements.

Key
A excitation: X-rays from X-ray source
B fluorescence: Characteristic X-ray
Figure 1 — Principle of XRF
The basic configuration of a
...