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Trends in Analytical Chemistry, Vol. 28, No. 2, 2009

Commonly used methodologies for inorganic analysis in international key comparisons

Yiu-chung Yip, James Chung-wah Lam, Wai-fong Tong

The Consultative Committee for Amount of Substance – Metrology in Chemistry (Comite´ Consultatif pour la Quantite´ de Matie`re, CCQM) has the task of organizing international key comparisons. The main purpose is to establish a technical basis for mutual recognition of measurement capabilities among national measurement institutes (NMIs) in the field of chemical measurement. More importantly, key comparison results provide an effective means of assessing the degree of equivalence of measurement standards used at different NMIs. Since 1998, the Inorganic Analysis Working Group of CCQM has been identifying and organizing key comparisons for the determination of analytes, such as elements, inorganic compounds and organo-metallic compounds in various matrices. Methodologies, including inorganic mass spectrometry [e.g., isotope dilution mass spectrometry (IDMS) and species-specific IDMS], inductively coupled plasma atomic emission spectrometry, neutron activation analysis, ion chromatography, high performance liquid chromatography, X-ray fluorescence spectrometry, flame atomic absorption spectrometry (AAS) and graphite furnace AAS, have provided satisfactory results in terms of accuracy and precision. Complex sample matrices examined so far include inorganic solutions and water (e.g., calibration solutions and natural water), metal and metal alloys (e.g., steel and aluminum alloy), biological fluids, materials and food (e.g., serum, rice, wine, shellfish, salmon fish, tomato and bovine liver), fuels (e.g., diesel), sediments and soils (e.g., sediments and sewage sludge). The use of IDMS for elemental analysis has attracted considerable attention. In this review, we focus on commonly used methodologies for inorganic analysis in CCQM key comparisons between 1998 and 2007, and we suggest potential areas for strategic research and development. ª 2008 Elsevier Ltd. All rights reserved.

Keywords: CCQM; Elemental analysis; Inductively coupled plasma atomic emission spectrometry; Inorganic analysis; Isotope dilution mass spectrometry; Key comparison; National measurement institute; Methodology; Neutron activation analysis; Species-specific isotope dilution mass spectrometry

Yiu-chung Yip*, Wai-fong Tong Government Laboratory, Ho Man Tin Government Offices, 88 Chung Hau Street, Kowloon, Hong Kong, Hong Kong Special Administrative Region, China

James Chung-wah Lam Center for Coastal Pollution and Conservation and Centre for Marine Environmental Research and Innovative Technology, Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, Hong Kong Special Administrative Region, China

* Corresponding author. Tel.: +852 27623862; Fax: +852 27151737; E-mail: ycyip@govtlab.gov.hk

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1. Introduction

Metrology is defined as the scientific study of measurement [1] . Kaarls has described significant developments in metrology in chemistry [2] . Ting et al. paid particular attention to the role of metrology in chemistry in upholding public health and food safety [3] . The need for measurement results that are traceable to the Interna- tional System of Units (Syste` me Interna- tional d Unite´ s, SI) and comparable worldwide is of concern to analytical lab- oratories, government authorities, indus- tries and the public. The Convention of the Meter forms the basis of metrology. On 20 May 1875, the representatives of seventeen nations signed the Convention in Paris [4] . The

purpose of the Convention is to establish

a permanent organization for member

governments to work on matters relating

to units of measurement. The Convention

gives authority to the General Conference on Weights and Measures (Confe´ rence

Ge´ ne´ rale des Poids et Mesures, CGPM),

the International Committee for Weights and Measures (Comite´ International des Poids et Mesures, CIPM) and the Inter- national Bureau of Weights and Mea- sures (Bureau International des Poids et Mesures, BIPM) to act in matters of metrology ( Fig. 1 ). Nowadays, 20 May is known as the World Metrology Day to mark this historic occasion. In 1960, the CGPM adopted the SI as the practical system of units of mea- surement. The seven base units are as

0165-9936/$ - see front matter ª 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2008.09.013

Trends in Analytical Chemistry, Vol. 28, No. 2, 2009

Trends

The Convention of the Meter CGPM CIPM BIPM • Ensure the propagation and improvement of
The Convention
of the Meter
CGPM
CIPM
BIPM
Ensure the propagation
and improvement of SI
• Provide worldwide
uniformity in units of
measurement
Provide the basis for a
single coherent system
of measurement that is
traceable to SI
CCQM
• Present activities
concerning primary
methods for measuring
the amount of substance
• Organize a series of
international key
comparisons for the
purpose of establishing
the technical basis for
mutual recognition of
measurement
capabilities among
NMIs in the field of
chemical measurement

Figure 1. Organizational structure of The Convention of the Meter, CGPM, CIPM, BIPM and CCQM.

follows: meter (m), kilogram (kg), second (s), ampere (A), Kelvin (K), mole (mol), and candela (cd) [5] . Among other base units, the mole is of interest to chemists. The CIPM defined the mole in 1967 and the CGPM adopted it (1971, Resolution 3) as fol- lows:

The mole is the amount of substance [6] of a

system that contains as many elementary entities as there are atoms in 0.012 kg of carbon 12, which are unbound, at rest and in their ground state [7] ; its symbol is ‘‘mol’’. (2) When the mole is used, the elementary entities must be specified and may be atoms, molecules, ions, electrons, other particles, or specified groups of such particles. The CIPM set up the Consultative Committee for Amount of Substance – Metrology in Chemistry (Comite´

(1)

Consultatif pour la Quantite´ de Matie` re, CCQM) in 1993. Two major tasks of the CCQM are:

(i) to present activities concerning primary methods for measuring the amount of substance; and,

(ii) to organize a series of international key comparisons

for the purpose of establishing a technical basis for mutual recognition of measurement capabilities among national measurement institutes (NMIs) in the field of chemical measurement [8] . Results of key comparisons are intended to support the statements of Calibration and Measurement Capabilities (CMCs), as listed in Appendix C of the Mutual Recogni- tion Arrangement of the International Committee for Weights and Measures (CIPM MRA) [9] . More impor- tantly, the results provide an effective means of assessing the degree of equivalence of measurement standards used at different NMIs. In this review, we focus on commonly used meth- odologies for inorganic analysis in CCQM key com- parisons between 1998 and 2007 and we suggest potential areas for strategic research and development. Moreover, we would like to share the article with green NMIs and designated institutes (DIs) that are committed to the development of metrology in chem- istry.

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Trends in Analytical Chemistry, Vol. 28, No. 2, 2009

Table 1. Measurement service categories and relevant key comparisons

 

Measurement service

Sub-category

Key comparison

category

 

1. High purity chemicals

1.1 Inorganic compounds; 1.2 Organic compounds;

 

1.3

Metals; 1.4 Isotopics; 1.5 Other

2. Inorganic solutions

2.1 Elemental; 2.2 Anionic; 2.3 Other

CCQM-K8 (Mono-elemental calibration solutions of aluminum, copper, iron and magnesium); CCQM-K29 & 29.1 (Anion calibration solutions)

3. Organic solutions

3.1 PAHs; 3.2 PCBs; 3.3 Pesticides; 3.4 Other

4. Gases

4.1 High purity; 4.2 Environmental; 4.3 Fuel; 4.4 Forensic; 4.5 Medical; 4.6 Other

5. Water

5.1 Fresh water; 5.2 Contaminated water; 5.3 Sea water; 5.4 Other

CCQM-K2 (Cadmium and lead in natural water)

6. pH

 

7. Electrolytic

conductivity

8.

Metal and metal

8.1

Ferrous metals; 8.2 Non-ferrous metals; 8.3

CCQM-K33 (Minor elements in steel); CCQM-K42 (Constituents of an aluminum alloy)

alloys

Precious metals; 8.4 Other

9.

Advanced materials

9.1 Semiconductors; 9.2 Superconductors; 9.3 Polymers and plastics; 9.4 Ceramics; 9.5 Other

 

10.

Biological fluids and

10.1

Blood serum; 10.2 Renal fluids; 10.3 Hair; 10.4

CCQM-K14 (Calcium in human serum); CCQM-K24 (Cadmium in rice); CCQM-K31 (Arsenic in shellfish); CCQM-K43 (Organo-mercury in salmon); CCQM-K45 (Toxic metals in food); CCQM-K49 (Toxic and essential elements in bovine liver) CCQM-K24; CCQM-K30 (Lead in wine); CCQM-K31; CCQM-K43; CCQM-K45; CCQM-K49 CCQM-K35 (Sulfur in diesel fuel)

materials

Tissues; 10.5 Bone; 10.6 Botanical materials; 10.7 Other

11. Food

11.1 Nutritional constituents; 11.2 Contaminants;

11.3

GMOs; 11.4 Other

12. Fuels

12.1 Coal and coke; 12.2 Petroleum products; 12.3

Bio-mass; 12.4 Other

 

13. Sediments, soils, ores

13.1

Sediments; 13.2 Soils; 13.3 Ores; 13.4

CCQM-K13 & 13.1 (Amount content of cadmium and lead in sediment); CCQM-K28 (Tributyltin in sediment); CCQM-K44 (Trace metals in sewage sludge)

and particulates

Particulates; 13.5 Other

14.

Other materials

14.1 Cements; 14.2 Paints; 14.3 Textiles; 14.4 Glasses; 14.5 Thin films; 14.6 Coatings; 14.7 Insulating materials; 14.8 Rubber; 14.9 Adhesives; 14.10 Other

 

2. Measurement service categories and key comparisons

Regarding the determination of analytes (e.g., elements, inorganic compounds and organo-metallic compounds), the Inorganic Analysis Working Group (IAWG) of CCQM

is responsible for planning and organizing key compar- isons that cover relevant measurement service categories (MSCs) in the context of existing or planned CMCs ( Table

1 ). Each key comparison has its own rationale for choosing a specific analyte (or several analytes) in a particular matrix. In view of the complexity of sample matrices and the difficulty of analyte determination, a pilot study is sometimes organized to obtain satisfactory agreement among participants prior to scheduling a key comparison. Participants are encouraged to employ their own methods of measurement. Coordinating lab- oratories are responsible for preparing test samples, homogeneity and stability tests, distribution of samples and the technical protocol (i.e. instructions to partici- pants), calculation of key comparison reference values (KCRVs) and equivalence statements, and compilation

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of final reports. Each KCRV can be calculated as mean, weighted mean, median, or mixture model median [10]. To facilitate our discussions, we briefly describe below the rationales of the key comparisons (1998–2007) under respective MSCs. Table 2 summarizes details of the key comparisons.

2.1. Inorganic solutions and water CCQM-K2 (Cadmium and lead in natural water; Table 2, Entry 1) [11] : The comparison was a continuation of CCQM-1 study ‘‘Lead in Water’’ and focused on the measurement of Cd and Pb in natural water. CCQM-K8 (Mono-elemental calibration solutions of aluminum, copper, iron and magnesium; Table 2 , Entry 2) [12] : Aqueous mono-elemental solutions are usually used as calibrants for elemental analysis. Inaccuracy with respect to declared values and quoted uncertainties has been found in some commercially available standards. The comparison provided NMIs with an opportunity to demonstrate their capabilities in the measurement of elements in pure solutions with high accuracy.

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217

Table 2. CCQM key comparisons (1998–2007)

 

Entry

CCQM (Time of measurement, Status)

Matrix

KCRV ± uncertainty (coverage factor, k; no. of participants results used for calculating KCRV, n ; where applicable)

Sample preparation and measurement

Range of relative uncertainties reported by participants (coverage factor, k; no. of participants involved, n)

Coordinating laboratory / Ref.

1

CCQM-K2 (1998,

Natural water

Cd (calculated as mean):

Measurement (instrument):

Cd: 0.27–4.6% ( k = 2; n = 9)

Institute for

approved for

(83.49 ± 0.83) nmol/kg (k = 1; n = 9) Pb: (calculated as mean):

IDMS (ICP-MS, ICP-SMS)

Reference Materials

equivalence)

Pb: 0.46–4.1% ( k = 2; n = 9)

and Measurements

 

(62.79 ± 1.33) nmol/kg (k = 1; n = 9) Al (gravimetric value):

 

(IRMM) [11]

2

CCQM-K8 (1999– 2000, approved for equivalence)

Calibration

Measurement (instrument):

Al: 0.03–0.60% (k = 1;

Swiss Federal

solutions

(0.99685 ± 0.00040) g/kg (k = 1) Cu (gravimetric value):(0.98819 ± 0.00003) g/kg ( k = 1) Fe (gravimetric value):(1.01966 ± 0.00010) g/kg ( k = 1) Mg (gravimetric value):(1.00428 ± 0.00009) g/kg ( k = 1) Cd (calculated as median):

IDMS (ICP-MS, TIMS)

n

= 13)

Laboratories for

ICP-MS ICP-AES Titrimetry Gravimetry Electrogravimetry Controlled potential coulometry

Cu: 0.02–0.53% (k = 1;

Materials Testing

 

n

= 13)

and Research

 

(EMPA) [12]

Fe: 0.02–0.52% (k = 1;

n

= 13)

Mg: 0.02–0.67% (k = 1;

 
 

n

= 13)

3

CCQM-K13 (2000,

Sediment

Sample preparation:

Cd: 1.1–5.5% (k: 2–3;

IRMM [25]

approved for

(5.41 ± 0.17) lmol/g ( k = 2; n = 12)

Microwave digestion / wet ashing / open system (HF, HNO 3 , HCl, HClO 4 , H 2 O 2 )

n

= 12)

equivalence)

 
 

Pb (calculated as median):

Measurement (instrument):

Pb: 0.4–3.7% (k: 2–2.2;

 

(169.9 ± 1.6) lmol/g ( k = 2; n = 14)

IDMS (TIMS, Q-ICP-MS, ICP-SMS)

n

= 14)

 

External standard calibration (ICP-SMS)

 

4

CCQM-K13.1

Sediment

Cd & Pb: KCRV assigned for CCQM- K13 was used.

Sample preparation:

Cd: 1.2–6.1% (k = 2; n = 2)

National Institute of Standards and Technology (NIST)

(2004, approved for equivalence)

Microwave digestion (HF, HNO 3 , HClO 4 ,

 

H

2 O 2 )

 

Measurement (instrument):

Pb: 0.8–3.0% (k = 2; n = 2)

[26]

IDMS (ICP-MS, ICP-SMS)

 

5

CCQM-K14 (2003,

Human serum

Ca (calculated as weighted mean):

Sample preparation:

Ca:

0.5–4.3%

(k = 2; n = 9)

IRMM [17]

approved for

(2.239 ± 0.011) mmol/kg (k = 2; n = 9)

Microwave digestion / digestion with a high pressure asher / digestion with a hot plate (HF, HNO 3 , HClO 4 , H 2 O 2 ) Cation-exchange chromatography

Measurement (instrument):

 

equivalence)

 

IDMS (TIMS, C/RC Q-ICP-MS, ICP-MS ‘‘cold plasma’’, ICP-SMS) ICP-AES and AAS

 

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Trends in Analytical Chemistry, Vol. 28, No. 2, 2009

Table 2. (continued)

 

Entry

CCQM (Time of measurement, Status)

Matrix

KCRV ± uncertainty (coverage factor, k; no. of participants results used for calculating KCRV, n; where applicable)

Sample preparation and measurement

Range of relative uncertainties reported by participants (coverage factor, k; no. of participants involved, n)

Coordinating laboratory / Ref.

6

CCQM-K24 (2001,

Rice

Cd (calculated as mean):

Sample preparation:

Cd: 0.4–2.7% (k: 1.97–2;

IRMM [18]

approved for

(14.418 ± 0.087) nmol/g (k = 2;

Microwave digestion / wet digestion (HF,

n

= 12)

equivalence)

n

= 12)

HNO 3 , HCl, HClO 4 , H 2 O 2 ) No sample dissolution / chemical separa- tion was needed for INAA

 

Measurement (instrument):

 

IDMS (TIMS, Q-ICP-MS, C/RC Q-ICP-MS, ICP-SMS, MC-ICP-MS) INAA comparator method

7

CCQM-K28 (2003,

Sediment

Tributyltin (calculated as median):

Sample preparation:

Tributyltin: 2.5–8.9% ( k = 2;

Laboratory of

approved for

(1.071 ± 0.023) nmol/g TBT + (k = 2;

Mechanical shaking / sonication / acceler-

n

= 6)

Government Chemist (LGC) and National Research Council of Canada (NRC) [27]

equivalence)

n

= 6)

ated solvent extraction / microwave- assisted extraction Derivatization

 

Measurement (instrument):

Species-specific IDMS (GC-ICP-MS, GC- ICP-SMS, HPLC-ICP-MS) GC-MS

8

CCQM-K29 (2003– 2004, approved for equivalence)

Calibration

Chloride (gravimetric value):

Measurement (instrument) for chloride:

Chloride:0.03–0.74% (k = 2;

EMPA [13]

solutions

(0.98854 ± 0.00024) g/kg ( k = 2)

Coulometry

n

= 10)

 

Titrimetry

 

Phosphate (gravimetric value):

Measurement (instrument) for phosphate:

Phosphate: 0.06–1.0% (k = 2; n = 10)

 

(1.00447 ± 0.00066) g/kg ( k = 2)

Titrimetry

 

Gravimetry

ICP-AES

 

IC / UV-visible spectrometry IC / ICP-AES

 

 

IC Ion-exchange chromatography followed by coulometry

 

( continued on next page)

9

CCQM-K29.1

Calibration

Chloride (gravimetric value):

Measurement (instrument) for chloride:

Chloride:0.03–0.48% (k = 2;

Slovak Institute of

(2005, approved for equivalence)

solutions

(1.00065 ± 0.00024) g/kg ( k = 2)

Coulometry

n

= 2)

Metrology (SMU)

 

Titrimetry

[14]

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219

measurement,

factor, k; no. of participants results used for calculating KCRV, n; where applicable)

 

uncertainties reported by participants (coverage factor, k ; no. of participants involved, n)

laboratory / Ref.

Status)

10 CCQM-K30 (2006– 2007, approved for equivalence)

Wine

Pb (calculated as mean):

Sample preparation:

Pb: 0.85–5.5% (k: 1.99–2.4;

LGC [19]

(2.99 ± 0.06) ng/g ( k = 2.3; n = 9)

Microwave digestion / water-bath diges- tion / digestion with a hot plate / sealed vessel (HNO 3 , H 2 O 2 )

n

= 9)

 

Measurement (instrument):

IDMS (Q-ICP-MS, ICP-SMS, MC-ICP-MS)

11 CCQM-K31 (2002– 2003, approved for equivalence)

Shellfish

As (calculated as mean):

Sample preparation:

As:

1.9–15% (k = 2; n = 5)

NIST [20]

(0.1117 ± 0.00615) mmol/kg (k = 2.78; n = 5)

Microwave digestion (HNO 3 ,H 2 O 2 )

No sample dissolution / chemical separa- tion was needed for INAA

 

Measurement (instrument):

External standard calibration (ICP-MS, C/ RC Q-ICP-MS, Flow injection-hydride generation-GFAAS) Standard addition (GFAAS) INAA comparator method

 

12 CCQM-K33 (2003– 2004, approved for equivalence)

Steel

Minor elements include: Cr (calculated as median):

Measurement (instrument):

Cr:0.35–3.6% (k: 2–2.2;

National Metrology

IDMS (ICP-MS)

n

= 8)

Institute of Japan (NMIJ), NIST and Federal Institute for

(0.5091 ± 0.0030) w % ( k = 2; n = 8) Mn (calculated as median):

ICP-MS

 

ICP-AES

Mn: 0.22–3.5% (k: 2–2.11;

(0.5063 ± 0.0016) w % ( k = 2; n = 8) Ni (calculated as median):

Spectrophotometry

n

= 8)

Materials Research and Testing (BAM)

XRF

Ni: 0.28–3.5% ( k: 1.97–2;

(2.5490 ± 0.0123) w % ( k = 2; n = 7) Mo (calculated as median):

INAA

n

= 7)

[15]

Titrimetry

Mo: 0.33–3.7% (k: 2–2.2;

(1.0393 ± 0.0058) w % ( k = 2; n = 8) S (calculated as mixture model median): (42.17 ± 1.32) lg/g (k = 2; n = 4)

n

= 8)

13 CCQM-K35 (2003– 2004, approved for equivalence)

Diesel fuel

Sample preparation:

S: 0.61–4.1% ( k: 2–2.31;

NIST [24]

Microwave digestion / digestion with a high-pressure asher / digestion with a Carius tube (HNO 3 , H 2 O 2 )

n

= 4)

 

Measurement (instrument):

IDMS (TIMS, ICP-SMS)

14 CCQM-K42 (2004– 2005, approved for equivalence)

Al alloy

Constituents include: Mn (calculated as mean): (0.1084 ± 0.0015) w % (k = 2; n = 7) Cu (calculated as mean):

Measurement (instrument):

Mn:1.0–4.6% ( k: 2.00–2.02;

BAM [16]

ICP-MS

n

= 7)

ICP-OES

 

INAA

Cu: 1.3–4.7% (k: 2.00–2.05;

 

(0.1098 ± 0.0009) w % ( k = 2; n = 6) Fe (calculated as mean):

XRF

n

= 6)

Fe: 1.4–4.7% (k: 2.00–2.03;

 

(0.2003 ± 0.0014) w % ( k = 2; n = 7) Cr (calculated as mean):

(0.0442 ± 0.0002) w % ( k = 2; n = 7) Zn (calculated as mean):

(0.1350 ± 0.0015) w % ( k = 2; n = 6)

n = 7)

Cr: 1.64–4.5% ( k: 2.00–2.14;

n = 7)

Zn: 0.9–5.6% ( k: 1.98–2.00;

n = 6)

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Trends in Analytical Chemistry, Vol. 28, No. 2, 2009

Table 2. (continued)

 

Entry

CCQM (Time of measurement, Status)

Matrix

KCRV ± uncertainty (coverage factor, k; no. of participants results used for calculating KCRV, n; where applicable)

Sample preparation and measurement

Range of relative uncertainties reported by participants (coverage factor, k; no. of participants involved, n)

Coordinating laboratory / Ref.

15

CCQM-K43 (2005,

Salmon fish

As: (calculated as mixture model

median): (58.1 ± 1.5) lmol/kg ( n = 9) Hg: (calculated as mixture model median): (0.3884 ± 0.0056) lmol/kg

Sample preparation for the analysis of As, Hg, Pb and Se:

Microwave digestion / digestion with a high-pressure asher (HNO 3 , HCl, aqua

As: 1.3–5.7% (k = 2; n = 9)

IRMM [21]

approved for

 

equivalence)

Hg: 0.67–4.8% (k = 2; n = 8)

 

(n

= 8)

regia, HClO 4 , H 2 O 2 ) No sample dissolution / chemical separa- tion was needed for INAA

Pb: (calculated as mixture model median): (3.82 ± 0.10) l mol/kg

Measurement (instrument) for As:

External calibration (ICP-MS)

Pb: 2.1–6.3% (k = 2; n = 5)

(n

= 5)

Se: (calculated as mixture model median): (7.32 ± 0.28) l mol/kg

Standard addition (C/RC Q-ICP-MS) Internal standardization (C/RC Q-ICP-MS) INAA / k 0 -NAA

Se:1.5–9.2% ( k = 2; n = 10)

(n

= 10)

Methylmercury: (calculated as mixture model median):

(0.373 ± 0.023) l mol/kg (n = 5)

Measurement (instrument) for Hg:

IDMS (Q-ICP-MS, C/RC ICP-MS, ICP-SMS, CV-ICP-MS)

Methylmercury: 2.3–6.7% ( k = 2; n = 5)

 
 

Measurement (instrument) for Pb:

IDMS (TIMS, Q-ICP-MS, C/RC Q-ICP-MS) External calibration (ICP-MS)

Measurement (instrument) for Se:

IDMS (C/RC ICP-MS) External calibration (ICP-MS)

 

INAA / k 0 -neutron activation analysis

Sample preparation for the analysis of methylmercury:

Extraction (concentrated HCl/NaDDTC, Protease type XIV, TMAH, KOH/MeOH) Derivatization [NaB(C 2 H 5 ) 4 , NaB(C 3 H 7 ) 4 , NaB(Ph) 4 ]

Measurement (instrument) for methylmercury:

Species-specific IDMS (GC-ICP-MS, GC- ICP-SMS, HPLC-ICP-MS) GC-MS

16

CCQM-K44 (2005,

Sewage sludge

Trace elements include: Cd and Hg:

Measurement (instrument):

-

IRMM

measurements

0.5–10 mg/kg Cr and Ni: 50–250 mg/ kg Cu and Pb: 300–1000 mg/kg Zn:

1000–5000 mg/kg The final report of the comparison has not been released and the KCRV for the 7 analytes are not finalized.

IDMS (TIMS, Q-ICP-MS) External standard calibration (XRF, FAAS, CVAAS) k 0 -NAA

 

completed)

 

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measurement,

factor, k; no. of participants results used for calculating KCRV, n; where applicable)

 

uncertainties reported by participants ( coverage factor, k; no. of participants involved, n)

laboratory / Ref.

Status)

17 CCQM-K45 (2005,

Tomato paste

Sn (calculated as mean):

Sample preparation:

Sn:

0.62–2.6% ( k = 2; n = 4)

LGC [22]

approved for

(227.1 ± 2.4) mg/kg (k = 2; n = 4)

Microwave digestion (HNO 3 , HCl, H 2 O 2 )

equivalence)

Measurement (instrument):

IDMS (Q-ICP-MS, C/RC Q-ICP-MS, ICP-SMS)

18 CCQM-K49 (2006, report in progress)

Bovine

Toxic and essential elements include:

Sample preparation for the analysis of Fe, Zn, Se,

Fe: 0.3–5.4% ( k: 2–2.06;

NIST [23]

liver

Fe

(calculated as mixture model

Cd, Pb, Cr and As:

n

= 14)

median): (198.1 ± 2.2) mg/kg ( n = 14)

Zn (calculated as mixture model

median): (181.9 ± 1.9) mg/kg ( n = 13)

Se (calculated as mixture model

median): (2.056 ± 0.077) mg/kg ( n = 5)

Cd (calculated as mixture model

median): (0.0976 ± 0.0016) mg/kg ( n = 8)

Pb (calculated as mixture model

median): (0.0619 ± 0.0012) mg/kg ( n = 9)

Cr (calculated as mixture model

Microwave digestion / digestion in an open system (HF, HNO 3 , HClO 4 , H 2 O 2 ) No sample dissolution / chemical separation was needed for INAA

Measurement (instrument) for Fe:

IDMS (ICP-MS)

External standard calibration (ICP-MS, ICP-

OES, FAAS) Standard additions (ICP-OES) INAA comparator method

Measurement (instrument) for Zn:

IDMS (ICP-MS, TIMS)

External standard calibration (ICP-MS, ICP- OES,FAAS)

Standard additions (ICP-OES) INAA comparator method

Measurement (instrument) for Se:

Zn:0.5–5.1% (k: 2–2.13;

n = 13)

Se: 1.3–5.3% ( k: 2–2.03;

n = 5)

Cd: 0.6–6.2% ( k:2–2.18;

n = 8)

Pb: 1.5–6.8% (k : 2–2.23;

n = 9)

Cr: 3.3–6.8% ( k: 2–2.3; n =5) As:4.4–14.9% ( k: 2–2.4;

n = 5)

median): (0.0514 ± 0.0033) mg/kg

IDMS (ICP-MS)

( n = 5)

External standard calibration (ICP-MS)

As (calculated as mixture model

median): (0.01965 ± 0.00131) mg/kg ( n = 5)

INAA comparator method

Measurement (instrument) for Cd:

IDMS (ICP-MS, TIMS)

External standard calibration (ICP-MS)

Standard additions (ICP-MS)

RNAA comparator method Measurement (instrument) for Pb:

IDMS (ICP-MS)

External standard calibration (ICP-MS)

Standard addition (ICP-MS) Measurement (instrument) for Cr:

IDMS (ICP-MS)

External standard calibration (ICP-MS)

Standard additions (ICP-MS)

INAA comparator method Measurement (instrument) for As:

External standard calibration (ICP-MS) Standard additions (ICP-MS, C/RC Q-ICP-MS) RNAA comparator method

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CCQM-K29 & 29.1 (Anion calibration solutions; Table 2 , Entries 8–9) [13,14] : Aqueous solutions of anions are widely used for calibration, particu- larly in environmental and medicinal investigations. As deviations up to several percent of the declared values have been found in some commercially avail- able standards, it is necessary to develop reliable methods for certification purposes.

2.2. Metals and metal alloys

CCQM-K33 (Minor elements in steel; Table 2 , Entry 12) [15] : To maintain the production of high quality steel and steel products, accurate control and determi- nation of minor elements (e.g., Cr, Mn, Ni and Mo) are of concern. The amounts of minor elements can affect product properties (e.g., tensile strength, hardness and ductility). For example, stainless steel should contain a minimum of 10% by weight of Cr. CCQM-K42 (Constituents of an aluminum alloy; Table 2 , Entry 14) [16] : The comparison focuses on the determination of constituent elements (Mn, Cu, Fe, Cr and Zn) in aluminum alloy. The availability of a robust method is important to guarantee the produc- tion of high quality alloy products. As the final report of the comparison has not been released, detailed information is not readily available.

2.3. Biological fluids, materials and food

CCQM-K14 (Calcium in human serum; Table 2 , Entry 5) [17] : The results of the determination of Ca in serum samples are usually used for screening bone diseases or calcium-regulation disorders. In order to support routine clinical measurements, there is a need to develop better methodology for analysis. CCQM-K24 (Cadmium in rice; Table 2 , Entry 6) [18] :

Cd, a suspected human carcinogen, may cause dys- functions and reproductive deficiencies in humans. As rice is the main foodstuff for approximately half of the world s population, it is necessary to keep the contaminant at a level that is toxicologically accept- able for consumption. CCQM-K30 (Lead in wine; Table 2 , Entry 10) [19] :

Wine is an important dutiable commodity trading all over the world. The ‘‘Office International de la Vigne et du Vin’’ recommends that the maximum mass fraction of Pb in wine be 0.2 mg/kg, which is the threshold value prescribed by the European Com- mission (EC) Regulation (466/2001). Analysis of toxic metals (e.g., Pb) in wine is therefore essential for reg- ulatory control. CCQM-K31 (Arsenic in shellfish; Table 2, Entry 11) [20] : Arsenic is a toxic element and its determination in shellfish tissues is of public health concern. As iso-

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tope dilution is not applicable to the analysis of mono-

isotopic elements, such as As, it is an analytical chal- lenge to develop accurate methods based on other techniques. CCQM-K43 (Organo-mercury in salmon fish; Table 2 , Entry 15) [21] : Methylmercury has a higher toxicity than inorganic Hg and is the major form present in fish and fish products. In order to protect public health, it is important to ensure that the level of the contaminant is below the Hg threshold value of 0.5 mg/kg, as stipulated in the EC Regulation (466/

2001).

CCQM-K45 (Toxic metals in food; Table 2 , Entry 17) [22] : The European Union (EU) regulatory limit

of Sn in food is 200 mg/kg. The scope of the com-

parison was to underpin the capability of NMIs in

the determination of Sn in food samples (e.g., toma-

to paste).

CCQM-K49 (Toxic and essential elements in bovine liver; Table 2, Entry 18) [23] : Bovine livers provide high levels of essential elements (Fe, Zn and Se). How- ever, toxic elements (Cd, Pb, Cr and As) may be accu- mulated due to environmental pollution. The IAWG designated the comparison as an ‘‘exemplary study’’, which requested all NMIs to carry out determination of Zn and Fe for capability evaluation.

2.4. Fuels

CCQM-K35 (Sulfur in diesel fuel; Table 2 , Entry 13) [24] : Diesel fuel with a sulfur content of less than 50 l g/g is commonly called ultra-low sulfur diesel (ULSD). The production of ULSD is costly for both petroleum industry stakeholders and consumers. Nonetheless, reduction of sulfur in fuel is expected to lower significantly atmospheric sulfur oxides, which are the major pollutants leading to the formation of acid rain. There is a demand for the provision of cer- tified reference standards of diesel fuel that contain sulfur near the EU regulatory limit of 50 l g/g (EURO

IV standard for fuel). Laboratories need reliable stan-

dards to validate the performance of the methods for the determination of S in diesel fuel. In this regard, a test sample with a sulfur level of approximately 40 lg/g was used in the comparison.

2.5. Sediments, soils, ores and particulates

CCQM-K13 & 13.1 (Amount content of cadmium and lead in sediment; Table 2 , Entries 3 and 4) [25,26] : The sample preparation of sediment is rela- tively complicated and tedious due to the presence of highly organic matrices. The comparison was in- tended to address several challenging issues, includ- ing analyte losses, higher blank values and matrix interferences.

Trends in Analytical Chemistry, Vol. 28, No. 2, 2009

CCQM-K28 (Tributyltin in sediment; Table 2 , Entry 7) [27] : In spite of the ban on the use of tributyltin as an anti-fouling agent in paints, the high residual levels of tributyltin in water and marine sediment samples continue to pose an eco-toxicological threat to the aquatic environment. Quantification of organotin spe- cies is difficult because instability of analytes has been observed during sample extraction. As such, it is nec- essary to develop robust methods for examination. CCQM-K44 (Trace metals in sewage sludge; Table 2 , Entry 16): The EU promotes the use of sewage sludge as a fertilizer on farmland and has set the concentration limits for metals such as Cd, Hg, Cr, Ni, Cu, Pb and Zn in sewage sludge (86/278/EEC Directive). The compari- son was intended to assess the capabilities of NMIs in the measurement of metals regulated by the Directive. Detailed information is not available because the final report of the comparison has not been released.

3. Methodologies

Methodologies commonly used for inorganic analysis in CCQM key comparisons include:

(i)

inorganic mass spectrometry (e.g., isotope dilution mass spectrometry (IDMS), species-specific IDMS, and inductively coupled plasma MS (ICP-MS));

(ii)

inductively coupled plasma atomic emission spec- trometry (ICP-AES); and,

(iii)

neutron activation analysis (NAA).

Our evaluation of methodologies primarily focuses on analytical considerations, advantages and limitations. We also briefly discuss other methodologies that are less frequently used [e.g., ion chromatography (IC), high performance liquid chromatography (HPLC), X-ray fluo- rescence spectrometry (XRF), flame atomic absorption spectrometry (FAAS), graphite furnace AAS (GFAAS), gravimetry, eletrogravimetry, titrimetry and coulometry].

3.1. Isotope dilution mass spectrometry At present, IDMS is the most extensively used method- ology in key comparisons for the determination of ele- ments in various sample matrices. It is noteworthy that the analytical consideration given in Section 3.1.1.8 (Weighing) is applicable to all methodologies that we subsequently discuss.

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Besides, analytical considerations provided in Sections 3.1.1.9 (Use of cleanrooms) and 3.1.1.10 (Sample dis- solution with acids/oxidants) should be taken into ac- count when preventive measures for contamination and complete sample dissolution are of concern. These two analytical considerations are also applicable to other methodologies (e.g., ICP-AES, FAAS and GFAAS).

3.1.1. Analytical considerations

3.1.1.1. Selection of mass spectrometers for isotope ratio

measurements (IRM). Accurate measurement of isotope ratios is one of the crucial factors for the success of IDMS. Various mass spectrometers have been employed in key comparisons, including thermal ionization mass spec- trometer (TIMS), quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS), inductively coupled plasma sector field mass spectrometer (ICP-SMS; also known as high resolution ICP-MS or double focusing ICP-MS), multiple collector inductively coupled plasma mass spectrometer (MC-ICP-MS), and quadrupole inductively coupled plasma mass spectrometer with a collision/reaction cell (C/RCQ-ICP-MS). Recently, we presented a concise summary of mass spectrometers currently available in the market for IRM

[28].

Table 3 shows the typical ranges of IRM precision achievable by various mass spectrometers [29,30]. As shown in Table 2, both ICP-SMS and Q-ICP-MS with or without a collision/reaction cell are frequently used for IDMS analysis.

3.1.1.2. Calibration strategies in IDMS. In a review

about characterization of reference materials by IDMS, Vogl suggested three major calibration strategies for analysis: double IDMS, matching IDMS and single IDMS

[31].

In double IDMS, a known amount of an isotopically enriched spike of an element is added to the sample. Once equilibration between the analyte isotope and the spike isotope has been reached, the ratio of the amounts of the two isotopes will be measured in the sample blend (blend isotope ratio = amount of analyte isotope/amount of spike isotope) using a mass spectrometer. Similarly, a

calibration blend is prepared by adding the same amount of spike to the primary assay standard, whose element

Table 3. Proposed periods of development for various instruments and typical ranges of precision for IRM

 

Period

Development of instrument

Precision for IRM (RSD)

Ref.

Since 1947

First commercial TIMS available Initial ICP-MS Q-ICP-MS ICP-SMS MC-ICP-MS ICP-TOF-MS C/RC Q-ICP-MS

0.005–0.01%

[29]

1978–83

1983–88

0.1–0.5%

[29]

1988–93

0.05–0.2%

[29]

1993–1998

0.005–0.02%

[29]

0.05–0.1%

[29]

1998–present

0.07–0.1%

[30]

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amount content is prepared to match the estimated element amount content of the sample. The element amount content of the sample is then calculated from that of the primary assay standard. In exact matching IDMS, first proposed by Henrion [32] , an iterative preparation of calibration blends is needed until an exact match is produced with respect to both blend isotope ratios and isotope signal intensities. Several sources of error (e.g., detector dead time and mass bias) can be negated. An additional advantage is that the purity of the spike does not make a contribution to the measurement uncertainty of the final analytical result. National Measurement Institute, Australia, suc- cessfully applied the exact matching IDMS approach to 14 international comparisons [33] [e.g., CCQM-P12 (Analysis of Pb in red wine)] [34] . More importantly, it has been demonstrated to be useful for reference mea- surements [e.g., Myors et al. presented the IDMS mea- surement of 10 trace elements (Cd, Cu, Cr, Hg, Mo, Ni, Pb, Se, Sn and Zn) in a test sample of fortified wheat flour for the provision of reference values to a proficiency testing scheme] [35] . In order to simplify time-consuming iterations and retain the benefits of the full matching procedure, ‘‘approximate matching’’ IDMS has been proposed [36] . Laboratory of Government Chemist, UK, developed an IDMS protocol for the determination of Ca in human serum using a quadrupole instrument operated in the H 2 -cell mode [37] . An ‘‘approximate match within ±5%’’ was made between the sample blend and the calibration blend. In addition, in the determination of Pb in a certified reference material (CRM) (NIST SRM 1547 Peach Leaves) using IDMS, Lam et al. reported the achievement of satisfactory analytical figures of merit [recovery: 99%; relative expanded uncertainty (coverage factor, k = 2): ±1.1%] based on the use of ‘‘approximate match within ±10%’’ [38] . The prerequisite for employing single IDMS is the availability of a certified spike that has been character- ized with respect to amount content and isotopic com- position. The element amount content of the sample can be calculated directly from that of the certified spike.

3.1.1.3. Equations for quantification. In key comparison CCQM-K24 (cadmium amount in rice), Equation (1) describes the measurement procedure of double IDMS proposed:

"

c x ¼ D c z m y

m z

K y R y K b R b

0

y

K b 0 R b 0 K z R z

K b R b K x R x K y R y K b 0 R 0

b

w m x m

where c x is the element amount content in the sample (mol/kg); c z is the element amount content in the pri-

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mary assay standard (mol/kg); m y is the mass of the spike in the sample blend (kg); m x is the mass of the sample in the sample blend (kg); m y is the mass of the spike in the calibration blend (kg); m z is the mass of the primary assay standard in the calibration blend (kg); K y is the mass bias correction factor for the isotope ratio in the spike; R y is the isotope ratio in the spike; K b is the mass bias correction factor for the isotope ratio in the sample blend; R b is the isotope ratio in the sample blend; K x is the mass bias correction factor for the isotope ratio in the sample; R x is the isotope ratio in the sample; K b 0 is the mass bias correction factor for the isotope ratio in the calibration blend; R b 0 is the isotope ratio in the calibra- tion blend; K z is the mass bias correction factor for the isotope ratio in the primary assay standard; R z is the isotope ratio in the primary assay standard; R( K xi Æ R xi ) is the sum of isotope ratios in the sample; R( K zi Æ R zi ) is the sum of isotope ratios in the primary assay standard; B is the procedural blank (mol/kg); D is the digestion factor; and, w is the fraction dry mass/factor for dry mass cor- rection. More details about equations employed for quantifi- cation purposes have also been reported [39,40] .

0

3.1.1.4. Optimum blend isotope ratio. In practice, the optimum blend isotope ratio is a compromise between the error propagation factor, EPF opt , and the ideal 1:1 blend isotope ratio. Furthermore, it should be set in the range 4:1–1:4 to maintain reasonable signal intensities for both analyte and spike isotopes. However, when samples with high analyte concentrations are examined, the rule of thumb becomes impractical because a very large amount of costly spike material is needed. To solve the problem, Hearn et al. demonstrated the use of a high blend-isotope ratio ( 32 S/ 34 S) of 14 in the analysis of a sample of diesel fuel containing approximately 4 mg/g sulfur [41]. Satisfactory recovery (>99%) was achieved in the analysis of a CRM (NIST SRM 1624d) when the blend isotope ratios of the sample and calibration blends were matched as closely as possible (within ±0.5%). The method demonstrated its suitability for the determina- tion of sulfur in test samples of diesel fuel for CCQM comparisons (e.g., CCQM-K35).

3.1.1.5. Detector dead time and mass bias. Precision and accuracy of IRM are affected by a number of factors [e.g., detector dead time, mass bias, instrument blank, spectral

P ðK xi R xi Þ

P ð K zi R zi Þ

# B

ð1 Þ

interferences (polyatomic and isobaric interferences)]. In order to have isotope ratios measured precisely and

Trends in Analytical Chemistry, Vol. 28, No. 2, 2009

accurately, appropriate corrective measures should be implemented as far as practicable. In the certification measurement of Pb in a red wine sample for International Measurement Evaluation Pro- gramme IMEP-16, Que´ tel et al. achieved the relative expanded uncertainty (k = 2) of 1.2% [42] . Q-ICP-MS was used for IDMS analysis. The uncertainty budget showed that the contribution from the correction for detector dead time effects on isotope signal intensities and the contribution from the measurements performed to correct for mass bias effects represented 23.1% and 12.3% of the combined standard uncertainty, respec- tively. To correct for detector dead time effects, the methods described by Nelms et al. were adopted [43] . Mass bias was corrected by using a certified isotopic reference material (NIST NBS-982). Note that the same wine sample (IMEP-16) was used for the other interna- tional comparison (CCQM-P12). Generally speaking, there are two ways to correct for mass bias. External standardization is applicable to ele- ments whose isotopic abundances are invariant in nat- ure. To establish mass, a standard solution of known isotopic composition is analyzed before and after the measurement of an isotopic blend (standard-sample bracketing approach). Mass bias correction factor is calculated according to Eq. (2) .

Standard-sample bracketing approach :

ð 2 Þ

R measured ¼ R true = K

where R measured is the experimental ratio of the isotope amount fractions measured by a mass spectrometer; R true is the true ratio of the isotope amount fractions calculated from the known composition data; and, K is the mass bias correction factor. However, internal standardization is recommended for elements whose isotopic abundances vary naturally (e.g., Pb). This requires the addition of an internal standard that has known isotopic composition. Three approaches are available for mass bias correction, including linear, exponential and power law functions [44–47] :

Linear law function : R measured ¼ R true ð 1 þ K 0 D M Þ ð 3 Þ

Exponential law function : R measured ¼ R true e ð K 0 D M Þ ð 4 Þ

ð 5 Þ

where K 0 is the mass bias per mass unit in each of the functions; and D M is the mass difference between the isotopes of interest.

Power law function : R measured ¼ R true ð 1 þ K 0 Þ DM

3.1.1.6. Instrument blank. Elburg et al. reported that MC-ICP-MS generally showed a detectable blank for all elements because of contamination or memory effects in different parts of the instrument [48] . Moreover, the re- search team found that the composition of the instrument blank was often related to the preceding standard or

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sample. In this regard, an empirical method was proposed for assessing the magnitude of the error introduced by performing blank corrections on MC-ICP-MS measure- ments. This was particularly important when samples of low analyte concentration levels were analyzed.

3.1.1.7. Reduction of spectral interferences. The advance of collision/reaction cell (C/RC) technology offers an effective way of reducing certain spectral interferences based on the proper use of ion-molecule reactions. Reduction of polyatomic interferences will be achievable if reactions between interfering ions and reagent gases are faster than those between analyte ions and reagent gases. Similarly, separation of isobaric interferences is feasible when reactions between isobaric ions (or analyte ions) and reagent gases proceed preferentially. In a perspective about C/RC in atomic MS, Koppenaal et al. delivered an overview of ion-molecule reactions, reagent gases used (H 2 , O 2 , CO, NH 3 , CH 4 , He, Xe) and applications of C/RC in the analysis of a range of matrices (biological, environmental, geological and nu- clear samples, and high purity reagents) [49] . Later, Olesik presented strategies for using ion-mole- cule reactions in a reaction cell [50] . Analytical con- siderations were discussed with respect to the selection of reagent gases, the adjustment of reaction-cell bandpass and the optimization of gas flow rates. Lastly, we reviewed current applications of C/RC in IDMS [51] . Commonly used reagent gases (e.g., H 2 , NH 3 and CH 4 ) were successfully employed in the determina- tion of various analytes (Se, selenomethionine, Fe, Ca, Cr and Cd) in biological and environmental samples. In the determination of Ca in human serum (CCQM- K14), Simpson et al. demonstrated that H 2 was effective in reducing possible interferences ( 26 Mg 16 O + , 40 Ar 1 H

2 , 40 Ca 1 H , 26 Mg 18 O + , 27 Al 17 O + , 28 Si 16 O + and 43 Ca 1 H + ) on a pair of isotopes 42 Ca and 44 Ca chosen for IDMS analysis [37] . The result submitted by the laboratory (2.236 ± 0.012 mmol/kg, k = 2) showed excellent agreement with the mean of all participants results (2.235 ± 0.035 mmol/kg, k = 2), with one of the lowest relative expanded uncertainties reported in the key comparison. ICP-MS operated under ‘‘cold plasma’’ conditions (application of a lower radio frequency power to ICP) has been shown to reduce argon-based interferences effec- tively [52] . Reduction of intense background peaks ( 38 Ar 1 H + , 40 Ar + , 40 Ar 1 H + and 40 Ar 1 H ) allowed the measurement of K and Ca isotopes ( 39 K + , 40 K + , 41 K + , 40 Ca + and 42 Ca + ). Murphy et al. reported the application of ‘‘cold plasma’’ to the IDMS analysis of Ca in the aforementioned serum sample (CCQM-K14) [53]. The method required matrix separation using cation exchange chromatogra- phy before ICP-MS measurements. The results showed good agreement with other participants results.

þ

þ

2

þ

2

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3.1.1.8. Weighing. Weighing plays a crucial role in not only IDMS, but also other methodologies. Due caution should be exercised when weighing test samples that are hygroscopic. Calibration of analytical balances against standard weights of appropriate classes should be con- ducted on schedule. Balances should be placed on anti-vibration weighing tables. Weighing is preferably performed in a room that fulfills OIML requirements for calibration of weights of class E 2 (temperature change:

±0.7 C/h with a maximum of ±1 C/12 h; range of rel- ative humidity: 40–60% with a maximum of ±10%/4 h) [54] . For IDMS analysis, standard solutions are prepared gravimetrically and are stored in containers made of particular materials, such as Teflon perfluoroalkoxy (PFA) and high-density polyethylene (HDPE). In order to eliminate electrostatic charges, ionizing blowers are recommended for use when weighing involves the use of such containers.

3.1.1.9. Use of cleanrooms. Cleanrooms are classified according to the size and the number of particles per- mitted per volume of air [55] . To minimize the risk of airborne contamination, cleanrooms of ISO Class 4, 5 or 6 (US FED STD 209E equivalent: Class 10, 100 or 1000, respectively) are suitable for the analysis of samples having analyte concentrations at trace levels. For example, Diemer et al. made use of the Ultra-Clean Chemical Laboratory (Class 10) to perform sample preparation for the measurement of Cu ( 220 ng/g) in a water sample by IDMS [56] . Other activities (e.g., drying of acid-washed Telfon/ HDPE bottles, polyethylene syringes and pipette tips, and preparation of sub-boiled nitric acid and ultra-pure water) are often conduced in cleanrooms.

3.1.1.10. Sample dissolution with acids/oxidants. Among other sample dissolution techniques (e.g., digestion with a high pressure asher or a Carius tube), microwave-as- sisted digestion is the most popular method of choice.

Trends in Analytical Chemistry, Vol. 28, No. 2, 2009

The criteria for the selection of acids or a combination of acids/oxidants are summarized in Table 4 [57] . In the certification of Cd, Cu and Pb in a rice material (IRMM-804) using IDMS, Vassileva et al. compared three different microwave-assisted digestion procedures (HNO 3 , HNO 3 /H 2 O 2 and HNO 3 /HF, respectively) [58] . As the rice sample was a complex food matrix that might contain mineral silicates, the use of HF was found nec- essary to ensure full solubilization of residual materials and complete spike equilibration. The optimized diges- tion conditions (HNO 3 /HF = 9:1) were eventually ap- plied to the determination of Cd in the rice sample for

CCQM-K24.

3.1.1.11. Procedural blank analysis. To determine the

procedural blank, Watters Jr. et al. suggested using 1% of the amount of spike that was added to the analytical

sample [59] . If the blank is 1% of the element amount content in the sample, it will have the same measured isotope ratio as the sample blend. The blend isotope ratio can be achieved with high precision. However, if the blank is far less than 1%, a much smaller blend isotope ratio will be obtained with poorer precision. Under cer- tain circumstances, the procedural blank can be esti- mated by external calibration [60] .

3.1.1.12. Correction for moisture/water content. Accord-

ing to Equation (1) , moisture/water content determina- tion will be necessary for IDMS analysis if the sample in question is hygroscopic. In CCQM-K24 (cadmium amount in rice), participants were requested to equilibrate the test sample of rice with ambient conditions (successive weights should not differ more than 0.001 g). The ‘‘equilibrated’’ sample was subsequently used for the measurement of moisture content and Cd amount content. Oven drying at a temperature of 85 ± 2 C was recommended. However, problems were encountered (e.g., high risk of contami- nation and difficulty of attaining equilibration due to changes of relative humidity and temperature). To

Table 4. Criteria for the selection of acids or a combination of acids/oxidants

 

Acid

HNO 3

HCl

HF

H 2 SO 4

HClO 4

Property

Strong oxidizing

Not an oxidizing agent Certain metal oxides/metals, amines, alkaloids, some organometallic

Not an oxidizing agent

Not an oxidizing agent Almost all organic materials, inorganic oxides, hydroxides, alloys, metals, and ores

Strong oxidizing

agent

agent

Suitable for

Biological and

Silicate-based materials

Organic materials

dissolution of

botanical matrices

sample matrix

Can be mixed with other acids/reagents

H 2 O 2 , HCl, HF, H 2 SO 4 or HClO 4

compounds Aqua regia (HNO 3 :HCl = 1:3 (v/ v))

HNO 3

HNO 3

HNO 3

Microwave

XXX

X

x (Explosion hazard)

operation

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address the influence of the correction for moisture/ water content, IRMM examined three different methods, namely oven drying, Karl Fischer titration and thermo- gravimetry, respectively [61] . The examination showed that the three methods did not give significantly different values for the Cd amount content.

3.1.1.13. Uncertainty estimation. In the Eurachem/ CITAC Guide [62] , Example A7 shows the application of Kragten s approach to the calculation of uncertainty for IDMS measurements [63] . This requires tedious estima- tion of experimental uncertainties of all measurement parameters that build the model equation [e.g., Eq. (1) ]. In order to simplify the work, Magnusson et al. suggested that only estimates that were >1/5 of the target value for uncertainty would be used for the estimation of expanded uncertainty [64] . The simplified approach for uncertainty estimation was successfully demonstrated in the determination of Ni in the steel sample for CCQM-K33 and achieved the relative ex- panded uncertainty of 1.1% ( k = 2), which fulfilled the target value of 2%.

3.1.2. Advantages

IDMS is a candidate primary method with satisfactory accuracy and precision. Once equilibration between the analyte isotope and the spike isotope has been reached, total recovery of analyte will be unnecessary and the loss of analyte will not affect the final analytical result. Many isotopically enriched spikes are commercially available for the determination of multi-isotopic elements. Any variations/drifts of instrumental sensitivity have no influence on the final value of the element amount content in the sample.

3.1.3. Limitations

Nevertheless, certain limitations are apparent:

first, resource implications need to be considered, par- ticularly the high costs of isotopically enriched spikes, mass spectrometers and training of competent ana- lysts; second, it is necessary to ensure attainment of com- plete spike equilibration; third, the determination of mono-isotopic elements such as Na and As by IDMS is not possible; and, finally, factors that affect the accuracy in the measurement of isotope ratios (e.g., detector dead time and mass bias) should be carefully con- trolled.

3.2. Species-specific isotope dilution mass spectrometry Accurate determination of organo-metallic species [e.g., methylmercury (MeHg) and tributyltin (TBT)] is a chal- lenging task. Problems (e.g., instability of analytes and

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derivatized products, low analyte concentration levels, and poor sample extraction efficiency) are commonly encountered in speciation analysis. Species-specific IDMS solves those problems provided that complete equilibra- tion between the analyte and the spike has been achieved. It is essential that the spike materials used for analysis should be isotopically enriched species of MeHg/TBT (i.e. the analyte and the spike are in the same chemical form). In their review about potential and limits of speciated isotope dilution analysis, Monperrus et al. discussed the possible applications of isotopically enriched species of MeHg and TBT, particularly in IDMS measurements and environmental tracer studies [65] .

3.2.1. Analytical considerations 3.2.1.1. Extraction, derivatization and separation/detection methods. A number of methodologies have been dem- onstrated to give satisfactory results in the analysis of MeHg in a sample of tuna fish relating to a pilot study (CCQM-P39) [66] . Each of the participants received a quartz ampoule containing 202 Hg isotopically enriched CH 3 HgCl, which was prepared by Institute for Reference Materials and Measurements (IRMM) for IDMS calibra- tion. When the separation of MeHg is performed by gas chromatography, sample preparation always involves a derivatization step. Several representative methodologies (extraction derivatization separation/detection) are summarized as follows:

Microwave extraction with tetramethylammonium hydroxide (TMAH) propylation GC-ICP-MS [67] Extraction with TMAH and diethyl-dithiocarbamate (DDTC) Grignard butylation GC-ICP-MS [68] Extraction with KOH/MeOH propylation solid- phase micro-extraction/GC-ICP-MS [69] Extraction with concentrated HCl and sodium diethyl- dithiocarbamate (NaDDTC) Grignard butyla- tion GC-ICP-MS [70] Besides, the use of HPLC-ICP-MS offers an alternative method for examination without derivatization. For example, Rai et al. developed a method for the mea- surement of inorganic Hg and MeHg in fish tissues by enzymatic hydrolysis (Protease type XIV) and HPLC-ICP- MS [71] . Method accuracy was demonstrated by the analysis of two reference materials (NRCC DORM-2 Dogfish and NIST RM 50 Albacore tuna). Most of the mercury in fish tissues examined in the study was present as MeHg (88–100%). In view of the satisfactory outcome of the pilot study, a follow-up key comparison (CCQM-K43) was arranged for the examination of a lower level of MeHg in salmon tissues. Most of the par- ticipants adopted GC-ICP-MS for analysis and obtained comparable results. Two reviews about methodologies for the analysis of organotin compounds in mussels and sediment are available in the literature. Pellegrino et al. compared 12 selected extraction methods for the determination of

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butyltin and phenyltin compounds in mussel samples [72] . Quevauviller et al. summarized methods suitable for the monitoring of TBT in mussels and sediment and reported results obtained in certification campaigns of a range of reference materials [73] . In order to address the analytical challenge of organotin speciation, a pilot study (CCQM-P18) for the determination of TBT in marine sediment was launched [74] . The Laboratory of Government Chemist (LGC) provided each participating laboratory with a vial con- taining a methanolic solution of 117 Sn isotopically en- riched TBTCl for IDMS calibration. GC-ICP-MS and HPLC-ICP-MS were the popular choices for analysis. Methodologies based on GC-ICP-MS (extraction derivatization separation/detection) are shown as fol- lows:

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conventionally synthesized and characterized by laboratories according to published methods (e.g., [ 198 Hg]MeHgCl [77] , [ 117 Sn]TBTCl [78] , and [ 118 Sn]TBTCl [79] ). The preparation work requires skillful analysts, high purity chemicals and reagents, contamination-free laboratory ware, and suitable mass spectrometers for characterization. In addition, the quantification of the element amount content of the synthesized spike against a primary assay standard using reverse isotope dilution is needed. To meet market demand, IRMM initiated a program for preparation and certification of a spike of 202 Hg isotopically enriched MeHgCl (named ERM-AE670)

[80] . Briefly, the starting material was 202 Hg isotopi- cally enriched HgO. The spike [ 202 Hg]MeHgCl was synthesized in three steps:

Sonication with acetic acid/MeOH ethyla- tion GC-ICP-MS

(i) reaction of HgO with Zn in hydrochloric acid to give HgCl 2 ;

Microwave extraction with acetic acid ethyla- tion GC-ICP-MS

(ii)

reaction between HgCl 2 and a Grignard reagent of MeMgCl to form Me 2 Hg; and,

(iii)

comproportionation between Me 2 Hg and HgCl 2 to

Microwave extraction with acetic acid/MeOH/tropo- lone ethylation GC-ICP-MS Other methodologies based on HPLC-ICP-MS (extrac- tion separation/detection) are listed below:

Accelerated solvent extraction with acetic acid/ MeOH HPLC-ICP-MS Microwave extraction with acetic acid HPLC-ICP- MS The satisfactory agreement of participants results in the pilot study encouraged a key comparison (CCQM- K28) to be scheduled subsequently and permitted the certification of a new reference material for TBT in marine sediment (HIPA-1). There is concern about the performance of separation (GC versus HPLC) and detection techniques (Q-ICP-MS versus ICP-SMS) employed for the analysis of TBT. In the comparison of GC-ICP-MS and HPLC-ICP-MS for the spe- cies-specific IDMS analysis of TBT in sediment after accelerated solvent extraction, Wahlen et al. found that the limit of detection (LOD) of TBT achieved by GC-ICP-MS (0.03 pg TBT as Sn) was two orders of magnitude better than that obtained by HPLC-ICP-MS (3 pg TBT as Sn) [75] . Q-ICP-MS was used for measurement in both cases. Given the superior sensitivity achievable by GC-ICP- MS, Yang et al. carried out a performance evaluation between Q-ICP-MS and ICP-SMS for the determination TBT in sediment [76] . ICP-SMS was found to provide better analytical figures of m erit, including isotope ratio measurement precision (ICP-SMS gave a more than two-fold improvement in precision of measured 120 Sn/ 117 Sn ratios in TBT standards when compared with Q-ICP-MS) and method detection limit for TBT (ICP-SMS: 0.4 ng/g; Q-ICP-MS: 0.9 ng/g).

3.2.1.2. Availability of isotopically enriched spikes. Isoto- pically enriched spikes of both MeHg and TBT are

produce MeHgCl. The amount content of MeHg in the spike was determined by subtracting the inorganic Hg content from the total Hg content. The Hg isotopic composi- tion of the spike was checked by Q-ICP-MS. An isochronous stability study was undertaken for one year. The relative expanded uncertainty ( k = 2) for the measurement of the amount content of MeHg was found to be ±3.5%, which included a factor account- ing for potential changes over 2 years shelf life. In- deed, the certified spike can help laboratories to apply direct IDMS for MeHg analysis. Fortunately, isotopi- cally enriched organotin species are also available in the market [81] .

3.2.1.3. Uncertainty contributions to single and double IDMS. The availability of isotopically enriched spikes allows the use of single IDMS for measurement. Double IDMS will be an option if spike materials are synthesized for intended use. To compare the performance of the two calibra- tion strategies, it is essential to take a full uncer- tainty budget into consideration. Clough et al. addressed the concern in the determination of MeHg in fish tissue by HPLC-CV-MC-ICP-MS [82] . MeHg was separated from inorganic Hg by HPLC, which was coupled to MC-ICP-MS via a cold vapor gen- eration system for the measurement of Hg isotope ratios. Both single and ‘‘approximate matching’’ double IDMS strategies gave comparable accuracy in the anal- ysis of CRMs (DORM-2 and BCR464). For single IDMS, two major contributions to the combined standard uncertainty (u c ) were identified:

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(i)

the standard uncertainty associated with the iso- tope ratio 200 Hg/ 199 Hg in the sample, which was

Mermet answered ‘‘Yes’’ to this question and suggested five remaining fields of research for consideration:

calculated from IUPAC isotopic abundance data (58% relative contribution); and,

(i)

sample introduction systems (e.g., direct solid anal- ysis);

(ii)

the standard uncertainty due to the mass fraction

(ii)

of the spike [ 199 Hg]MeHgCl (40% relative contribu- tion). By contrast, in the double IDMS approach, the largest contributions to u c resulted from the uncertainty asso- ciated with the measured isotope ratios in the sample

3.2.2.

Advantages

photon collection and detection (e.g., background noise reduction);

(iii) intelligent software (e.g., automatic selection of analytical wavelengths); (iv) analytical performance (e.g., improvement in LODs); and,

blend (14–43% relative contribution) and the calibration

(v)

method validation (e.g., uncertainty estimation

blend (34–74% relative contribution).

and traceability of analytical results to SI) [83] . Similar research fields are also applicable to other spectrometric techniques (e .g., FAAS, GFAAS and ICP-

3.3.1. Analytical considerations

For the determination of total element amount con- tent, spike equilibration occurs as a result of sample

MS). It is not surprising to see few publications on the use of ICP-AES in CCQM exercises in the literature,

dissolution with acids/oxidants. As all isotopes of the element of interest are reacted to have the same oxi- dation state, speciation information is lost. However, species-specific IDMS is a very promising method that provides information of individual analyte species when the following three criteria are met:

because participants often use approved analytical procedures that may not necessarily show novel sug- gestions.

(i)

spike equilibration is attained;

3.3.1.1. Use of internal standards. The use of internal

(ii)

quantitative extraction methods are used; and,

standards in ICP-AES measurements has been shown to

2175).

(iii)

appropriate hyphenated techniques (e.g., GC-ICP-

achieve satisfactory accuracy and precision. With a view

MS and HPLC-ICP-MS) are used. Once spike equilibration has been achieved, species transformation (e.g., demethylation of MeHg and deg- radation of TBT to dibutyltin) will not affect the final analytical result [65] .

to determining major inorganic constituents in solution with relative expanded uncertainties ( k = 2) of the order of 0.1%, Salit et al. reported a novel ICP-AES-calibration strategy that compared the analyte-to-internal standard signal ratio measured in an unknown sample to those

3.2.3. Limitations

ratios measured in mixtures whose amount ratios were

There are several constraints on species-specific IDMS. Complicated processes for synthesis and characterization of isotopically enriched spikes sometimes hinder the availability of materials. The stability of synthesized spikes should be closely monitored to check whether decompo- sition occurs within the anticipated shelf life. Selection of chromatographic columns with high separation effi- ciency is critical. Caution should be exercised on the co- elution of species. It is necessary to choose appropriate flow rates of carrier gases and proper mobile phases for GC-ICP-MS and HPLC-ICP-MS examinations, respec-

3.3. Inductively coupled plasma atomic emission

well known [84] . The internal standards used for anal- ysis included Sc, Mn, Se, In, Sr, Y, Co, Zr and Mo. The methodology showed satisfactory performance in both certification and international comparison exercises, including the certification of 64 different single-element standard solutions in the NIST SRM 3100 series [85] , the analysis of mono-elemental calibration solutions of Al, Cu, Fe and Mg (CCQM-K8), and the certification of major constituents of a refractory alloy (NIST SRM

 

3.3.1.2.

Matching of matrix elements. The presence of

tively. Incomplete species extraction should be strictly avoided. When new species/matrices are encountered, extraction conditions should be thoroughly examined to ensure that quantitative extraction is achieved.

spectrometry ICP-AES is a robust methodology, and has an impressive track record of accurate and simultaneous determination of multi-elements in a wide range of matrices. However, the following question has been raised: ‘‘Is it still possible, necessary and beneficial to perform re- search in ICP-AES?’’ In a recent perspective article,

percentage levels of heavy metals in a sample matrix often causes difficulties in the determination of ele- ments of interest at parts-per-million (ppm) levels. In order to compensate for strong matrix effects, standard solutions used for calibration should be fortified with the same matrix elements at levels similar to the sample. A typical example is the examination of minor ele- ments in steel samples. Sheila et al. developed an exact matching technique for the determination of minor ele- ments (Mn, Mo, Cr and Ni) in steel by ICP-AES [86] . Three important criteria that should be observed were as follows:

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(i) the concentrations of sample and standard were matched so that the emission intensity ratio of sample to standard was 1;

(ii)

comparison of NAA with other analytical methods based on conventional spectrometric techniques [96,97] ;

(ii) both sample and standard were doped with an

(iii)

in vivo analysis of trace elements [98,99] ; and,

internal standard solution of Au to correct for instrumental drift; and, (iii) both sample and standard were matched with re- spect to the acid strength and the dominant matrix element of Fe (within ±3%).

(iv)

accurate determination of element amount con- tents for various purposes (e.g., international inter- comparisons, biological studies, environmental monitoring, geological examinations, and forensic investigations).

The method was validated by a CRM (NIST SRM 2171 Low Alloy Steel) and gave a measurement uncertainty of 1% at the 95% confidence interval. The research team eventually applied the method to a key comparison for the examination of elements in steel (CCQM-K33) and achieved satisfactory agreement with other participants results.

3.4.1. Analytical considerations The basic principles and instrumentation have been shown in the literature [100] . As NAA is a less common technique for ordinary laboratories, we briefly describe analytical considerations with respect to measurement process, quantification and classification. Measurement usually involves three basic steps:

3.3.2. Advantages

Spectrometers for ICP-AES can measure up to 70 ele- ments simultaneously in a single sample analysis. Dual viewing of the plasma offers LODs down to parts-per-bil- lion (ppb) levels (axial viewing) and extends the working ranges for percentage concentration measurements (ra- dial viewing). The choice of alternative wavelengths for the analytes of interest allows analytical results free from spectral interferences. Modern solid-state detectors (e.g., segmented-array charge-coupled device detectors [87] ) usually provide uniform resolution at all wavelengths. Simultaneous background correction can be performed adjacent to the analytical wavelengths. The technical difficulty of direct analysis of samples containing organic solvents has recently been solved by using a special sample introduction system. For example, Grindlay et al. designed a microwave-based thermal nebulizer that per- mitted nebulization of 10–40% (w/w) organic solvents (e.g., formic acid, acetic acid, methanol, ethanol and propan-2-ol) [88,89] .

3.3.3. Limitations

ICP-AES is unsuitable for the analysis of some elements (e.g., As and Se) because of their high ionization potentials, thus resulting in poor LODs. Inter-element interferences may not be completely resolved, even using

the sophisticated detection system. Appropriate correc- tive measures (e.g., inter-element correction equations [90] and multi-component spectral fitting [91] ) should be adopted as far as feasible.

3.4. Neutron activation analysis NAA is a powerful technique for inorganic analysis and plays an important role in chemical metrology [92,93] . Generally speaking, four major areas of applications are:

(i) certification of candidate reference materials

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First, the sample is irradiated with a flux of neutrons. Neutron fluxes can be divided into three types accord- ing to their kinetic energies: thermal (<0.5 eV), epi- thermal (0.5 eV – 0.5 MeV) and fast (>0.5 MeV). Neutron reactors (based on fission of 252 Cf), neutron generators (based on deuterium-tritium or deute- rium-deuterium fusion reactions) and particle acceler- ators are the common neutron sources. Second, transformation of stable isotopes of a target element into radioactive isotopes occurs upon neutron irradiation. Prompt c -rays are emitted from an instan- taneous decay of radioactive isotopes. Delayed c -rays are produced according to the characteristic half-lives of radioactive isotopes varying from seconds to years. Finally, characteristic c -radiations of specific energies are measured and quantified. c -ray spectrometers equipped with Ge(Li) or hyper-pure Ge semiconductor detectors are ideal for the measurement of c -rays. Two quantification approaches are widely used. In the ‘‘comparator method’’, the sample and the standard are irradiated and measured under identical conditions. The standard used for calibration contains either an indi- vidual mono-element or multiple elements. The con- centration of the sample is calculated according to Equation (6) :

c x ¼ c z m z

A x

m x A z

ð6 Þ

where c x is the element amount content in the sample (mol/kg); c z is the element amount content in the stan- dard (mol/kg); m x is the mass of the sample (kg); m z is the mass of the standard (kg); A x is the activity of the sample (Bq or disintegrations per second); and, A z is the activity of the standard (Bq or disintegrations per sec- ond). Furthermore, Zeisler et al. provided a detailed mathe- matical expression to describe the measurement process for determination of Cr in a CRM of stainless steel (NIST SRM 11521a) using instrumental NAA (INAA) [101].

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For ‘‘ k 0 method’’, a single comparator ( 197 Au standard) is used to determine a k 0 normalization factor for all elements being measured [102] . NAA can be classified into several types with respect to:

including solids, liquids, gases and suspensions/slurries. The technique is particularly suitable for the examina- tion of antiques/valuables and samples that are difficult to be decomposed. Matrix effects are often negligible because matrix elements (e.g., H, C, O and N) can hardly

(i) the necessity of carrying out chemical dissolution of radioactive samples and chemical separation of radionuclides {radiochemical NAA (RNAA) [103– 105] and INAA [106–117] , which requires no sample dissolution/chemical separation};

form radioactive isotopes during INAA measurements. Only small quantities of samples (100–200 mg) are needed for analysis. About 70% of the elements shown in the periodic table ( Fig. 2) can be examined by NAA, which is regarded as complementary to MS techniques.

(ii)

measurement of c -radiations {prompt gamma NAA (PGNAA) [118–123] and delayed gamma NAA (DGNAA)};

In view of the advantageous features, NMIs have em- ployed NAA (mainly INAA and RNAA) for the deter- mination of As, Cd, Cr, Cu, Fe Mn, Mo, Ni, Se and Zn in

(iii)

use of neutron fluxes for irradiation {thermal NAA (TNAA), epithermal NAA (ENAA) and fast NNA (FNAA)}; and,

several key comparisons (CCQM-K24, K31, K33, K42, K43, K44 and K49). Results of NAA are comparable to those of IDMS in terms of high accuracy and precision.

(iv)

measurement conducted inside the body [ in vivo

NAA (IVNAA)]. There are no hard and fast rules governing which type of NAA is best for a new application. Nonethe- less, a review by Witkowska et al. is a valuable ref- erence, which describes recent applications of various types of NAA (TNAA, ENAA, FNAA, IVNAA, PGNAA, INAA and RNAA) for the study of human and environmental samples [124] . Furthermore, Fig. 2 shows for reference purposes a periodic table of the types of NAA for the analysis of specific elements. As the information is not exhaustive, analysts are strongly recommended to conduct a literature search before examination.

3.4.2. Advantages The methodology is non-destructive (except RNAA) and can measure many elements simultaneously. It usually provides the total element amount content of the sample. As sample dissolution is not needed prior to analysis (except RNAA), contamination due to acids and reagents can be avoided. Samples can be in various forms,

However, it is imperative to note that mono-isotopic elements (e.g., As and Mn) are measurable by NAA but not determinable by IDMS.

3.4.3. Limitations The use of NAA is limited to a few NMIs because of huge resource implications, safety concerns about neutron reactors and the availability of competent personnel. Another drawback is that several elements (e.g., Pb) can hardly be determined by NAA. Unless NAA is combined with chromatographic separation, speciation information will not be readily available. Among other nuclear analytical techniques, Chai et al. highlighted several examples of speciation of Se, Hg, Cr and I in biological and environmental samples based on the combination of chromatography (e.g., an- ion exchange and gel filtration) and NAA (e.g., INAA and RNAA) [125] . In addition, Shi et al. demonstrated the use of HPLC-NAA for As speciation in natural water [126] . However, due to the limited availability of facili- ties, chromatography combined with NAA is still less widely used in speciation studies than chromatography

H

 

He

(P)

Li

Be

 

B

C

N

O

F

Ne

(P)

(V)

(P,V)

(P,V)

(I)

Na

Mg

Al

Si

P

S

Cl

Ar

(I,R,P)

(I,R,P)

(I,R,P)

(P)

(I,P,V)

(P)

(I,R,P)

K

Ca

Sc

Ti

V

Cr

Mn

Fe

Co

Ni

Cu

Zn

Ga

Ge

As

Se

Br

Kr

(I,V,P)

(I,R,P,V)

(I,R,P)

(I,R,P)

(I,R,P)

(I,R)

(I,R,P)

(I,P)

(I,R,P)

(I,P)

(I,R,P)

(I,P)

(I,R)

(R)

(I,R)

(I,R)

(I,R)

Rb

Sr

Y

Zr

Nb

Mo

Tc

Ru

Rh

Pd

Ag

Cd

In

Sn

Sb

Te

I

Xe

(I)

(I,R)

(R)

(I,R)

(I,R)

(I,R)

(I,R)

(I,R)

(I)

(I,R,P)

(I,R)

(I,R)

(I,R)

(I,R)

(I,R)

Cs

Ba

La

Hf

Ta

W

Re

Os

Ir

Pt

Au

Hg

Tl

Pb

Bi

Po

At

Rn

(I,R)

(I,R)

(I,R)

(I,R)

(I,R)

(I,R)

(I,R)

(I)

(I,R)

(I)

(I,R)

(I,R)

Fr

Ra

Ac

 
 

Ce

Pr

Nd

Pm

Sm

Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

 

(I,R)

(I,R)

(I,R,P)

(I,R)

(R,P)

(I,R)

(I,R,P)

(I,R)

(I,R)

(I,R)

(I,R)

(I,R)

Th

Pa

U

(I,R)

(I,P)

Figure 2. A periodic table showing the types of NAA for the analysis of specific elements (Abbreviations for acronyms are as follows: I : INAA [106–117]; R: RNAA [103–105]; P : PGNAA [118–124]; and, V : IVNAA [98,99,124]).

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combined with ICP-MS (i.e. HPLC-ICP-MS and GC-ICP- MS).

3.7. Flame atomic absorption spectrometry and graphite furnace atomic absorption spectrometry The well-established techniques of FAAS and GFAAS are

and cold vapor (CVAAS) techniques are suitable for the

3.5.

Ion chromatography/high performance liquid

often used for single-element determinations. These

chromatography (IC/HPLC)

Not long ago, Haddad et al. reviewed recent develop- ments and emerging directions in ion chromatography (IC) [127] . Topics of the review included:

instruments are less costly than ICP-AES and ICP-MS. When appropriate accessories are coupled to atomic absorption spectrometers, hydride generation (HGAAS)

(i)

new stationary phases;

analysis of hydride-forming elements (e.g., As and Se)

(ii)

miniaturized IC systems;

and Hg, respectively.

(iii)

expansion of peak capacity in IC; and,

Matrix interferences can possibly be overcome in two

(iv)

hyphenated IC systems for speciation analysis and

ways:

metallomics. IC has been traditionally coupled with a range of detectors (e.g. conductivity, ultraviolet-visible and elec- trochemical detectors) for the determination of anions and cations [128] . Nowadays, the hyphenation of IC and MS allows speciation analysis. Ionization sources, including ICP and electrospray ionization (ESI), are usually employed in hyphenated IC systems [129] . Among others, studies of selenium-containing species [130–132] and arsenic-containing species [133,134] in environmental and biological samples have been the most extensively developed areas in recent speciation analysis. New stationary phases developed for IC provide remarkable efficiency for the separation of a wide range of complex selenium and arsenic species. A pilot study (CCQM-P86) relating to the speciation analysis of selenomethionine (SeMet) in pharmaceutical yeast tablets is noteworthy [135] . As revealed in the report, IC-ICP-MS (i.e. HPLC-ICP-MS) was the most fre- quently used technique for the species-specific IDMS analysis of SeMet. We expect key comparisons focusing on selenium/ arsenic speciation to be arranged in the near future.

3.6. X-ray fluorescence spectrometry (XRF)

XRF is a mature technique for elemental analysis and significant improvements continue to appear. Recent reviews available [136–138] covered the latest devel- opments [e.g., instrumentation and detectors, matrix correction and spectrum analysis procedures, total reflection XRF (TXRF)]. A critical review on TXRF analysis has also been published [139] . The recent trends are towards the use of TXRF for metallic con- tamination control in semiconductor nanotechnology [140] . Advantages in surface and thin-layer analysis by TXRF, especially for wafers (thin slices of semiconductor material) have been discussed [141]. Although XRF has not been widely used in previous key comparisons (CCQM-K33, K42 and K44), we anticipate that the technique will be suitable for the analysis of metal contaminants in advanced materials (e.g., semiconductors).

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(i)

matrix modification (e.g., use of ionization suppres- sants when analyzing easily ionized elements by FAAS, addition of matrix modifiers for GFAAS); and,

(ii)

method of standard additions.

AAS based on external standard calibration/standard additions has provided satisfactory results in some key comparisons (e.g., CCQM-K14, K31 and K49). In an account of recent developments in on-line electrothermal (graphite furnace) AAS, Burguera et al. evaluated several on-line analyte pre-concentration systems (e.g., precipitation or co-precipitation/dissolu- tion reactions, sorption pre-concentration and solvent extraction) and on-line analyte separation approaches (e.g., microdialysis separation, electrochemical processes and chemical vapor generation) [142] . Advancement in on-line techniques allows analysis of complex samples with low analyte concentrations. More importantly, the coupling of these techniques to ICP-AES and ICP-MS can definitely offer a wide range of appli- cations because of their multi-element measurement capability.

3.8. Gravimetry, eletrogravimetry, titrimetry and coulometry All four methodologies are the oldest techniques in quantitative analysis. They are regarded as candidate primary methods of measurement in chemical analysis [143] . As both theoretical and technical aspects have been well documented [144] , we do not provide addi- tional information in this review. Although remarkable analytical methods based on MS are available for inor- ganic analysis, these methodologies remain active for standardization processes.

4. The way forward

So far, relevant key comparisons under respective MSCs have been successfully organized. Three fundamental issues of chemical metrology are properly addressed:

(i) establishing traceability of analytical results to SI (i.e. mol and kg);

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(ii)

enabling worldwide comparability of results; and,

(iii)

showing the degree of equivalence of national mea-

surement standards maintained by NMIs. In addition, laboratories have taken the opportunity to develop novel methodologies for chemical measure- ments. With a view to providing a more comprehensive scope of measurement services, we suggest including two additional MSCs, namely ‘‘Drugs/Medicines’’ and ‘‘Metalloproteins’’. Metal-containing drugs/medicines (metallodrugs) are widely used for chemotherapy purposes. For example, carboplatin is a chemotherapeutic drug used for the treatment of ovarian cancer. It comprises Pt and a bidentate cyclobutane dicarboxylate moiety. The rec- ommended dosage will be correctly applied to patients only if the active ingredient of the drug is accurately determined. This is important to prevent over-dosing and adverse toxic effects. Species-specific IDMS can be the method of choice for the accurate quantification of carboplatin. However, isotopically enriched spikes are not readily available. In order to rise to the challenge, Koellensperger et al. reported the first synthesis of 194 Pt isotopically enriched carboplatin [145] . In the quanti- fication of carboplatin in urine by species-specific IDMS, both LC-ICP-MS and LC-ESI -TOF-MS (liquid chroma- tography-electrospray ionization-time-of-flight mass spectrometry) were found to be effective for analysis. It was important to note that the LODs achieved by the two techniques were 0.1 ng/g and 15 ng/g, respec- tively. Metalloproteins are responsible for many biological processes. Some transition metals bind to proteins with high affinity interactions. Examples of important metalloproteins (element) include cytochrome oxidase (Cu), hemoglobin (Fe), glutathione peroxidase (Se), carboxypeptidase A (Zn) and glutamine synthetase (Mn). In a recent review, Garcia et al. described trends in metalloprotein analysis with respect to four areas, including protein-separatio n techniques, metal quanti- fication in proteins, ligand identification and the latest challenges in metallomics [146] . To explore the feasi- bility of using species-specific IDMS analysis of metal- loproteins, Harrington e t al. used a Cu-containing protein, rusticyanin (Rc), as a model system for exam- ination [147] . The protein is involved in the respiratory electron transport chain of a bacterium called Acido- thiobacillus ferrooxidans . Rc containing an enriched isotope of 65 Cu was produced by cell-culture and pro- tein-expression systems. The isotopically enriched pro- tein was isolated from the bacterium and characterized by standard biochemical assays based on UV-visible spectrometry and electrospray MS. The work showed that the metal center was stable under the HPLC-ICP- MS conditions examined and that the approach could

Trends

form the basis of a method for the accurate determi- nation of metalloproteins by IDMS. Study of distributions and compositions of all metal- loproteins in a proteome comprises the scientific field of metalloproteomics, which has attracted attention to the development of new methodologies. To this end, Gao et al. recently evaluated several advanced nuclear ana- lytical techniques for metalloproteomics (e.g., NAA, XRF, Mo¨ssbauer spectrometry, X-ray absorption spec- trometry, and neutron scattering and diffraction) [148] . That evaluation clearly described the advantages, the limitations and the applications of the techniques, so we do not go into detail about these important aspects. The advancement of analytical techniques allows the accurate determinations of metallodrugs and metallo- proteins. Under the current structure of 14 MSCs ( Table 1 ), the analysis of these two classes of analytes may not be easily classified into any specific category. It is therefore desirable to review the present scope of MSCs and consider the two proposed MSCs. We believe that this will help promote the development of novel meth- odologies for the analysis of such important analytes. International key comparisons focusing on the anal- ysis of challenging analytes in more complex matrices attract the development of advanced methodologies for inorganic analysis. These give benefits to activities such as certification of materials and the provision of accurate and SI-traceable reference values of analytes [149] . Analytical field laboratories can validate the methods that they employ for routine analysis through the use of matrix-matched CRMs and their participation in inter- laboratory comparisons (e.g., IMEP), whose independent reference values (SI-traceable, where possible) are determined by candidate primary methods (e.g., IDMS). The efforts of NMIs/DIs eventually enhance the compe- tence of analytical field laboratories by disseminating these methods.

Acknowledgements The authors are indebted to Dr. T.L. Ting (Government Chemist), Ms. S.Y.K Tam, Dr. W.M. Sin, Dr. C.S. Mok, Mr. W.C. Sham and Mr. F.W. Lee for their encourage- ment, advice and help. We sincerely thank Drs. J. Vogl, D. Schiel, W. Pritzkow, R.E. Sturgeon, L. Yang, C.R. Que´ tel, M. Sargent, L.G. Mackay, R.B. Myors, M. van Son, R.R. Greenberg, K. Chiba, K. Inagaki, E. Hwang, O.F.X. Donard and E. Krupp for their great support during the development of protocols for IDMS analysis. Last but not least, we thank Dr. A.W.L. Leung for searching relevant information during manuscript preparation. The contents of this article do not neces- sarily reflect the views of the Government of the Hong Kong Special Administrative Region, nor does mention

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