ISO/TC 146/SC 2/WG 2 - Inorganic particulate matter

This document specifies a method for collecting samples of airborne particulate matter for subsequent determination of metals and metalloids using inductively coupled plasma — atomic emission spectrometry (ICP-AES). Samples obtained using the method described herein can also be subsequently analysed for elemental composition by other instrumental methods, such as atomic absorption spectrometry (AAS) or inductively coupled plasma mass spectrometry (ICP-MS). The method is not applicable to the sampling of mercury, which is present in air in the vapour phase at ambient temperatures; inorganic compounds of metals and metalloids that are permanent gases, e.g. arsine (AsH3); or inorganic compounds of metals and metalloids that are present in the vapour phase at ambient temperatures, e.g. arsenic trioxide (As2O3). NOTE Although the method does not describe a means of collecting inorganic compounds of metals and metalloids that are present in the vapour phase, in most instances this is relatively easily to achieve by using a back-up filter which has been pre-treated to trap the compound(s) of interest, e.g. a back-up paper pad impregnated with sodium carbonate is suitable for collecting arsenic trioxide (see ISO 11041[2]). The method is applicable to personal sampling of the inhalable, thoracic or respirable fraction of airborne particles, as defined in ISO 7708, and to static sampling. This document excludes sampling of surfaces or bulk materials. Guidance on collection of samples for surfaces may be found in ASTM D7659[7].

This document specifies a number of suitable methods for preparing test solutions from samples of airborne particulate matter collected using the method specified in ISO 15202‑1, for subsequent determination of metals and metalloids by ICP‑AES using the method specified in ISO 15202‑3. It contains information about the applicability of the methods with respect to the measurement of metals and metalloids for which limit values have been set. The methods can also be used in the measurement of some metals and metalloids for which limit values have not been set but no information about its applicability is provided in this case. NOTE The sample preparation methods described in this document are generally suitable for use with analytical techniques other than ICP‑AES, e.g. atomic absorption spectrometry (AAS) by ISO 8518[5] and ISO 11174[10] and inductively coupled plasma mass spectrometry (ICP‑MS) by ISO 30011[11]. The method specified in Annex B is applicable when making measurements for comparison with limit values for soluble metal or metalloid compounds. One or more of the sample dissolution methods specified in Annexes C through H are applicable when making measurements for comparison with limit values for total metals and metalloids and their compounds. Information on the applicability of individual methods is given in the scope of the annex in which the method is specified. The following is a non-exclusive list of metals and metalloids for which limit values have been set (see References [14] and [15]) and for which one or more of the sample dissolution methods specified in this document are applicable. However, there is no information available on the effectiveness of any of the specified sample dissolution methods for those elements in italics. Aluminium Calcium Magnesium Selenium Tungsten Antimony Chromium Manganese Silver Uranium Arsenic Cobalt Mercury Sodium Vanadium Barium Copper Molybdenum Strontium Yttrium Beryllium Hafnium Nickel Tantalum Zinc Bismuth Indium Phosphorus Tellurium Zirconium Boron Iron Platinum Thallium Caesium Lead Potassium Tin Cadmium Lithium Rhodium Titanium ISO 15202 is not applicable to the determination of elemental mercury or arsenic trioxide, since mercury vapour and arsenic trioxide vapour are not collected using the sampling method specified in ISO 15202‑1.

This document specifies performance requirements and test methods for the evaluation of procedures for measuring metals and metalloids in airborne particles sampled onto a suitable collection substrate. This document specifies a method for estimating the uncertainties associated with random and systematic errors and combining them to calculate the expanded uncertainty of the measuring procedure as a whole, as prescribed in ISO 20581. This document is applicable to measuring procedures in which sampling and analysis is carried out in separate stages, but it does not specify performance requirements for collection, transport and storage of samples, since these are addressed in EN 13205-1 and ISO 15767. This document does not apply to procedures for measuring metals or metalloids present as inorganic gases or vapours (e.g. mercury, arsenic) or to procedures for measuring metals and metalloids in compounds that could be present as a particle/vapour mixture (e.g. arsenic trioxide).

ISO 17733:2015 specifies a procedure for determination of the time-weighted average mass concentration of mercury vapour and inorganic mercury compounds in workplace air. Mercury vapour is collected on a solid sorbent using either a diffusive badge or a pumped sorbent tube. Particulate inorganic mercury compounds, if present, are collected on a quartz fibre filter. Samples are analysed using either cold vapour atomic absorption spectrometry (CVAAS) or cold vapour atomic fluorescence spectrometry (CVAFS) after acid dissolution of the mercury collected. This International Standard is applicable to the assessment of personal exposure to mercury vapour and/or particulate inorganic mercury compounds in air for comparison with long-term or short-term exposure limits for mercury and inorganic mercury compounds and for static (area) sampling. The lower limit of the working range of the procedure is the quantification limit. This is determined by the sampling and analysis methods selected by the user, but it is typically in the range 0,01 µg to 0,04 µg of mercury (see 13.1). The upper limit of the working range of the procedure is determined by the capacity of the diffusive badge, sorbent tube or filter used for sample collection, but it is at least 30 µg of mercury (see 13.2). The concentration range of mercury in air for which this International Standard is applicable is determined in part by the sampling method selected by the user, but it is also dependent on the air sample volume. The diffusive badge method is not applicable to measurements of mercury vapour when chlorine is present in the atmosphere, e.g. in chloralkali works, but chlorine does not interfere with the pumped sorbent tube method (see 13.12.1). Gaseous organomercury compounds could cause a positive interference in the measurement of mercury vapour (see 13.12.2). Similarly, particulate organomercury compounds and gaseous organomercury compounds adsorbed onto airborne particles could cause a positive interference in the measurement of particulate inorganic mercury compounds (see 13.12.3).

ISO 17091:2013 specifies a method for the determination of the time-weighted average mass concentration of lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), and calcium dihydroxide [Ca(OH)2] in workplace air by collection of the particulate hydroxides on a filter and analysis of the corresponding cations using ion chromatography. For aerosol sampling, the method is applicable to the personal sampling of the inhalable fraction of airborne particles, as defined in ISO 7708, and to static (area) sampling. The method is applicable to the determination of masses of 0,005 mg to at least 2,5 mg of lithium per sample and 0,01 mg to at least 5 mg of sodium, potassium, and calcium per sample. The concentration range of particulate LiOH, NaOH, KOH, and Ca(OH)2 in air for which the measuring procedure is applicable is determined by the sampling method selected by the user. For a 1 m3 air sample, the working range is approximately 0,002 mg m−3 to at least 20 mg m−3 for all four hydroxides. For a 30 l air sample, the lower limit of the working range is approximately 0,1 mg m−3 for all four hydroxides. The procedure does not allow differentiation between the hydroxides and their corresponding salts if both are present in the air. If the cations are present alone in the form of hydroxides, the method is specific for these basic compounds. In other circumstances, the results obtained represent the highest concentration of the hydroxides that could be present in the sampled air.

ISO 30011:2010 specifies a procedure for the use of quadrupole inductively coupled plasma mass spectrometry (ICP‑MS) for analysing test solutions prepared from samples of airborne particulate matter collected as specified in ISO 15202‑1. Method development, performance checks, and a routine analysis method are specified. Test solutions for analysis by ISO 30011:2010 are prepared as specified in ISO 15202‑2. ISO 30011:2010 is applicable to the assessment of workplace exposure to metals and metalloids for comparison with limit values.

ISO 21438-3:2010 specifies a method for the determination of the time-weighted average mass concentration of soluble particulate fluorides and hydrofluoric acid (HF) in workplace air by collection of the particulate fluorides on a pre-filter and HF on an alkali-impregnated filter and analysis by ion chromatography. The method is only applicable to determination of particulate fluorides that are soluble using the sample preparation procedure specified. For aerosol sampling, the method is applicable to the personal sampling of the inhalable fraction of airborne particles, as defined in ISO 7708, and to static (area) sampling. The method is applicable to the determination of masses of 0,005 mg to at least 1,25 mg of particulate fluorides per sample and 0,012 5 mg to at least 1,2 mg of HF per sample. The concentration range of particulate fluorides and HF in air for which the measuring procedure is applicable is determined by the sampling method selected by the user. For a 120 l air sample, the working range is approximately 0,04 mg m-3 to at least 10 mg m-3 for particulate fluorides and approximately 0,13 mg m-3 to at least 10 mg m-3 for HF. HF can react with co-sampled particulate matter on the pre-filter, causing an interference on the measured concentration.

ISO 21438-2:2009 specifies a method for the determination of the time-weighted average mass concentration of hydrogen chloride (HCl) gas and hydrochloric acid mist, hydrogen bromide (HBr) vapour and hydrobromic acid mist and nitric acid (HNO3) vapour and mist in workplace air by collection on an alkali-impregnated quartz fibre filter and analysis by ion chromatography. For mist sampling, the method is applicable to the personal sampling of the inhalable fraction of airborne particles and to static (area) sampling. The analytical method is applicable to the determination of masses of 0,01 mg to 2,5 mg of HCl, HBr and HNO3 per sample. The range of concentrations of HCl, HBr and HNO3 in air for which the measuring procedure is applicable is determined by the sampling method selected by the user. For a 240-litre air sample, the working range is approximately 0,04 mg/m3 to 10 mg/m3 for HCl, HBr and HNO3. The procedure is intended to differentiate between the acids and their corresponding salts. If both are present in the air, particulate salts are trapped on a pre-filter. Co-sampled particulate matter trapped on the pre-filter and/or deposited on the walls of the sampler may be analysed, if desired. Acids can react with co-sampled particulate matter on the pre-filter, causing interference with the measurement of the acid concentration.

ISO 21438-1:2007 specifies a method for the determination of the time-weighted average mass concentration of sulfuric acid and phosphoric acid in workplace air by ion chromatography. The method is applicable to the personal sampling of the inhalable fraction of airborne particles, as defined in ISO 7708 and to static (area) sampling. The analytical method is applicable to the determination of masses of 0,005 mg to 2,000 mg of sulfuric acid and phosphoric acid per sample, without dilution. The concentration range of sulfuric acid and phosphoric acid in air for which the measuring procedure is applicable is determined by the sampling method selected by the user. For an air sample of volume 1 m3, the working range is approximately 0,005 mg/m3 to 2,000 mg/m3. The method is not applicable to the determination of sulfur trioxide. The procedure does not allow differentiation between the acids and their corresponding salts if both are present in the air. The procedure does not allow differentiation between phosphoric acid and diphosphorus pentoxide (phosphoric anhydride) if both are present in the workplace.

ISO 20552:2007 specifies a procedure for determination of the mass concentration of mercury vapour in workplace air using a method of gold-amalgam collection with analysis by either cold vapour atomic absorption spectrometry (CVAAS) or cold vapour atomic fluorescence spectrometry (CVAFS). The procedure specifies a number of sampling methods for different applications. The procedure is suitable for making short-term measurements (e.g. 15 min) when sampling at a flow rate of between 100 ml per min and 1 000 ml per min. For assessment of long-term exposure, such as 8 h, this procedure can be used with sampling flow rate of 100 ml per min in workplaces where the concentration of mercury vapour is expected to be lower than 20 micrograms per cubic metre. If the expected concentration of mercury vapour is higher than 20 micrograms per cubic metre, it is necessary to use the procedure prescribed in ISO 17733. ISO 20552:2007 is unsuitable for making measurements of mercury vapour in air when chlorine is present in the atmosphere, e.g. in chloralkali works. Gaseous organo-mercury compounds can cause a positive interference.

ISO 16740:2005 specifies a method for the determination of the time-weighted average mass concentration of hexavalent chromium in workplace air. Separate sample preparation methods are specified for the extraction of soluble and insoluble hexavalent chromium. The method for insoluble hexavalent chromium can also be used to prepare samples for determination of total hexavalent chromium, if desired. ISO 16740:2005 is applicable to the personal sampling of the inhalable fraction of airborne particles, as defined in ISO 7708, and to static (area) sampling. The analytical method is applicable to the determination of masses of 0,01 micrograms to 10 micrograms of hexavalent chromium per sample, without dilution. The concentration range of hexavalent chromium in air for which the measuring procedure is applicable is determined by the sampling method selected by the user. For a 1 cubic metre air sample, without sample dilution, the working range is approximately 0,01 micrograms per cubic metre to 10 micrograms per cubic metre.

ISO 15202-3:2004 prescribes a procedure for the use of inductively coupled plasma atomic emission spectrometry for analysing test solutions prepared as prescribed in ISO 15202-2 from samples of airborne particulate matter collected as prescribed in ISO 15202-1. Method development, performance checks and a routine analysis method are prescribed. The procedure suffers from no significant spectral interferences, provided that suitable analytical wavelengths are used. However, inaccurate background correction and/or inadequate matrix-matching can adversely affect results. ISO 15202-3:2004 is applicable to the following non-exclusive list of metals and metalloids for which limit values have been set; however, there is no information available on the effectiveness of any of the sample dissolution methods specified in ISO 15202-2 for those elements in italics: aluminium, antimony, arsenic, barium, beryllium, bismuth, boron, caesium, cadmium, calcium, chromium, cobalt, copper, hafnium, indium, iron, lead, lithium, magnesium, manganese, mercury, molybdenum, nickel, phosphorus, platinum, potassium, rhodium, selenium, silver, sodium, strontium, tantalum, tellurium, thallium, tin, titanium, tungsten, uranium, vanadium, yttrium, zinc and zirconium. ISO 15202-3:2004 is not applicable to determination of elemental mercury, since mercury vapour is not collected using the sampling method specified in ISO 15202-1. The results obtained may be used for the assessment of workplace exposure to metals and metalloids for comparison with limit values.

Specifies methods for the determination of the mass concentration of particulate cadmium and cadmium compounds in workplace air by electrothermal atomic absorption spectrometric method (ETAAS) applicable to the determination of mass concentrations of 10 ng to 600 ng Cadmium per sample or flame atomic absorption spectrometric method (FAAS), applicable to the determination of mass concentrations of 0,15 g to 96 g Cadmium per sample.

Gives a method by hydrid generation for the atomic absorption spectrometric determination of the mass concentration of particulate arsenic, arsenic compounds and arsenic trioxide vapour in workplace air. Applicable to the determination of mass concentrations of approximately 100 ng to 125 g of arsenic per sample. Not suitable for the determination of arsenic in the form of metal arsenides.

ISO 15202-1:2012 specifies a method for collecting samples of airborne particulate matter for subsequent determination of metals and metalloids using inductively coupled plasma ? atomic emission spectrometry (ICP-AES). Samples obtained using the method described herein can also be subsequently analysed for elemental composition by other instrumental methods, such as atomic absorption spectrometry (AAS) or inductively coupled plasma mass spectrometry (ICP-MS). The method is not applicable to the sampling of mercury, which is present in air in the vapour phase at ambient temperatures; inorganic compounds of metals and metalloids that are permanent gases, e.g. arsine (AsH3); or inorganic compounds of metals and metalloids that are present in the vapour phase at ambient temperatures, e.g. arsenic trioxide (As2O3). The method is applicable to personal sampling of the inhalable or respirable fraction of airborne particles, as defined in ISO 7708, and to static sampling.

1.1 This part of ISO 15202 specifies a number of suitable methods for preparing test solutions from samples of airborne particulate matter collected using the method specified in ISO 15202‑1, for subsequent determination of metals and metalloids by ICP‑AES using the method specified in ISO 15202‑3. It contains information about the applicability of the methods with respect to the measurement of metals and metalloids for which limit values have been set. The methods can also be used in the measurement of some metals and metalloids for which limit values have not been set but no information about its applicability is provided in this case. NOTE The sample preparation methods described in this part of ISO 15202 are generally suitable for use with analytical techniques other than ICP‑AES, e.g. atomic absorption spectrometry (AAS) by ISO 8518[5] and ISO 11174[10] and inductively coupled plasma mass spectrometry (ICP‑MS) by ISO 30011[11]. 1.2 The method specified in Annex B is applicable when making measurements for comparison with limit values for soluble metal or metalloid compounds. 1.3 One or more of the sample dissolution methods specified in Annexes C through H are applicable when making measurements for comparison with limit values for total metals and metalloids and their compounds. Information on the applicability of individual methods is given in the scope of the annex in which the method is specified. 1.4 The following is a non-exclusive list of metals and metalloids for which limit values have been set (see References [15] and [16]) and for which one or more of the sample dissolution methods specified in this part of ISO 15202 are applicable. However, there is no information available on the effectiveness of any of the specified sample dissolution methods for those elements in italics. Aluminium Calcium Magnesium Selenium Tungsten Antimony Chromium Manganese Silver Uranium Arsenic Cobalt Mercury Sodium Vanadium Barium Copper Molybdenum Strontium Yttrium Beryllium Hafnium Nickel Tantalum Zinc Bismuth Indium Phosphorus Tellurium Zirconium Boron Iron Platinum Thallium Caesium Lead Potassium Tin Cadmium Lithium Rhodium Titanium ISO 15202 is not applicable to the determination of elemental mercury or arsenic trioxide, since mercury vapour and arsenic trioxide vapour are not collected using the sampling method specified in ISO 15202‑1.

ISO 17733:2004 specifies a procedure for determination of the time-weighted average mass concentration of mercury vapour and inorganic mercury compounds in workplace air. Mercury vapour is collected on a solid sorbent using either a diffusive badge or a pumped sorbent tube. Particulate inorganic mercury compounds, if present, are collected on a quartz fibre filter. Samples are analysed using either cold vapour atomic absorption spectrometry (CVAAS) or cold vapour atomic fluorescence spectrometry (CVAFS) after acid dissolution of the mercury collected. ISO 17733:2004 is applicable to the assessment of personal exposure to mercury vapour and/or particulate inorganic mercury compounds in air for comparison with long-term or short-term exposure limits for mercury and inorganic mercury compounds and for static (area) sampling. The lower limit of the working range of the procedure is the quantification limit. This is determined by the sampling and analysis methods selected by the user, but it is typically in the range 0,01 g to 0,04 g of mercury (see 13.1). The upper limit of the working range of the procedure is determined by the capacity of the diffusive badge, sorbent tube or filter used for sample collection, but it is at least 30 g of mercury (see 13.2). The concentration range of mercury in air for which ISO 17733:2004 is applicable is determined in part by the sampling method selected by the user, but it is also dependent on the air sample volume. The diffusive badge method is not applicable to measurements of mercury vapour when chlorine is present in the atmosphere, e.g. in chloralkali works, but chlorine does not interfere with the pumped sorbent tube method (see 13.11.1). Gaseous organo-mercury compounds could cause a positive interference in the measurement of mercury vapour (see 13.11.2). Similarly, particulate organo-mercury compounds and gaseous organo-mercury compounds adsorbed onto airborne particles could cause a positive interference in the measurement of particulate inorganic mercury compounds (see 13.11.3).

The method is applicable to the determination of masses of 10 µg to 200 µg of lead per sample using the normal procedure without dilution. The concentration range for lead in air for which this procedure is applicable is determined in part by the sampling procedure selected by the user. The method is applicable to personal and fixed location sampling. The normal sample dissolution procedure is not effective for all lead compounds.