MDHS

Methods for the Determination of Hazardous Substances

Health and Safety Laboratory
INTRODUCTION Requirements of the COSHH Regulations 1 The Control of Substances Hazardous to Health (COSHH) Regulations1 are designed to ensure that the exposure of people at work to substances which could damage their health is either prevented, or where that is not reasonably practicable, adequately controlled. Employers are required to make an assessment of the health risk created by such work, and to prevent or control exposure to the substances involved. The COSHH Regulations also require that people who could be exposed to substances hazardous to health receive suitable and sufficient information, instruction and training. Employers must ensure that their responsibilities under the COSHH Regulations are fulfilled before allowing employees to undertake any procedure described in this MDHS. 2 Guidance is given in the Approved Codes of Practice for the Control of Substances Hazardous to Health Regulations, the General COSHH ACOP, and the Control of Carcinogenic Substances Regulations, the Carcinogens ACOP, which are included in a single publication with the COSHH Regulations.2 Occurrence, properties and uses

96

Volatile organic compounds in air (4)

Laboratory method using pumped solid sorbent tubes, solvent desorption and gas chromatography March 2000

Health effects 4 The health effects of many VOCs are summarised in EH643 Summary criteria for occupational exposure limits. Some are covered more fully in EH654 Criteria document for an occupational exposure limit, EH725 Risk assessment document, or Toxicity Reviews.6 See Table 1 for relevant Guidance Notes and Toxicity Reviews for specific compounds. Health and safety precautions 5 Prevention and control of exposure, emergency procedures and health surveillance are described more fully in HSE publications on COSHH.7,8,9,10,11 6 VOCs are typically solvents, used principally for cleaning or degreasing, or for dissolving another component (eg a paint or adhesive), or they may be chemical intermediates in their own right. Workers may be exposed wherever VOCs are manufactured, stored, used or disposed of, but they are most likely to be exposed when:

vapour arises from the handling of solvent in the liquid phase; vapour is formed from a fugitive escape; vapour is produced by a drying film.

3 Occurrence, properties and uses of many volatile organic compounds (VOCs) are summarised in HSEs Guidance Note EH643 Summary criteria for occupational exposure limits. Some are covered more fully in EH654 Criteria document for an occupational exposure limit or EH725 Risk assessment document. See Table 1 for relevant Guidance Notes for specific compounds. Note 1: No specific meaning is intended for VOCs. The definition includes all organic compounds of medium volatility, in a boiling point range of approximately 0-400C or vapour pressures in the range 0.10-100 kPa. Paragraph 12 indicates compound classes within this broad definition for which this method is appropriate.

Exposure limits 7 Regulation 7 of the Control of Substances Hazardous to Health Regulations 19991,2 lays down the requirements for using maximum exposure limits (MELs) and occupational exposure standards (OESs) for achieving adequate control of worker exposure. MELs are published in EH4012 Table 1, and OESs in Table 2. The criteria on which the limits are based are documented in EH643 and EH 65.4

8 The Health and Safety Commission has approved an OES or an MEL, 8-hour time-weighted average (TWA) and/or short-term (15-minute) exposure limit for some VOCs. See Table 1 for relevant OELs for specific compounds. Analytical methods 9 There may be alternative methods available for the determination of a particular analyte. With the exception of a few cases, where an exposure limit is linked to a specific method (eg rubber fume or asbestos), the use of methods not included in the MDHS series13 is acceptable, provided that they have been shown to have the accuracy and reliability appropriate to the application. 10 Within this MDHS series,13 there are three other general methods for volatile organic compounds. The first,14 MDHS72, is a laboratory method using pumped solid sorbent tubes, thermal desorption and gas chromatography. The second,15 MDHS80, is a laboratory method using diffusive solid sorbent tubes, thermal desorption and gas chromatography. The third,16 MDHS88, is a laboratory method using diffusive samplers, solvent desorption and gas chromatography. MDHS72 includes and replaces MDHS2 (acrylonitrile), MDHS22 (benzene), MDHS23 (glycol ethers), MDHS31 (styrene), MDHS40 (toluene), MDHS53 (butadiene) and MDHS60 (mixed hydrocarbons). MDHS80 includes and replaces MDHS43 (styrene), MDHS50 (benzene), MDHS55 (acrylonitrile), MDHS63 (butadiene) and MDHS66 (mixed hydrocarbons). MDHS88 includes and replaces MDHS44 (styrene), MDHS64 and 69 (toluene), and MDHS74 (hexane). This MDHS includes and replaces MDHS1 (acrylonitrile), MDHS15 (carbon disulphide), MDHS17 (benzene), MDHS20 (styrene), MDHS21 (glycol ethers), MDHS24 (vinyl chloride), MDHS26 (ethylene oxide), MDHS28 (chlorinated hydrocarbons), MDHS32 (dioctyl phthalate), MDHS36 (toluene) and MDHS45 (ethylene dibromide). There may also be some alternative MDHS methods for specific compounds, for example diethyl sulphate and dimethylsulphate (MDHS89).

workplace atmospheres. It is appropriate for a wide range of VOCs, including hydrocarbons, halogenated hydrocarbons, ester, glycol ethers, ketones and alcohols. A number of sorbents are recommended for the sampling of these VOCs, each sorbent having a different range of applicability. However, activated coconut shell charcoal is frequently used. Very polar compounds may require derivatisation; very low boiling compounds will only be partially retained by the sorbents and can only be estimated qualitatively. Semi-volatile compounds will be fully retained by the sorbents, but may only be partially recovered. Note 2: The sorbents listed in Appendix 1 and elsewhere in this MDHS are those known to perform as described. Each sorbent that is identified by a trade marked name is unique and has a sole manufacturer; however, they are widely available from many different suppliers. 13 The sorbent tubes described here are supplied pre packed and ready to use. Validation data are available principally from US regulatory authorities, ie NIOSH17 and OSHA.18 Manufacturers products are generally equivalent, although there may be some batch-to-batch variation in coconut shell charcoal (see paragraphs 38-40). 14 The method is generally valid for the measurement of airborne VOC vapour in the concentration range of approximately 1-1000 mg/m3 of VOCs for a 10 l sample size. The upper limit of the range depends on the sorptive capacity of the carbon or other sorbent for specific VOCs and on the linear dynamic range of the gas chromatographic column and detector. The lower limit of the exposure dose depends on the noise level of the detector and on blank levels of analyte on the sorbent. 15 HSG17319 advises employers about how they should conduct investigations into the nature, extent and control of exposure to substances hazardous to health which are present in workplace air. The objective of air monitoring is usually to determine worker exposure, and therefore the procedures described in this method are for personal sampling in the breathing zone and result in a TWA value of the concentration. The method may also, however, be used for background or fixed location sampling. Alternative on-site procedures, such as portable gas chromatography, infra-red spectrophotometry or a total organic analyser, should be used to monitor rapidly changing concentrations of single substances or mixtures.

PRINCIPLE 11 A measured volume of sample air is drawn through one (or more) sorbent tubes in series. An appropriate sorbent (or sorbents) is selected for the compound or mixture to be sampled. Provided suitable sorbents are chosen and the breakthrough volume is not exceeded, volatile organic components are fully retained by the sorbent tube and thus are removed from the flowing air stream. The collected vapour is desorbed by a solvent, typically carbon disulphide, and the solution is analysed with a gas chromatograph equipped with a flame ionisation detector, mass spectrometer or other selective detector.

SAMPLING EQUIPMENT Sorbent tube 16 A sampling tube, typically consisting of a glass tube with both ends flame-sealed, 70 mm long with an outside diameter of 6 mm and an inside diameter of 4 mm, containing two sections of sorbent. In the case of charcoal, the sorbing section usually contains 100 mg of charcoal and the back-up section 50 mg. The sections are separated and their contents are held in place with an inert material, eg glass wool plugs (preferably silanised). Glass tubes should be held in protective holders to prevent breakage.

SCOPE 12 The method described is for pumped tubes containing a sorbent and used for the determination of the time-weighted average concentrations of VOCs in

17 Sorbents other than charcoal may be used for certain applications. A description of sorbent types is given in Appendix 1. Recommended sorbents and appropriate tube sizes for particular VOCs are given in Tables 2 and 3. Equivalent sorbents may be used. 18 Instead of commercial two-section tubes, two single-section tubes in series may be used. This arrangement has the advantage that it is not necessary to store tubes at sub-ambient temperatures after sampling, to prevent migration of the sorbed compounds from one section to the other. 19 Tubes meeting these requirements are commercially available; however, the user can make them. Metal tubes may also be used with appropriate end caps. Self-packed samplers should not be used unless they can be shown to have reproducible and constant sorption properties. 20 Polyurethane plugs may be used in place of silanised glass wool; however, they are known to sorb certain pesticides20 for which this MDHS is inapplicable. 21 When it is desirable to sample highly volatile compounds for extended periods, or at a high-volume flow rate, a larger sampling device can be used, provided the proportions of the tube and its charcoal contents are scaled similarly to the base dimensions, to provide nominally the same linear flow rate and contact time with the charcoal bed. Polyethylene end caps 22 Custom-made to fit snugly over the sorbent tubes (paragraph 16) to prevent leakage. Sampling pumps 23 Sampling pumps, complying with the provisions of BS EN 1232,21 with an adjustable flow rate, incorporating a flowmeter or a flow fault indicator, capable of maintaining the selected flow rate to within 5% of the nominal value throughout the sampling period, and which people can wear without impeding their normal work activity. Flowmeter 24 Flowmeter, portable, capable of measuring the appropriate flow rate to within 5%, and calibrated against a primary standard.22 Flowmeters incorporated in sampling pumps are not suitable for accurate measurement of the flow rate. However, they can be useful for monitoring the performance of samplers, provided they are sensitive enough. Tubing 25 Plastic or rubber tubing about 90 cm long of appropriate diameter to ensure a leak-proof fit to both pump and sample tube or tube holder, if used. Clips should be provided to hold the sorbent tube and connecting tubing to the wearer's lapel area. It is not recommended to use tubes with any tubing upstream of the sorbent as sample losses may occur.

LABORATORY APPARATUS Glassware 26 A selection of laboratory glassware, including volumetric flasks complying with the requirements of BS 1792.23 Disposable gloves 27 Disposable gloves, impermeable, to avoid the possibility of contamination from the hands and to protect them from contact with harmful substances. Vinyl or nitrile gloves are suitable. Balance 28 A balance, calibrated against a primary standard, for the preparation of the internal standard solution and calibration standards. The balance should be capable of weighing to 0.01 mg over the range 0-100 mg. Micropipettes 29 A set of adjustable positive displacement micropipettes, calibrated against a primary standard, for the preparation of calibration and sample solutions.24 Gas chromatograph 30 A gas chromatograph fitted with a flame ionisation detector is suitable. In some applications, involving the analysis of complex mixtures, a high-resolution capillary column and a selective detector or mass spectrometer may be required. Alternatively, if these detectors are not available, two columns with phases of different polarity may be connected in parallel to one injector. A wide range of gas chromatographic columns are capable of separating the analytes of interest from other components. Suitable choices might be a 50 m x 0.22 mm fused silica capillary coated with dimethylsiloxane (eg BP-1) or 7% cyanopropyl, 86% methyl siloxane (eg BP-10) at 0.5-1.0 m film thickness. Note 3: BP-1 and BP-10 are proprietary phases of SGE Ltd. Some examples of equivalent phases are SPB-1 and SPB-1701 (Supelco), HP-1 and HP-1701 (HewlettPackard), CP-Sil 5CB and CP-Sil 19CB (Chrompack). Autosampler 31 These are commercially available with liquid-chilled sample trays, suitable for the analysis of volatile solvents. Integrator 32 The sensitivity and dynamic range of the integrator should correspond to that of the detector output and its sampling frequency must be sufficient to measure peak areas with appropriate precision.

REAGENTS 33 During the analysis, use only reagents of a recognised analytical grade.

Note 4: Safety precautions: carbon disulphide vapour is toxic. Exposure by all routes should be avoided. Usage should be restricted to a well-ventilated hood. Carbon disulphide is highly flammable. Many of the compounds to be analysed are also toxic, eg benzene; see HSE Guidance Notes for more information. Exposure by all routes should be avoided, eg during the preparation of standard solutions. Calibrants 34 Most analytes listed in Tables 2-3 are commercially available in at least 98% purity. Where only technical grades of 90-95% can be obtained for calibration standard preparation, consider either correction from a purity measurement before use or purification by, eg, fractional distillation. Water as an impurity is not measured by the flame ionisation detector. If significant water content is suspected, it is recommended that gas chromatographymass spectrometry (GC-MS) is used for purity measurements, or if an MS detection is not feasible, a thermal conductivity detector could be substituted. Desorption solvents 35 The desorption or elution solvent, commonly carbon disulphide, should be of chromatographic quality. It must be free from compounds co-eluting with the substances of interest. Suitable high-purity carbon disulphide (benzene <1 g/ml) is commercially available. Carbon disulphide is normally recommended for the desorption of non-polar compounds from activated carbon. 36 For polar compounds and mixtures of polar and non-polar compounds there is no ideal universal desorption solvent. Dichloromethane, methanol, higher alcohols, dimethylformamide and acetonitrile have been used as eluants, either singly or mixed with each other or carbon disuphide. Tables 2 and 3 give examples of suitable desorption solvents other than pure carbon disulphide. 37 The use of carbon disulphide desorption solvent can result in problems when polar analytes are collected from humid atmospheres. Polar analytes may be soluble in a water phase which forms following desorption with carbon disulphide when sufficient water is collected with the sample. A desorption solvent modifier should be present at a sufficient concentration to result in a homogeneous solution in desorbed samples. Dimethylformamide may be suitable for this purpose. Sorbents 38 Normally, charcoal is used as the collection medium. A particle size of 0.35-0.85 mm is recommended. Before packing the tubes, the charcoal should be heated in an inert atmosphere, eg high-purity nitrogen, at approximately 600C for 1 hour. To prevent recontamination of the charcoal, it should be kept in a clean atmosphere during cooling to room temperature, storage, and loading into the tubes. Tubes prepacked by the manufacturer with pre-conditioned charcoal are also available and require no further conditioning. 39 Activated charcoal is usually processed from coconut shells. For some applications, petroleum-based

charcoal is preferred (see Table 1). Some methods or manufacturers recommend synthetic carbons as alternatives to charcoal of biological origin. 40 The sorptive capacity and desorption efficiency of different batches of activated charcoal may vary. Commercial tubes, if used, should be purchased from the same batch and in sufficient number to provide consistent performance for a definite period of time. 41 Sorbents other than charcoal may be used for certain applications (see paragraph 17).

SAMPLING Sampling procedure 42 Select a sampler appropriate for the compound or mixture to be sampled. Published methods giving further information on sampling and analysis details for specific VOCs are referenced in Tables 2 and 3. The source references give details of suitable flow rates and recommended sampling times for particular VOCs. For some more volatile VOCs, a standard tube may not have the capacity to sample for a full 8 hours (note that an 8 hour TWA concentration may be derived from the results of two or more consecutive samples, as described in HSG17319). Calibration of pump 43 Calibrate the pump with a representative sorbent tube assembly in line, using an appropriate external calibrated meter (paragraph 24). One end of the calibrated flow meter should be at atmospheric pressure to ensure proper operation. Blanks 44 Field blanks should be prepared by using tubes identical to those used for sampling and subjecting them to the same handling procedure as the samples except for the actual period of sampling. Label these as blanks. Preparation of sampling equipment 45 Break open both ends of the sample tube, ensuring that each opening is at least one half the inside diameter of the tube. Insert the tube into its protective holder and attach to the sampling pump with the connecting tubing such that the back-up (50 mg) section is nearest the pump and ensuring that no leaks can occur. If sampling is not to start immediately, seal the open end of the sample tube with a protective end-cap. Collection of samples 46 Fix the sampler to the worker, on the lapel and as close to the mouth and nose as possible. Then, either place the sampling pump in a convenient pocket or attach it to the worker in a manner that causes the minimum inconvenience, eg to a belt around their waist. When ready to begin sampling, remove the protective end-cap from the

sampler and switch on the pump. Record the time at the start of the sampling period, and if the pump is equipped with an elapsed time indicator, ensure that this is set to zero. 47 Since it is possible for a sample tube to become clogged, monitor the performance of the sample periodically, a minimum of every two hours. Measure the flow rate with the calibrated flowmeter and record the measured value. Terminate sampling and consider the sample to be invalid if the flow rate is not maintained to within 5% of the nominal value throughout the sampling period. 48 Regular observation of the flow fault indicator is an acceptable means of ensuring that the flow rate of flow stabilised pumps is maintained satisfactorily, provided that the flow fault indicator indicates malfunction when the flow rate is outside 5% of the nominal value. 49 At the end of the sampling period, measure the flow rate with an accuracy of 5% using the calibrated flowmeter, switch off the sampling pump, and record the flow time and the time. Also observe the reading on the elapsed time indicator, where fitted. Consider the sample to be invalid if the reading on the elapsed time indicator and the timed interval between switching on and switching off the sampling pump do not agree to within 5%, since this may suggest that the sampling pump has not been operating throughout the sampling period. Reseal the sampler with its protective cover and disconnect it from the sampling pump. 50 Carefully record the sample identity and all relevant sampling data. Calculate the mean flow rate by averaging the flow rate measurements throughout the sampling period and calculate the volume of air sampled, in litres, by multiplying the flow rate in l/min by the sampling time in minutes. 51 With each batch of ten samples, submit for analysis at least two unused samplers from the same lot of tubes used for sample collection. Subject these blank samplers to the same handling procedure as the samples, but draw no air through them. 52 Record air temperature and barometric pressure periodically during sampling if it is desired either to express concentrations reduced to specific conditions (paragraph 72) or to express concentrations in volume fraction (paragraph 73). Transportation and storage 53 There are no special requirements for transportation. Samples of very volatile materials, such as vinyl chloride, should be stored in dry ice; for less volatile materials, refrigeration is sufficient. If samples are not to be analysed within 8 hours, they are to be placed in a clean, uncoated, sealed metal or glass container.

Cleaning of glassware 55 Before use, clean all glassware to remove any residual grease or chemicals. Soak overnight in laboratory detergent solution and then rinse thoroughly with water. Preparation of sample and blank solutions Desorption 56 Pipette 1.0 ml of desorption solvent (paragraph 35) into a septum vial of suitable capacity and cap the vial immediately. Score the sorbent tube containing the sample in the front (largest) section and break open the tube. Remove the glass wool and discard it. Open the vial and transfer the front section of sorbent into the desorption solvent and re-cap it. Agitate the vial occasionally over a period of 30 minutes to ensure maximal desorption. Repeat the same procedure for the second, back-up section, using a different vial. Desorb the sample blanks in the same way as the samples. In each case, carry out the desorption in a clean atmosphere in a fume hood. 57 When using sorbent tubes containing more than 150 mg (100 + 50 mg) sorbent, use a larger vial and a larger volume of desorption solvent pro rata. Other volumes of desorption solvent may be used for special applications. 58 For the desorption of samples of very volatile materials, such as vinyl chloride, the vial and desorption solvent should be pre-chilled before the addition of the sorbent. Preparation of calibration standards 59 Prepare at least six calibration standards to cover the range of applicability. In air concentration (mg/m3), this range will vary with the relevant exposure limit - see Table 1. For an example VOC with a limit value of 100 mg/m3, a 10 l sample collected and desorbed in 1 ml will result in a solution of 1 mg/ml. To cover a typical range of 0.1-2 times the limit value, solutions in the range 0.1-2 mg/ml will be needed. 60 Standard solutions of the compounds of interest in the elution solvent may be prepared gravimetrically, using either a microsyringe or pipette, by adding pure compounds or pre-weighed blends to flasks partially filled with solvent. Where small quantities of a few microlitres are added to partially-filled flasks, it is recommended that the pure compounds or blends are injected through a silicone septum, such as a Suba Seal. Further standard solutions to cover the range of interest can be prepared by serial dilution of the first solution. The concentration range of the standard solutions should exceed the concentration range of the desorbed samples. Prepare fresh standard solutions with each batch of samples. 61 The purpose of gravimetry is to avoid the need for calibration of volumetric apparatus and to reduce errors caused by evaporation of very volatile compounds.

ANALYSIS 54 Wear disposable gloves during analysis to reduce the possibility of contamination and to protect the hands from harmful solvents/reagents.

However, it is common practice to use some combination of gravimetry and volumetry, or pure volumetry, in the preparation of standard solutions. It is acceptable to use volumetry, provided that the apparatus is calibrated appropriately with the liquids actually used in the analysis. The use of some volumetric apparatus certified with mercury or water, particularly microsyringes and pipettes, can give errors of up 3%. 62 An internal standard is optional. It must not interfere with the compounds of interest and it must not be removed from the elution solvent by the sorbent. In the context of this method, the purpose of the internal standard is to correct for small variations in the injection volume. The use of an internal standard as a surrogate to correct for desorption efficiency (eg n-propyl acetate in the analysis of n-butyl acetate) is not recommended. Desorption efficiency should be determined directly with the compounds of interest (paragraph 72). 63 In the analysis of complex mixtures, calibration blends of the pure compounds may be prepared before dilution with the elution solvent. Examples of three calibration blends are listed here. These have been used in the analysis of mixed solvents in paints, thinners, adhesives, cleaning fluids and miscellaneous commercial products. The components are arranged to give resolved peaks on both BP-1 and BP-10 phases. Other blends may be more appropriate on different columns or in other applications.

System calibration 65 Inject into the gas chromatograph a known fixed volume of each standard solution in the range 1-5 l. A standardised injection technique should be used so that repeatable peak heights or areas are obtained. Typically, for a series of replicate injections, the relative standard deviation should be better than 2%. Autosamplers normally achieve better than 1%. 66 Prepare a log-transformed calibration graph by plotting the 10logarithm of the areas of the analyte peaks corrected for blank levels on the vertical scale against the 10logarithm of the concentration of the analyte, in g/ml, in the injected aliquot of the calibration blend solutions. Other methods of weighting calibration points, such as linear, exponential or polynomial plots, may be more or less suitable, depending on the linearity of the detector response and the software available. Samples 67 Inject into the gas chromatograph the same fixed volume of solution from the desorbed sample. Read from the calibration graph the concentration of the analyte in the desorbed sample. Analyse the sample blank and the samples used to determine desorption efficiency in the same way. Where high VOC concentrations are found, dilute the sample solutions with solvent to bring the concentration back within the calibration range. Repeat the analysis and record the dilution factor. 68 Correspondence of retention time on a single column should not be regarded as proof of identity. The retention indices of about 160 VOCs on BP-1 and BP-10 phases are given in Table 4. They are a useful guide to elution order on these phases or their near equivalent, but are not definitive, since exact values depend on temperature programme, carrier flow-rate and other factors. 69 If the back-up section contains more than 10% of the sample, discard that sample as unreliable.

Blend 1 consists of: n-hexane, n-heptane, n-octane, n-decane, n-undecane, n-dodecane, benzene, toluene, o-xylene, p-xylene, n-propylbenzene, iso-propylbenzene, m-ethyltoluene, o-ethyltoluene, p-ethyltoluene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, n-propyl acetate, n-butyl acetate, iso-butyl acetate, butoxyethyl acetate. Blend 2 consists of: iso-propanol, iso-butanol, n-butanol, 1-methoxy-2-propanol, butoxyethanol, toluene, ethylbenzene, 1,2,3-trimethylbenzene, ethyl acetate, ethoxyethyl acetate. Blend 3 consists of: acetone, 2-butanone, 4-methylpentan-2-one, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, iso-propyl acetate, n-nonane, toluene.

CALCULATION OF RESULTS Volume of air sample 70 Calculate the volume, V, in litres, of each air sample.

Concentration of VOC in air Mass concentration of analyte 71 Calculate the weight, in g, of VOC in the sample by using the calibration graph prepared for the standard solutions. Also calculate the weights of VOC in the blank samplers. Then: concentration of VOC in air (mg/m3) 1000 (mfront + mback - mblank) = DxV

Chromatography 64 Set up the gas chromatograph for the analysis of volatile organic compounds. A variety of chromatographic columns may be used for the analysis of these compounds. The choice will depend largely on which compounds, if any, are present that might interfere in the chromatographic analysis. Examples of suitable choices are given in paragraph 30. Typical operating conditions for these columns might be temperature programming from 50-200C at 5C/min with a carrier gas flow of 0.7-0.8 ml/min helium.

where:
C = concentration of VOC in air (mg/m3);
mfront = weight (g) of VOC on sample tube front
section; mback = weight (g) of VOC on sample tube back section; mblank = weight (g) of VOC on blank tube; D = desorption efficiency, as read from the desorption efficiency curve, taking mfront as the weight recovered; V = volume of air sampled (litres). 72 If it is desired to express concentrations reduced to specified conditions, eg 25C and 101 kPa, then: 101 Ccorr = C x P x 298 T

analytes are desorbed with pure carbon disulphide, the mutual concentration effect on D is generally negligible. If the composition of a mixture of polar and non-polar analytes is known approximately, D values should be established with a similar mixture. More information on the determination of desorption efficiency is given in Appendix 3. Detection limits 76 The qualitative and quantitative detection limits for VOCs, defined as three times and ten times the standard deviation of a blank determination, have not been determined systematically, as the blank is normally insignificant compared with the measured concentrations. Instead, method performance has normally been established over the range 0.1-2.0 x the US Permissible Exposure Limit (see paragraph 79). Overall uncertainty

where:
P = the actual pressure of the air sampled, in kPa;
T = the actual temperature of the air sampled, in
Kelvin. Volume concentration of analyte 73 Alternatively, the concentration of VOC in the sampled air may be expressed in ppm.

77 The overall uncertainty for a measuring procedure is defined in BS EN 482 as the quantity used to characterise as a whole the uncertainty of the result given by a measuring procedure, and is quoted as a percentage combining bias and precision using the following equation.25 x - xref Overall uncertainty = xref + 2s x 100

Concentration of VOC in air = (ppm) where: 24.5 M

24.5 C x M x

T x 298

101 P

where :
x is the mean value of results of a number n of
repeated measurements; xref is the true or accepted reference value of concentration; s is the standard deviation of measurements.

= molar volume (litres) at 298 K and 101 kPa; = molecular mass of VOC.

METHOD PERFORMANCE Determination of the breakthrough volume 74 The source references in Tables 2 and 3 give typical values for the breakthrough volumes, and hence suitable sampling flow rates and sampling times, of single VOC components. These breakthrough volumes may be concentration dependent. Where mixtures of non-polar analytes are sampled together, the mutual concentration effect on breakthrough volume is generally negligible. However, polar compounds, and especially high humidity, may reduce breakthrough volumes of non-polar analytes significantly. If the composition of a mixture of polar and non-polar analytes is known approximately, breakthrough volumes should be established with a similar mixture. More information on the determination of breakthrough volumes is given in Appendix 2. Desorption efficiency 75 The source references in Tables 2 and 3 give typical values for the desorption efficiency of single VOC components. These desorption efficiency values may be concentration dependent. Where mixtures of non-polar

78 An additional 5% is usually added to the overall uncertainty percentage calculated using the equation in paragraph 77, to allow for the variability of the pump flow rate. The performance requirements quoted in BS EN 482 for overall uncertainty, where the task is 'measurement for comparison with limit values', are 50% for samples in the range 0.1-0.5 LV and 30% for samples in the range 0.5-2.0 LV (LV = limit value).12 79 The method has been examined as part of the NIOSH Standards Completion Programme.17 This gives values of between approximately 5 and 10% for the combined pump and analytical precision (as a coefficient of variation) over the range 0.1-2.0 x the US Permissible Exposure Limit (PEL). In most cases, the PEL is equivalent to exposure limits in other countries. 80 The NIOSH Standards Completion Programme acceptance criterion is broadly equivalent to overall uncertainty in EN 482,25 using the test methods in EN 1076.26 Allowing 5% for the maximum bias expected, the overall uncertainty (EN 482) will always be within 30%. However, biases greater than 5% may be introduced through the use of incorrect desorption efficiencies (see paragraph 75).

Interferences 81 Organic components that have the same or nearly the same retention time as the analyte of interest during the gas chromatographic analysis will interfere where a non-selective detector is used. Interferences can be minimised by proper selection of gas chromatograph columns and conditions. 82 High humidity may affect the recovery of some compounds from samplers, particularly for those using activated charcoal. The original method validation (eg references 17 and 18) should be consulted for specific advice. Stability of calibration blends 83 Calibration blends 1-3 (paragraph 63) are stable for at least one year when stored in dark glass bottles with PTFE-lined screw-caps below 4C. Stability of calibration solutions 84 Storage times for calibration solutions vary according

to application. Typically, carbon disulphide dilutions should be freshly prepared weekly, or more frequently if evidence is noted of decomposition or evaporation. QUALITY CONTROL MEASURES 85 An appropriate level of quality control should be employed when using this method. Analytical quality requirements, guidance on the establishment of a quality assurance programme and details of internal quality control and external quality assessment schemes are fully described in MDHS 71.27 86 It is strongly recommended that all laboratories undertaking the determination of hazardous substances in workplace air should participate in an external quality assessment scheme such as HSE's Workplace Analysis Scheme for Proficiency (WASP). Details of WASP are given in MDHS 71.27 TEST REPORT 87 Appendix 4 gives recommendations for information to be included in the test report.

Table 1

Limit values and published HSE guidance by compound name HSE Guidance Note EH40 limit values12 MEL or OES long-term ppm mg/m3 10 750 40 2 2 3 1 5 2 200 0.5 1000 10 100 25 25 10 200 10 2 0.5 50 10 1000 25 1810 68 4.4 4.8 7.6 4 16 13 1080 5.3 6190 22 308 123 135 53 966 32 13 1.9 234 37 3590 short-term ppm mg/m3 15 1500 60 4 6 37 3620 102 9.7 15 EH64/C57, EH72/8 EH64/C5, TR4 EH64/E20* 3 250 1200 50 150 19 1340 7430 154 462 EH64/C7 EH64/D9 EH64/D90, TR10 ** Other HSE guidance3, 6, 11

Compound name

Acetic acid Acetone Acetonitrile Acrylonitrile Allyl alcohol 2-Aminoethanol Aniline Benzene Benzyl chloride (-Chlorotoluene) Bornan-2-one (Camphor) Bromochloromethane (Chlorobromomethane) Bromoform Bromotrifluoromethane (Trifluorobromomethane) Butadiene Butan-1-ol (n-Butyl alcohol) Butan-2-ol (sec-Butyl alcohol) 2-Butoxyethanol Butyl-2,3-epoxypropyl ether (Butyl glycidyl ether) n-Butyl acetate sec-Butyl acetate Carbon disulphide Carbon tetrachloride 1-Chloro-2,3-epoxypropane (Epichlorohydrin) Chlorobenzene 2-Chlorobuta-1,3-diene (-Chloroprene) Chlorodifluoromethane

OES OES OES MEL OES OES MEL MEL OES OES OES OES MEL OES OES OES OES OES OES MEL OES MEL OES OES OES

EH64/D2 EH64/C2

250

1210 EH64/C8, TR3 EH64/D11, EH65/10 EH64/C38, EH65/6 EH64/D15 EH64/D16, EH65/7

1.5

5.8

Compound name

HSE Guidance Note EH40 limit values12 MEL or OES long-term ppm mg/m3 1000 2 50 5 1000 25 100 50 25 300 100 0.5 25 1000 200 5 200 10 100 400 10 10 250 1000 0.05 10 5 10 25 25 0.2 50 1000 10 10 400 5 100 100 0.2 5 50 50 5 20 5 50 2 100 2700 9.9 105 22 7110 125 350 208 102 1020 872 3.9 153 5030 823 21 806 43 350 1230 30 49 1060 3160 0.26 36 25 19 148 91 1.3 241 1920 37 55 1460 21 308 441 1.3 20 237 237 49 72 21 241 12 541 short-term ppm mg/m3 1250 1 100 1250 75 300 100 150 50 50 1250 400 250 300 500 25 310 1250 20 10 3380 3.4 210 9980 375 1050 408 1310 306 306 6280 1650 1010 1060 1540 76 1310 3950 72 50

Other HSE guidance3, 6, 11

Chloroethane (Ethyl chloride) 2-Chloroethanol (Ethylene chlorohydrin) Chloroform Chloromethane (Methyl chloride) Cresols, all isomers Cryofluorane (1,2-Dichlorotetrafluoroethane) Cumene Cyclohexane Cyclohexanol Cyclohexanone Cyclohexene Dibromodifluoromethane (Difluorodibromomethane) Dibromoethylene (Ethylene dibromide) 1,2-Dichlorobenzene 1,4-Dichlorobenzene Dichlorodifluoromethane 1,1-Dichloroethane 1,2-Dichloroethane (Ethylene dichloride) 1,2-Dichloroethylene Dichlorofluoromethane Dichloromethane (Methylene chloride) Diethyl ether (Ethyl ether) Diethylamine 2-Diethylaminoethanol Diisopropyl ether (Isopropyl ether) Dimethoxymethane (Methylal) Dimethyl sulphate Dimethylacetamide N,N,-Dimethylaniline Dimethylanmine 2,6-Dimethylheptan-4-one (Diisobutyl ketone) Dioxane Diphenyl 2,3-Epoxypropyl isopropyl ether (Isopropyl glycidyl ether) Ethanol 2-Ethoxyethanol 2-Ethoxyethyl acetate Ethyl acetate Ethyl acrylate Ethyl formate Ethylbenzene Ethylene glycol dinitrate Furfuryl alcohol Heptan-2-one (Methyl n-amyl ketone) Heptan-3-one (Ethyl butyl ketone) Heptane Hexachloroethane (vapour) n-Hexane 2-Hexanone 4-Hydroxy-4-methylpentanone (Diacetone alcohol) Iodomethane (Methyl iodide) Isopentyl acetate (Isoamyl acetate)

OES OES OES OES OES OES OES OES OES OES OES OES MEL OES OES OES OES MEL OES OES MEL OES OES OES OES OES MEL OES OES OES OES OES OES OES OES MEL MEL OES OES OES OES OES OES OES OES *** OES OES OES OES MEL OES

EH64/D17 EH64/D18, EH65/11

EH64/D21, EH65/8 EH64/D23

EH64/C10 EH64/D25 EH64/D26, EH65/9 EH64/D27, EH65/4 EH64/C36

EH64/C37, EH64/E19,* EH74/1 EH64/D74 EH64/E24*

EH64/C45, EH65/27 EH64/D68, EH65/3 EH64/24

100 0.6 75

366 3.8 362 EH64/C12, TR10 EH64/C13, TR10 EH64/E26*

15 150 125 0.2 15 100 100

62 462 552 1.3 61 475 475

EH64/D76 EH64/D76

EH64/D34 75 125 362 EH64/C49, EH65/25 67

Compound name

HSE Guidance Note EH40 limit values12 MEL or OES long-term ppm mg/m3 150 724 short-term ppm mg/m3 187 200 250 903 849 333

Other HSE guidance3, 6, 11

Isopentyl acetate (Isobutyl acetate) Isopropyl acetate Kerosene Methanol 2-Methoxyethanol 2- Methoxyethyl acetate 2-Methoxymethyl-methoxy propanol 1-Methoxypropyl acetate Methyl acetate Methyl acrylate Methyl t-butyl ether Methyl methacrylate 3-Methylbutan-1-ol (Isoamyl alcohol) 1-Methylbutyl acetate (sec-Amyl acetate) Methylcyclohexane Methylcyclohexanol Methylcyclohexanone 5-Methyl-3-heptanone 4-Methylpent-3-en-2-one (Mesityl oxide) 4-Methylpentan-2-ol (Methyl isobutyl carbinol) 4-Methylpentan-2-one (Methyl isobutyl ketone) 2-Methylpropan-2-ol (t-Butyl alcohol) 2-Methylpropan-1-ol (Isobutyl alcohol) 1-Methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone) Methylstyrenes, all isomers except -methylstyrene Naphthalene Nicotine Nitrobenzene Nitroethane Nitroglycerine 2-Nitropropane Nitrotoluene(s) Octane Pentan-2-one (2-Pentanone) Pentane Pentyl acetates (Amyl acetates) Petroleum ether Phenol Phenyl 2-3-epoxypropyl ether (Phenyl glycidyl ether) 2-Phenylpropene (-Methylstyrene) Propan-1-ol (n-Propyl alcohol) Propan-2-ol (Isopropyl alcohol) n-Propyl acetate Propylene oxide Pyridine Rubber solvent Styrene p-tert-Butyltoluene 1,1,2,2-Tetrabromoethane 1,1,2,2-Tetrachloro-1,2- difluoroethane 1,1,1,2-Tetrachloro-2,2- difluoroethane Tetrachloroethylene

OES OES *** OES MEL MEL

EH64/D40

200 5 5

266 16 25

EH64/C21, TR10 EH64/C22, TR10 EH64/E27* EH64/E28* 250 75 100 125 150 75 75 25 40 100 150 75 75 150 770 275 416 458 812 356 350 102 170 416 462 231 309 736 EH64/D104, CHAN 12 1.5 10 1.9 EH64/C40 10 250 150 10 57 895 812 39 EH64/E29* EH64/D45 EH64/D98 EH64/D80, EH65/16

OES OES OES OES OES OES *** OES OES OES OES OES OES OES OES OES OES OES OES OES OES MEL OES *** OES OES *** OES OES OES OES OES OES MEL OES *** MEL *** OES OES OES OES

200 10 25 50 100

616 36 92 208 366

50 50 25 15 25 50 100 50 25 100

237 233 133 61 106 208 308 154 103 491 0.5 5.1 312 1.9 19 29 716 541 20 6.2 500 999 849 12 16 430 7.2 847 847 345

EH64/D81

EH64/D102, EH72/10

1 100 0.2 5 5 200 100 5 1 200 400 200 5 5 100 0.5 100 100 50

2 0.2

100 250 500 250 10 250

491 625 1250 1060 33 1080

EH64/D52

EH64/C52, EH65/21

EH64/C26, TR1

100 100 100

847 847 689

EH64/D93

10

Compound name

HSE Guidance Note EH40 limit values12 MEL or OES long-term ppm mg/m3 100 50 0 1000 200 100 1000 50 300 91 0.89 770 1110 430 5710 306 short-term ppm mg/m3 200 150 599 574

Other HSE guidance3, 6, 11

Tetrahydrofuran Toluene o-Toluidine 1,2,4-Trichlorobenzene 1,1,2-Trichloro-2,2-trifluoroethane 1,1,1-Trichloroethane Trichloroethylene Trichlorofluoromethane (Fluorotrichloromethane) 1,2,3-Trichloropropane 3,5,5-Trimethylcyclohex-2-enone (Isophorone) Turpentine Vinyl acetate Vinyl chloride Vinylidine chloride Xylene 2,4-Xylidine

OES OES MEL OES OES MEL OES OES OES OES OES MEL MEL OES OES

EH64/D89 EH64/D63 EH64/C54, EH65/20 EH 64/E30* EH64/D94, TR9 TR6

1250 400 150 1250 75 5 150 20

9740 2220 820 7140 460 29 850 72

EH64/D65

100 10 7 10 100 2

566 36 40 441 10

EH63, EH64/C29 EH64/C30 150 10 662 50 EH64/D67 EH64/C28

* OEL under review - see COSHH 1999: Proposals for MELs, OESs and biological monitoring guidance values HSE Consultative Document 150, included in EH64,3 Part E. ** *** Table 2 OEL under review. See Reciprocal calculation procedure for mixtures of hydrocarbon solvents, Part 3 of EH40.12 Published methods giving further information on sampling and analysis details for specific VOCs - HSE methods Test compounds Acrylonitrile Benzene Carbon disulphide Dichloromethane [a] Chloroform Carbon tetrachloride 1,1-Dichloroethane 1,2-Dichloroethane 1,1-Dichloroethylene 1,2-Dichloroethylene [a] 1,1,1-Trichloroethane 1,1,2-Trichloroethane Trichloroethylene 1,1,2,2-Tetrachloroethane [b] Tetrachloroethylene Chlorobenzene o-Dichlorobenzene 1,2-Dichoropropane [a,b] Di(2-ethylhexyl)phthalate 'Diisooctyl' phthalate Ethylene dibromide Ethylene oxide 2-Butoxyethanol 2-Ethoxyethanol 2-Methoxyethanol 2-Butoxyethyl acetate 2-Ethoxyethyl acetate 2-Methoxyethyl acetate Sorbent* C C C C Desorption solvent CS2 CS2 toluene CS2 MDHS method no13 1 17 15 28

Method name Acrylonitrile Benzene Carbon disulphide Chlorinated hydrocarbons

C T [c] T C [e] C

Dioctyl phthalates Ethylene dibromide Ethylene oxide Glycol ether and glycol ether acetates

85:15 cyclohexane: acetone cyclohexane hexane CS2 95:5 CH2CI2:methanol

28 32 45 [d] 26 21

11

Method name Styrene Toluene Vinyl chloride

Test compounds Styrene Toluene Vinyl chloride

Sorbent* C C C [f]

Desorption solvent CS2 CS2 CS2

MDHS method no13 20 36 24

* C = charcoal (100 + 50 mg tube), T = Tenax (100 + 50 mg tube) [a] [b] [c] [d] [e] [f] 400 + 200 mg tube petroleum-based charcoal 200 mg or 30 + 15 mg tube analysis by CG/electron capture Columbia JXC charcoal 800 + 200 mg tube

Table 3

Published methods giving further information on sampling and analysis details for specific VOCs - NIOSH methods Test compounds* Sorbent** QS C C [f] C t-Butyl alcohol Isopropyl alcohol Ethanol n-Butyl alcohol Isobutyl alcohol sec-Butyl alcohol n-Propyl alcohol Allyl alcohol Isoamyl alcohol Methyl isobutyl carbinol Cyclohexanol Diacetone alcohol 2-Butoxyethanol 2-Ethoxyethanol 2-Methoxyethanol Diethylamine Dimethylanmine Aniline o-Toluidine 2,4-Xylidine N,N,-Dimethyl-p-toluidine N, N,-Dimethylaniline 2-Aminoethanol 2-Dibutylaminoethanol 2-Diethylaminoethanol C C C Desorption solvent ethyl acetate formic acid 85:15 methylene chloride:methanol 98:2 CS2:acetone 99:1 CS2:2-propanol 99:1 CS2:2-propanol NIOSH method no17 2506 [k] 1603 1606 1604 1400

Method name* Acetone cyanohydrin Acetic acid Acetonitrile Acrylonitrile Alcohols I

Alcohols II

1401

Alcohols III

95:5 CS2:2-propanol

1402

Alcohols IV

95:5 CH2Cl2:methanol methanol dil H2SO4 in 10% aq. methanol 95% ethanol

1403

Allyl chloride Amines Aliphatic Amines Aromatic

C S S

1000 2010 2002

Aminoethanol compounds I Anisidine Butadiene Butyl glycidyl ether Carbon disulphide -Chloroprene Cresols and phenol

S [m]

80% methanol

2007

o-Cresol m-Cresol p-Cresol Phenol

XAD-2 [n] C [f] C C [o] C XAD-7

methanol methylene chloride CS2 toluene CS2 methanol

2514 [a] 1024 1616 1600 [p] 1002 2546

12

Method name* Dichlorodifluoromethane etc Dichlorofluoromethane 1,1-Dichloro-1-nitroethane Difluorodibromomethane Dimethylacetamide Dimethyl sulphate Dioxane Diphenyl Epichlorohydrin Esters I

Test compounds* Dichlorodifluoromethane 1,2-Dichlorotetrafluoroethane Chlorodifluoromethane

Sorbent** C [c]

Desorption solvent methylene chloride

NIOSH method no17 1018

n-Amyl acetate n-Butyl acetate 2-Ethoxyethyl acetate Ethyl acrylate Methyl isoamyl acetate n-Propyl acetate Isobutyl acetate sec-Amyl acetate sec-Butyl acetate Isoamyl acetate

C [d] C C [e] S P C T [q] C C

CS2 CS2 2-propanol methanol diethyl ether CS2 carbon tetrachloride CS2 CS2

2516 1601 1012 2004 2524[l] 1602 2530 1010 1450

Ethyl acetate Ethyl bromide Ethyl chloride Ethylene chlorohydrin Ethylene dibromide Ethyl ether Ethyl formate Fluorotrichloromethane Furfuryl alcohol Glycidol Hexachlorobutadiene Hexachloro-1,3cyclopentadiene Hydrocarbons BP 36-126

C C C [f] C [g] C C C C [f] Q C XAD-2 T [i] Benzene, Toluene Pentane thro' Octane Cyclohexane Cyclohexene Methylcyclohexane Benzene Cumene Naphthalene -Methylstyrene Styrene Vinyltoluene p-tert-Butyltoluene Ethylbenzene Toluene Xylene Chloroform Tetrachloroethylene o- & p-Dichlorobenzene Bromoform Methyl chloroform Chlorobromomethane 1,2-Dichloroethane 1,1,1-Trichloroethane 1,1,2-Trichloroethane 1,2-Dichloroethylene Tetrachloroethylene Carbon tetrachloride Ethylene dichloride C

CS2 2-propanol CS2 95:5 CS2:2-propanol 99:1 benzene:methanol ethyl acetate CS2 CS2 acetone tetrahydrofuran hexane hexane CS2

1457 1011 2519 2513 1008 1610 1452 1006 2505 1608 2543 [h] 2518 [h] 1500

Hydrocarbons Aromatic

CS2

1501

Hydrocarbons Halogenated

CS2

1003

13

Method name*

Test compounds* Chlorobenzene Hexachloroethane 1,2,3-Trichloropropane

Sorbent**

Desorption solvent

NIOSH method no17

Isophorone Isopropyl acetate Isopropyl ether Isopropyl glycidyl ether Ketones I

Ketones II

Acetone Cyclohexanone Diisobutyl ketone 2-Hexanone Methyl isobutyl ketone 2-Pentanone Camphor Ethyl butyl ketone Mesityl oxide 5-Methyl-3-heptanone Methyl n-amyl ketone

C [g] C C C C

CS2 CS2 CS2 CS2 CS2

2508 1454 1618 1620 1300

99:1 CS2:methanol

1301

Methanol Methyl acetate Methyl acrylate Methylal Methyl cellosolve acetate Methyl chloride Methyl cyclohexanol Methyl cyclohexanone Methylene chloride Methyl methacrylate Methyl t-butyl ether Methyl iodide Naphthas

2-Methoxyethyl acetate

Dichloromethane

Kerosine Petroleum ether Rubber solvent Stoddard solvent, etc

S [r] C C C C C [c] C Q C [j] XAD-2 [f] C [f] C C

5% 2-propanol in water CS2 CS2 hexane CS2 methylene chloride methylene chloride acetone CS2 CS2 CS2 toluene CS2

2000 1458 1459 1611 1451 1001 1401 2521 1005 2537 1615 1014 1550

Nicotine Nicotine Nitro-aromatic compounds Nitrobenzene Nitrotoluene(s) 4-Chloronitrotoluene

XAD-2 XAD-4 S

ethyl acetate ethyl acetate + 0.01% triethylamine methanol

2544 [k] 2551 [k] 2005

Nitroethane 2-Nitropropane Nitroglycerin and Ethylene glycol dinitrate N-Methyl-2-pyrrolidone 1-Octane thiol Pentachloroethane Phenyl ether Phenyl ether/diphenyl mixture Phenyl glycidyl ether Propylene oxide Propylene dichloride Pyridine Terpenes

XAD-2 [s] 106 T C T R C S C C C [g] C C

ethyl acetate ethyl acetate ethanol 95:5 methylene chloride: methanol acetone hexane CS2 benzene CS2 CS2 85:15 cyclohexane: acetone methylene chloride CS2

2526 2528 2507 1302 2510 [k] 2517 [h] 1617 2013 1619 1612 1013 [l] 1613 1552

1,2-Dichloropropane

Limonene -Pinene -Pinene 3-Carene

1,1,2,2-Tetrabromoethane

Tetrahydrofuran

2003

14

Method name* 1,1,1,2-Tetrachloro 2,2-difluoroethane etc 1,1,2,2-Tetrachloroethane Tetrahydrofuran Trichloroethylene 1,1,2-Trichloro-1,2,2trifluoroethane Trifluorobromomethane Turpentine Vinyl acetate Vinyl bromide Vinyl chloride Vinylidine chloride

Test compounds* 1,1,1,2-Tetrachloro-2,2 1,1,2,2-Tetrachloro1,2-difluoroethane

Sorbent** C

Desorption solvent CS2

NIOSH method no17 1016

C [g] C C C C [c] C CMS C [f] C [e] C

CS2 CS2 CS2 CS2 methylene chloride CS2 95:5 methylene chloride:methanol ethanol CS2 CS2

1019 1609 1022 1020 1017 1551 1453 1009 1007 1015

1,1-Dichloroethene

* Some names in the NIOSH list are different from those in EH40. See Table 1 for synonyms. ** C = charcoal (100 + 50 mg tube); CMS = carbon molecular sieve (160 + 80 mg tube); P = Porapak P (100 + 50 mg tube); Q = Porapak Q (150 + 75 mg tube); QS = Porapak QS (100 + 50 mg tube); R = Porapak R (70 + 35 mg tube); S = Silica gel (150 + 75 mg tube); T = Tenax (100 + 50 mg tube); 106 = Chromosorb 106 (100 + 50 mg tube); XAD-2 (100 + 50 mg tube); XAD-4 (80 + 40 mg tube); XAD-7 (100 + 50 mg tube). [a] analysis by high pressure liquid chromatography/ultra-violet (HPLC/UV) [b] analysis by gas chromatography/thermal conductivity (detection) (GC/TCD) [c] two tubes 400/200 + 100/50 mg [d] two tubes 400/200 + 400/200 mg [e] two tubes, 150 + 150 mg [f] 400 + 200 mg tube [g] petroleum-based carbon [h] analysis by GC/electron capture (detection) (ECD) [i] two tubes 75 + 25 mg [j] two tubes 100/50 + 100/50 mg [k] analysis by GC/nitrogen-phosphorus detection (NPD) [l] analysis by GC/conductivity (Hall) [m] 300 + 150 mg tube [n] 150 + 75 mg tube [o] uses a sodium sulphate drying tube in front [p] analysis by GC/flame photometric (detection) (FPD) [q] 20 + 10 mg tube [r] 100 + 50 mg tube [s] 600 + 400 mg tube

15

Table 4

Retention indices of selected VOCs on BP-1 and BP-10 phases

BP-1 propane dichlorodifluoromethane (Freon 12) methyl chloride 1,2-dichloro-1,1,2,2-tetrafluoroethane (Freon 114) isobutane methanol chloroethene (vinyl chloride) butane methyl bromide ethyl chloride ethanol acetonitrile trichlorofluoromethane (Freon 11) enflurane acetone 2-methylbutane iso-propanol dichlorofluoromethane (Freon 21) pentane dimethoxymethane methyl acetate 1,1-dichloroethene (vinylidene chloride) dichloromethane 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113) 2,2-dimethylbutane n-propanol halothane vinyl acetate cyclopentane 2-methylpentane 2,3-dimethylbutane 2-butanone 3-methylpentane cis-1,2-dichloroethene ethyl acetate chloroform n-hexane iso-butanol methoxyethanol 1,2-dichloroethane methylcyclopentane 1,1,1-trichloroethane n-butanol iso-propyl acetate benzene 1-methoxy-2-propanol (PGME) cyclohexane carbon tetrachloride 2-methylhexane 2,3-dimethylpentane 3-methylhexane cyclohexene 1,2-dichloropropane tert-butyl acetate 2,2,4-trimethylpentane trichloroethene ethoxyethanol n-propyl acetate methyl methacrylate 300 311 348 359 364 370 378 400 421 434 450 470 482 486 487 488 488 491 500 511 511 513 514 524 532 539 541 560 562 563 563 571 579 592 596 600 600 610 616 627 627 634 643 643 652 658 662 663 664 668 674 678 684 687 691 691 695 695 696 propane dichlorodifluoromethane (Freon 12) 1,2-dichloro-1,1,2,2-tetrafluoroethane (Freon 114) isobutane butane methyl chloride chloroethene (vinyl chloride) 2-methylbutane methyl bromide ethyl chloride methanol pentane trichlorofluoromethane (Freon 11) 2,2-dimethylbutane 1,1,2-trichloro-1,2,2-trifluoroethane dichlorofluoromethane (Freon 21) dimethylethanolamine propylene oxide 1,1-dichloroethene (vinylidene chloride) ethanol 2-methylpentane 2,3-dimethylbutane 3-methylpentane acetone n-hexane iso-propanol methyl acetate enflurane dichloromethane acetonitrile methylcyclopentane halothane vinyl acetate 2-methylhexane n-propanol 2,3-dimethylpentane 3-methylhexane cyclohexane ethyl acetate cis-1,2-dichloroethene 2,2,4-trimethylpentane methyl acrylate 2-butanone 1,1,1-trichloroethane carbon tetrachloride chloroform n-heptane cyclohexene benzene iso-propyl acetate iso-butanol 2,4-dimethylhexane methylcyclohexane 1,2-dichloroethane methoxyethanol trichloroethene tert-butyl acetate 2-methylheptane 1-methoxy-2-propanol

BP-10 300 318 353 359 400 402 420 478 482 492 500 500 503 528 528 532 553 553 555 559 561 561 582 589 600 601 603 607 608 637 642 644 644 662 665 669 673 676 685 685 687 690 693 693 697 700 700 712 723 727 739 736 736 745 755 755 763 768 773

16

BP-1 n-heptane methoxyflurane cis-1,2,dichloropropene methylisobutylketone methylcyclohexane 2,4-dimethylhexane 1-ethoxy-2-propanol trans-1,2-dichloropropene sec-butyl acetate 1,1,2-trichloroethane 2-ethoxy-1-propanol iso-butyl acetate toluene 2-methylheptane hexanal diethyleneglycol diethyl ether 1,2-dibromoethane propoxyethanol n-butyl acetate n-octane furfuralmethoxyethyl acetate tetrachloroethene 2,4-dimethylheptane furfuryl alcohol chlorobenzene diacetone alcohol 1-methoxy-2-propyl acetate ethylbenzene amyl acetate p-xylene m-xylene 4-methyloctane allyl glycidyl ether cyclohexanone 3-methyloctane tetrahydrofurfuryl alcohol ethoxyethyl acetate styrene 1,1,2,2-tetrachloroethane o-xylene butoxyethanol n-nonane iso-propylbenzene bromobenzene ethanediol monoacetate 2-methylcyclohexanone 3-methylcyclohexanone 4-methylcyclohexanone benzaldehyde -pinene n-propylbenzene phenol m-ethyltoluene p-ethyltoluene 1,3,5-trimethylbenzene 3-methylnonane -methylstyrene o-ethyltoluene 1,2,4-trimethylbenzene benzyl chloride benzyl chloride n-decane 700 706 720 723 728 735 738 739 745 747 754 757 761 765 777 783 787 790 795 800 807 807 824 830 837 842 843 855 859 864 864 865 868 871 873 874 876 881 886 887 890 900 919 921 925 930 931 937 940 941 949 951 956 958 963 972 972 975 990 996 997 1000 3-methylheptane n-butanol 1,2-dichloropropane methyl methacrylate n-propyl acetate n-octane methoxyflurane 2,4-dimethylheptane ethoxyethanol cis-1,2-dichloropropene sec-butyl acetate toluene methylisobutyl ketone iso-butyl acetate 1-ethoxy-2-propanol tetrachloroethene diethylene glycol diethyl ether trans-1,2-dichloropropene 3-methyloctane 1,1,2-trichloroethane hexanal nonane di-n-butyl ether 1,2-dibromoethane propoxyethanol ethylbenzene chlorobenzene p-xylene m-xylene methoxyethyl acetate amyl acetate isomer amyl acetate isomer o-xylene -pinene styrene iso-propylbenzene (cumene) furfural allyl glycidyl ether n-decane ethoxyethyl acetate N-methyl-2-pyrrolidone cyclohexanol n-propylbenzene butoxyethanol furfuryl alcohol m-ethyltoluene furfuryl alcohol p-ethyltoluene 1,3,5-trimethylbenzene cyclohexanone 1,1,2,2-tetrachloroethane ethanediol monoacetate o-ethyltoluene -methylstyrene 2-methylcyclohexanone 1,2,4-trimethylbenzene 3-methylcyclohexanone 4-methylcyclohexanone 1,2,3-trimethylbenzene p-dichlorobenzene n-undecane 1-methyl-2-isopropylbenzene

BP-10 774 777 778 782 784 800 806 820 820 821 823 825 831 840 843 846 854 862 872 876 891 900 905 905 913 922 922 929 929 940 948 951 960 962 968 983 987 999 1000 1002 1009 1010 1014 1015 1019 1022 1023 1023 1029 1030 1045 1046 1047 1050 1060 1060 1088 1095 1097 1099 1100 1104

17

BP-1 p-dichlorobenzene p-dichlorobenzene N-methyl-2-pyrrolidone 1,2,3-trimethylbenzene o-dichlorobenzene o-cresol indane 1-methyl-2-iso-propylbenzene indene propenylbenzene p-cresol m-cresol 1,4-diethylbenzene n-butylbenzene butoxyethyl acetate 1,3-dimethyl-4-ethylbenzene vinyl pyrrolidone nonanal 2,6-xylenol n-undecane isophorone 2,4-xylenol 2,5-xylenol decanal 3,5-xylenol 2,3-xylenol 3,4-xylenol 2-(isopropyl)phenol naphthalene n-dodecane ethylhexyl acrylate 1,1,2,3,4,4-hexachloro-1,3-butadiene n-tridecane 2-methylnaphthalene 1-methylnaphthalene 2,6-bis(isopropyl)phenol biphenyl n-tetradecane n-pentadecane 1004 1004 1009 1019 1027 1027 1033 1034 1039 1041 1047 1047 1051 1052 1061 1075 1077 1085 1093 1100 1113 1127 1127 1129 1144 1158 1171 1175 1196 1200 1215 1223 1300 1310 1328 1346 1388 1400 1500 benzaldehyde 1,3-diethylbenzene indane propenylbenzene 1,4-diethylbenzene n-butylbenzene benzyl chloride ethanediol diacetate o-dichlorobenzene 1,3-dimethyl-4-ethylbenzene indene benzyl chloride butoxyethyl acetate n-dodecane phenol 1,1,2,3,4,4-hexachloro-1,3-butadiene o-cresol 2,6-xylenol tridecane ethylhexyl methacrylate isophorone p-cresol m-cresol vinyl pyrrolidone naphthalene 2,4-xylenol 2,5-xylenol 2,3-xylenol 3,5-xylenol n-tetradecane tetrahydrofurfuryl methacrylate 3,4-xylenol 2-methylnaphthalene 1-methylnaphthalene n-pentadecane 2,6-bis(isopropyl)phenol biphenyl n-hexadecane n-hexadecane

BP-10 1105 1111 1117 1117 1118 1120 1128 1130 1135 1146 1147 1162 1185 1200 1222 1270 1274 1296 1300 1308 1308 1311 1311 1322 1328 1360 1360 1400 1400 1400 1400 1434 1447 1470 1500 1524 1538 1600 1600

Notes 1 Retention index data for selected VOCs in Table 4 were compiled from HSL in-house sources. Most compounds listed in Tables 2 and 3 are found here, but no exact correspondence of the two lists is implied. 2 GC retention indices based on the n-alkanes indicate the order of elution, but the absolute values are not intended to be definitive. Most were measured using the GC conditions in paragraph 64. Interpolated values are affected by temperature programming rates and other factors. They are normally reproduced to within 5 units with equivalent phases and similar conditions. 3 More retention indices of 150 gasoline hydrocarbons on OV 1701, equivalent to BP-10, are listed in MDHS 60.28

18

APPENDIX 1 Description of sorbent types Sorbent Carbon Carbon Anasorb 727* Type

Coconut shell Petroleum-based Beaded microporous polymer with hydrophobic surface Chromosorb 106* Beaded microporous polymer with hydrophobic surface Anasorb 747 Beaded active carbon derived from petroleum precursors Silica gel Tenax TA Poly (diphenyloxide) Porapak R * believed to be equivalent

Determine the effect of moisture on the breakthrough volume by humidifying the gas stream to approximately 80% relative humidity and repeating the test described above. Humidify the gas stream by diluting, in a ratio of 1:4 by volume, a primary gas stream at five times the concentration generated above with a stream of moist clean air at 100% relative humidity. Do not pass the VOC gas stream through water to humidify it. The relative humidity specified (80%) is a practical value; it does not imply that the method is invalid at higher relative humidities, provided due attention is given to the restriction on sampling volumes at high humidity (paragraph 73). Calculate the breakthrough volume by multiplying the flow rate in l/min by the time, in minutes, between zero and the moment when 5% of the plateau value has been reached.

APPENDIX 3
AnasorbTM is a trademark of SKC Inc, USA.
ChromosorbTM is a trademark of Manville Corp, USA.
TenaxTM is a trademark of Enka Research Institute, NV, NL.
PorapakTM is a trademark of Waters Associates Inc, USA.

Determination of desorption efficiency The desorption efficiencies (D) of VOCs can vary with the type and batch of sorbent used. Thus it is necessary for each type of sorbent and for each analyte to determine D over the sample concentration range. This can be done by sampling from a standard atmosphere at appropriate concentration, temperature, humidity etc. Generation of standard atmospheres may not be practicable and since it is equivalent to measuring effective uptake rate where D is a hidden variable, it is recommended that D be measured directly by doping the sorbent of unused blank samplers and treating as for exposed samplers. For doping very small quantities, it may be necessary to use a mixture of components diluted in the elution solvent. Alternatively, in the phase equilibrium method, millilitre amounts of standard solutions are added to unused blank samplers with a pipette and the difference in concentration measured before and after addition. With some compounds the phase equilibrium method may give a higher value for D than direct spiking methods.17-20 D equals the weight (in g) recovered divided by the weight (in g) applied. Plot the D values against the weight recovered for each sampler load level. If the D at the load level is less than 0.75 (75%) a sample result corresponding to that level should be discarded (but see paragraph 51). Where mixtures of non-polar analytes are desorbed with pure carbon disulphide, the mutual concentration effect on D is generally negligible. If the composition of a mixture of polar and non-polar analytes is known approximately, D values should be established with a similar mixture. It may not be possible to achieve greater than 75% D for all components of such a mixture with a single desorption solvent. Provided that it can be established that the D is consistent and that no better solvent can be found, then a compromise is acceptable, although where possible, the taking of a second sample and optimising desorption conditions for both polar and non-polar analytes is preferred. This doping method may not take account of high humidity at the time of sampling. Adsorbed water vapour is a factor which could be simulated by addition of water to the sorbent.

APPENDIX 2 Determination of the breakthrough volume The breakthrough volume for a sorbent tube/analyte combination is the volume of a vapour-in-air sample that can be passed through the front section of a sorbent tube before the eluting concentration of the analyte (VOC) vapour reaches 5% of the applied test concentration. Prepare dynamic standard atmospheres of VOC vapour in air as in MDHS 329 or 4.30 The temperature of the delivered concentration should be typical of the intended use of the sampler. Assemble a sampling train consisting of the dynamic standard atmosphere generator delivering a concentration of twice the relevant exposure limit for the substance analysed, a sorbent tube (as in paragraph 16, but omitting the back-up section), a flow meter (range 20-200 ml/min) and a flame ionisation or similar detector. Pass the gas through the sample train at a known constant rate between 20 ml/min and 200 ml/min. Use a value in this range which is suitable for the sampling rate intended (see paragraph 42). Note the time when the flow was initiated. When the VOC vapour begins to emerge, the detector will show a response. Continue the measurement until a plateau corresponding to the input concentration is reached or until the response is determined to be caused principally or totally by the VOC used. Determine the time at which 5% of the plateau value has been reached. Usually, the dead volume of the sampling train is small in comparison with the breakthrough volume. If this is not the case, determine the dead volume by repeating the determination with an empty tube in the sampling train and correct the result accordingly.

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APPENDIX 4 Recomendations for the test report It is recommended that the test report should include the following information: complete identification of the sample, including the date and place of sampling; reference to this MDHS and a description of any deviation from the procedures described; the type and size of sample tube used; the type of sampling pump and flowmeter used, the primary standard against which it was calibrated, and the range of flow-rates for which the flowmeter was calibrated; the duration of the sampling time in minutes and/or the time at the start and at the end of the sampling period; the volume of air sampled, in litres; the name of the person who collected the sample; the time-weighted average concentration found in the air sample, in milligrams per cubic metre; the overall uncertainty of the method; the name of the analyst; the date of the analysis; and any unusual features noted during the determination.

3 Health and Safety Executive Summary criteria for occupational exposure limits EH64 HSE Books 1999 ISBN 0 7176 2469 2 4 Health and Safety Executive Criteria for an occupational exposure limit EH65 HSE Books various dates 5 Health and Safety Executive Risk Assessment Documents EH72 HSE Books various dates 6 Health and Safety Executive Toxicity Reviews TR in series HSE Books various dates 7 Health and Safety Executive Health risks management: a guide to working with solvents INDG272 HSE Books 1998 8 Health and Safety Executive Working safely with solvents INDG273 HSE Books 1998 9 Health and Safety Executive A step-by-step guide to COSHH assessment HSG97 HSE Books 1993 ISBN 0 7176 1446 8 10 Health and Safety Executive Health surveillance at work HSG61 HSE Books 1999 ISBN 0 7176 1705 X 11 Health and Safety Executive CHAN series Chemical Hazard Alert Notices HSE free leaflets various dates 12 Health and Safety Executive Occupational Exposure Limits 1999 EH40/99 HSE Books 1999 ISBN 0 7176 1660 6 updated annually 13 Health and Safety Executive Methods for the Determination of Hazardous Substances MDHS in series HSE Books 1981-2000 14 Health and Safety Executive Volatile organic compounds in air (1) MDHS72 HSE Books 1993 ISBN 0 11 885692 8* 15 Health and Safety Executive Volatile organic compounds in air (2) MDHS80 HSE Books 1995 ISBN 0 7176 0913 8* 16 Health and Safety Executive Volatile organic compounds in air (3) MDHS88 HSE Books 1997 ISBN 0 7176 2401 3* 17 NIOSH Manual of Analytical Methods 4th edition 1994-date US Dept of Health and Human Services Publication 94-113 18 US Occupational Safety and Health Administration OSHA Manual of Analytical Methods USDOL/OSHA 1989-date 19 Health and Safety Executive Monitoring strategies for toxic substances HSG173 HSE Books 1997 ISBN 0 7176 1411 5

ADVICE Advice on this method and the equipment used can be obtained from the Health and Safety Executive, Health and Safety Laboratory, Broad Lane, Sheffield S3 7HQ (tel: 0114 2892000, fax: 0114 2892500, e-mail hslinfo@hsl.gov.uk). The Health and Safety Executive wishes, wherever possible, to improve the methods described in this series. Any comments that might lead to improvements would therefore be welcome and should be sent to the above address.

REFERENCES 1 Control of Substances Hazardous to Health Regulations 1999 (SI 1999/437) TSO ISBN 0 11 082087 8 2 Health and Safety Executive General COSHH ACOP (Control of substances hazardous to health) and carcinogens ACOP (control of carcinogenic substances) and biological agents ACOP (control of biological agents). Control of Substances Hazardous to Health Regulations 1999: Approved Codes of Practice L5 HSE Books 1999 ISBN 0 7176 1670 3

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20 Turner B C and Glotfeldy D E Field sampling of pesticide vapours with polyurethane foam Anal Chem 49 1977 7-10 21 British Standards Institution Workplace atmospheres - General requirements for the performance of procedures for the measurement of chemical agents BS EN 1232 1997 ISBN 0 580 28328 3 22 Health and Safety Executive General methods for sampling and gravimetric analysis of respirable and inhalable dust MDHS 14/3 HSE Books 2000 ISBN 0 7176 1749 1 23 British Standards Institution Specification for onemark volumetric flasks BS 1792 1993 ISBN 0 580 12754 0 24 British Standards Institution Piston and/or plunger operated volumetric apparatus (POVA) Part 3: Methods of test BS 7653-3 1993 ISBN 0 580 022125 3 25 British Standards Institution Workplace atmospheres - General requirements for the performance of procedures for the measurement of chemical agents BS EN 482 1994 ISBN 0 580 23644 7 26 British Standards Institution Workplace atmospheres - Pumped sorbent tubes for the determination of gases and vapours - Requirements and test methods BS EN 1076 1997 ISBN 0 580 28358 5

27 Health and Safety Executive Analytical quality in workplace air monitoring MDHS 71 HSE Books 1995 ISBN 0 11 885976 5 28 Health and Safety Executive Mixed hydrocarbons (C3 to C10) in air MDHS 60 HSE Books 1992 ISBN 0 11 885998 6 29 Health and Safety Executive Generation of test atmospheres or organic vapours by the syringe injection technique MDHS 3 HSE Books 1990 ISBN 0 7176 0228 1 30 Health and Safety Executive Generation of test atmospheres or organic vapours by the permeation tube method MDHS 4 HSE Books 1990 ISBN 0 7176 0271 0

Amendments may be made to the above publications occasionally and readers should ensure that they are using the current edition. Advice on the availability of HSE publications may be obtained by phoning the HSE InfoLine on 08701 545500, or writing to the HSE Information Centre at the address under Advice. *These publications do not at present carry series designations (1-3). These will be added at the next revisions.

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TITLES IN THE MDHS SERIES

1 2 3 4 5 6/3 10/2 12/2 14/3 15 16 17 18 19 20 21 22 23 24 25/2 26 27 28 29/2 30/2 31 32 33 35/2 36 37 38 39/4 40 41/2 42/2 43 44 45 46/2 47 48 49 50 51/2 52/3 53 Acrylonitrile charcoal tube/gas chromatography (GC) Acrylonitrile pumped thermal desorption/GC Standard atmospheres syringe injection Standard atmospheres permeation tube On-site validation of methods Lead atomic absorption (AA) Cadmium AA Chromium AA Respirable and inhalable dust gravimetric Carbon disulphide charcoal tube/GC Mercury adsorbent tube (Hydrar) AA Benzene charcoal tube/GC Tetra alkyl lead continuous monitoring Formaldehyde colorimetric (Chromotropic acid) Styrene pumped charcoal tube/GC Glycol ethers charcoal tube/GC Benzene thermal desorption/GC Glycol ethers thermal desorption/GC Vinyl chloride charcoal tube/GC Organic isocyanates reagent bubbler/HPLC Ethylene oxide charcoal tube/GC Diffusive sampler evaluation protocol Chlorinated hydrocarbons charcoal tube/GC Beryllium AA Cobalt AA Styrene pumped thermal desorption/GC Phthalate esters solvent desorption/GC Adsorbent tube standards HF and fluorides ion-selective electrode Toluene charcoal tube/GC Quartz in respirable airborne dust direct infra-red Quartz in respirable airborne dust KBr disc technique Asbestos fibres light microscopy (European reference version) Toluene thermal desorption/GC Arsenic AA Nickel AA Styrene diffusive/thermal desorption/GC Styrene diffusive/solvent desorption/GC Ethylene dibromide solvent desorption/GC Platinum AA Rubber fume in air measured as total particulates and cyclohexane soluble material Newspaper print rooms: measurements of total particulates and cyclohexane soluble material in air Aromatic isocyanates acid hydrolysis/ diazotisation Benzene diffusive/thermal desorption/GC Quartz in respirable dusts X-ray diffraction (direct method) Hexavalent chromium in chromium plating mists colorimetric (1,5-diphenylcarbazide) 1,3 Butadiene thermal desorption/GC

Protocol for assessing the performance of a pumped sampler for gases and vapours 55 Acrylonitrile diffusive/thermal desorption/GC 56/2 Hydrogen cyanide ion-selective electrode 57 Acrylamide liquid chromatography 59 Manmade mineral fibres 60 Mixed hydrocarbons 61 Total hexavalent chromium compounds in air colorimetric 62 Aromatic carboxylic acid anhydrides 63 Butadiene diffusive/thermal desorption/GC 64 Toluene charcoal diffusive/solvent desorption/GC 65 Mine road dust: determination of incombustible matter 66 Mixed hydrocarbons (C5 to C10) in air diffusive/ thermal desorption/GC 67 Total (and speciated) chromium in chromium plating mists colorimetric (1,5-diphenylcarbazide) 68 Coal tar pitch volatiles 69 Toluene diffusive/solvent desorption/GC 70 General methods for sampling airborne gases and vapours 71 Analytical quality in workplace air monitoring 72 Volatile organic compounds in air 73 Measurement of air change in factories and offices 74 n-Hexane in air diffusive/solvent desorption/GC 75 Aromatic amines solid sorbent/thermal desorption/GC 76 Cristobalite in respirable dusts X-ray diffraction (direct method) 77 Asbestos in bulk materials 78 Formaldehyde diffusive/solvent desorption/liquid chromatography 79 Peroxodisulphate salts mobile phase ion chromatography 80 Volatile organic compounds diffusive/thermal desorption/GC 81 Dustiness of powders and materials 82 The dust lamp 83 Resin acids GC 84 Oil mist from mineral oil-based metalworking fluids 85 Triglycidyl isocyanurate in air pumped filter/ desorption/liquid chromatography 86 Hydrazine in air 87 Fibres in air 88 Volatile organic compounds in air diffusive/solvent desorption/GC 89 Dimethyl sulphate and diethyl sulphate thermal desorption/GC-mass spectrometry 90 Alkyl 2-cyanoacrylates liquid chromatography 91 Metals and metalloids XRF 92 Azodicarbonamide high performance liquid chromatography 93 Glutaraldehyde HPLC 94 Pesticides pumped filters/sorbent tubes/GC 95 Metalworking fluid AA/plasma-atomic emission spectrometry 96 Volatile organic compounds solid sorbent/solvent desorption/GC

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