ࡱ> 9 ]bjbj hY l4h$,T)<JJ```N$P$P$P$=$$&$($* ,(y^(+``)+++>``N$+N$++!:!"`> Ή* v" "$)0T)" N-N-"+The International Manganese Institute Guidelines for workplace monitoring of airborne manganese May 2000 Occupational Health, Environment and Safety Commitee International Manganese Institute 17, avenue Hoche, 75008 Paris, France Tel.: + 33 (1) 45 63 06 34 Fax: + 33 (1) 42 89 42 92 e-mail: manginst @ aol . com Guidelines for workplace monitoring of airborne manganese Reviewed by : P Rousseau Erachem-Europe, Tertre Belgium F Gaidou Eramet Paris 1991 edition prepared by: R. Hart, W Pioli, A Pennock, T White Occupational Health, Environment and Safety Commitee Contents 1.- Introduction 1.1. Scope 1.2. Manganese forms considered 2.- Air monitoring 3.- Monitoring strategy 4.- General sampling guide 4.1. Introduction 4.2. Equipment 4.2.1. Pump 4.2.2. Flowmeters 4.2.3. Records 4.2.4. Repeat calibrations 4.2.5. Static eliminator 4.2.6. Sampling devices 4.2.7. Transportation 4.2.8. Analytical equipment 4.3.- Sampling procedure 5.- Where to find information on the web ? Appendices: A.1.: Calculating exposure concentrations. A.2.: Source of useful information A.3.: Reference documents Introduction 1.1. Scope These guidelines provide detailed information on the monitoring of airborne manganese as encountered in the manganese mining, smelting industries or other manganese transformation industries. Additionally, a general monitoring strategy is provided. 1.2. Manganese forms considered Guidance is presented on monitoring for manganese in dust and fumes and as a constituent of welding fume. Manganese will take various forms in the different industries. Mining and ore processing: exposure is usually to the dioxide (MnO2) dust although the tetroxide (Mn3O4) and the carbonate (MnCO3) are also mined. Metallurgy: manganese Mn3O4 from sintered manganese ore fines, dust of various oxides in raw materials and by-product (slag) processing, fume during furnace tapping, metal dust in product processing. Synthetic manganese dioxide (chemical and electrolytic): the lower oxides (MnO) and the sulfate (MnSO4) will be present in addition to the dioxide. Dry cell batteries: exposure potential would be limited to the dioxide. There also exists potential exposure to manganese dust and fume during application of manganese products such as welding, steel making, and further sizing. 2.- Air monitoring Up to now, data on speciation of manganese compounds have not allowed to distinguish between water soluble and insoluble compounds for OELs. However, recent manganese standards generally differentiate particle sizes. The International Standard Organization (ISO) (1), Comit Europen de Normalisation (CEN) (2) and the ACGIH (3) have established a standardized curve relating inhability (I) to the particles aerodynamic diameter (D). I = 0.5 [1 + exp (-0,06 D)]. Standardized definitions of conventional respiratory fractions (4) The standard definition has specified that (4): the inhalable fraction is the mass fraction of total airborne particles, which is inhaled through the nose and mouth, the thoracic fraction is the mass fraction of inhaled particles penetrating beyond the larynx, the respirable fraction is the mass fraction of inhaled particles penetrating the unciliated airways. In the near future, Occupational Exposure Limits (OELs) for aerosols will be based on this curve. This curve will become the reference for performances of instruments for measuring the inhalable fraction. New sampling equipment has been developed, which measures inhalable aerosols (5). The Edimburgh Institute of Occupational Medicine (IOM) proposed a personal inhalable aerosol sampler, first described by Mark and Vincent (5). Sampling collected by the IOM sampler is different from that collected by the plastic 37 mm cassette used worldwide, e.g. in North America. Both samplers have quite the same characteristics for the respirable fraction, but for coarser particles (inhalable), the IOM sampler measures a more important fraction. Two consequences of that difference are: OELs values, which may be reevaluated in some cases, requirement for a correlation table between both types of sampling. Werner et al (6) proposed workplace conversion factors for translating total into inhalable exposure:  ______________________________________________________________ Aerosol classification Industrial category Proposed conversion factors ______________________________________________________________ Dust 2.5 Mist 2.0 Hot process 1.5 Welding 1.0 Smokes and fume 1.0 ______________________________________________________________ 3.- Monitoring strategy Any monitoring program must be aimed at producing sufficient representative samples in order to accurately determine workers exposure. The strategy should take account of: the nature and toxicity of the contaminants, period since last monitoring, changes to process during that period, variability of process, level of contaminants when last monitored, control measures in place. This monitoring program also depends on the goal of the sampling program, whether it is to ascertain compliance, to provide data for research, or to investigate a particular workplace problem (NiPERA). Personal sampling devices can be used for following and assessing workers exposure (IOM or 37 mm sampler devices). Static sampling devices can be used to analyse workplace conditions and put critical exposure areas of the plant in evidence. Speciation on the basis of chemical forms, is currently being considered as a research procedure since it is time-consuming and expensive. As the importance of manganese speciation may become more recognized by researchers and regulators alike, it may become more commonplace, or even mandatory, to analyse samples for specific species. Alternatively, it may be considered adequate to first characterize the workplace atmosphere by a detailed species analysis and then use conventional methods to measure manganese exposure and apportion the results to specific species (NiPERA). 4.- General sampling guide 4.1. Introduction A successful air monitoring program begins with a good understanding of the physical layout and processes of the workplace. Before any monitoring is undertaken, a visual survey of the site and a critical discussion on Material Safety Data Sheets (MSDSs) with employees should be conducted in order to identify potential areas of significant exposure. Air monitoring is a complex task that is best done by trained personnel. For facilities that lack the appropriate staff, certified occupational hygiene consultants are the suggested alternative. Governmental organizations may provide assistance on air monitoring or advice on where to obtain skilled help. Principal steps of an air monitoring program are: development of a sampling strategy, purchase or rental of sampling equipment and supplies, calibration of equipment, sample collection, sample analysis, calculation of exposure concentrations, determination of compliance status, notification of employees of the results, documentation and record keeping (NiPERA). 4.2. Equipment: 4.2.1. Pumps: A good quality battery powered pump able to maintain a predetermined flow rate to within +5% over a period of at least eight hours is required. Pumps should be of the constant flow type and have a pulsation ratio of less than 0.2. Caution: in flammable or explosive atmospheres, pumps must be safe intrinsically and comply with local regulations. 4.2.2. Flowmeters: A primary flowmeter such as a soap film flowmeter, wet test gas meter or beel spirometer is required. A soap film flowmeter can consist of an inverted, accurately calibrated, glass burette. It should be of a constant diameter, such that a soap bubble may readily be formed and will travel its entire length without bursting. The burette should have a volume equal to that drawn by the pump in 15 to 30 seconds. A stopwatch able to measure elapsed time to an accuracy of 1% is required. The primary flowmeter may be used to calibrate a secondary flowmeter as follows: i) turn on the pump, ii) clean and moisten the burette to ensure smooth flow of the bubble, iii) assemble the apparatus using tubing of the same dimension as that to be used in the field in the order - burette, secondary flowmeter, sampling device and pump, iv) when the pump has stabilized (see 4.3.1.), adjust the flow to the predetermined level, v) raise the soap solution to the burette and time its travel between appropriate graduations, vi) repeat step v) until three consecutive results agree to within 1% of the mean volume, vii) the flow rate is calculated from: Q = v/t where: Q = is the true flow rate under calibration in millimiters per second, v = is the volume between graduations in millimiters, t = is time taken for the bubble to move between the graduations in seconds. Cautions: 1) Flow pulsation can be a major source of error with variable orifice (rotameter) flowmeters. It is important the calibration is conducted under conditions similar to those used in the field. 2) Theoretically, the water vapour content of the air in the burette should be taken into account. However, for practical purposes acceptable, accuracy is obtained without this correction. 4.2.3. Records: A record must be kept of calibration which shall include: i) identification or unambigous description of the pump used and flowmeter tested, ii) capacity of burette/calibrated tube, iii) nominal flow rate as indicated by flowmeter during calibration, iv) average time (tav) and the value of three consecutive results from which the average time was calculated, v) true flow rate, Q, vi) name of the person/organization conducting the testing and the date of calibration, vii) any additional information which will assist in the correct interpretation of the results e.g. unduly warm-up time, instability in pump flowmeter, difficulty in obtaining three consecutive results to agree within + 1% of the mean value. 4.2.4. Repeat calibrations: This calibration should be repeated: i) as indicated by experience with the stability and maintenance history of the flowmeter, ii) when sampling is to be conducted at an altitude which differs by more than 500 meters or at a temperature which differs by more than 15C from the previous calibration. 4.2.5. Static eliminator: An alpha article source e.g. polonium -210 radioisotope of activity 2 x 105 becquerel (Bq). Such a source will have an effective life of 1 to 2 years. Alternatively, a high voltage static eliminator may be used. Note: a government licence may be required for the polonium radioisotope. 4.2.6. Sampling devices: Conditioning filters: The weight of some filters, particularly those of cellulose ester, may vary with humidity changes. In order to minimize these errors, filters should be placed in clean, individually labelled containers with the lids slightly ajar and allowed to come to equilibrium with the balance room air over a period of several hours prior to weighing, both before and after sampling. The weight of the filters sould be adjusted to the variation in weight of blank filters subjected to all but the sampling process. Preweighing filters: After filters are conditioned, they are to be passed over the static eliminator to remove static (several passes may be required), weighed and the mass recorded. The filters are then placed in a sampling head approved for the test contaminant. Ten percent of filters (with a minimum of two) should be retained as blanks, being subjected to all but the sampling process. Weighing used filters: After filters are conditioned, they are to be passed over the static eliminator over filters to dissipate any electrostatic charge prior to reweighing. Weigh each filter and record the mass in milligrams (mg). Note: If the dust is hygroscopic, the weighing procedure may be impaired unless steps are taken to minimize weighing errors. Note: In the majority of instances, the mass of manganese on the filter will be determined by the chemical analysis. The weighings will allow the concentration of inspirable dust to be determined for the sampling period. 4.2.7. Transportation: The layer of dust collected on the filter is fragile and can easily be disturbed; shock or vibration may cause loss of material unless precautions are taken during transport. The best method of transportation is by using a reliable person who is aware of the need for care. For long distances, the filters shall be packed in such a way that normal transportation shocks do not cause loss of material. It is strongly recommended that analysis be conducted close to the sampling site. Filters should not be removed from sampling heads by unskilled people, due to possible filter or dust deposit damage. To minimize the risk of dust loss during transportation, filter loading should be limited to 2 mg. 4.2.8. Analytical equipment: i) Microbalance capable of reading + 0.01 mg at the 90% confidence level in the range 0-60 mg. The balance should be calibrated as recommended by the manufacturer or appropriate national authority. The accuracy should be checked with a standard mass before and after each series of weighings. ii) Analysis of the filters for manganese content will normally be by Atomic Absorption or Inductively Coupled Plasma Spectro-metry. NIOSH Method 7300 (7) Elements by Inductively Coupled Plasma Spectrometry (ICP) is effective for the analysis of manganese in dust, fume or welding fume. NIOSH Method 7200 (8) Welding and Brazing Fume by X-Ray Fluorescence Spectro-metry (XRF) and other methods which can be shown to produce accurate results may also be used. The laboratory performing the analysis should be competent in the field and where possible certified as such by its national certifying authority. 4.3. Sampling procedure: 4.3.1. Turn on the pumps and allow them to run for up to 15 minutes to stabilize. Some automatic flow control pumps do not require this stabilisation period. 4.3.2. Calibrate the flow rate against the secondary flowmeter with the sampling train (pump, filter, head filter and tubing) in line. The equipment should be such that the flow rate can be measured with an accuracy of + 5%. 4.3.3. Sampling times of individuals exposed should be as long as is reasonably practicable. Six to eight hours is representative of a time weighted average exposure and 15 minutes is representative of a ceiling exposure. The procedure shall be as follows: (a) Attach the sampling pump to the worker. (b) Fasten the sampling head containing a preweighed filter to the workerss clothing, within the breathing zone. The breathing zone is defined as the hemisphere of radius 30 cm in front of the face centered at the mid-point of the line joining the ears. A sample in a workers breathing zone can be placed outside his or her clothing on the lapel attached to a safety helmet near the workers nose and mouth. Ensure that the tubing is free from kinks, and the sampling train is located to minimize incon-venience to the worker. (c) When ready to commence sampling, turn on the pump and record the following information: i) sampling head identification number, ii) pump identification number, iii) date and starting time of pump, iv) initial flow rate of pump, v) workers name (if necessary), vi) description of task undertaken during sampling period, vii) ventilation controls and atmospheric conditions, viii) name of person doing the sampling, ix) any other relevant data e.g. whether some form of personal protection is required and a description of protective devices worn. (d) At the conclusion of the sampling period, record the time, remeasure the flow rate (a later check may give false results due to the temporary recovery of a discharged battery), switch off the pump and remove the sampling system from the worker. Note: The final flow rate should not differ from the initial flow rate by more than 5%. If the flow rates vary by more than + 5%, the sample should be rejected. (e) Immediately, place the sampling head in a prelabelled dust-free box ensuring that it cannot be inadvertently used again. Transport filters according to 4.2.7. Notes 1. Long sampling times ensure heavier deposits on the filter, which minimize weighing errors. Six to eight hours is representative of a time weighed average exposure and 15 minutes is representative of a ceiling exposure. 2. Care should be taken to ensure material is not lost from an excessively heavy deposit. 3. To ensure stability, run the pumps for 15 minutes prior to the initial flow measurement. 4. It is prudent to check the pump within 30 minutes after the commencement of sampling and then periodically (e.g. every two hours) to ensure correct operation. A visual check of the filter may assist in avoiding excessive deposition. 5. If the filter loading is excessive, continue sampling for the full period but change the filters as described in 4.3. Where to find information on the web ? OrganismNorm referencehttp : // addressISOISO 7708www.Iso.ch/CENEN 481, 482www.cenorm.be/NIOSH0500, 0600, 7300www.cdc.gov/niosh/nmam/nmammenu.htmlBritish Standard Institute-www.bsi.org.ukBritish HSEMDHS 14/2www.hse.gov.uk/iondocs/Australian Standards3640 Inhalable / 2985 respirablewww.standards.com.auEPAList of Designated Reference and equivalent methodswww.epa.gov/ttn/amtic/criteria.html A.1. Calculating exposure concentrations A.4.1. The mass of manganese on the filter will be available directly from the chemical analysis while the mass of dust or fume may be calculated from the following equation: m = ml - mo where m = mass of dust collected on the filter, in milligrams (mg), ml = mass of used filter corrected for mass changes in the blank filters in milligrams (mg), mo = mass of unladen filter, in milligrams (mg). A.4.2. Calculate the volume of air passed through the filter or tube in the duration of sampling from the following equation: V = (t x F)/1000 where V = volume of air passed through the filter, in cubic meters (m3), t = sampling time, in minutes (min.), F = average flow rate of sampling head, in liters per minute (L/min.). If the final flow rate differs from the initial flow rate, the average flow rate shall be calculated. Corrections to the volume for any difference in air temperature or pressure between the area where calibration is performed and the area where air is sampled should be made using the ideal gas laws: T2 P1  V2 = x x V1 T1 P2 P1 and T1 are conditions during calibration. P2 and T2 are sampling conditions. V1 is the calculated sample volume. V2 is the corrected volume. A.4.3. Calculate the average concentration of contaminant from the following equation: c = m/V where c = average concentration of contaminant in milligrams per cubic meter, m = mass of manganese found by analysis or mass of dust calculated in A.4.1. APPENDIX A.2 - SOURCES OF USEFUL INFORMATION AMERICAN CONFERENCE OF GOVERNMENTAL INDUSTRIAL HYGIENISTS 1330 Kemper Meadow Drive Cincinnati, Ohio 45240 USA Telephone : 1 513 742 2020 Telefax : 1 513 742 3355INTERNATIONAL ORGANIZATION FOR STANDARDIZATION P.O. Box 56 1, rue de Varembe CH-1211 Geneva 20 - Switzerland Telephone : 41 22 749 01 11 Telefax : 41 22 733 34 30COMMISSION OF THE EUROPEAN COMMUNITIES Directorate-General Employment, Social Affairs and Education Health and Safety Directorate V/E Btiment Jean Monnet Rue Alcide de Gasperi L-2920 Luxembourg Grand Duchy of Luxembourg Telephone : 352 43013 2719 Telefax : 352 43013 4511NATIONAL INSTITUTE FOR OCCUPATIONAL SAFETY AND HEALTH Robert A. Taft Laboratories 4676 Columbia Parkway Cincinnati, Ohio 45226-1998 - USA Telephone : 1 800 356 4674 Telefax : 1 513 533 8573HEALTH AND SAFETY EXECUTIVE Broad Lane Sheffield S3 7HQ - United Kingdom Telephone : 44 742 892345 Telefax : 44 742 892 333NATIONAL OCCUPATIONAL HEALTH AND SAFETY COMMISSION (WORKSAFE AUSTRALIA) GPO Box 58 Sydney NSW 2001 - Australia Telephone : 61 2 565 9500 Telefax : 61 2 563 9205INTERNATIONAL LABOUR ORGANIZATION International Occupational Safety and Health Information Centre CH-1211 Geneva 22 Switzerland Telephone : 41 22 799 67 40 Telefax : 44 22 798 62 53OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION Office of Information and Customer Affairs Room N3647 Washington, DC 20210 Or OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION Directorate of Health Standards Room N3718 Washington, DC 20210 Telephone : 1 202 219 8148 Telefax : 1 202 219 5986INTERNATIONAL OCCUPATIONAL HYGIENE ASSOCIATION Principal Office and Secretariat British Occupational Hygiene Society Great Northern Road Georgian House, Suite 2 Derby DE1 1LT United Kingdom Telephone : 44 332 298 101 Telefax : 44 332 298 099WORLD HEALTH ORGANIZATION International Programme on Chemical Safety 20 Appia CH-1211 Geneva 27 Switzerland Telephone : 41 22 791 21 11 Telefax : 41 22 791 07 46 A.3. Reference documents (1) ISO: International Standards Organization (1992), Air quality-particle size fraction definitions for health related sampling. Technical report No.ISO/TR/7708-1983. Geneva: International Standards Organization. (2) CEN: Comit Europen de Normalisation (1994), General requirements for the performance of procedures for workplace measurements. Draft standard pr EN482. Brussels: Commission of European Communities. (3) ACGIH American Conference of Governmental Industrial Hygienists (1993-94). Threshold limit values for chemical substances and physical agents and biological exposure indices. Cincinnati: ACGIH. (4) CEN: Comit Europen de Normalisation (1993). Workplace atmospheres - size fraction definitions for measurement of airborne particles. European Standard EN481. Brussels: Commission of European Communities. (5) Mark, D., Vincent, J.H. (1986). A new personal sampler for airborne total dust in workplaces. Ann. Occup. Hyg. 30, No.1, p. 89-102. (6) Werner, M.A., Spear, T.H., Vincent, J.H. (1996). Investigation into the impact of introducing workplace aerosol standards based on the inhalable fraction. Analyst, 121, p. 1207-1214. (7) NIOSH: National Institute of Occupational Safety and Health. (1994). Method No.7300: Elements. In: NIOSH manual of analytical methods. 4th ed. Issue 2. (8) NIOSH: National Institute of Occupational Safety and Health. (1984). Method No. 7200: Welding and brazing fume. In: NIOSH manual of analytical methods. 3rd ed. 1. Cincinnati, OH: National Institute for Occupational Safety and Health, DHHS (NIOSH) publication No.84-100.  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