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Method Num ber: Matrix: OSHA Perm issible Lim its Final Rule Lim its Tim e W eighted Average (TW A): Short-Term Exposure Lim it (STEL): Transitional Lim it (TW A): Collection Device:
0.1 ppm * 0.3 ppm * 0.1 ppm An air sam ple is collected using a calibrated sam pling pum p and a two-piece polystyrene cassette containing two nitrite-im pregnated glass fiber filters (IGFFs). During collection, ozone reacts with the nitrite im pregnated on the filter collection device and converts it to nitrate via oxidation.
Recom m ended Sam pling Rate (See Special Precautions below) TW A: 0.25 to 0.5 liter per m inute (L/m in) STEL: 1.5 L/m in Recom m ended Air Volum e TW A: 90 L (180 m in at 0.5 L/m in). Longer sam pling tim es can be used (up to 480 m in) when using 0.25 L/m in flow rate. STEL: 22.5 L (1.5 L/m in for 15 m in) Analytical Procedure: The reaction product is extracted from the filters and blanks using deionized water and the extracts are analyzed by ion chrom atography as nitrate using UV-VIS detector at 200 nm wavelength. A conductivity detector can also be used. Detection Lim it Qualitative: 0.008 ppm (90-L air sam ple) 0.032 ppm (22.5-L air sam ple) Quantitative: 0.03 ppm (90-L air sam ple) 0.11 ppm (22.5-L air sam ple) Accuracy TW A STEL Validated Range: 0.070 to 0.224 ppm 0.330 ppm CV T(pooled): 0.045 0.054 (CV 2) Bias: +0.014 -0.015 Overall Error: ±10.4% ±12.3% Method Classification: Validated Method Special Precautions: Slight breakthrough (~7.5%) of ozone was noted at approxim ately 0.4 ppm . If the expected ozone (O 3) concentration is m ore than 0.2 ppm , the recom m ended sam pling rate can be reduced to 0.25 L/m in. Chem ist: Jam es C. Ku
Date: March 1995
* The U.S. Court of Appeals, Eleventh Circuit, has ruled that Final Rule Lim its of 29 CFR 1910.1000 be vacated. The Final Rule definition of “TW A” and “STEL” have been retained. Although the Final Rule Lim its have been vacated, OSHA encourages industry and governm ent to abide by these lim its established by scientific evidence (m em orandum for Directorate Heads, Office Directors and Regional Adm inistrator from Roger Clark, Director of Com pliance Program s OSHA, 3/30/93). Com m ercial m anufactures and products m entioned in this m ethod are for descriptive use only and do not constitute endorsem ents by USDOL/OSHA. Sim ilar products from other sources can be substituted. Branch of Inorganic Methods Developm ent OSHA Salt Lake Technical Center Salt Lake City, Utah
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1. Introduction This m ethod describes the sam ple collection and analysis of airborne ozone (O 3). Air sam ples are taken in the breathing zone of workplace personnel, and analysis is perform ed by ion chrom atography (IC) equipped with a UV-VIS and conductivity detector. Nitrate analysis by conductivity is well established since the 1970s. Both UV-VIS and conductivity detectors are suggested in this m ethod to allow versatility and offer the possibility of excluding interferences by switching detectors. This m ethod is not applicable for collection and analysis of bulk or wipe sam ples. 1.1 History Many previous attem pts were m ade to m easure ozone in occupational environm ents. All have various shortcom ings and dem onstrate the past degree of difficulty in developing an adequate m ethod. A chronological presentation of som e of the m ethods OSHA has used or evaluated is discussed below: 1.1.1 Detector tubes: The m ajor drawback of detector tubes is the need to use a cum bersom e statistical technique to assess Tim e W eighted Average (TW A) exposures. KI and AKI m ethods: An early m ethod to determ ine occupational exposure to ozone in the workplace involved collection in neutral potassium iodide (KI) solution and analysis by colorim etry (Ref. 5.1). A m odification involved collecting sam ples in an alkaline potassium iodide (AKI) solution and analyzing them by colorim etry after acidifying with sulfam ic acid (Ref. 5.2). It has been reported (Ref. 5.3) that the reaction of ozone with AKI to produce iodine is not quantitative and is concentration dependent. Therefore, a conversion equation m ust be used to convert the values equivalent to the neutral KI m ethod. OSHA KIBRT (potassium iodide-potassium brom ide-sodium thiosulfate) (Ref. 5.4): This m ethod resolved som e of the stability and interference problem s associated with prior m ethods which used KI. Trans-stilbene (Ref. 5.5): Previous work has been reported using glass beads coated with trans-stilbene for collecting ozone (Ref. 5.6). Prelim inary tests showed that this m ethod was affected by hum idity as low as 50% relative hum idity (RH) (Ref. 5.7). To com pensate for this hum idity problem , an im pinger sam pling m ethod using a collection solution (as stated in chronological list below) was developed at the OSHA-SLTC (Ref. 5.5). Although this m ethod could be used under controlled conditions as a reference m ethod in the laboratory, the 90% acetonitrile in water is flam m able and should not be used for field use. Alternative non-flam m able collection solutions were not found during this study. Direct-Readers AID Model 560 (Ref. 5.8) or AED-030 (Ref. 5.9): A strip chart recorder to record data was used to docum ent for both direct-readers com pliance m onitoring. The AID Model 560 also required a battery recharge every 8 to 10 hours, m aking it inconvenient. The AED-030 can be used for only 4 to 5 hours with batteries; a line voltage power converter or replacem ent batteries is necessary for longer periods. Recently, it has been reported (Ref. 5.10) that the m easurem ent of ozone can be done using a com m ercially available passive sam pling device containing a nitrite-im pregnated filter. According to the m anufacturer, the shelf-life of the sam pling portion of the passive device is conservatively 4 weeks from the nitrite im pregnation date to the analysis date. Based on the nitrite principle, OSHA Method ID-214 was developed as an active sam pling system . The com m ercially available passive system was initially tested and som e of the data is included in the backup report (Section 4.) Because of sensitivity (Section 4.10) and potential interference considerations of the passive sam pler, this active sam pling m ethod is m ore suitable for OSHA com pliance purposes.
A chronological sum m ary of OSHA SLTC ozone m onitoring techniques is shown below:
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and Bubbler.Date 1960s present Method Detector tubes Principle Collection Medium Oxidation of indigo by Direct-read ozone resulting in white color Reaction with KI 1% KI.8 1% KI. Flammable liquid. and sensitive interferences from all oxidants Simple. very bulky instrument specific requiring ethylene (flammable gas) or Ethychem (ethylene in CO2) Simple.05% transmesitol stilbene + 0. sensitive and O3 bubbler used for specific sample collection No data logging capacity. rapid. The second IGFF serves as a backup filter. The m ethod is also capable of m onitoring Food and Drug Adm inistration lim it of 0.12 ppm for a 1-hour average.05 ppm O 3 in enclosed spaces (21 CFR 801. 2% KBr excess I2 Reaction with olefins Glass beads coated with trans-stilbene 1990 91 (Lab use only) 1990 91 (Lab use only) Glass beads trans-stilbene 1992 present This method 1. amount of Measurement of thiosulfate.1 This m ethod has adequate sensitivity for determ ining com pliance with the OSHA Perm issible Exposure Lim it (PEL) of 0.0 N NaOH. (AED-030) sensor instrument sensitive and easy to use IGFF Reaction with nitrite Nitrite-coated IGFFs Simple. pH>11 Before 1977 1977 80 1% Neutral buffered KI Alkaline KI Reaction with KI 1983 92 Ozone meter (AID Chemiluminesence Model 560) Direct reading instrument 1986 Neutral buffered (KIBRT) Reaction with KI and 1% KI. rapid. sensitive sampling rate dependence. pH=6. rapid Bubbler. sampling rate Simple. Recovery dependent sensitive and O3 on humidity specific Simple. rapid. and Bubbler. 1. stable from all oxidants.5% mesitol in a mixture of acetonitrile/water (9:1) Ozone meter Semi-conductor Direct reading Simple. rapid. rapid Interferences. unstable. rapid. A gravim etric conversation factor is used to calculate the am ount of O 3 collected from the am ount of NO 3G found.2 trans-stilbene and Reaction with olefins 0.1 ppm for O 3 exposure. and some Potential independence from contamination.3. more a spot check for exposure measurement Simple. 1. instrument treads to drift Interference from SO2 Ozone is collected using two nitrite-im pregnated glass fiber filters (IGFFs). Environm ental Protection Agency (EPA) has established a National Am bient Air Quality Standard (NAAQS) for O 3 at 0.3 Advantages and Disadvantages 1. No data logging and direct-reading. The m ethod is capable of m onitoring for the EPA lim it provided a sam pling rate of at least 3 of 29 T-ID214-FV-01-9503-M . a known Na2S2O3. unstable. rapid. interferences sensitive. and interferences from all oxidants Very sensitive. phosphate buffer. The collected O 3 converts nitrite (NO 2G) to nitrate (NO 3G) via oxidation as shown by the following chem ical reaction: The resultant NO 3G is analyzed by IC using a UV-VIS detector at a wavelength of 200 nm .S. sensitive Principle Major Advantages Major Disadvantages Simple. The U .415).
03 ppm O 3 for a 90-L air volum e.7 1.4 Methods Perform ance A synopsis of the m ethod perform ance is presented below.4. This corresponds to 0. All three lim its have been used to determ ine Indoor Air Quality (IAQ) in relation to O 3 exposure. Exam ples of soluble substances are potassium or sodium nitrate.22 ppm O 3. such as nitrogen dioxide (NO 2).6 The collection efficiency at 2 tim es the PEL was 100%.25 µg (as NO 3G) when using a 5-m L solution volum e.37 µg/m L or 1. two breakthrough tests were perform ed at concentrations of 0.014 ±10.070 to 0.3.4 1.4. The total pooled coefficient of variation (CV). An air volum e of 90 L and a flow rate of 0.3).4.3. CA).8 1.3. The sensitivity was 3.20 ppm O 3 for 180 m in at 0. bias. and easily autom ated.1 This m ethod was validated over the concentration range of 0. A pretube containing a chrom ate com pound can be used to rem ove any SO 2 and allow O 3 to react with the IGFFs.4.5 to 10.6.5 L/m in is used.045 +0.5 L/m in.3 The m ethod is sim ple.3. Significant levels of soluble nitrate substances should not norm ally be encountered in an occupational setting unless these substances are in use. The qualitative detection lim it was 0. and contains no liquid. Using a sam pling tim e of 240 m in and an average sam ple flow rate of 0. 1.5 1.3.4 1. Another disadvantage of the m ethod is the tedious preparation and storage of the IGFFs (Section 2. when using the instrum ent param eters listed in Section 3. Further inform ation can be found in Section 4. The m ethod is “relatively” specific for O 3 (as NO 3G) in the presence of other nitrogencontaining substances.5 L/m in were used.3% 1. Sam ples can be analyzed using either a UV-VIS or conductivity detector.5 1. CV Bias OE 1. 1.7 × 10 5 area units per 1 µg/m L. The sam pling device is sm all.3. Desorption and preparation of sam ples for analyses involve sim ple procedures and equipm ent.5 L/m in.3 1.224 ppm .7 For TW A m easurem ents.054 -0. no breakthrough was found at a concentration of 0.2 126.96.36.199 µg (as NO 3G) when using a 5-m L solution volum e.0 µg/m L NO 3G).4 ppm O 3. Sam ples were collected from a generated test atm osphere of 0. and the average 4 of 29 T-ID214-FV-01-9503-M .015 ±12.008 ppm O 3 for a 90-L air volum e.4% STEL 0.4.0. One disadvantage is that sulfur dioxide (SO 2) gas and soluble particulate nitrate com pounds interfere when collected on the sam e IGFFs (Section 4.2 1. The m ajority of the validation was perform ed using a UV-VIS detector. The sensitivity of the analytical m ethod. portable. This corresponds to 0. A 50-µL sam ple loop and a detector setting of 2 absorbance units (AU) for full-scale output were used.6 1.1.22 and 0.9).4.3. was calculated from the slope of a linear working range curve (0. 1. Sunnyvale. A Dionex Series 4500i ion chrom atograph with a Linear UVIS-206 UV detector and AI450 com puter software was used (Dionex. and total overall error (OE) for TW A and STEL-type determ inations are shown below: TWA 0. The quantitative detection lim it was 1. rapid.25 µg/m L or 6.
4. Ozone is also used as: an oxidizing agent in several chem ical processes (acids.25 L/m in and a sam pling tim e of 240 m in.5 µg on Day 0 (as total nitrate). Sulfur dioxide in the presence of O 3 will also interfere (negative). steroid horm one form ation. strength.1 Sam pling: Because O 3 is analyzed as nitrate. such as the tube com m only used for converting NO to NO 2 (OSHA Method ID-182 or ID190).5 L/m in. 1. Analytical: Any substance that absorbs UV at 20 nm and has the sam e retention tim e as NO 3G is an interference when using the UV-VIS detector. and ketones from unsaturated fatty acids). and as a bactericide.6.4. changing the analytical conditions (detector settings. 1.breakthrough was 7.6 ppm O 3 after reducing the flow rate to approxim ately 0. Substances that have the sam e retention tim e as NO 3G and are conductive m ay interfere when analyzed by conductivity. If interference from SO 2 is expected.33 ppm O 3 using a sam pling tim e of 15 m in and an average sam ple flow rate of 1. The m ean blank recovery after 30 days storage was 5 µg com pared to 1.6 Industrial Uses and Products of Ozone (Ref.8 Sam ples can be stored at am bient (20 to 25 °C) tem perature for a period of 30 days. These oxidizer tubes m ust be passivated in the ozone atm osphere prior to use.e. chrom atographic colum n. production of peroxides. changing from conductivity to UV-VIS or vice-versa). rem oval of chlorine from nitric acid. etc. industrial waste treatm ent.. 5. A final solution volum e of 5 m L was used. For STEL.9 1. oils. no breakthrough was found at a concentration of 0. eluent flow rate.5. aldehydes. an oxidizer pretube. can be used to effectively rem ove SO 2 and allow O 3 to pass through the IGFFs.2 1. and oxidation of phenols and cyanides. Most interferences m ay be resolved by changing detectors (i. 1.4 ppm O 3. However. bleaching of waxes. particulate nitrate com pounds m ay interfere (positive) in the analysis if collected on the sam e IGFFs.6. wet paper. If the possibility of an interference exists.2 5 of 29 T-ID214-FV-01-9503-M .5% at a concentration of 0. and textile. no breakthrough was found at a concentration of 0.1 Ozone is used m ainly for: purification of drinking water.11) 1.) m ay circum vent the problem . 1.5 Interferences 1. deodorization of air and sewage gases.5. Results show the m ean sam ple recovery after 30 days storage was within ±10% of results at Day 0.
1 Calibrated personal sam pling pum ps capable of sam pling within ±5% of the recom m ended flow rate of 0. However. Chem ical form ula Form ula weight Specific gravity Melting point Boiling point Vapor density (air = 1) Synonym Appearance and odor 10028-15-6 O3 47.1 Equipm ent 2.6 (liquid) @ -183 °C -192 °C -112 °C 1. If particulate nitrate com pounds are present in the air. 1.2 6 of 29 T-ID214-FV-01-9503-M . such as the tube used for converting NO to NO 2. 5.65 Triatom ic oxygen Colorless at concentrations noted in industry. and is highly toxic by inhalation. 5. and allow O 3 to pass through to the IGFFs. 2. Tygon or other flexible tubing for connecting pum ps to sam ples. however. If these com pounds are soluble and present in sufficient quantity.13) Inform ation listed within this section is a synopsis of current knowledge of the physiological effects of O 3 and is not intended to be used as a basis for OSHA policy. for 12 weeks showed significant adverse changes in lung function. W elders exposed to m axim al ozone concentrations of 9 ppm were observed to have pulm onary congestion.5 ppm ozone for 3 hours per day. a pretube. an alternate m ethod em ploying direct-reading instrum ents m ay have to be used. detector tubes (OSHA SLTC Product Evaluation No. Pungent characteristic odor usually associated with electric sparks. contact OSHA-SLTC. 12 for recom m ended tubes) can be used to screen the area or a long-term sam pling m ethod (OSHA SLTC Method ID-200) can be used to determ ine if SO 2 is present prior to O 3 sam pling.1. if interference from SO 2 is expected.12. Recent studies indicate ozone m ay contribute to inflam m ation in hum an bronchial tubes. It is m ore soluble in water than oxygen. the m inim al solubility results in the liberation of significant am ounts of ozone after water is purified with ozone. Hum an volunteers exposed to 0. 2. It is strong oxidizing agent and a dangerous fire and explosion risk when in contact with organic m aterials.11-5.1. can be used to effectively rem ove SO 2. Further inform ation regarding toxic effects of ozone can be found in Ref.7 Physical and Chem ical Properties (Refs. 2.8 Toxicology (Ref. Hum an populations chronically exposed to lower concentrations of ozone were observed to have adverse changes in lung function. CAS No. Sam pling Note: Particulate nitrate com pounds or SO 2.1.5 L/m in are used.997 1. 6 days per week. is a strong irritant. Another report showed a 20 percent reduction in tim ed vital lung capacity in persons exposed to average concentrations of ozone of 1.5 ppm for 2 hours. A study in which young m ice were exposed to 1 ppm ozone for 1 or 2 days reported dam age to alveolar tissue. gas interfere in the analysis of NO 3G if collected on the sam e IGFFs. Ozone is highly injurious and potentially lethal to experim ental anim als at concentrations as low as a few parts per m illion (ppm ).12) Ozone has a pungent odor. If the am ount of SO 2 in the area to be sam pled is unknown. 5.
c) d) e) f) g) 2.These should be at least reagent grade or better to avoid nitrate contam ination: Sodium nitrite (NaNO 2). Make sure the rough sides of two IGFFs are face up. and record the date..e. Various lengths of polyvinyl chloride (PVC) tubing to connect sam pling tubes to pum ps. After preparation. Slowly spike 0.1. MAW P037 AO.1. 97+% Potassium carbonate (KCO 3). (Note: The sides of the IGFF have different textures. im m ediately place two IGFFs into a clean cassette. 400 .and 1 m L of glycerol to 100 m L DI H 2O. A conservative shelf-life of 4 weeks should be observed. MI) Glass beakers. seal with plastic end plugs. Clean approxim ately 100 GFFs thoroughly by carefully placing the filters using forceps into a thoroughly cleaned beaker (1. 0.. They will react with any atm ospheric ozone present. and careful handling of both the chem icals and IGFFs is required to avoid contam ination from soluble nitrate-containing substances. place a shrinkable gel band around each cassette.5% Im pregnated glass fiber filters (IGFFs) are prepared by chem ically treating 37-m m GFFs according to the following procedure: a) b) Prepare an "im pregnating solution" by adding 0. Millipore Corp. 61652.3 Sam pling m edia: Im pregnated glass fiber filters (IGFFs) are used for sam ple collection and are obtained from OSHA-SLTC for OSHA use. Ann Arbor. the IGFFs m ust be stored in clean cassettes and sealed with scaling bands before use.) IGFFs prepared in this fashion are stable for at least 28 days (Section 4. no. Type A/E.3 g NaNO 2. 500/pkg.1. Bedford.5 2. Carefully and slowly rem ove all beakers or Erlenm eyer flasks from the oven and allow to cool to room tem perature. (Note: Do not allow the filters to stand once they have cooled to room tem perature and prior to placem ent in cassettes.28 g K 2CO 3. Set each GFF on the top of a 10-m L beaker or a 25-m L Erlenm eyer flask.500-m L and 10 . MA) Principal chem icals . 0 . i. The filters can also be prepared as explained below: Note: Before im pregnation.10). Filter im pregnation requires the use of very pure chem icals.or 2-L) with approxim ately 400-500 m L DI H 2O. Decant. Decant and rinse by adding another 400 to 500 m L DI H 2O.15-m L (or 25-m L Erlenm eyer flasks) Oven. facing the incom ing sam ple.2. 99. the other is woven and has a waffle-like appearance. Gelm an Sciences.4 m L of im pregnating solution on each GFF m aking sure the entire filter is saturated. Carefully place each beaker or Erlenm eyer flask (on which each IGFF is sitting) into an oven and dry at 100 °C for 30 m in.) Using forceps. 37-m m diam eter (part no. 99% Glycerol.1.4 2. 37-m m (Prod. Oxidizer tube for rem oving SO 2 in the sam pled air 7 of 29 T-ID214-FV-01-9503-M .200 °C Forceps Cassette gel sealing bands Plastic end plugs Two-section polystyrene cassettes.6 A stopwatch and bubble tube or m eter to calibrate pum ps. a) b) c) d) e) f) g) h) Glass fiber filters (GFFs). One side is rough. glass fiber filters (GFFs) m ust be thoroughly cleaned with deionized water (DI H 2O to rem ove any trace am ounts of soluble nitrate com pounds. and then dry the filters in the oven at 100 °C for 60 m in or until com pletely dry.
5 L/m in flow rates.2. and a shelf-life after passivation of one to two years should be observed.5 L/m in and a sam pling tim e of 180 m in. A 0. Oxidizer tubes and any Tygon tubing used in sam pling m ust be conditioned with ozone using the following procedure (Note: The O 3 generation system used to validate this m ethod and condition the oxidizer tubes and Tygon tubing is further discussed in Section 4. Place the sam pling device on the em ployee such that air is sam pled from the breathing zone. Oxidizer tubes can be obtained from SKC Inc. PA as a Special Order item .If there is reason to suspect the sam pled air could contain SO 2. 2) 3) 4) 2.. however. the contents of the tubes m ust be passivated with O 3 prior to use.3 8 of 29 T-ID214-FV-01-9503-M . m aking sure the sam pled air enters the rough side of the IGFF. Eighty Four. The shelf-life of the oxidizer should be 1 to 2 years.2 Use a flow rate of 0.) Set the O 3 concentration for the generation system at approxim ately 0. Connect the other end of the open oxidizer tube to each sam pling pum p using Tygon tubing.1.2.2. Take additional sam ples as necessary. Condition the oxidizer tubes for 4 h.1 ppm . 2. After sam pling. Figure 1. Use an oxidizer tube only if SO 2 is suspected of being present in the sam pled air (Figure 1). Other com parable system s can be used. an oxidizer tube m ust be used to rem ove the SO 2. im m ediately replace both plastic end plugs tightly in the cassette and apply OSHA Form 21 seals in such a way as to secure the end plugs.): 1) Connect one end of each open oxidizer tube to the ozone generation system with short pieces of Tygon tubing. Oxidizer tubes norm ally used to convert nitric oxide to nitrogen dioxide will suffice.25 L/m in flow rate and a sam pling tim e up to 480 m in can also be used. 2.2 Sam pling Procedure 2.9 for further details.2. Set the sam pling pum ps at approxim ately 0. (Note that this tubing will also be passivated and should be used as the oxidizer-cassette connector when taking a sam ple using an oxidizer tube.1 Rem ove both plastic end plugs from the cassette and connect the cassette to the calibrated sam pling pum p. The m anufacturer or the user can passivate the oxidizer tubes prior to use. Stop the sam pling pum ps and cap the tubes using plastic caps or flam e seal. Passivation requires special ozone-generating equipm ent. Ozone sampler with oxidizer tube. See Figure I below and also Section 4.
5-m L sam ple vials/caps (Dionex part no. Cassette opener (SKC E-Z Opener. Observe laboratory safety regulations and practices.3 3. Laboratory autom ation system : Ion chrom atograph interfaced with a data reduction system (AI450.2. Forceps. etc. Handle a blank filter and cassette in exactly the sam e m anner as the sam ple cassettes except that no air is drawn through it. anion (Model HPIC-AS9 and AG9. Send the sam ples and blanks to the laboratory as soon as possible with the OSHA 91A paperwork requesting ozone analysis. Syringe prefilters. 3.1. It is suggested that SOPs be prepared for each type of instrum ent used in a lab to enhance safe and effective operation.2. Separator and guard colum ns.Bedford. Analysis 3. record such inform ation and transm it with the sam ples.3.or anion-free.5 3. Use the sam e lot and preparation date of IGFF/cassettes for blank and collected sam ples.8 3. Many chem icals are hazardous. Reno. CA) equipped with a UV-VIS detector (Linear UVIS-206. UV-VIS detector or spectral array detector m aintenance m anual.6 3. on the OSHA 91A. 3. 2. Sunnyvale.4 3.2. Autom atic sam pler (Dionex Model AS-1) and 0.14). Review any MSDSs provided with reagents and sam ples. SLSR 025 NS. and the Standard Operating Procedure (SOP) for proper instrum ent operation (Ref.1.2 Equipm ent 3. Note: The SOP is a written procedure for a specific instrum ent..9 Note: Som e syringe prefilters are not cation. 0. 225-13-5. SKC) or sim ilar tool such as a coin or a screwdriver.5 2. Linear Instrum ents Corporation. Cat. Prepare at least one blank filter and cassette for each batch of ten sam ples.1 Ion chrom atograph (Model 4000i or 4500i Dionex. W hen other com pounds are known or suspected to be present in the air. 3.2.2. Observe all precautions. and lab coat when handling these chem icals. 38011). MA). Disposable beakers (10 and 50 m L).2. gloves.2.6 3. air volum e.2. Blank reagent solutions should be filtered and analyzed first to determ ine potential contam ination and suitability with the analyte. flow rate.1 Safety Precautions 3.1. No. Use appropriate personal protective equipm ent such as safety glasses. goggles. Millipore Corp. Multiple wavelength detector. Dionex).7 3.2. Dionex). Disposable syringes (1 m L).5-µm pore size (part no.2.2.2 3. NV) or a conductivity detector. 9 of 29 T-ID214-FV-01-9503-M . 5.2.2. face shields.1 Review appropriate IC instrum ent m anuals.4 Record the sam pling conditions such as sam pling tim e.2 3.
Erlenm eyer flasks. ultrasonic bath). 20 m L.1 Prepare NO 3G working standards in eluent. 99% Sodium nitrate (NaNO 3).3.4.3. Scintillation vials.11 3.or Teflon-lined caps.5 1.0 m M Na 2CO 3 + 1. 3. 3.0 8. Treated glass fiber filters (IGFFs from Section 2. Depending on the capabilities of the program .Prepare fresh prior to beginning the analysis.2 aliquot (mL) 5.2. 100. as last resort. independent quality control (QC) program in place and QC sam ples of the analyte should be routinely analyzed along with field sam ples. and 1 µg/m L: Pipette appropriate volum es of the 1.2.336 g NaHCO 3 in 4.0 10.0 5.4.12 3.13 3. pipette an appropriate aliquot (Aliquot) 10 of 29 T-ID214-FV-01-9503-M .2.14 3. Analytical balance (0. Sonicate this solution and degas under vacuum for 15 m in. two different standard stock solutions should always be prepared and these solutions should routinely be com pared to each other. volum etric flasks. from different lots. A suggested schem e for preparing a series of working standards using 10-m L final solution volum es is shown below: working std std solution (µg/mL) (µg/mL) 0.3. or m edia can be spiked with the analyte (NO 3G).0 2.1. graduated cylinders. Prepare m onthly. Note: The laboratory should have an effective.0 10.2 Eluent (1.2.0 5.1 Principal reagents: Sodium carbonate (Na 2CO 3).0 m M NaHCO 3): Dissolve 0. 3. QC sam ples can either be generated using the collection m edia and substance (O 3) under controlled conditions.0 5.0 2.0 188.8.131.52 Reagents . 99% Sodium bicarbonate (NaHCO 3).0 - To prepare each working standard (W orking Std) listed above.9% Deionized water (DI H 2O) 3.0* 1.2.0 * Already prepared in Section 3.3) for spiking or m atrix m atching (if necessary). Prepare every 6 m onths.All chem icals should be at least reagent grade.0 L DI H 2O.424 g Na 2CO 3 and 0.4 Nitrate (N0 3G) standard solutions.0 10.3710 g of NaN0 3 to 1.0 10. with polypropylene. 3.4 W orking Standard Preparation . lf QC sam ples are not routinely prepared and analyzed.0 L with DI H 20. 3.4 3.3. transfer an appropriate am ount of the Std Solution to a disposable beaker.000 µg/m L as NO 3G stock standard into volum etric flasks and dilute to the m ark with eluent. 10.10 Miscellaneous volum etric glassware: Pipettes.0 eluent added (mL) 5. and beakers. Always prepare the stocks from two different sources or. 99.01 m g). 3.000 µg/m L): Dissolve and dilute 1. Equipm ent for eIuent degassing (vacuum pum p.3 Nitrate (NO 3G) stock standard (1.
5. 3. A new colum n could be used or the eluent strength m ay be changed to facilitate separation. pipette each aliquot into a 10-m L volum etric flask and dilute to volum e with eluent. If the sam ple solutions contain particulate.3 As an alternative. Pipette 5. and analyzing this solution prior to analysis. If m atrix-m atching of standards and sam ples is the only alternative. standards should be prepared with treated filters in the sam e fashion as sam ples. Erlenm eyer flask. If a com parison of a spiked sam ple and a nitrate standard indicates poor separation or significantly different NO 3G retention tim es. Add the specified am ount of eluent (Eluent Added). 3.14) with eluent. retention tim es appear very close.4) from the disposable beaker to an appropriate container (scintillation vial.4 Allow the sam ples to sit for at least 15 m in.0 m L of DI H 2O into each vial. 3. Make sure the filter is wetted.of the specified standard solution (prepared in Section 3. and there is adequate separation of nitrite and nitrate.4.3. 5-m L volum es will allow for analysis of ozone (as NO 3G) within the range of the standards specified. The chrom atogram shown below (Com parison of a Standard and a Sam ple) dem onstrates the peaks obtainable from a sam ple and a standard without any m atrix-m atching.1 Carefully open each cassette with a cassette opener (or sim ilar tool. Occasionally swirl each solution.2.5 Sam ple Preparation 3. 3.).5.3 3. rem ove the particles using a prefilter and syringe. 11 of 29 T-ID214-FV-01-9503-M . rem ove each IGFF and transfer each filter using a clean forceps into separate 20-m L scintillation vials.5. such as a coin or a screwdriver). Cap the vials using polyethylene-lined plastic caps.5. etc. 3. This can be assured by desorbing an IGFF (Section 3. m atrix-m atching or a change in analytical conditions should occur. spiking the solution with a known am ount of nitrate working standard.6 Analysis It is im perative that the large nitrite peak (from the sam pling m edia) is adequately separated from the nitrate peak. For m ost industrial hygiene sam ples. Peak characteristics of the nitrate in the standard and sam ple are sim ilar.2 Note: Alternate desorption volum es can be used and are dependent on the analytical sensitivity desired.
eluent strength.14).3.6. 12 of 29 T-ID214-FV-01-9503-M .5. Response to nitrate using either detector is sim ilar and appears to be dependent on colum n conditions. Soluble nitrate com pounds can interfere when using either UV or conductivity detector.3 *For detection using a conductivity detector. and sensitivity settings. Set up the ion chrom atograph in accordance with the SOP (Ref.00 m in for NO 3G ~900 psi 2 m L/m in 1. Place a filtercap into each vial.0 m M NaHCO 3 am bient AG9 AS9 2 absorbance units full scale (AUFS) 5 sec 50 µL 3. 5. The large filter portion of the cap should face the solution.0 m M NaCO 3/1. All other settings are sim ilar.to 0.1 Pipette or pour a 0.2 3.6. output range and rise tim e are not used.6-m L portion of each standard or sam ple into separate autom atic sam pler vials. standards. Typical operating conditions for a Dionex 4000i or 4500i with a UV-VIS detector (Spectral Array detector) and an autom ated sam pler are listed below: Ion chrom atograph with UV detector* at 200 nm wavelength Eluent: Colum n tem perature: Anion precolum n: Anion separator colum n: Output range: Rise tim e: Sam ple injection loop: Pum p Pum p pressure: Flow rate: Chrom atogram Run tim e: Peak retention tim e: 5 m in ~3. Load the autom atic sam pler with labeled sam ples. and blanks.6. A sensitivity setting on the conductivity detector of 0.1 µS is used.
6. 5. and blanks according to SOP (Ref. and retention tim es are instrum ent dependent and were obtained using equipm ent specified in Section 3.4 3.5.7. standards.3 Then calculate the air concentration of O 3 (in ppm ) for each air sam ple: where: Ab As A (µg/m L NO 3G) b (µg/m L NO 3G) s (Sol Vol) b = = = = = = Total µg O 3 in blank Total µg O 3 in sam ple µg O 3 after blank correction Am ount found (from calibration curve) in blank Am ount found (from calibration curve) in sam ple Blank solution volum e (m L) from Section 3.1 After the analysis is com pleted. Obtain hard copies of chrom atogram s from a printer. Peak heights. 3.14). Perform a blank correction for each IGFF.2.2 Prepare a concentration-response curve by plotting the peak areas or peak heights versus the concentration of the NO 3G standards in µg/m L. Determ ine total µg for each sam ple and blank. retrieve the peak areas or heights. peak area. Subtract the total µg blank value from each total µg sam ple value.3.2 (norm ally 5 m L) 13 of 29 T-ID214-FV-01-9503-M .142 µg/mL height 218782 area 2202892 *Relative absorbance units using a UV-VIS detector Note: The nitrate norm ally contained in a blank is only shown for illustration purposes.7.22 component name nitrate concentration 6. 3.7.7 Analyze sam ples. A chrom atogram of a sam ple collected at an ozone concentration of approxim ately 2 tim es the PEL for 180 m in is shown below: ret time 3. Calculations 3.
Report possible breakthrough as a note on the report form . 8. An analysis of 20 spiked sam ples (7 sam ples each at 1 and 2 tim es. 10. In addition. A determ ination of the sam pling m edium collection efficiency at approxim ately 2 tim es the TW A PEL. If a significant am ount of analyte (>25% of first filter) is found on the back-up (second) filter. 7. 130404. and 8 sam ples at 0. A determ ination of potential breakthrough. The passive m onitor (Ogawa & Co. 2. and 6 sam ples at 0.5 tim es the TW A PEL) to evaluate analytical recovery as desorption efficiency (DE).3. 6. USA. Interference study. The m ethod validation was conducted at different concentration levels near the OSHA TW A PEL of 0. a separate experim ent of a passive m onitor for O 3 was conducted early in the .7742 Molar volum e (L/m ol) = 24. Report results to the industrial hygienist as ppm O 3. Type A/E.evaluation. 5. Product no. In addition. two separate cassettes containing one IGFF each per sam ple were used.3 ppm ) were also taken. The 37-m m GFFs were obtained com m ercially from Gelm an Sciences (Lot no. OPS). 9. 61652.(SoI Vol) s CF Mol Vol AV Mol W t 3.5 tim es the TW A PEL) collected from dynam ically generated test atm ospheres at 50% RH to determ ine bias and overall error. 4. Com parison of sam pling m ethods . The sam pling m edium used during the validation consisted of a two-section polystyrene cassette containing two IGFFs. FL) operates on a principle sim ilar to the reaction used for this active sam pler. 3. The second IG FF serves as a backup filter. A determ ination of any significant hum idity effects during sam pling.45 (25 °C and 760 m m Hg) Air volum e (L) Molecular weight for O 3 = 47. Inc.5 L/m in.2 (norm ally 5 m L) Conversion factor = O 3/NO 3G = 0.9 4..3 ppm .5. Ann Arbor. breakthrough m ay have occurred. 180-m in sam ples taken at a flow rate of 0. A determ ination of the qualitative and quantitative detection lim its. treated filter vs. Backup Data This m ethod has been validated for 90-L. 15-m in sam ples were also validated near the OSHA Final Rule STEL of 0.997 (g/m ol) Add the results of the first and second filters to give one final O 3 concentration. 14 of 29 T-ID214-FV-01-9503-M . IGFF vs.. 3.1. During collection efficiency and breakthrough tests.im pinger vs. The IGFFs were prepared as described in Section 2. MI). Sum m ary. The validation consisted of the following experim ents and discussion: 1.8 = = = = = Sam ple solution volum e (m L) from Section 3. Sam ples at a concentration near the STEL (0. A sam pling and analysis of 22 sam ples (7 sam ples each at 1 and 2 tim es. The m onitor was tested to determ ine potential OSHA com pliance use. Pom pano Beach. passive m onitor (AKI vs. 11. An evaluation of storage stability at room (20-25 °C tem peratures for 26 collected sam ples. Shelf-life of the IGFFs.1 ppm O 3.
0.A generation system was assem bled as shown in Figure 2. All sam pling tests were conducted using side-by-side IC and AKI sam ples.or 50-µL syringe (Ham ilton Microliter/Gastight Syringe. Possible outliers were deter-m ined using the Treatm ent of Outliers Test (Ref. The overall error (OE) (Ref. Figure 2 4. 5. 4.1 Procedure: Each IGFF was spiked using a 25. All results were calculated from concentration vs.2) were tested for hom ogeneity of variance.17). 5. To test the relative analytical capability of this m ethod. 5..5. The IGFF sam ples were inside cassettes when spiked with aqueous solutions.1. response curves and statistically exam ined for outliers. 1. Spikes were either 11. and used for all experim ents except the analysis. and detection lim it determ inations.1) and sam pling and analysis results (Section 4. and 2 tim es the TW A PEL for a 15 of 29 T-ID214-FV-01-9503-M . 23. In addition.1 Analytical Recovery Ozone oxidizes sodium nitrite to sodium nitrate on the filter. These levels correspond to approxim ately 0.0 ug NO 3G. 5. NV). Statistical evaluation was conducted according to the Inorganic Methods Evaluation Protocol (Ref. Hom ogeneity of variance was determ ined using Bartlett's test (Ref.2).15).16).5. All sam ples were analyzed by IC using a UVVIS detector. 5. and 46. sodium nitrate was used as the analytical spike. shelf-life study. the analytical recovery (Section 4.17) was calculated using the equation: OE i% = ±(|bias i| + 2CV i) X 100% (at the 95% confidence level) W here i is the respective sam ple pool being exam ined. Ham ilton Co. These sam ples were then analyzed using the conditions recom m ended in their m ethods. Twenty sam ples were prepared by adding known am ounts of NO 3 (as NaNO 3) stock solution to the IGFFs to determ ine desorption efficiencies (DEs) for the analytical portion of the m ethod. All known concentrations of generated test atm ospheres were determ ined using the AKI m ethod for ozone (Ref. Reno.
16 of 29 T-ID214-FV-01-9503-M .2. The dilution airstream was adjusted using the m ass flow controller of the Miller-Nelson system . CA) was used to control and condition the dilution airstream .1 Procedure: 1) Test atm ospheres of O 3 were generated using two ozone generators (Model 565. Pum p flow rates were approxim ately 0. the system was set to generate test atm ospheres at 50% RH and 25 °C.979 0.5 and 1. Caldwell.2 Results: The results are shown in Tables 2a and 2b. 4. IGFF/cassette sam ples were attached to the Teflon sam pling m anifold using Gilian GilAir SC pum ps (Gilian Instrum ent Corp. W . Test atm osphere concentrations were approxim ately 0.5. flow. Dynam ic generation system A Miller-Nelson Research Inc. 2) 4.47 0. A glass m ixing cham ber was used to facilitate blending of ozone with the diluent air. known concentrations of O 3 were generated. and analyzed.Desorption Efficiency (DE) level (G) N mean DE SD CV1 0.977 0.029 0. the average DE is very close to 1. No DE corrections are necessary for O 3 collection using IGFFs. NJ) to draw the O 3 test atm osphere through the IGFF sam ples. MA) sim ultaneously to achieve as high O 3 concentrations as possible.2 Results: Desorption efficiencies are presented in Table 1.045* *CV1 (pooled) 4.055 0.90-L air sam ple at a 0.048 all levels 20 0. and 2 tim es the OSHA TW A PEL and at the OSHA STEL. Therm oElectron Instrum ents. Monterey.5-L/m in flow rate.994 0.0. As shown. The spiked sam ple (Table 1) and test atm osphere sam ple (Table 2a) results each passed the Bartlett's test and were pooled to determ ine a CV T for the TW A sam pling and analytical m ethod. The cassettes were allowed to sit overnight and then analyzed.056 1 ×PEL 7 1.5 L/m in and sam pling tim es were 180 and 15 m in for TW A and STEL experim ents. sam ples were collected.025 0. and hum idity control system (Model HCS-301. All generation system fittings and connections were Teflon. The O 3 gas was diluted with filtered. The O 3 concentrations were varied by adjusting the dilution airstream Volum e. respectively. hum idified air using the system shown in Figure 2 and discussed below.1. tem perature. 4.2.2 Sam pling and Analysis To determ ine the precision and accuracy of the m ethod.5 × PEL 6 0. For this experim ent. 1. 3) 4) The total flow rate of the generation system was m easured using a dry test m eter.028 2 × PEL 7 0.. Hopkinton. Table 1 Ozone (as NO3G) Analysis .
Results: The results in Table 3 show a CE of 100%.3 all levels 22 1.33 ppm) N mean ppm found SD CV recovery 5 0.204 ND 100. % 1 0.) Table 2b Ozone Sampling and Analysis .054 98.203 ND 100.5 8 1.9 1 7 1.014 OET = 10.032 0.3% Collection Efficiency Procedure: Seven IGFF/cassettes were used to collect a concentration of approxim ately 2 tim es the OSHA TW A PEL for 180 m in at 0.5 L/m in (50% RH and 25 °C.0 6 0.Table 2a Ozone sampling and Analysis .** OE2 (pooled) The total pooled coefficients of variation (CV T).16-5.030 12.018 0.5% level(G) STEL 4.022 11.014 0.5 L/m in for 240 17 of 29 T-ID214-FV-01-9503-M .5 L/min for 180 min.206 ND 100.0 Notes: (a) Sampled at 0.211 ND 100.25 °C .028 0.0 5 0.0 4 0. bias.3) was used with two exceptions: In addition to the 2 X concentration.STEL PEL Determination (Known O3 Concentration = 0.071 0.937 0.7** *CV2 (pooled) .5 2 7 0. and sam ples were taken at approxim ately 0.TWA PEL Determinations level (G) N ave recovery SD CV2 OE2 (±%) 0.220 ND 100.0 mL (c) ND = None detectable (< 0.023 0.059 14. No O 3 was found in the second IGFF for the CE experim ent and indicates the IGFFs have adequate collection Of O 3 near the PEL. (b) Samples desorbed using a sample solution volume of 5.325 0.4% (Note: The CVT and OET values include data from Section 4.4 Breakthrough (Note: Breakthrough is defined as > 5% loss of analyte from the first IGFF to a backup IGFF at 50% RH) Procedure: The sam e procedure as the CE experim ent (Section 4. 5. the generation concentration was increased to a level approxim ately 4 tim es the TW A PEL.060 0.0 2 0.008 ppm O3) 4.1 and are calculated using equations specified in Refs. 1st IGFF 2nd IGFF CE. and total overall error (OE T) are as follows: CVT (pooled) = 0.0 7 0. The am ounts of O 3 gas collected on the first and second IGFFs were determ ined.045 bias = + 0.216 ND 100.50% RH ppm O3 sample no.041* 9. Table 3 Collection Efficiency (CE) 2 × PEL .0 3 0.3 OE ±12. The collection efficiency (CE) was calculated by dividing the am ount of O 3 collected in the first filter by the total am ount of O 3 collected in the first and second IGFFs.17.209 ND 100.
227 ND 0 5 0.586 ND 0 4 0. Table 4a Breakthrough Study .238 ND 0 6 0.0.5 L/min 2 × PEL .0 mL. Due to lim itations on the O 3 generators and the generation system .363 ND 0 5 0. For the STEL.008 ppm O3) Table 4b Breakthrough Study .661 ND 0 5 0.0 mL.566 ND 0 6 0.50% RH ppm O3 sample no.563 ND 0 2 0.25 °C .0. no breakthrough was found at approxim ate concentration of 0. 1st IGFF 2nd IGFF CE.25 L/m in. mean = 7.50% RH ppm O3 sample no. the average breakthrough was 7. larger O 3 concentrations could not be achieved. 1st IGFF 2nd IGFF Breakthrough.5.2 ppm O 3 (Table 4a).5 L/m in sam ple collection flow rate. CV = 0.25 L/m in for 240 m in.25 °C .385 ND 0 3 0.3 ppm O 3 (Table 4d) for 15 m in at 1. However. the first IGFF was desorbed using larger sample solution volumes of 10. The am ount of breakthrough for each sam pling cassette was calculated by dividing the am ount collected in the second IGFF by the total am ount of O 3 collected in the first and second IGFFs.0.395 ND 0 4 0. Another test was conducted for 6 tim es the TW A PEL using a sam pling rate of approxim ately 0.215 ND 0 (a) Sampled at . % 1 0.5.281 ND 0 3 0.6 ppm O 3 (Table 4c) when using a lower flow rate of 0. SD = 1.25 L/min 4 × PEL .383 ND 0 6 0.20 Table 4c Breakthrough Study . and indicates the first IGFF has adequate retention of O 3 at 2 tim es TW A PEL.5 L/min for 240 min (b) Due to the larger sampling period and thus larger mass collected.50% RH ppm O3 sample no. (c) ND = None detectable (< 0. no breakthrough of O 3 into the second section was found at an approxim ate concentration of 0.5% at an approxim ate concentration of 0. 1st IGFF 2nd IGFF Breakthrough.425 ND 0 2 0.558 ND 0 (a) Sampled at .190 ND 0 4 0.4 ppm O 3 (Table 4b) for 240 m in at 0.0. Results: For m easurem ents near the TW A PEL.600 ND 0 3 0.0.5 L/min for 240 min (b) Due to the larger sampling period and thus larger mass collected.25 °C .5 L/m in flow rate.N = 8. No break-through was found at the approxim ate concentration of 0. % 1 0. the first IGFF was desorbed using larger sample solution volumes of 15.m in.0.% 1 0. Statistical analysis .342 ND 0 (a) Sampled at .5 L/min 4 × PEL .242 ND 0 2 0.25 L/min for 240 min 18 of 29 T-ID214-FV-01-9503-M Notes: Notes: Notes: .
038 99.334 ND 0 (a) Sampled at .6 6 0. All sam ples were stored under norm al laboratory conditions (20-25 °C) in a plastic bag in a drawer. as shown in Table 5 and Figure 3 below.0 mL.0 mL (c) ND = None detectable (< 0.1. % 1 0.1 ppm was perform ed.8 6 0.306 ND 0 6 0.036 97.308 ND 0 3 0.346 ND 0 5 0.333 ND 0 4 0.008 ppm O3) Table 4d Breakthrough Study .25 °C . 1st IGFF 2nd IGFF Breakthrough. Table 5 Storage Stability .5 L/min 1 × PEL . (c) ND = None detectable (<0.005 0. NO 3G on the IGFFs.50% RH ppm O3 sample no.2 7 0.052 94.015 109.004 0.120 0. followed by six sam ples at 15.5 L/min for 15 min (b) Samples desorbed using a sample solution volume of 5.006 0.1.002 0. A room tem perature storage stability study using 26 sam ples taken near the OSHA TW A PEL of 0.(b) Due to the larger sampling period and thus larger mass collected.116 0. seven m ore sam ples were desorbed and analyzed after 5 days. respectively.3 Notes: 4.032 ppm O3) Storage Stability Procedure: A study was conducted to assess the stability of the NO 2G + O 3 reaction product. Results: The m ean of sam ples analyzed after 30 days was within 10% of the m ean of sam ples analyzed the first day.135 0.440 ND 0 2 0.123 ppm) N Mean O3 SD CV Recovery (%) Found 7 0. and 50% RH) (Known O3 Concentration = 0.122 0. Seven sam ples were initially desorbed and analyzed. the first IGFF was desorbed using larger sample solution volumes of 10.5 Day 1 5 15 30 19 of 29 T-ID214-FV-01-9503-M .Ozone (25 °C. and 30 days.
the calculated F values are m uch sm aller than critical F values (Ref.2. 5. As shown.5. 20 of 29 T-ID214-FV-01-9503-M .6 Hum idity Study Procedure: A study was conducted to determ ine any effect on recovery results when sam ples are collected at different hum idities. An F test was used to determ ine if any significant effect occurred when sam pling at different RHs. Test atm ospheres were generated at 25 C and at approxim ately 0.Figure 3 4. 1. 50%.16) for all the concentrations tested. and 80% were used at each concentration level tested. and 2 tim es the OSHA TW A PEL. no significant difference in results occurred across the RH ranges tested. Relative hum idities of 30%. Results: Results of the hum idity tests are listed in Table 6. at the 99% confidence level. therefore. Sam ples were taken using the generation system and procedure described in Section 4.
55* 4. % 30 50 80 30 50 80 30 50 80 N 7 8 7 6 7 7 7 7 7 1 × PEL 2 × PEL Table 6 Humidity Test . Procedure: Low concentration sam ples were prepared by spiking aqueous standards prepared from NaNO 3 (Section 3.98 2.5 Fcrit 5.98 4 2.09 5.058 0.1 µg/mL 0.007 0. respectively.Level 0.027 0. Table 7 Qualitative and Quantitative Detection Limits (NIOSH Method) O3 (as NO3G) Level Blank 0.059 0.68 4.073 0.224 0.03 2. The qualitative detection lim it is 0.37 µg/m L as NO 3G at the 99.008 ppm and 0.69 3. Sam ples were analyzed using a 50-µL sam ple injection loop and a UV-VIS detector setting of 2 AUFS.237 Recovery.Integrated Peak Area (NO3G)/100.070 0.005 0.024 0.12 5.101 0.79 3.006 0.81 * Outlier PA .5 × PEL RH.99 3 2.60 3.02 6.02 2.93 Fcalc 0.098 0.004 0. 5.15 4.62 6.000 The average responses of the low-level calibration sam ples were plotted to obtain the linear regression equation (Y = m X + b). and the predicted responses (ì i) at each X.003 0.059 0. PA PA PA PA PA 1 2.072 0. Using the equations: 21 of 29 T-ID214-FV-01-9503-M .5 µg/mL 1.73 2.028 0.25 3.006 0.231 0.02 1.070 0.030 0.15 3.3.022 0.21 4.001 0.8% confidence level.74* 2.60 3.03 ppm . the qualitative and quantitative detection lim its are 0.19) was used to calculate detection lim its.81* 3.1 97. Using a 90-L air volum e and a 5-m L sam ple solution volum e.71 4.11 2.76 5 2.222 0.17 5.15 4.119 0.05 2.0 µg/mL Sample No. respectively.18-5. Results: The IGFF spiked sam ple results are shown in Table 7 for qualitative and quantitative detection lim its.172 0.2 µg/mL 0.7 Qualitative and Quantitative Detection Lim it Study A m odification of the National Institute for Occupational Safety and Health (NIOSH) detection lim it calculations (Refs.022 0.008 0.4) at five different concentrations on the IGFFs.060 0.24 5. % 104 103 103 103 107 103 101 99.81 6 1.115 0.110 0.25 ug/m L as NO 3G.002 0.174 0. as O 3. The quantitative detection lim it is 1.Ozone 25 °C Mean O3 SD CV Taken Found 0.87 2 1.01 2.118 0.107 0.23 4.
the AKI sam ples.006 0. developed by the Harvard School of Public Health (HSPH).036 IGFF 0.073 4 0. The Ogawa passive sam pler (OPS).8 Com parison of Sam pling Methods This m ethod was com pared with the classical AKI approach and a passive m onitor m ethod.008 0. Table 8 Comparison of Methods (Summary) (25 °C and 50% RH) Set # Method O3 Found. 4.017 0.20) 22 of 29 T-ID214-FV-01-9503-M . the sam pling rate was exam ined. The IGFF/cassettes and OPSs were analyzed by IC. 5. sam pling rates are critical to the perform ance of the passive m onitor during this com parison.21667 num ber of data points qualitative detection lim it quantitative detection lim it The Correlation Coefficient (r) and Coefficient of Determ ination (r2) for the above data were r = 0. Results: Table 8 shows the results of the com parison study.110 3 0. the IGFF/cassettes (this study). and OPSs were collected side by side from the generation system at approxim ately 0.004 0.018 IGFF 0. the IGFF/cassettes. The average sam pling rate as determ ined by SLTC for the face velocity achieved. The reaction principle and analysis are sim ilar to this IGFF m ethod. Q1 = (3S y)/m = 0.027 ppm O 3 (90-L air volum e) where: B b m SY N Q1 Q2 = = = = = = = m ean blank response intercept of the regression analytical sensitivity or slope as calculated by linear regression standard error of the regression = 0.008 ppm O 3 (90-L air volum e) Q2 = (3. 5. 972.072 8 0. ppm N SD CV 1 AKI 0.986 and r 2 = 0.025 OPS 0.33)Q1 Y 0. the im pregnating solution is slightly different (and proprietary for the passive system ). however.Therefore. and the sam ples are analyzed by IC for nitrate ion using conductivity detection instead of UV-VIS Prior to using the OPS m ethod for this com parison.2) IGFF Impregnated glass fiber filter (this study) OPS Ogawa passive sample for ozone (Refs.224 3 0.086 IGFF 0.070 3 0.210 7 0. AKI sam ples. and OPSs are in good agreem ent except that OPSs are slightly higher for 1 tim es and lower for 2 tim es PEL.2. Due to face velocity dependence.056 OPS 0. The determ ination of sam pling rate is detailed in the Appendix.93 cm 3/m in.187 7 0. 1 and 2 tim es the PEL.129 7 0.003 0.029 OPS 0. was originally designed to sam ple for nitrogen oxides in the environm ent.064 where: AKI Alkaline potassium iodide (Ref. 5.118 7 0.85 µg as NO 3G (5-m L sam ple volum e) Y 0. As shown.10 and 5. The AKI sam ples were analyzed by a colorim etric procedure further described in Ref.006 0.002 0.012 0. was used for OPSs.5.003 0.041 2 AKI 0. Modifications allowed its use to m onitor am bient environm ental ozone. 21.37 µg/m L as NO 3G Y 1. Procedure: In order to com pare perform ance.132 3 AKI 0.
The generation system concentration was approxim ately 1. 1) 2) 3) 4) 5) 6) 7) 8) 9) Description O 3 with and without NO 2 O 3 with and without SO 2 (3.35 ppm ) O 3 + SO 2 with and without OS oxidizer O 3 + SO 2 with OS oxidizer before and after conditioning O 3 + SO 2 with and without MS oxidizer O 3 + SO 2 with MS oxidizer before and after conditioning Com parison study between 50% and 80% RH for O 3 +SO 2 with MS oxidizer after conditioning. All sam ples were taken at a flow rate of about 0. These tests included two different SO 2 concentrations and use of oxidizer tubes for rem oval of SO 2 from the sam pled air prior to O 3 reaction with the treated filters. PA) and are used to convert nitric oxide (NO) to nitrogen dioxide (NO 2) during sam pling for NO. Using the m anufacturer's stated detection lim it of 200 ppb-h as analyzed using IC and a conductivity detector (the m anufacturer's recom m ended analytical technique).9 Interference Study As previously discussed in Section 1. Chrom ate im pregnated sorbent has been shown to effectively rem ove SO 2 during ozone sam pling (Ref.4). present.1 to 0. In a recent paper (Ref. Results: Table 9 shows the results of the IGFF/cassette sam ple sets: Sam ple Set No.2. Several tests were conducted to evaluate any possible interference from NO 2 or SO 2. The two types of oxidizer tubes are: Tube Label Oxidizer Special Misc-Spec Substrate Chromate impregnated sand Chromate impregnated material (Composition of substrate unknown) Abbrev.41 ppm ) O 3 with and without SO 2 (1. Several tests were conducted to evaluate any SO 2 interference by com paring results of six sam ples with SO 2 to another four to six sam ples without SO 2. 5.5 L/m in for 180 m in.10). for STEL or interm ittent sam pling the m onitor still appears not sufficiently sensitive). detection lim it calculations indicate potential problem s m ay be incurred for OSHA com pliance use. (Eighty Four.9).to 8-h sam pling and would not be ' conducive to STEL or interm ittent sam pling occasionally required in m onitoring situations. 5.1-5. an 8-h detection lim it of 0. OS MS Both tube labels are designations given by SKC..2 ppm O 3) are present or 7. A test was conducted by taking four sam ples at approxim ately 6 ppm NO 2 and com pared to four sam ples without NO 2 which served as "control" sam ples. the authors indicated that SO 2 should not interfere with the passive sam pler collection of O 3. Procedure: Possible interferences from NO 2 and SO 2 were tested using several sets of IGFF/cassette sam ples.to 8-h sam pling is perform ed.025 ppm would be obtained (using a UV-VIS detector SLTC indicates a quantitative detection lim it of about 0.1 ppm -h.06 ppm ) O 3 with and without SO 2 (0. 23 of 29 T-ID214-FV-01-9503-M .NOTE: Although the passive m onitor perform ed reasonably well during the com parison. The monitor was originally designed for environm ental (24-h) use. The m onitor appears beneficial in industrial hygiene situations provided large concentrations ( > 0. Both were m anufactured by SKC Inc. 4.21). oxidizing gases have interfered with the determ ination of O 3 in previous m ethods (Refs.5 tim es the TW A PEL for ozone. experim ents to verify this were not presented in the paper. Two different kinds of oxidizer tubes were evaluated. The study to determ ine applicability was halted after prelim inary determ inations indicated the passive m onitor also suffered from the sam e negative interference from SO 2 as the active sam pler (Section 4. 5. This would necessitate 7. 5. however. however.
35 NA NA 6 0. the passive m onitor. 0 NA NA 4 0.Note: Oxidizer tube conditioning is based on the procedure discussed in Section 2.008 CV% 5. # Concn. appears to display the sam e SO 2 interference as the active sam pler.1 3.1 0.169 No NA 6 ND 4 SO2.001 0.009 0.1 ppm O 3 As shown in Sam ple Set #1.007 0. 1. ppm 0.003 0.Ozone (25 °C .005 0. #3 and #4. Side-by-side active and passive sam ples were taken while varying the am ount of SO 2.013 0. 1.6 3.5 tim es TW A PEL ozone. 0 5 SO2. 24 of 29 T-ID214-FV-01-9503-M .141 NA NA 6 0. 0 NA NA 4 0. 0. Both passive and active sam ples were prepared using the procedure stated in this m ethod for IGFFs. 0 6 SO2. the procedure. 1. 0. 6.8 (a) NA = Not applicable (b) ND = None detectable (< 0.141 vs. Sam ple Set #9 shows no significant difference in O 3 recovery when SO 2 is present at 50% and 80% RH.153 ppm when conditioned).169 SO2 .5 7. regardless of treatm ent in-house or from Ogawa. 6.38 No NA 4 0.013 0.7 6.5 20. they were still low and it is recom m ended to passivate either type of oxidizer tube.06 Yes Yes 6 0.009 0.5 ×PEL) Sample Set Interferant Oxidizer Conditioning N Mean O3 .5 L/m in (d) Sam ple Solution Volum e for Desorption = 5.06 Yes Yes 6 0.8 6. Although.06 Yes NA 6 0. Sam ple Sets #6 and #8 show the difference in recovery when using conditioned and unconditioned oxidizer tubes. 1. ppm (Yes or No) (Yes or No) # ppm 1 NO2.108 SO2.129 NO2 . 1.008 ppm 0 3) (c) Flow Rate = 0. An additional test was conducted to determ ine if the passive m onitor would be adversely affected by SO 2 in a sim ilar fashion as the active sam pler.50% RH and 1. 1.1 5. 1.141 7 SO2. the recoveries im proved for the MS oxidizer without conditioning (0.009 0.06 Yes No 6 0. 1. As shown in Table 10. 1.009 0. and am ount of chem icals used in their treatm ent preparation is unknown.06 Yes NA 6 0. Detection lim its are sim ilar to what is stated earlier for both active and passive sam plers. 0 NA NA 6 0.06 Yes No 6 0. a negative interference equal to 100% of an equim olar concentration of ozone is noted as shown in Sam ple Sets #2.005 0. 3.153 SO2. type.8 7.014 0.06* Yes Yes 5 0.3 6. (Section 2. 0 NA NA 6 0.141 SO2.3 3.9 9.38 ppm NO 2 caused no interference when sam pling at 1.134 2 SO2.06 Yes Yes 6 0.142 SO2 .145 * 80% RH was used instead of 50% Notes: SD O3. the oxidizer gave results about 23% lower when it was not conditioned (0.108 vs. 5. As shown.1) Additional passive sam plers were also purchased from Ogawa. 0.41 No NA 6 ND SO2 .005 0.012 0.153 9 SO2. W hen SO 2 is present along with ozone.154 8 SO2. Sam ple Sets #5 and #7 show no interference occurs when using the oxidizer tubes.153 SO2 . Table 9 Interference Study .168 3 SO2.0 10.06 No NA 6 ND SO2 .141 ppm O 3 when conditioned).0 m L (e) All oxidizers were conditioned for 4 h at a concentration of approxim ately 0.
89 6 ND Note: N = number of samples taken. The m ean peak area of the IGFFs analyzed after 22 days was only a 9% increase over the Day 0 value and alm ost a 50%increase after a 45-day storage. Set 2) Set 3) Set 4) Results: Results are listed in Table 11 and further discussed below: Set 1) The conversion of nitrite to nitrate does not significantly occur under the storage conditions specified above for a period of approxim ately 20-30 days. the extent of nitrite conversion to nitrate on stored filters was used to indicate stability and was m easured over a period of up to 58 days.164 0. The m anufacturer indicates an 8-week life-span can be used if necessary and appropriate blank corrections are perform ed. the rem aining four IGFFs were desorbed and analyzed after a 45-day storage. Sets 1 and 2 used identical Ogawa sample holders. desorbed with DI H 2O and analyzed for total nitrite using peak area.130 0. this set was used to assess ability to collect sam ples after storage.1 Sample Set #2 represents passive samplers purchased from Ogawa.15 ppm O 3) after 58 days of storage. Sample Set #1 represents passive samplers prepared using 13-mm glass fiber filters prepared as stated in Section 2.007 0.132 0. After 45 days.3 to determ ine the potential shelf-life of the nitrite-im pregnated filters. Procedure: Four tests were conducted to assess IGFF shelf life: Set 1) The first test was perform ed using 15 IGFFs which were stored in a clean and sealed plastic bag after preparation.1 1 Passive 1. SO2 Mean O3. however.0 2 Passive 1. Set # Passive Concn (ppm) # ppm ppm % 1 Active 0 4 0.5 2 Active 1. Set 2) 25 of 29 T-ID214-FV-01-9503-M . The passive m onitors use a reaction principle sim ilar to the active sam pling filters in this m ethod. Previous reports indicate the Ogawa passive m onitors have a conservative shelf-life due to aging of four weeks. Passive Sampler .006 3. SD O3 .012 9.89 3 ND 1 Passive 0 6 0. This set of four filters was prepared sim ilar to the third set. finally. A third test was perform ed using 11 IGFFs which were placed in cassettes. Five IGFFs were initially taken and served as “control” IGFFs. A second test was conducted with ten m ore filters. The m ean of the IGFFs analyzed after 28 days was only a 2% increase over the value of Day 6.89 6 ND 2 Active 0 2 0. and four filters analyzed after 28 days.SO2 Interference Sample Active or N CV Interferant.167 0. 4.5 1 Active 1. conversion appears evident. and stored in a clean and sealed plastic bag after preparation.89 3 ND 2 Passive 0 6 0. The cassettes were then sealed with gel bands and plastic plugs. or eventual conversion to nitrate appears to be facilitated by oxygen and sm all am ounts of ozone in the atm osphere. six were analyzed after 6 days.017 10. The aging. then six IGFFs were desorbed and analyzed after 22 days.Table 10 Active vs.1. For this active sam pling m ethod.10 Shelf Life of the IGFFs Thirty-nine IGFFs were prepared according to the procedure described in Section 2. Three of the IGFF/cassettes were used to collect O 3 vapor (0.
CV % 1. could be collected on the IGFFs during sam pling.20 0.93 0. For O 3 concentrations above 0. it appears that 7.24).45 1. For sam ples taken in the SO 2/O 3 atm osphere without oxidizer tubes.7 3.200 4 2.25 L/m in were not perform ed due to lim itations in the test atm osphere generation system .5 L/m in for 240 m in. Detection lim its (as NO 3G) are adequate when sam ples are taken for 180 m in at 0.5%. which could oxidize nitrite to nitrate.11 Sum m ary Day i 0 22 45 6 28 0 57 Peak area. The m echanism of the SO 2/O 3 interference which dim inishes the O 3 conversion of nitrite to nitrate is unknown.22) that the chem istry of SO 2 in am bient air and on surfaces is com plex.00 1. Breakthrough is not evident at lower concentrations.6 ppm using a sam ple collection rate of 0. The conversion of nitrite on the IGFFs appears lim ited up to 28 days after im pregnating if the 2 treated filters are stored in a clean. Presum ably the SO 2 can react with any ozone or oxygen in the presence of nitrite (and possibly glass fiber filters) to form sulfite and eventually sulfate.23). Other environm ental pollutants which could potentially adversely affect this ozone sam pling m ethod have been considered in the literature. Mean O 3 found was 0. The perform ance during collection efficiency.Set 3) The m ean of the IGFFs analyzed after 57 days was a 23% increase over the value of Day 0. however.025 6 2. IGFFs were placed and stored in cassettes. such as peroxyacetyl nitrate (PAN). The SO 2 interference appears to be a sam pling phenom ena occurring at the surface of the IGFFs and is not dependent on analysis. The ability of glass fiber filters to capture and convert SO 2. a flow rate of 0.71 0. storage stability. was previously noted in OSHA Method ID-200 for sulfur dioxide.7 22. sealed plastic bag.100 6 2. Ratio of IGFFs (mean peak area of Day 1 compared to that of mean Day 0). For exam ple.4 ppm O 3 at 0. 5. Table 11 Shelf-Life Test of IGFF N Mean* SD # ×105 ×105 5 2.5 L/m in. After blank correction and 58-day storage. 26 of 29 T-ID214-FV-01-9503-M . For the breakthrough study.17). and hum idity tests is adequate.25 L/m in can be used.4 ppm . However.180 Set 4) Sample Set # 1 2 3** * Xi/Xo ** 4.091 6 4. Experim ents above approxim ately 0. 5.080 4 2. 5. Fortunately.2 Ratio Xi/X0 1. due prim arily to their slightly basic nature.02 0. if present.5 8.5% breakthrough occurs onto a second IGFF at a concentration of 0.02 1.740 5 5.4 ppm . under typical am bient conditions this positive interference probably represents less than 5% of the nitrate form ed during the nitrite/ozone reaction (Ref. 5. a corresponding loss of O 3 was not noted. the m ean recovery of the O 3 collected was 95.00 1. and 4.3 3.8 15. Although the second filter effectively captures the analyte at 0. the second IGFF should always be analyzed to assure capture of all analyte. nitric acid vapor. Further study m ay be needed to determ ine other oxidized or reduced com pounds which may coexist with O 3 and cause either positive or negative interferences. an oxidizer tube appears to com pletely rem ove SO 2 from the sam pled stream .143 ppm after blank IGFF correction.0% CV. a strong oxidant.33 0.00 1. Using the AED-030 (sem iconductor sensor) direct-reading instrum ent side-by-side with the IGFFs while sam pling an SO 2/O 3 atm osphere.23 The validation results indicate the m ethod m eets both the OSHA criteria for accuracy and precision (Ref. Since am bient concentrations of PAN are typically 10-20 tim es sm aller than ozone concentrations. No significant increase in the sulfate content over background am ounts was noted in the chrom atogram s of IGFF sam ples taken after using oxidizer tubes to sam ple an SO 2/O 3 atm osphere.6 3. a significant increase in sulfate content was noted from the resultant oxidation of SO 2.30 1. It has been reported in the literature (Ref. significant interference in m ost locations is not expected (Ref.37 0.09 1. precautions should be taken at higher concentrations. scaled with scaling bands and plastic plugs.
Governm ent Printing Office. J. 1989.9 5. Koutrakis. R. I 11th ed.G.2 5. J. pp. G. H. M. National Institute for Occupational Safety and Health: Docum entation of the NIOSH Validation Tests by D. Prior to com pletion of the m ethod another chem ist was given approxim ately 25 field sam ples to analyze and indicate any problem s that m ay occur during routine analysis. Industrial Health 22: 117-126 (1984). 1987.E. C.: Ozone Portable Analyzer. and E. Environm ental Protection Agency: Evaluation of I Percent Neutral Buffered Potassium Iodide Procedure for Calibration of Ozone Monitors by M.6 5.13 27 of 29 T-ID214-FV-01-9503-M . P. 1988.D. Assoc. New York: Van Nostrand Reinhold Co. Volum e 11.C. Technical Document. 1992. Precautions should be taken to assure adequate separation prior to sam ple analysis regardless of which detector is used.: Ozone Hunter. D. Hirano and J.10 5. J. UT: Occupational Safety and Health Adm inistration Salt Lake Technical Center.S. 53: 672 (1992). Hawley. P.3 5. Am Ind. Sam ple concentrations covered a wide range and were analyzed both by UV and conductivity detection.5 5. N. Beard. Environm ental Monitoring Series. A conductivity detector was used to assess potential interference byproducts such as sulfite/sulfate concentrations.: U. Salt Lake City.: Personal Dosim eter for Ozone using the Ozonolysis of Trans-stilbene. Froehlich.S. Kupel and ". 2519-2520. Anal. Taylor.C. NIOSH Analytical Methods for Standard Com pletion Program (Method No..8 5. "Ozone" Federal Register 54:12 (19 Jan. Hyg. A. UT: Occupational Safety and Health Adm inistration Salt Lake Technical Center. 1977. S8 .O zone). Occupational Safety and Health Adm inistration Salt Lake Technical Center: Ozone (Stilbene) in W orkplace Atmospheres (USDOL/OSHA-SLCAL Method No. 411-439. Bunyaviroch.7 5. Sm ith: Instability of Ozone Sam ples Collected in Alkaline Potassium Iodide Solution. 1990 unpublished. Hekm at. 77-185). More crucial to analysis is the ability to separate the nitrite and nitrate peaks using appropriate colum ns.: Private Notes. Fung. Margeson. Bryant (DHEW -NIOSH publication No. Technical Document. Ku. Analytical Instrum ental Developm ent Inc.12 5. AET . In USA Inc. Sawatari. Section H. In 1988 Annual Book of ASTM Standards. 5. ID-209).. PA: ASTM.. Avondale.This m ethod was validated using a UV-VIS detector.. Either detector should have adequate sensitivity and capability. pp. 65: 209-214(1993). W olfson. ID-150). Model 560. K. S. 1980.C.M. A difference in ozone results was not noted between the two detectors. E. and R.030. Newtonville. W ashington. References 5. Occupational Safety and Health Adm inistration Salt Lake Technical Center: Ozone (KIBRT) in W orkplace Atmospheres (USDOL/OSHA-SLCAL Method No. Philadelphia. Chem. PA: Analytical Instrum ental Developm ent Inc.4 5. J. The IC conductivity detector has been used for nitrate determ ination since its inception over 15 years ago. K. MA: In USA Inc..1 U.03. Am erican Society for Testing and Materials (ASTM): Standard Practice for Safety and Health Requirements Relating to Occupational Exposure to Ozone (E591-80). 1984. 1977. 1989).11 5. Ellis (EPA600/4-77-005). Salt Lake City. The UV detection technique m ay be less prone to interferences because of the greater selectivity (wavelength specificity) for each analyte. Mulik: Measurem ent of Am bient Ozone Using a Nitrite-Coated Filter. Research Triangle Park.: The Condensed Chemical Dictionary. 5..
1 cm 3/m in is for higher face velocities. and J. 1977. NY: John W iley and Sons. This exposure cham ber was in series with a Teflon sam pling m anifold where the active sam plers were collected. Finlayson-Pitts. Generation of Aerosols and Facilities for Exposure Experiments edited by K. pp. Ann Arbor. Pitts: Atmospheric Chemistry. National Institute for Occupational Safety and Health: Standard Operating Procedures for Industrial Hygiene Sampling and Chemical Analysis. In Proceedings of the 82nd Annual Meetingof the Air and W aste Managem ent Association. Chang. 282-285. Kupel. IGFFs.: Accuracy and Precision. OH: National Institute for Occupational Safety and Health.14 Occupational Safety and Health Adm inistration Salt Lake Technical Center: Ion Chrom atography Standard Operating Procedure (Ion Chrom atographic Com m ittee)..A. New York. W ashington. Inc.21 5.: General Procedures for Lim it of Detection Calculations in the Industrial Hygiene Chem istry Laboratory.021 ft 2). 1980. Evaluation and Interpretation of Analytical Results. In OSHA Analytical Methods Manual. 1. 1991. Appendix Sam pling Rate . and AKI sam ples were collected side-by-side from the generation system at approxim ately 0. 2nd ed. Mueller: Paper No.3 ft/m in.18 5. The face velocity (air m ovem ent in front of the passive m onitor) was 8.. 77-185).. Bryant (DHEW /NIOSH Pub.: The Ogawa Passive Sampler for Ozone Operation Manual. National Institute for Occupational Safety and Health: Documentation of the NIOSH Validation Tests by D.: Sulfur Com pounds ' in Am bient Environm ents and Their Sim ulation in the Laboratory. Burkart. Elving. O H: National Institute for Occupational Safety and Health. 1993. J. NY: John W iley &Sons.17 5. B. FL: Ogawa & Co. pp.W illeke. Salt Lake City.19 5.63 cm 2 or 0. the m ass collected by the passive sam pler when exposed to various concentrations of ozone was m easured.. Cincinnati. and J.. Cincinnati. The m anufacturer's stated rate of 18. Ogawa & Co. pp.16 5. Kolthoff and P. Koutrakis.Ogawa Passive Sam plers for Ozone 5. USA. Pom pano Beach. Procedure: A "known" concentration was determ ined from the IGFF m ethod and confirm ed by the AKI m ethod. Inc. 2nd ed.5. UT: Occupational Safety and Health Adm inistration Salt Lake Technical Center. Taylor.C. 1977. J. P. The sam pling rate m ust be determ ined if this face velocity is used in m ethod com parisons. Occupational Safety and Health Adm inistration Salt Lake Technical Center: Evaluation Guidelines of the Inorganic Methods Branch.N. Inc. 1978. 1992. and the open end of the buret was sealed with a cork stopper. 1. Com m ittee on Medical and Biologic Effects of Environm ental Pollutants: Ozone and Other Photochemical Oxidants. New York. Cincinnati.. 264. edited by 1. M. The OPSs.23 5. Revised Sept. Ind.20 5. MI: Ann Arbor Science Publishers.4. Norm al face velocities in general industry typically range from 25 to 100 28 of 29 T-ID214-FV-01-9503-M . D. SOP 018. The low face velocity was necessary due to dependence on the generation system design and concentrations generated. R. Mandel. To verify the passive m onitor sam pling rate. Vol. The sam pling sim plicity of the m onitor is very attractive to com pliance officers. J. p. The passive m onitors were placed in a 1-L buret (area section = 19. D. OH: Am erican Conference of Governm ental Industrial Hygienists. 1: 153-155 (1986). The Treatm ent of Outliers.. 89-71.22 5. I18. Hyg.15 5. National Academ y of Sciences. 1986. P. in progress. and the possibility of offering both active and passive sam plers for O 3 was explored. and 2 tim es PEL. In Treatise On Analytical Chemistry. Appl.Y. 1989.5. p. USA. 302-304.P..24 The OSHA-SLTC was interested in exam ining perform ance of the passive m onitor for potential OSHA com pliance use. No. 1-12.
93 ± 2.5 m L and GF = Gravim etric factor = 48/62 = 0.52 1.072 1. 5. m L X GF O 3 found (ug) = ug/m L. 5. the average sam pling rate is 21. Results: The Table below shows the calculated sam pling rates at the different O 3 concentrations. NO 3 × sam pling volum e.ft/m in. The sam pling tim e was 480 m in.8. As shown.7742 are used 24.95 4.8 Average Sampling Rate = 21.507 4 22.10).1 2 × PEL 0.864 7 19.10). Sam pling for the passive m onitors was conducted according to the OPS instruction m anual (Ref. 24.93 ± 2. 18.06 3. The sam pling rate was calculated based on diffusion theory.3 1 × PEL 0.3 ft/min Face Velocity* and 480-min Sampling Time) Mean SD CV Level O3 Concn Mean O3 Mass N ppm Found.28 cm 3/m in.021 ft2) and test atmosphere flow rate of 5 L/min through the chamber. ** Values calculated based on the following equation: where: O 3 found (ug) = ug/m L.28 cm3/min * Calculated from 1-L buret used as an exposure chamber (area section = 19. Sampling Rate Validation for Ogawa Ozone Passive Samplers (25 °C .210 3.22 0.g.46 = Molar volum e at 25 °C and 760 m m Hg 47. NO 3 × 1.1 ± 1.39 14.50% RH .5 × PEL 0.9355*** ***If sam pling volum e = 2.118 2.997 = Molecular weight of ozone 29 of 29 T-ID214-FV-01-9503-M .9 cm 3/m in reported by HSPH (Ref..5 cm 3/m in and the observed value. cm3/min 0. Ref.676 7 24. µg # Sampling cm3/min % Rate**.33 6. Note that this rate lies between the theoretically predicted rate.63 cm2 or 0. A m ore detailed description about diffusion theory (Fick's First Law of Diffusion) and specific application can be found elsewhere (e. 5.20).
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