Effects of Relative Humidity on Impregnated Filters Used in Measurement of Airborne Sulfur Dioxide.

Impregnated filters treated with alkali and humectant were first used as collection media to assess occupational exposure to sulfur dioxide (SO2), as outlined in the National Institute for Occupational Safety and Health Method 6004 in 1979. Since then, updated treatment protocols have been proposed with decreased amounts of alkali and glycerol, which claim the same filtering capacity. However, there has been no report on how the collection of SO2 on such impregnated media is influenced by relative humidity (RH). This study investigated the role of glycerol (G) amount on impregnated filters (G2 and G10, referring to 2 and 10% glycerol, respectively) in the collection of SO2 (100 l of 10 ppm at 1 l per minute) under low, medium, and high RHs. The testing results show that RH significantly impacted G2 filters with respect to breakthrough time, capacity, and recovery. At low RH, the 5% breakthrough time was less than 10 min and its recovery was merely 42%; at medium and high RHs, although the recovery was satisfactory, the 5% breakthrough time was still less than 100 min. By contrast, G10 filters illustrated nearly 100% recovery and evaluation by analysis of variance showed no significant effect of RH on recovery. In summary, the current treatment protocol of 2% glycerol leads to a significant underestimation of the exposure to SO2 in a low-RH environment; increasing the glycerol content can be an effective alternative to compensating for the effect of RH.

Development of a thoracic personal sampler system for co-sampling of sulfuric acid mist and sulfur dioxide gas.

A novel personal sampler was designed to measure inorganic acid mists and gases for determining human exposure levels to these acids in workplaces. This sampler consists of (1) a parallel impactor for classifying aerosol by size following the ISO/CEN/ACGIH defined human thoracic fraction, (2) a cellulose filter to collect the residual acid mist but allowing penetration of sulfur dioxide gas, and (3) an accordion-shaped porous membrane denuder (aPMD) for adsorbing the penetrating sulfur dioxide gas. Acid-resistant PTFE was chosen as the housing material to minimize sampling interference. To test the performance of the parallel impactor, monodisperse aerosol was created by a vibrating orifice aerosol generator. The results showed that the penetration curve of the impactor run at 2 LPM flow rate agreed well with the defined thoracic fraction. Almost all sampling biases were within 10% for particle size distributions with MMAD between 1-25 µm and GSD between 1.75-4, which meets the criteria of the EN 13205 standard. To evaluate the performance of the aPMDs, sulfur dioxide gas was sourced directly from a cylinder. The aPMDs maintained a gas collection efficiency greater than 95% for 4 hr when sampling 8.6 ppm of sulfur dioxide gas. While the aPMD had similar performance to the commonly adopted annular or honeycomb denuders made of glass, this shatterproof aPMD is only half of the volume and 1/25th the weight of the honeycomb denuder. Testing of the entire sampler with a mixture of sulfuric acid mist and sulfur dioxide gas showed the system could sample both with negligible interference. All the test results illustrate that the new sampler, which is flat, lightweight, and portable, is suitable for personal use and is capable of a more accurate assessment of human exposure to inorganic acid mist and SO2 gas.

Minimization of artifacts in sulfuric acid mist measurement using NIOSH Method 7903.

NIOSH Method 7903 employs a silica gel tube for sulfuric acid mist measurement in workplaces. However, SO2 gas present in the sample volume can be transformed into sulfate in the sampling process causing an artifact that is reported as sulfuric acid. A sampling train incorporating a honeycomb denuder system was applied for field sampling at seven phosphate fertilizer plants to evaluate its use for reducing the artifact sulfate concentration while preserving the actual sulfuric acid mist concentration. The denuder system was designed to remove SO2 gas before the air entered the silica gel tube and to monitor SO2 concentration at the same time. A deactivation model was also applied to correct for the presence of the artifact. The denuder system had 95.7 +/- 6.8% collection efficiency for SO2 gas, and the impact of sulfate aerosol on SO2 collection was negligible. SO2 concentrations at the seven plants ranged from 34 ppb to 5.6 ppm. The honeycomb denuder system and the deactivation model were shown to reduce the artifact sulfate concentration by 70% and 39%, respectively. However, they were still higher than the sulfate aerosol concentration measured by a cascade impactor. One possible reason is the residual sulfate in the glass fiber filter and the silica gel.

Positive artifact sulfate formation from SO2 adsorption in the silica gel sampler used in NIOSH Method 7903.

NIOSH Method 7903, which uses one section of glass fiber filter and two sections of silica gel, has been developed to determine the total concentrations of acid mists in workplace air, although certain gases are suspected to cause interference. In this study, experiments were performed to investigate the roles of sulfur(IV) oxidation and sulfur dioxide (SO2) adsorption in causing artifacts in sulfuric acid measurement. First, sulfur(IV) oxidation, under four combinations of water bath temperature and Na2CO3 solution concentration, was examined to investigate the effect of the extraction process of NIOSH Method 7903. It was shown that sulfur(IV) oxidation to form sulfate could reach 100% within just 2-3 min, following the extraction process of NIOSH Method 7903. The results demonstrate that, using the procedure, SO2 adsorbed by the silica gel and the glass fiber filter easily yields artifact sulfate. Sulfur dioxide adsorption under various flow rates, SO2 concentrations, and sampling times was also investigated. The experimental data were fitted to a deactivation model to determine the adsorption rate constant and the deactivation rate constant. The model can serve as a tool for estimating the artifact sulfate if the SO2 concentration is available.

TENORM aerosols in the Florida phosphate industry--assessment of lung fluid solubility and annual effective dose to workers.

Inhalation exposure to workers in the Florida phosphate industry due to TENORM aerosols has not been adequately addressed owing to lack of aerosol information. One of the more critical factors is the absorption rate of inhaled radionuclides into blood. In this study, this parameter was characterised using an in vitro dissolution test. The solubility data and other aerosol information were then used for individualised dose assessments at six different Florida phosphate facilities. The solubility data support the selections of ICRP Publication 66 Type M for uranium and lead isotopes and Type S for thorium isotopes. Total annual effective doses are 0.34 +/- 0.12 mSv at granulator areas, 0.30 +/- 0.10 mSv at storage areas and 0.23 +/- 0.02 mSv at shipping areas. These findings are considerably lower than originally postulated in previous studies where no site-specific information on particle size and lung fluid solubility had been available.

Chemical characteristics of aerosol mists in phosphate fertilizer manufacturing facilities.

Of the carcinogens listed by the National Toxicology Program (NTP), strong inorganic mists containing sulfuric acid were identified as a known human carcinogen. In this study, aerosol sampling was conducted at 24 locations in eight Florida phosphoric acid and concentrated fertilizer manufacturing plants and two locations as background in Winter Haven and Gainesville, Florida, using dichotomous samplers. The locations were selected where sulfuric acid mist may potentially exist, including sulfuric acid pump tank areas, belt or rotating table phosphoric acid filter floors, sulfuric acid truck loading/unloading stations, phosphoric acid production reactors (attack tanks), and a concentrated fertilizer granulator during scrubbing with a weak sulfuric acid mixture. An ion chromatography system was used to analyze sulfate and other water soluble ion species. In general, sulfate, fluoride, ammonium, and phosphate were the major species in the fertilizer facilities. For the rotating table/belt phosphoric acid filter floor, phosphate and fluoride were the dominant species for PM10, and the maximum concentrations were 170 and 106 microg/m3, respectively. For the attack tank, fluoride was the dominant species for PM10, and the maximum concentration was 462 microg/m3. At the sulfuric acid pump tank, sulfate was the dominant species, and the maximum PM10 sulfate concentration was 181 microg/m3. The concentration of PM10 sulfate including ammonium sulfate, calcium sulfate, and sulfuric acid were lower than 0.2 mg/m3 at all locations. The aerosols at the filter floor and the attack tank were acidic. The coarse mode aerosol at the sulfuric acid pump tank (an outdoor location) was acidic, whereas the fine mode aerosol was neutral to basic.

Size-resolved sulfuric acid mist concentrations at phosphate fertilizer manufacturing facilities in Florida.

Strong inorganic acid mists containing sulfuric acid were identified as a 'known human carcinogen' in a National Toxicology Program (NTP) report where phosphate fertilizer manufacture was listed as one of many occupational exposures to strong acids. To properly assess the occupational exposure to sulfuric acid mists in modern facilities, approved National Institute for Occupational Safety and Health (NIOSH) Method 7903 and a cascade impactor were used for measuring the total sulfuric acid mist concentration and size-resolved sulfuric acid mist concentration, respectively. Sampling was conducted at eight phosphate fertilizer plants and two background sites in Florida and there were 24 sampling sites in these plants. Samples were analyzed by ion chromatography (IC) to quantify the water-soluble ion species. The highest sulfuric acid concentrations by the cascade impactor were obtained at the sulfuric acid pump tank area. When high aerosol mass concentrations (100 micro g m(-3)) were observed at this area, the sulfuric acid mists were in the coarse mode. The geometric mean sulfuric acid concentrations (+/-geometric standard deviation) of PM(23) (aerodynamic cut size smaller than 23 micro m), PM(10) and PM(2.5) from the cascade impactor were 41.7 (+/-5.5), 37.9 (+/-5.8) and 22.1 (+/-4.5) micro g m(-3), respectively. The geometric mean (+/-geometric standard deviation) for total sulfuric acid concentration from the NIOSH method samples was 143 (+/-5.08) micro g m(-3). Sulfuric acid mist concentrations varied significantly among the plants and even at the same location. The measurements by the NIOSH method were 1.5-229 times higher than those by the cascade impactor. Moreover, using the NIOSH method, the sulfuric acid concentrations measured at the lower flow rate (0.30 Lpm) were higher than those at the higher flow rate (0.45 Lpm). One possible reason for the significant differences between the results from the cascade impactor and the NIOSH method is the potential artifact resulting from the interaction of SO(2) with silica gel and glass fiber used in the NIOSH method.

Effective dose scaling factors for use with uranium series cascade impactor data: a reassessment using the IMBA code.

Air sampling with a multi-stage cascade impactor enables one to assess airborne radioactivity as a function of particle size, significantly enhancing the accuracy of the dose assessment. The application of cascade sampling data to inhalation dose assessments can require more computational effort if something other than a mono-sized distribution per impactor stage is to be considered. To overcome this limitation, Kim et al. (Health Phys 89:359-374; 2005) introduced the concept of an effective dose scaling factor SF(E) enabling one to consider more realistic impactor stage radioactivity distributions (uniform, linearly decreasing, or linearly increasing variations with particle size). The SF(E) is the ratio of the effective dose given under a uniform or linearly changing radioactivity distribution across the particle size interval to that given for a mono-sized radioactivity distribution for the same impactor stage. The latter approach can initially be used (which requires less computational effort) followed by a rescaling of the effective dose either upward or downward by the SF(E) value. In this earlier study, the LUDEP code was employed which utilizes the ICRP 66 human respiratory tract model along the radionuclide biokinetic models given in ICRP Publication 30. In the present study, inhalation dose coefficients and effective dose scaling factors were reexamined for several radionuclides of the (238)U series using the IMBA program, which employs more recent and physiologically realistic biokinetic models published by the ICRP. An update of the effective dose scaling factors is thus the primary focus of this study rather than an extensive inter-comparison of the IMBA and LUDEP codes. Inhalation dose coefficients calculated by the two programs differ by up to a factor of 5 for Type F (238)U and (234)U, but are within only 2% of each other for Type S radionuclides. The ICRP 69 biokinetic model of uranium predicts retention in bone and kidneys that is slightly higher than predicted in ICRP Publication 30, but is significantly higher in the liver and other soft tissues by up to 1 or 2 orders of magnitude. Nevertheless, effective dose scaling factors generated using the IMBA program are nearly identical to those calculated by the LUDEP program as their magnitude is primarily dictated by the dependence of particle deposition and lung clearance with particle size, and less by the systemic biodistribution of the radionuclide following absorption to blood. For both codes, greater than 10% re-scaling of the effective dose is required for third-stage (4.5 to 12 microm) and filter-stage (0.03 to 0.35 microm) particles in the approximation of uniform or linearly decreasing radioactivity distributions per particle stage. For linearly increasing distributions, greater than 10% corrections in the effective dose are found irregularly across impactor stage, radionuclide, and solubility class, especially for rather steep (1:5) impactor stage activity ratios.

Influence of particle size distribution on inhalation doses to workers in the Florida phosphate industry.

Previous studies have indicated that inhalation exposures to TENORM aerosols are potentially a major contributor to the annual total effective dose to workers in the Florida phosphate industry. Further research was deemed necessary to characterize the particle size distribution of these aerosols containing various radionuclides of the U decay series. In the present study, individualized assessments of worker committed effective doses are reported in which detailed information is used on the particle size distribution, particle density, particle shape, and radioactivity concentrations from sampled aerosols at 6 different phosphate facilities and at various worker areas within these facilities. Inhalation dose assessments are calculated using the ICRP 66 human respiratory tract model as implemented within the LUDEP and IMBA computer codes. Under the least conservative assumptions of radionuclide-specific lung solubility, the annual total effective doses are shown to be 0.31+/-0.12, 0.27+/-0.07, and 0.22+/-0.02 mSv at granulator, storage, and shipping areas, respectively, and thus all annual doses are below the annual limits to the members of the general public (1 mSv y). In contrast, the most conservative assumptions of lung solubility by radionuclide yield annual total effective doses of 2.24+/-2.53 mSv at granulator areas, 1.26+/-1.19 mSv at storage areas, and 0.56+/-0.36 mSv at shipping areas. In this later case, some 44%, 31%, and 15% of individual dose assessments yield worker doses above the annual dose limit. The study thus demonstrates the importance of facility- and area-specific particle solubility data in dose assessments for regulatory compliance and for making decisions regarding worker respiratory protection.

Effective dose scaling factors for use with cascade impactor sampling data in tenorm inhalation exposures.

When assessing the effective dose to workers following radio-aerosol inhalation exposures, significant reductions in dose uncertainty can be achieved through direct measurement of the particle-size distribution. The University of Washington Mark III cascade impactor is one such air sampling device that permits the user to determine aerosol mass and radioactivity concentrations as a function of particle size within eight different size intervals (each corresponding to a different impactor stage or end filter). Traditionally, dose assessments made using the LUDEP code or other internal dosimetry software utilize this air sampling information by assigning the radioactivity measured at each stage as concentrated at a single representative size central to the size interval. In this study, we explore more realistic assumptions that the measured radioactivity distributes uniformly, linearly increases, or linearly decreases across the particle size interval for each impactor stage. The concept of an effective dose scaling factor, SF(E), is thus introduced whereby (1) the former approach can be used (which requires less computational effort using the LUDEP code), and (2) the resulting values of effective dose per stage can then be rescaled to values appropriate to a linear radioactivity distribution per stage. For a majority of (238)U-series radionuclides, particle size ranges, and absorption classes, differences in these two approaches are less than 10%, and thus no corrections in effective dose per particle stage are needed. Significant corrections, however, were noted in select cases. For uniform or linearly decreasing radioactivity distributions, end-filter particles (0.03 to 0.35 microm) of type F, M, or S radionuclides were assigned values of SF(E) ranging from 1.15 to 1.44, while 3(rd) stage particles (4.5 to 12 microm) of type M and S radionuclides were assigned values of SF(E) ranging from 1.11 to 1.53. When the cascade impactor measurements indicate a linear increase of activity across a given impactor-stage size range, values of SF(E) range from a high of 1.11 (6(th) stage particles of type F radionuclides) to lows of 0.85 to 0.91 (4(th) stage and end-filter particles of type M and S radionuclides). In these cases, the inhalation dose coefficient varies non-linearly across the particle size range, and the assumption of a mono-size distribution per impactor stage either underestimates (SF(E) > 1) or overestimates (SF(E) < 1) that stage's contribution to the worker effective dose.