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A Method for Determining Crystalline Silica in Bulk Samples by Fourier Transform Infrared Spectroph
Life Sciences & Medicine T he Annals of Occupational Hygiene Volume 46, Issue 7 Pp. 609-615.

Annals of Occupational Hygiene

annhyg.oxfordjournals.org Ann Occup Hyg (2002) 46 (7): 609-615. doi: 10.1093/annhyg/mef077

A Method for Determining Crystalline Silica in Bulk Samples by Fourier Transform Infrared Spectrophotometry
DA VE K. VERMA *, DIA NE M. JO HNSO N an d KA REN DES TO MBE + Author Affiliations

Abstract
A method for determining crystalline silica (-quartz) in bulk samples has been developed. This procedure requires the bulk sample to be homogenized and sieved down to particle sizes <10 m in diameter. The obtained fraction is analysed by Fourier transform infrared spectrophotometry. Method validation was carried out using 55 real-world bulk samples, containing between 1 and 75% (w/w) -quartz. The method is capable of quantifying -quartz down to 1% (w/w) in routine analysis. However, the method is unlikely to allow routine quantification at 0.1% (w/w) as currently mandated by regulations.
Key words
Keywords: bulk silica; crystalline silica; Fourier transform infrared spectrophotometry; particle size; silica analysis

Received 1 March 2002; in final form 27 June 2002

INTRODUCTION
Occupational exposure to crystalline silica occurs in the mining, manufacturing and construction industries. It is well known that prolonged inhalation of dust containing crystalline silica can cause silicosis, a fibrotic lung disease [American Conference of Governmental Industrial Hygienists (ACGIH, 2000)]. Recently, the International Agency for Research on Cancer (IARC) revised its classification of crystalline silica to a Group I human carcinogen, indicating that there was sufficient evidence of carcinogenicity in humans (IARC, 1997). The ACGIH has also classified crystalline silica as a category A2 carcinogen, i.e. a suspected human carcinogen (ACGIH, 2000). The recognition of crystalline silica as a potential carcinogen led the US Occupational Health and Safety Administration (OSHA), under the Hazardous Communication Standard, to require any product containing 0.1% crystalline silica (by weight) or more to be labelled as a potential carcinogen (Federal Register, 1998). This also implied that methods should exist for determining crystalline silica in bulk samples, ideally capable of detecting 0.1% (w/w) using routine analytical methods. Historically, until 1970 analysis of bulk samples for crystalline silica was an integral part of the hazard assessment. Prior to the introduction of measurement methods for respirable dust and respirable crystalline silica, the dust hazard was assessed in North America using the impinger method with reference to the threshold limit value (TLV) given in millions of particles per cubic foot of air (m.p.p.c.f.). This required collection of a large amount of airborne dust using a high volume air sampling pump. Alternatively, a bulk sample or some settled material could be collected and analysed colourimetrically (Talvitie, 1964). The observed percentage by weight of crystalline silica in the bulk sample was used to calculate the applicable TLV. Prior to 1970, the TLV was defined as 250/(% SiO2 + 5) m.p.p.c.f. In 1970, the gravimetric respirable dust standard still required percentage crystalline silica in the sample for use in the denominator of the TLV formulae, which for respirable dust was 10 mg/m3/(% repirable quartz + 2) and for total dust was 30 mg/m3/(% quartz + 3). With the adoption of the gravimetric dust standards and respirable crystalline silica sampling methodology, bulk sample analysis was no longer required for assessing the airborne crystalline silica

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A Method for Determining Crystalline Silica in Bulk Samples by Fourier Transform Infrared Spectroph

hazard since methods employing X-ray diffraction (XRD), infrared (IR) and ultravioletvisible spectrophotometry (UV-VIS) allow crystalline silica to be measured directly on sampled filter media. Analysis of bulk samples is still important in the USA for the labelling of products containing silica which, if 0.1% by weight, must be designated as a potential carcinogen (Federal Register, 1998). This analysis is also important in the preparation of material safety data sheets (MSDS), which list the chemical ingredients of a product. MSDS for products containing crystalline silica are required in many countries, including the USA, Canada, the UK and Europe. In Canada this requirement is part of the Workplace Hazardous Material Information System (WHMIS) (Evans, 1994). A MSDS similar to that required under the US OSHA programme has to be supplied for any product containing crystalline silica, giving an estimated percentage of crystalline silica. There are numerous papers describing the various aspects of crystalline silica analysis. Readers can obtain a very comprehensive synopsis from three key review papers: Andersen (1975), Madsen et al. (1995) and Miles (1999). Collectively, they provide reviews with extensive references of the studies of crystalline silica analysis from the past to the present. A recent paper (Verma and Shaw, 2001) raises an important issue regarding the use of an appropriate calibration standard. Analysis of crystalline silica in airborne dust samples collected on filters using a size selective sampler (i.e. a 10 mm nylon cyclone) is simple to perform routinely by instrumental methods such as XRD [National Institute for Occupational Safety and Health (NIOSH, 1994a)], IR (Dodgson and Whittaker, 1973; NIOSH, 1994b) and the colorimetric method employing UV-VIS (NIOSH, 1994c). However, the development of a detailed protocol for analysing bulk samples has not been reported. In this paper, we describe an analytical approach for measuring the crystalline silica content of bulk samples. The method consists of sample preparation, by grinding and sieving, with subsequent analysis of the finer fraction by Fourier transform infrared spectrophotometry (FT-IR). The objectives of this paper are to: 1. describe the method and its applicability to bulk sample analyses; 2. show the degree of difference observed for different fractions; 3. determine the useful range of the method; 4. comment on the ability of the method to measure 0.1% crystalline silica or less by weight in typical bulk samples.

MATERIALS AND METHODS

The method requires all bulk samples, whether a piece of rock, coarse material or powder, to be ground and sieved. The smallest size achieved by a mechanical sieve is a 38 m fraction. This fraction is then hand sieved through a 10 m nickel mesh sieve, where the <10 m particles in the sample are washed through the sieve using ethyl alcohol. This <10 m fraction is then analysed for crystalline silica (-quartz) by NIOSH method 7602 using a Nicolet model 510P FT-IR instrument (Nicolet Instrument Corp., Madison, WI). The US National Bureau of Standards Standard Reference Material, NBS-SRM 1878 (-quartz), now referred to as National Institute of Standards and Technology NIST-SRM 1878, was used to prepare the crystalline silica calibration standard. The time and cost involved in sieving poses the question: is there a significant difference in quantification of the ground bulk material, the sieved <38 m or the sieved <10 m particle size fractions? In this investigation, 55 bulk samples were analysed as two size fractions, <38 and <10 m. Thirteen of the bulk samples were also evaluated as ground unsieved fractions. Thus, a total of 123 samples were assessed. The 55 samples were real-world bulk samples that had been submitted to our laboratory for determination of crystalline silica over a period of time. The bulk samples were ground using a Spex Mixer/Mill for 20 min (Spex Industry, Metuchen, NJ) in order to achieve an appropriate particle size distribution for sieving. Each ground sample was sieved through a 38 m mechanical sieve to produce the <38 m fraction. A portion of each <38 m fraction was gradually wet sieved with 95% ethanol through a 10 m hand sieve, producing the <10 m portion. Incremental sieving of each sample was done to prevent clogging of the very fine openings of the sieve. Approximately 1 mg of dust, weighed on a Cahn 25 Electro balance, and 250 mg of dried KBr, weighed on a Mettler H54AR semi-microbalance, were transferred to a stainless steel vial and mixed using a Vibromill (model 196610; Beckman Coulter, Fullerton, CA) for 40 s. The mixture was transferred at 10000 kg pressure for 2 min using a Beckman press. This produced an IR-transparent KBr disc for analysis. The disc was scanned by a FT-IR spectrophotometer (model 510P). Each disc was scanned

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A Method for Determining Crystalline Silica in Bulk Samples by Fourier Transform Infrared Spectroph

three times, being rotated 120 between scans. The scans were quantified for crystalline silica (-quartz) by the Nicolet computer software, using the peak height absorbance for the spectral peak at 798 cm 1 and the previously prepared NBS/NIST-SRM 1878 (-quartz)-based calibration curve. The average weight of crystalline silica from the three scans was calculated and adjusted for pellet weight loss. The percentage of crystalline silica of each fraction was calculated using the average weight of crystalline silica present and the weight of bulk used.

RESULTS
Sample spectra of the three fractions from a typical bulk sample are presented in Fig. 1. The peak of interest is the -quartz doublet at 798 cm 1. Figure 2 is a plot of the relationship of the <38 m fraction to the <10 m fraction originating from the same sample. Figure 3 is a plot of the relationship of ground unsieved fraction to the <10 m fraction. Fig. 1. Comparison of FT-IR response to -quartz in the three different bulk sample fractions. (a) <10 m diameter fraction; (b) <38 m diameter fraction; (c) ground unsieved fraction. Note that the quartz peak is located at 798 1 cm .
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Fig. 2. Relationship of the <38 m diameter fraction to the <10 m diameter fraction originating from the same sample.

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Fig. 3. Relationship of the ground unsieved fraction to the <10 m diameter fraction originating from the same sample.

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DISCUSSION
The difference in peak heights of the 798 cm 1 peak with respect to the three fractions, as depicted in Fig. 1, is very apparent. The ground unsieved fraction peak absorbance is significantly smaller than that of either the <10 m or <38 m fractions. Furthermore, the <38 m fraction peak is slightly smaller than that of the <10 m fraction. The question arises: is the difference in absorbance sufficient to warrant hand sieving the bulk samples? All analytical methods for crystalline silica analysis (XRD, IR and UV-VIS) are particle size dependent, as summarized in a recent paper (Verma and Shaw, 2001). For example, it is well known that as particle size increases, the response of XRD increases while the response of IR decreases. Ideally, the particle size

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A Method for Determining Crystalline Silica in Bulk Samples by Fourier Transform Infrared Spectroph

distribution of the calibration standard would closely match that of the samples being analysed; however, it is rarely possible to match these size fractions in practice. The calibration standard used (NBS/NIST-SRM 1878) closely reflects the respirable dust criteria and the finer fraction (<10 m) (Verma and Shaw, 2001). From a health perspective, this fraction is also the most important. Since an internationally recognized certified standard is currently only available for respirable quartz, crystalline silica in the fine fraction (<10 m) was considered to be the most appropriate for quantification. The plot of Fig. 2 shows that by relying on the analysis of the <38 m fraction for determining the percentage of crystalline silica, the value reported would be underestimated by 15%. For example, a bulk sample containing 10% crystalline silica would be reported as 8.5% crystalline silica from an analysis of the <38 m fraction. Figure 3 illustrates the relationship between the <10 m fraction and the ground unsieved sample, illustrating that analysis without sieving would be inappropriate. If these experiments were repeated using XRD techniques employing the same NBS/NIST-SRM 1878 calibration standard, the <38 m fraction would indicate a higher percentage of crystalline silica than the <10 m fraction because of particle size effects. Thus, we recommend analysis of the <10 m fraction by XRD. It is possible to eliminate steps 3 and 4, as shown in Fig. 4a, and analyse a <10 m fraction obtained from the homogenized sample of step 2 (Fig. 4b). Fig. 4. Flow diagram of the crystalline silica analysis. (a) Investigation method; (b) recommended method.

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Miles (1999) summarized the quantitative analyses of quartz by IR methods. He quoted Johnson, who reviewed various IR methods and considered the FT-IR analysis of KBr pellet techniques to be the most promising for bulk material. Johnson found numerous studies of quartz in respirable dust, but no published IR studies of crystalline silica in bulk material. The investigation described in this paper offers information currently lacking in the literature. The method assumes that the crystalline silica in the finer fraction (<10 m) obtained from grinding, homogenizing and sieving is a reasonably true representation of crystalline silica in the original bulk sample. However, due to the relative hardness of some matrices, for example sandstone (harder) and clay (softer), the sieved <10 m fraction may contain a larger percentage of the softer component, and hence result in an underestimate of crystalline silica content in a given sample. This scenario may also be a function of grinding time, i.e. harder materials must be ground longer to achieve the optimum particle size for analysis. The analysis of the <10 m fraction, in the absence of any other published procedure, would appear to be the most appropriate. This fraction matches the calibration standard and is the most relevant from the health hazard point of view. It should be apparent that measuring crystalline silica in bulk material is not directly comparable to the crystalline silica inhalation hazard. Inhalation risk is dependent upon the amount of crystalline silica in the airborne respirable dust, as measured by devices such as the 10 mm nylon cyclone sampler. The crystalline silica in bulk samples provides an indirect estimate of the potential respirable hazard. The hazard would vary depending upon how the bulk samples are used in workplaces. For example, refractory bricks containing a very high percentage of silica will present a negligible inhalation crystalline silica hazard if used only in that form and not subjected to any further treatment such as crushing or grinding. A river sand, comprised predominately of coarse silica, will present less of a respirable dust hazard risk than silica flour, primarily a very fine powder, which would pose a vastly enhanced risk. Although the three above-mentioned products may give a similarly high percentage of crystalline silica in the bulk sample, they pose different crystalline silica inhalation hazard risks. The method described here is capable of measuring crystalline silica down to 1%

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by weight in the bulk sample. Although this would be sufficient for most situations, the requirement in the USA of reporting crystalline silica down to 0.1% does present a significant problem. The bulk samples analysed in this study ranged between 1 and 75% crystalline silica. It is felt that this method is not capable of detecting crystalline silica below 1% with a reasonable degree of accuracy and precision. Johnson (quoted by Miles, 1999) considered the IR method to be very sensitive to small quantities of crystalline silica; however, he stated that matrix effects limit the practical threshold quantification to 1%, a conclusion with which we concur. This is especially true for routine sample analysis. It may be possible to lower the quantification limit of 1% by precleaning the sample with procedures such as acid treatment, but this is not feasible for all routine samples. According to Miles (1999), the X-ray diffraction method can detect quartz and cristobalite in bulk samples at levels approaching 0.1%. Whether this can be done for routine sample analysis is not known. An additional investigation was carried out to see if cristobalite could be detected by FT-IR in bulk samples. In this case, a cristobalite standard obtained from NIOSH was used as the calibration standard. It is generally accepted that polymorphs, such as cristobalite and tridymite, are more accurately measured by XRD than IR (Miles, 1999). We found that cristobalite, by our method, could only be detected at levels at or above 4% in the bulk sample.

CONCLUSIONS
A systematic method of measuring crystalline silica (-quartz) in bulk samples has been described. It involves homogenizing the bulk sample, sieving it to a <10 m fraction, then analysing it by FT-IR. The method is capable of measuring crystalline silica down to 1% in routine bulk sample materials. Using this method, the percentage of crystalline silica (by weight) would be 15% less for the analysis of the <38 m diameter than for the <10 m fraction. Ground homogenized, but unsieved, samples show 42% less crystalline silica (by weight) than the <10 m diameter fractions and a great deal of variability. Thus analysing ground unsieved material is not recommended. The limit of quantification of 1% by weight for this method can be reduced, with care, by pretreating the bulk sample, but detection of 0.1% by weight is not possible. AcknowledgementsWe thank Don Shaw and Paul Verma for their help in the preparation of this manuscript.

Footnotes
* Author to whom correspondence should be addressed. Tel: +1-905525-9140; fax: +1-905-528-8860; e-mail: vermadk@mcmaster.ca

References
ACGIH. (2000) Silica, crystalline-quartz. In Documentation of TLVs and BEIs, 6th edn and supplements. Cincinnati, OH: American Conference of Governmental Industrial Hygienists. Andersen PL. (1975) Free silica analysis of environmental samplesa critical review. Am Ind Hyg Assoc J ; 36: 76778. Dodgson J, Whittaker W. (1973) The determination of quartz in respirable dust sample by infrared spectrophotometry1. The potassium bromide disc method. Ann Occup Hyg; 16: 37387. Evans HL. (1994) Implementation of a workers right to know programme. Ann Occup Hyg; 38: 8993. Federal Register. (1998) US Code of Federal Regulations 29CFR-1910.1200. Hazard communication. Washington, DC: Federal Register National Archives and Records Administration. IARC. (1997) IARC monographs on the evaluation of the carcinogenic risk of chemicals to humans, Vol. 68, Silica, some silicates, coal dust and para aramide fibrils. Lyon: International Agency for Research on Cancer. Madsen FA, Rose MC, Cee R. (1995) Review of quartz analytical methodologies: present and future needs. Appl Occup Environ Hyg; 10: 9911002.
CrossRef

Miles JM. (1999) Review papers on analytical methods. Issues and controversy: the measurement of crystalline silica. Am Ind Hyg Assoc J ; 60: 396402. NIOSH . (1994a) Method 7500. Silica, crystalline, by XRD. In Eller PM, editor. NIOSH manual of analytical methods, 4th edn. DHHS (NIOSH) publication no. 94-113. Cincinnati, OH: National Institute for Occupational Safety and Health. NIOSH. (1994b) Method 7602. Silica, crystalline, by IR. In Eller PM, editor. NIOSH

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manual of analytical methods, 4th edn. DHHS (NIOSH) publication no. 94-113. Cincinnati, OH: National Institute for Occupational Safety and Health. NIOSH. (1994c) Method 7601. Silica, crystalline, by VIS. In Eller PM, editor. NIOSH manual of analytical methods, 4th edn. DHHS (NIOSH) publication no. 94-113. Cincinnati, OH: National Institute for Occupational Safety and Health. Talvitie NA. (1964) Determination of free silica: gravimetric and spectrophotometric procedure applicable to air-borne and settled dust. Am Ind Hyg Assoc J ; 25: 16978. Verma DK, Shaw DS. (2001) A comparison of international silica (-quartz) calibration standards by Fourier transform-infrared spectrophotometry. Ann Occup Hyg; 45: 42935.

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