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Resource Utilization and Hazardous Waste Management, Athens, Greece

Crystalline silica dust determination in limestone aggregate quarries in

Greece

M. Galetakis, G. Alevizos and I. Aspirtakis

Department of Mineral Resources Engineering, Technical University of Crete, Hania, Greece

ABSTRACT mostly of quartz, where as the quartz content of

crushed stone will vary from region to region
The aim of this study was to determine the per-
(USBM, 1992; Watts and Parker, 1995).
sonal exposure to respirable dust and free crys-
Crystalline silica dust has been recognized as
talline silica in an aggregate quarry. Personal
an occupational health hazard to the respiratory
and stationary samples were obtained and ana-
system since chronic overexposure to respirable
lyzed by X-ray diffraction (XRD). Dust surveys
silica dust (particle diameter < 10 microns)
were also conducted by on-line dust analyzers to
leads to the progressive lung disease known as
investigate the main dust sources. Results indi-
silicosis (IARC, 1997; American Thoracic Soci-
cated that the exposure levels for respirable
ety, 1997).
crystalline silica are below the permissible lim-
In surface mining this silica dust is created
its. However the estimated limits for the sever-
from several sources and activities such as drill-
ity showed that the monitoring of the dust must
ing or crushing of rock material. In the quarry-
be continued and possible actions to reduce the
ing sector and particularly in crushed limestone
occupational risk must be examined.
aggregates quarries, crystalline silica is found in
small quantities as an inherent constituent of the
1. INTRODUCTION limestone deposit.
Occupational Safety and Health Administra-
The generic term silica refers to the chemical tion (OSHA) has an established Permissible Ex-
compound silicon dioxide (SiO2), which occurs posure Limit (PEL), which is the maximum
naturally in crystalline and amorphous states. amount of crystalline silica to which employees
Crystalline silica exists in seven different forms may be exposed during an 8-hour work shift.
four of which are extremely rare. The three ma- Dusts containing more than 1% of crystalline
jor forms, quartz, cristobalite, and tridymite, are silica are considered fibrogenic and PEL is es-
stable at different temperatures. In nature, quartz timated as below:
in its alpha, or low form, is a very common
mineral. It is a major component of rocks, and ⎧ 10
mineral ores and is the second most common ⎪⎪ q + 2 if q > 1%
mineral in the earth’s crust, next to feldspar. PEL ( mg / m ) = ⎨
3 (1)
Because of its abundance in the earth, silica, in ⎪
both its crystalline and non-crystalline states, is ⎩⎪ 5 if q ≤ 1%
present in nearly all mining operations. It is in Where q is % wt of crystalline silica in the
the host rock, in the ore being mined, as well as respirable dust and PEL is expressed as a con-
in the overburden. Most ores are mined from centration of respirable dust in milligrams per
deposits containing crystalline silica. The min- cubic meter. For inert dusts, containing less than
eralogy of the deposit and, to some extent, the 1% of crystalline silica, PEL is 5 mg/m3. In the
processing of the ore determines the quartz con- Greek Regulations for Mining and Quarrying
tent of the final product. Sand and gravel consist (GRMQ, 1985) the above limits have been
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Resource Utilization and Hazardous Waste Management, Athens, Greece

adopted for respirable dusts containing free diffractometry, indicated that it is consisting
crystalline silica. Monitoring the respirable mainly of calcite (85-99%), dolomite (0.5-8%)
quarry dust exposure for compliance with regu- and other minor minerals such as quartz (0.2-
lations is mandatory to protect the health of 1.0%), clay minerals (<0.5%) and iron oxides
working personnel. (<0.5%).
In this study total and respirable full-shift The aggregates are produced via traditional
personal and fixed-position dust samples were quarrying methods. The limestone is obtained
collected from several workplaces of a lime- by blasting a quarry face, then crushing and
stone aggregate quarry, in Crete, Greece. Sam- screening material to produce a wide range of
pling and analysis of crystalline silica was de- aggregates in various sizes and to specified
termined according to MDHS101 (HSE, 2005). quality limits.
According to this method a sample of respirable As a consequence, workers are exposed to
dust is collected on a membrane filter using a the risk of inhaling dusts during all of the quar-
respirable dust sampler. The filter is then placed rying phases (drilling, loading, conveying and
directly into the sample beam of either an infra- dumping) as well as during crushing, screening
red spectrophotometer or an X-ray diffractome- and handling of produced aggregates and the as-
ter. The mass of crystalline silica on the filter is sociated by-products.
determined from the infrared or X-ray diffrac-
2.2 Sampling and analysis
tion response, calibrated against filters loaded
with known amounts of standard quartz or cris- To determine the concentration of total and res-
tobalite or tridymite (Virji et al., 2002). Since pirable dust from all the emission sources of the
the volume of air sampled is known, the concen- quarry several samples were collected. The dust
tration of airborne crystalline silica is readily survey was conducted at the dump/crusher facil-
calculated. The choice of analytical technique, ity, on trucks and front-end wheel loader drivers
i.e. infrared spectroscopy or X-ray diffractome- to determine which activity during the produc-
try, depends largely on other materials present tion cycle generated the greatest potential for
on the filter which may interfere in the analysis exposing the operator to silica dust. Respirable
(Page, 2006). In this study the X-ray diffracto- airborne dust was sampled using a suitable sam-
metry was used. pler, filter and an air pump.
The Higgins-Dewell conductive cyclone
sampler with 25 mm diameter filters was used
2. MATERIALS AND METHODS
2.1 Geological characteristics of quarry and
phases of extraction
For the purposes of this project, airborne dust
samples (total and respirable) were collected a
quarry located in the area of the Island of Crete,
at Southern Greece. The quarry produces
800000 t of aggregates annually and supplies
the nearby concrete and asphalt-mixture manu-
facturers. Aggregates are extracted from car-
bonate sedimentary formations consisting main-
ly of limestone in the upper part, and from
dolomitic limestone and dolomites in the lower
part. Maximum stratigraphic thickness of these
formations is at places measured up to 300 m.
Aggregates are extracted mainly from lime-
stone layers, which are medium bedded, and are
visually distinguished from its light grey to dark
grey color. The mineralogical composition of Figure 1: Personal sampler for the respirable airborne
the extracted limestone, determined by X-ray dust.
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Resource Utilization and Hazardous Waste Management, Athens, Greece

(Fig. 1). The selected type filter was the GF/A-

1.6 μm-25 mm type. This type of filter has a
capture efficiency greater than 90% and is suit-
able for collection of samples containing free
crystalline silica. It was also suitable for X-ray
diffraction analysis since it has have no interfere
with the diffraction peaks of the dust constitu-
ents.
The SKC pump (Model -224-PCXR8) was
used. This sampling pump has an adjustable
flow rate, and incorporates a flowmeter with a
flow fault indicator (Fig. 1). It is capable of
maintaining the selected flow rate to within
±5% of the nominal value throughout the sam- Figure 2: On-line monitor for respirable airborne dust.
pling period.
time the concentration of the respirable dust
During sampling the cyclone was attached to
must be known. For this purpose a particle ana-
the worker’s lapel and as close to the mouth and
lyzer (TSI DustTrak 8520) which measures and
nose in order to determine respirable dust in the
records the concentration of respirable airborne
breathing zone. Samples of airborne respirable
dust (includes all dust types and particulate) us-
dust at fixed points were also taken.
ing a light scattering technique (Fig. 2). Light-
For fixed-position samples the sampler was
scattering instruments offer only a relative
mounted at approximately head height, away
measure of concentrations but provide a con-
from obstructions, fresh air inlets or strong
tinuous record of dust levels so that concentra-
winds. The sampling procedures are otherwise
tions can be evaluated over any time interval
the same as for personal sampling. Fixed-
during the sampling period. Taking into account
position samples may be useful in identifying
the DustTrak measurements (from 0.7 to
the main sources of crystalline silica exposure.
3.4 mg/m3 with an average value of 2.8 mg/m3),
Comparison of airborne concentration meas-
the airflow rate of the pump the measuring time,
urements from personal and fixed point samples
for both personal and fixed samples, was se-
may give some indication of the extent to which
exposure arises from local or general conditions lected to 420 min. The volumetric flow was set
to 2.2 l/min, to an accuracy of ±5%
(Bahrami et al., 2008).
(MDHS14/316, 2000).
Personal and fixed-position samples were ob-
tained during February 2008. The sampling At the end of the sampling period the volu-
metric flow rate and the sampling time were re-
aimed to monitor truck drivers, loader drivers
corded. The filters were removed from the sam-
and crusher operators through the loading-
transportation-dumping-crushing cycle, to pro- pler and were transported to the laboratory in a
container capable of preventing damage. The
file their dust exposure during these different
filters were conditioned in a desiccator for 24 h
operations. Fixed samples were taken from
crushers, which are considered the main source at 25°C and weighed by a balance with an accu-
racy of 0.01 mg. The same procedure was ap-
of the airborne dust. Samples were also obtained
plied for the determination of weigh of the
from the offices for monitoring the exposure of
the administrative personnel to the respirable empty filters. The weight of the filter before and
after sampling was used to determine the con-
dust.
centration of airborne dust (gravimetric method)
The determination of sampling time is crucial
in sampling airborne dust. A long sampling time according to the following formula:
ensures a heavier deposit of dust on the filter, Wafter − Wbefore
thus reducing measurement inaccuracies. How- D = 1000 ⋅ (2)
VF ⋅ ST
ever overloaded filters are problematic in trans-
portation and particular care must be taken to Where, D is the concentration of airborne
prevent material being dislodged from the filter. dust in mg/m3, Wbefore and Wafter are the weights
For the determination of the optimal sampling of the filter before and after sampling in mg, VF
3rd AMIREG International Conference (2009): Assessing the Footprint of 116
Resource Utilization and Hazardous Waste Management, Athens, Greece

Table 1: Results of the gravimetric estimation of the respirable dust.

Respirable Volume of Respirable dust
Sampling Sampling rate
Site/employee dust weight air sampled concentration
time (min) (l/min)
(mg) (m3) (mg/m3)
Crusher 420 2.2 2.91 0.924 3.15
Dumper driver 420 2.2 3.2 0.924 3.46
Loader driver 420 2.2 2.74 0.924 2.97
Office 420 2.2 2.38 0.924 2.2

is the flow rate of pump in l/min and ST is the mated.

sampling interval in minutes. 3. RESULTS-DISCUSSION
The analysis was done by X-ray diffraction
The results of the gravimetric determination of
(XRD) using a Brucker AXS (Model D8 Ad-
respirable dust are given in Table 1. The X-ray
vanced) diffractometer. Initially samples of total
diffraction analysis of the total airborne dust is
airborne dust as well as respirable dust depos-
shown in Figure 3. Dust contains mainly calcite
ited on the filters were analyzed. These samples
with, small amounts of dolomite and lesser
were analyzed, without any further treatment, to
amounts of quartz. The analysis of the insoluble
identify the major minerals of the collected dust.
residual of the respirable dust indicated that is
To improve the accuracy of the estimation of
consisting of quartz, muscovite and albite
crystalline silica content in the respirable dust,
(Fig. 4). The free crystalline silica in all ana-
the filters were treated with a 2N HCl solution
lyzed samples is exclusively in the form of
to dissolve calcite and dolomite. The acid in-
quartz (low temperature quartz).
soluble residual was then analyzed by X-ray dif-
The concentration of respirable quartz (expo-
fraction. The mineralogical constituents of the
sure), the permissible exposure levels (PELs)
dust were determined and the concentration of
and the severity were calculated and shown in
crystalline silica (quartz, cristobalite and tridy-
Table 2. Severity is derived by dividing the ex-
mite) in the respirable dust was calculated. Sub-
posure by the PEL.
sequently the concentration of respirable crys-
talline silica in mg/m3 and the respective per-
missible exposure limits (Eq. 1), were esti-
15000
14000
Calcite

13000

12000

11000

10000

9000

8000

7000

6000
Sqrt (Counts)

5000

4000
Calcite

Calcite
Calcite

Calcite
Calcite

3000
Calcite

2000
Calcite
Quartz

Calcite

1000
Dolomite

100

10

16 20 30 40 50

2-Theta - Scale
Figure 3: X-ray diffraction diagram showing the main minerals of the total airborne dust.
3rd AMIREG International Conference (2009): Assessing the Footprint of 117
Resource Utilization and Hazardous Waste Management, Athens, Greece

2400

2300

2200

2100

2000 Qz = Quartz
1900

1800
Ab = Albite
1700

1600 Mu = Muscovite
1500
Lin (Counts)

1400

1300
Qz
1200

1100

1000
Ab

900

800
Qz
Ab

700
Mu

Ab

600
Mu

Mu

Ab

500
Qz

Mu

Qz
400

Qz
300

200

100

9 10 20 30 40 50 60 70

2-Theta - Scale
Figure 4: X-ray diffraction diagram showing the main minerals of the insoluble residue of the respirable dust.

measured exposure is over the PEL. However, if

Exposure ( mg / m 3 ) LCL is lower than 1 this may indicate that expo-
Severity = (3)
PEL ( mg / m 3 ) sure is below the PEL. In this case the monitor-
ing of the exposure should be continued and it is
Considering that the total sampling and ana-
recommended to take appropriate actions to re-
lytical error for quartz determination is ~0.3%
duce exposure. When severity and LCL is
wt, the confidence limits (Upper Control Limit
greater than 1 the exposure is over the PEL and
or UCL and Lower Control Limit or LCL) were
appropriate actions must be taken to reduce the
estimated. UCL and LCL calculations were car-
exposure.
ried out by using the web-based e-tool for silica
Results, summarized in Table 2, indicated
crystalline, developed by OSHA (2009). Ac-
that the concentration of quartz in respirable
cording to OSHA, a severity less than or equal
dust is below to 1%. Therefore the dust is char-
to 1 means that the measured exposure is under
acterized as inert and the permissible exposure
the PEL. However if UCL is greater than 0.5, it
level is 5 mg/m3. Personal and site sampling in-
is recommended to examine the workplace for
dicated that respirable dust concentration was
possible actions that can be taken to further
below the permissible exposure level. The expo-
lower exposure. When UCL is greater than 1,
sure levels of truck drivers are the highest, fol-
additional measurement are required to confirm
lowed by crusher operators and loader drivers.
that the exposure is below the PEL, and it is
The office employees were the least exposed.
recommended to take appropriate actions to re-
Data from the dust survey, conducted by the
duce exposure.
DustTrak on-line analyzer, confirmed that a ma-
A severity greater than 1 indicates that the
Table 2: Results of the gravimetric estimation of the respirable dust.
Exposure mg/m3 (res- Permissible Ex-
Quartz
Site/employee pirable dust concentra- posure Level Severity UCL LCL
%
tion in air) mg/m3
Crusher 3.15 0.85 5 0.63 0.93 0.33
Dumper driver 3.46 0.65 5 0.69 0.99 0.39
Loader driver 2.97 0.71 5 0.59 0.89 0.29
Office 2.20 nd* 5
not determined
3rd AMIREG International Conference (2009): Assessing the Footprint of 118
Resource Utilization and Hazardous Waste Management, Athens, Greece

jor source of dust exposure for the truck drivers 404-408.

was the unloading of the truck at the dump. Page, S., 2006. Crystalline Silica Analysis: A Comparison
of Calibration Materials and Recent Coal Mine Dust
Respirable dust from the loading operation had Size Distributions. ASTM Symposium on Silica:
a lower contribution of dust exposure. The esti- Sampling and Analysis, 22-23 April, Salt Lake City,
mated severity was less than 1 but the UCL was UT.
greater than 0.5 and slightly lower than 1.0. Watts, W.S. and D.R. Parker, 1995. Quartz Exposure
These values indicated that the monitoring of Trends in Metal and Nonmetal Mining. Appl. Occup.
the dust must be continued and possible action Environ. Hyg. 10(12), 1009-1018.
Occupational Health and Safety Agency, (OSHA). 2009.
for the further reduction of the exposure must be www.osha.gov/SLTC/etools/silica/index.html.
examined. Greek Regulation for Mining and Quarrying (GRMQ),
1985. www.ypan.gr/fysikoi_poroi/emne_vasiki_no-
mothesia.htm
4. CONCLUSIONS
In this study the crystalline silica content of to-
tal and respirable dust from a limestone aggre-
gates quarry was determined. The crystalline sil-
ica was exclusive found in the form of quartz,
while its concentration in respirable dust was
measured between 0.65 and 0.85%. The expo-
sure levels of trucks’ drivers were the highest
while the major source of dust generation was
the unloading of the truck. Although the expo-
sure levels were under the PELS, the UCL value
for severity indicated that the monitoring of the
dust must be continued and possible action for
the further reduction of the exposure must be
examined.

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