Atmospheric Environment 77 (2013) 725e737

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Fluoride and sulfur dioxide indoor pollution situation and control in

coal-burning endemic area in Zhaotong, Yunnan, China
Yonglin Liu a, b, Kunli Luo a, *, Ling Li a, b, Muhammad Zeeshaan Shahid b, c
a

Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences, Beijing 100101, China
University of the Chinese Academy of Sciences, Beijing 100049, China
c
Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing, China
b

h i g h l i g h t s

To provide the gaseous F and SO2 pollution level in the coal-burning uorosis areas.

Gaseous F and SO2 pollution in the baking room with open stoves is serious.

Use calcined dolomite instead of clay can reduce F and S release greatly.

It is a useful way to control gaseous F and SO2 pollution in the uorosis areas.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 7 November 2012
Received in revised form
10 May 2013
Accepted 17 May 2013

The presented study aims to investigate the gaseous uoride and sulfur dioxide (SO2) pollution level in the
kitchen, traditional ue-curing barn and outdoor environment and to nd economically feasible method
to reduce uorine and sulfur release. The gaseous uoride and SO2 concentrations in air of outdoor
environment, kitchen and traditional ue-curing barn were determined in 56 households in coal-burning
endemic uorosis areas of Zhaotong. Among these, 21 households in Yujiawan Village, Zhenxiong County,
Zhaotong City were chosen for this experiment to reduce gaseous uoride and SO2 concentration in
traditional ue-curing barn air by using calcined dolomitic siliceous limestone (CDSL) instead of clay
mixed with coal. The result showed that: (1) gaseous uoride and SO2 concentration in the outdoor air in
Mangbu Township area was 0.51 mg dm2,day and <0.05 mg m3, respectively and in Xiaolongdong
Township was 2.7 mg dm2 day and <0.05 mg m3, respectively while in Zhaotong City these concentration were lower than the ambient air standard (3 mg dm2,day and 0.5 mg m3, respectively). (2) The
indoor gaseous uoride concentration (3.7 mg m3) in air of kitchen with the improved coal stove was
within the reference value (10 mg m3); SO2 concentration (0.94 mg m3) in kitchen air had decline, but its
concentration was still higher than indoor air quality standard (0.5 mg m3). (3) Average concentration of
gaseous uoride and SO2 in air of traditional ue-curing barn of Xiaolongdong Township was 7.2 mg m3
and 6.8 mg m3 respectively, and in Yujiawan village were 10.1 mg m3 and 14.4 mg m3, respectively. (4)
After using the calcined dolomitic siliceous limestone instead of clay mixed with coal, gaseous uoride and
SO2 concentration in the traditional ue-curing barn air decreased of 45% and 91%, respectively. The
gaseous uoride and SO2 pollution in the traditional ue-curing barn is very serious. The corn and chili
baked by open stoves in traditional ue-curing barn (baking room) was also seriously polluted by uoride
and sulfur. After using the calcined dolomitic siliceous limestone instead of clay mixed with coal, gaseous
uoride and SO2 concentration in the traditional ue-curing barn air have declined markedly. The way of
adding calcined dolomitic siliceous limestone instead of clay as a binder for briquette-making is an
economically feasible way to control the indoor pollution of uorine and sulfur in coal-burning endemic in
Zhaotong, Yunnan.
2013 Elsevier Ltd. All rights reserved.

Keywords:
Coal-burning endemic uorosis
Gaseous uoride and sulfur dioxide
pollution level
Control research
Calcined dolomitic siliceous limestone

1. Introduction
* Corresponding author. Tel.: 86 10 64856503; fax: 86 10 64851844.
E-mail addresses: liuyl.10b@igsnrr.ac.cn, liu3986130@163.com (Y.
kunliluo@sohu.com (K. Luo).
1352-2310/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.atmosenv.2013.05.043

Liu),

Coal is one of the main fuels used by the rural households in

China (Sinton et al., 2004). Hundreds of harmful pollutants, such as

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Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

gaseous uoride, sulfur dioxide (SO2) and suspended particles are

emitted during the coal burning (Ando et al.,1998; Dai et al., 2004; Jin
et al., 2006). Exposure to indoor air pollution from the combustion of
coal can cause many diseases including endemic uorosis, arseniasis
and respiratory diseases (Liang et al., 1993a; Ando et al., 1998;
Finkelman et al., 1999; Jin et al., 2006; Zhang and Smith, 2007). The
indoor gaseous uoride pollution in coal-burning endemic uorosis
areas in China have been studied in many areas, such as Longli
County (Ando et al., 1998, 2001; Dai et al., 2004), Guiding County
(Yang et al., 2010) in Guizhou Province, Wushan County of Chongqing
City (Liang et al., 1993b; Ando et al., 1998, 2001) and Southern
Shaanxi (He et al., 2005). Zhaotong City of Yunnan Province is the
typical coal-burning endemic uorosis area in China (Ye et al., 2004a,
2004b, 2005a, 2005b; Sun, 2005; Cao, 2001; Luo et al., 2007, 2008).
Liang et al. (1993a) have reported the indoor and outdoor gaseous
uoride and SO2 pollution in Xiaolongdong Township, Zhaotong City.
25 gaseous uoride samples (46 mg m3) and 99 SO2 samples
(1.72 mg m3) in the kitchen were collected and measured. But the
types of stove used by households were not introduced and the
gaseous uoride and SO2 pollution level in the traditional ue-curing
barn (baking room) was not studied. Wang et al. (2001) have determined 20 gaseous uoride samples (1.5 mg m3) in the kitchen with
the improved coal stove in Qinggangling Village, Qinggang Township, Zhaotong City. But there is no data available about the gaseous
uoride and SO2 concentration in the traditional ue-curing barn air
with the open stove.
The uoride (F) content in coal in Zhaotong City was 77 mg kg1
(Luo et al., 2007), that is similar to the Chinese average of 82 mg kg1
(Luo et al., 2004; Ren et al., 2006), to the F average of 83 mg kg1 in
Western Guizhou (Dai et al., 2004) and to the world average of
80 mg kg1 (Swaine, 1990). Therefore, the coal used by households
in Zhaotong City is the low-uorine coal. The F sources in endemic
uorosis area in Zhaotong City are the high uorine clay as an additive for coal-burning and as a binder for briquette-making (Li et al.,
1995; Luo et al., 2007, 2008). So, we need to know the gaseous
uoride and SO2 concentrations caused by low-uorine coal (LFC)
mixed with high-uorine clay (HFCL) in Zhaotong City.
Ando et al. (1998, 2001) indicated that direct inhalation
accounted for 1.9e3.4% of total uoride dose, 94.5e97.3% of total
uoride exposure was caused from dietary food consumption and
only 0.8e2.1% of total uoride dose was caused from drinking water
in the coal-burning uorosis area in Longli County of Guizhou
Province and Pengshui County of Chongqing City.
Therefore, it is clear that the F sources in endemic uorosis area
in Zhaotong City are the high uorine clay as an additive for coalburning and as a binder for briquette-making (Li et al., 1995; Luo
et al., 2007, 2008). So, theoretically, if abandon the high-uorine
clay (HFCL) as an additive for coal-burning and as a binder for
briquette-making, the gaseous uoride pollution in the traditional
ue-curing barn would be reduced dramatically in Zhaotong City.
So, the gaseous uoride and SO2 pollution levels in the traditional
ue-curing barn need to be determined.
Zhaotong City is one of the main areas of middle and high sulfur
(S) coal producing area, and average S content of coal in Zhaotong is
2.36% (Table 2). So, in the coal-burning endemic uorosis areas, the
sulfate SO4 2 and inorganic anions change to acidic compounds
very easily in the moisture containing atmosphere, which is more
harmful to human respiratory system (Zhao, 1992; Liang et al.,
1993a; An et al., 1995; Yan, 1996). Liang et al. (1993a) studied that
if high concentration of gaseous uoride and SO2 coexisted in air, it
would exacerbate the endemic uorosis. Thus SO2 pollution level
along with the uorine pollution from coal burning in coal-burning
endemic uorosis in Zhaotong also needs to study.
The technology of uorine and sulfur retention with calciumbased materials in coal combustion had been studied in different

Table 1
The parameters of the portable gas detector.
Parameter

Range

Parameter

Range

Sucking rate of
aspirator
pump

300 ml min1

Operating
environment

Detecting
range
Accuracy

0.02e200 ppm

Span drift

Temperature: 10  C
to 45  C
Humidity: 90% RH
(non-condensing)
5% (F.S)/4 h

5% (F.S)

Zero drift

2% (F.S)/4 h

years (Cao, 1992; Zhang et al., 2002; Liu et al., 2006; Yamada et al.,
2008; Chen et al., 2009; Yang et al., 2010) and satisfactory results
had been achieved.
Coal briquette in previous study is all honeycomb briquettes. But
in the rural area of Zhaotong City, local resident are more perfect to
use the briquette that is only mixture of clay and coal together
(Fig.A.1, Fig. 1), not shape up them as a special model like the
honeycomb briquettes, to bake the corn and chili, or for living used.
Domestic coal in Zhaotong is mainly crushed coal, accounting
for more than 70% of coal yield, and the price is only 1/3e1/2 of the
lump coal. If the crushed coal is directly added into the coal stove in
the practical operation, it can cut off from the air, resulting in the
re to extinguish. Therefore, binder has to be added into the
crushed coal.
There is abundant carbonate rock-dolomite, dolomitic limestone
and limy dolomite in Zhaotong (Fig.A.2), which contain low contents of uorine (Luo et al., 2007). We try to use the local low
uorine calcined carbonate rock to instead of clay as a binder for
briquette-making. Theoretically, if using the low uorine calcined
dolomitic siliceous limestone (CDSL) instead of high uorine clay
mixed with coal, the gaseous uoride and SO2 concentration in the
traditional ue-curing barn air would declined markedly. So, we
need to know the both gaseous uoride and SO2 concentrations in
indoor air by low-uorine coal (LFC) mixed with low-uorine calcium-based materials in Zhaotong City.
This study will focus on the following problems: 1), what are the
indoor and outdoor gaseous uoride and SO2 pollution level in the
endemic uorosis areas in the improved stove used area in Zhaotong City. 2), what are the gaseous uoride and SO2 pollution level
in traditional ue-curing barn (baking room) by open stoves to
bake the corn and chili in Zhaotong City. 3), the gaseous uoride
and SO2 concentration in the traditional ue-curing barn in the
Table 2
F and total S in the ne coal, clay, CDSL and coal slime.
Elements

No.

S (%)

F (mg kg1)

Fine coal

MB4
MB7
MB39
LD2
LD5
LD12
MB33
MB35
MB38
LD9
LD14
LD15
MB
LD
MB3
MB15
MB31

2.94
2.73
2.11
2.30
2.10
2.00
0.14
0.03
B.D
0.82
0.13
B.D
0.10
0.41
2.10
1.80
1.80

124.5
106.0
99.8
95.5
115.8
40.3
1303
178.0
1214.0
1181.0
1663.0
2422.0
137.0
78.8
161.0
145.0
157.0

Clay

CDSL
Coal slime

Note: MB: Mangbu Town, Zhenxiong County, Zhaotong City; LD: Xiaolongdong
Town, Zhaoyang District, Zhaotong City; B.D: Below detection; CDSL: Calcined
dolomitic siliceous limestone.

Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

727

Fig. 1. The mode of baking corn and chili and building structure of traditional ue-curing barn.

households after use the calcined dolomitic siliceous limestone

(CDSL) instead of clay mixed with coal in Zhaotong City.
1.1. Study areas
Zhaotong is the typical karst region (Fig.A.2) in the Southwest
area of China. The major strata are Early and Later Paleozoic strata
and Early Mesozoic strata, which are thousands meter carbonate
deposits (dolomite and limestone mainly). If this natural carbonate
rock can be utilized, it not only makes full use of local materials, but
also reduces cost and secondary pollution in the industrial Cabased sorbent production process. The Ca-based and Mg-based
materials are suitable for inconvenient trafc and economic lessdeveloped mountainous areas in the Southwestern area of China.

Yujiawan Village (Fig. 2) is located in Mangbu Township, about

1 km northwest of Mangbu Town with average elevation 1625.8 m,
mean annual temperature 10.8  C, annual rainfall 1388 mm and frostfree period more than 250 days. Xiaolongdong Township (Fig. 2) is
located in the eastern of Zhaoyang District, Zhaotong City, about
10.3 km from Zhaotong Urban Area. The elevation is from 1910 m to
3152 m. The annual temperature is 11  C and the annual rainfall is
750 mm. The frost-free period is more than 200 days. So, the township is a typical cold indigent area. Group 22 (Fig. 2) is located in the
southeast of Xiaolongdong Township, about 12 km from the Xiaolongdong Town. In two severe endemic uorosis areas in Zhaotong
the improved coal stove with chimney is used for heating and cooking
from 1990s. The popularization test on reducing uorine and sulfur in
uorosis areas was done in Yujiawan Village, Zhaotong City.

Fig. 2. Location map of the experimental sites. Note: Administrative division of China is divided into six government levels, that is, Province, Prefecture-level city (Prefecture),
County (District), Township, Village (Administrative Village) and Natural Village (group).

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Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

1.2. The mode of cooking and heating and baking foodstuffs

In most households of coal-burning uorosis area, including the
study households, fuels such as coal briquettes are burned in
improved stove (with furnace cover and chimney leading out of the
roof) all day in the whole year for cooking and heating (Fig.A.3).
Some households use the open furnace for cooking and heating.
The corn and chili are usually baked by the open furnace (Fig.A.1) in
the traditional ue-curing barn (Fig. 1). Meanwhile, the study area
is the indigent area in China. The study area is typical karst
mountain area and has a complicated landform and physiognomy
(Fig.A.2). The house structure is generally 2e3 m high ranch house
with 3 rooms connecting to each other, and each room is about 10e
20 m2. Most of kitchen in many households are the living-room.
The kitchen in some households is not only the living-room but
also the sleeping room. Even if the kitchen, the living-room and the
bedroom are not the same room, they usually connect to each other
for heating and saving energy. For the most part, the traditional
ue-curing barn (baking room) in Zhaotong City, Yunnan Province
is separate and does not connect with other rooms. In addition, the
kitchen is closed and is used as temporary traditional ue-curing
barn and it also does not connect with other rooms in the harvest
season.
2. Experiment and analytical method
2.1. Sampling method of gaseous uoride and SO2 in air
To determine gaseous uoride in the air, lime-paper sampling
(LTP) was used (Li et al., 1989). Lime suspension liquid was prepared
using following method: 56 g calcium oxide was mixed with 250 ml
distilled water in the 2000 ml beaker, meanwhile, slowly adding
250 ml of 72% perchloric acid under stirring. A mixed solution was
heated until white smoke emitting. After cooling, 200 ml distilled
water was added, and then mixture was heated until white smoke
emit. The whole procedure was repeated three times. After cooling,
mixture was ltered by glass sand funnel (G3). Then, 1000 ml of
2.5 M sodium hydroxide solution was added to the ltrate under
stirring. The solution was depositing, keeping static, dumping supernatant into 5000 ml volumetric ask. Every time the supernatant
must be dumped into 5000 ml volumetric ask. 1% calcium hydroxide suspension liquid was nished at last. Lime lter paper was
prepared using following method: 12.5 cm qualitative lter paper
was placed into the rst glass culture dish with 1% calcium hydroxide suspension liquid. After soaking and draining lter paper
(calcium hydroxide suspension liquid must be replaced after
impregnating 5e6 pieces of lter paper), it was placed into the
second glass culture dish with 1% calcium hydroxide suspension
liquid. Drained lter paper was spread on a big qualitative lter
paper (cleanliness and no-uoride). The impregnated lter paper
was baked at 60  C in electric drying oven. The baked lter paper was
placed in a plastic sealed bag, and then it was put into dry cabinet.
The method of hanging the lime lter paper in outdoor air is as
follows: a piece of lime lter paper should be place on the bottom of
the sampling box and be xed by the circlip. The sampling box with
lter paper should be far away from the chimney of the stove and is
fastened above a xed object, about 3.5w4 m away from the
ground. The method of hanging the lime lter paper in indoor was:
a piece of lime lter paper should lie on the bottom of the sampling
box and be xed by the circlip (Fig.A.4). The sampling box with
lter paper should be 1.5 m away from the stove and about 1.5 m
away from the ground. Two pieces of lime lter paper should be
xed in every room. The surface of lime lter paper must face
down. The top of sampling box should be covered, in order to
prevent y ash from falling on the lter paper. The lime lter paper

must be exposed to air more than 7 days. When the sampling box
was collected, the lime lter paper was put into a plastic seal bag
immediately. After that the lime lter paper should be put into dry
cabinet in the lab. The determination of F content must be nished
within 6 weeks. The specic sampling method may be referred to
Ministry of Environmental Protection of the Peoples Republic of
China (2003).
The method of sampling SO2: Because the temperature in the
traditional ue-curing barn is very high, air sampler and aspirator
pump would be damaged while SO2 is sampled by the method of
formaldehyde absorbing-pararosaniline spectrophotometry. Therefore, the portable gas detector (Beijing Xinhualao Science & Trade Co.,
Ltd) was used to determine the indoor and outdoor SO2 concentration. Table 1 is the parameters of portable gas detector. In order to
ensure measurement accuracy, zero correction and range correction
must be done.
Zero correction: When the digital readout display is stable in the
clean air, it shows the value on the liquid crystal display (LCD)
screen is 000 through adjusting the zero potentiometer. Range
correction: whether the show value returns to zero, the digital
readout display is stable in the clean air. The bag lled up with
standard SO2 gas must be connected to the instrument inlet with an
air duct, and dont adjust the potentiometer S until the indication
value stays stable, then stop gas input when the value shows no
difference with the sample concentration value. This procedure
should be repeated once. If the difference between two values is
within error, the correction is nished. If the difference exceeds the
error range, the corrective procedure should be repeated. When the
SO2 concentration is determined in situ, the gas detector should be
1 m away from the stove, about 1 m high from the ground (Fig.A.5).
Evacuation time must be more than 45 min. Meanwhile, the temperature and pressure in situ should be recorded.
2.2. Analytical methods
2.2.1. Analytical method of uoride in air
The gaseous uoride content was determined by uoride ionselective electrode (ISE) method. 0.1, 0.2, 0.4, 1.0, 2.0, 4.0, 8.0, 16.0
and 40 mg ml1 of uoride standards were prepared using the
100 mg ml1 of uoride standard solution. The standard curve was
drawn by using semi logarithmic chart. Related coefcient of the
regression equation was greater than 0.999; Slope was within the
(54 0.2t) mv.
Determination of sample: The lime lter paper was cut in
squares of 5 mm by 5 mm, and put into 100 ml plastic beaker. 25 ml
of total ionic strength adjustment buffer (TISAB) and 25 ml of
distilled water were added into 100 ml plastic beaker. Mixture was
cleaned 30 min in the ultrasonic cleaner. The 100 ml plastic beaker

3
5
c

2
1

11
12

13

10

1- colorimetric cylinder; 2-condensing tube; 3- high-temperature combustion

furnace; 4-silica boat; 5-quartz tube; 6-push rod; 7-water mouth;8-explosionproof ball; 9-distillation flask;10-temperature adjusting slot;11-thermocouple;
12-temperature controller;13-oxygen bottle
Fig. 3. Combustion hydrolysis set to determine F content in solid samples.

Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

Table 3
Gaseous uoride and SO2 concentration in outdoor air in Yujiawan village, Mangbu
Township and Group 22, Xiaomi Village.
SO2 (mg m3)
(one-hour average)

Study areas

Number of
samples

Gaseous uoride
(mg dm2 day)
(daily average)
Min

Max

Mean

Min

Max

Mean

Yujiawan
Group 22,
Xiaomi
Village

9
6

<0.05
0.7

1.1
5.9

0.5
2.7

<0.05
<0.05

<0.05
<0.05

<0.05
<0.05

was taken out and placed over night. The F concentration of sample
was determined by using ISE and read by using the calibration
curve.
Determination of blank value: 4e5 pieces of unused lime lter
paper was cut. 0.5 ml of 10 mg ml1 uoride standard solution was
added into 100 ml plastic beaker. The total volume of the determined solution was 50 ml. The sample concentration was determined by using ISE. The uoride concentration of unused lime lter
paper was the difference in value between measured value and the
uoride standard content (5 mg).
Analysis and calculations: C(F) (WeW0)/(S  n). C(F): the
uoride concentration in air (unit: mg/(dm2 day)); W: the uoride
content of sample in the lime lter paper (unit: mg); W0: the
average uoride content in the unused lime lter paper (unit: mg);
S: the area of the lime lter paper (unit: dm2); n: exposure time
(unit: day; Accuracy: 0.1 day). To control experimental accuracy, 5
standard sample of lime lter paper whose uorine content was
50.0 mg were determined, and relative error is 0.23%. The specic
analytical method must be referred as Ministry of Environmental
Protection of the Peoples Republic of China (2003).
2.2.2 Analytical method of solid sample
Determination of F content in solid samples: Solid samples were
crushed and ground to less than 200 mesh for analysis. F content in
solid samples was determined by the combustion-hydrolysis
(Fig. 3) uoride ion-selective electrode (ISE) method according to
the Chinese standard method (SBTPRC, 1997; Feng et al., 2004). The
sample was combusted in tubular electric furnace at 1100  C and
the condensate was received by 0.2 M sodium hydroxide solution,
then 5 ml total ionic strength adjusting buffer (TISAB) was added to
tested solutions before determination by an F-electrode and a
calomel reference electrode (Shang-hai Precision and Scientic
Instrument Co. Ltd., China). TISAB was prepared using the following

729

method: 145 g sodium chloride and 7.35 g sodium citrate were

dissolved in 143 ml acetic acid, and then the pH of solution was
adjusted to 5.0e5.5 using 40% sodium hydroxide solution (Feng
et al., 2004) (Fig. 3). For quality control, standard reference materials (GBW11122 [coal, China], GBW07406 [soil, China]) were
randomly analyzed with each batch of solid samples. In all our
uorine analyses, the relative standard deviation was less than 10%.
The F content in the solid samples was calculated by the following
formula: C (50  (M-Blank))/G; C: the F content of the sample
(mg g1); M: the F content of the solution (mg mL1); Blank the F
content of reagent blank (mg mL1); G: sample weight (g).
Determination of total S in solid (rock, soil, coal): Total S in solid
was determined by Coulomb Titration Method (GAQS and IQPRC,
2007). Electrolyte preparation: 5.0 g potassium iodide (KI) and
5.0 g potassium bromide were dissolved in 250 ml of distilled water,
and then 10 ml glacial acetic acid (GR) was added into the mixture.
Samples were crushed and ground to less than 200 mesh for
geochemical analyses. Samples of 50  0.2 mg were weighed into
the porcelain boat, a layer tungsten trioxide covered on the surface
of samples. Samples were decomposed at 1150  C in the coulombsulfur instrument (Model: HB-S500; Hebi Hengbo Instrument and
Meter Co.). Sulfur dioxide and sulfur trioxide were produced by the
burning of sulfur reacted with water in the electrolyzer. The
chemical process produced sulfurous acid and sulfuric acid, which
would break the potential balance of iodine (I)eKI. New potential
balance will be built by electrolyzing KI automatically. According
to the Faradays law of electrolysis, the total S content can be
determined. For quality control, standard reference materials
(GBW11103g [coal, China], GBW11104f [coal, China], GBW11113c
[coal, China]) were randomly analyzed after every determining ve
samples.
Total plant S was determined by digestion with nitric and
perchloric acid followed by HI reduction (Lisle et al., 1994).
2.3. Method of calculation
2.3.1. Calculation formula of uoride
In order to analyze and compare with indoor air quality standard, the unit of mg/(dm2 day) was converted into the unit of
mg m3. Conversion formula of F content had been studied widely
(Li et al., 1989; Liu et al., 1991; Wu, 1982). Conversion formula in
outdoor air was (Wu, 1982): C 6.11  Q 0.22 (r 0.734);
Conversion formula in indoor air was (Li et al., 1989):
Q 3.1 0.23  C (r 0.9815). C: test value (mg/(dm2 day)); Q:
calculated value (mg m3).

Fig. 4. Gaseous uoride (a) and SO2 (b) concentration in the kitchen air before and after improvement.

730

Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

Table 4
Gaseous uoride and SO2 concentration in the traditional ue-curing barn air in
Zhaotong City.
Study areas

Parameters

Min

Max

Mean

S.D

Skew

Yujiawan

F (mg m3) (daily average)

SO2 (mg m3) (one-hour
average)
F (mg m3) (daily average)
SO2 (mg m3) (one-hour
average)

1.92
2.62

28.0
57.3

10.1
14.4

9.78
18.5

1.57
2.24

1.21
2.37

20.7
14.8

7.2
6.8

7.54
4.00

1.40
1.08

Group 22,
Xiaomi
Village

Note: S.D: standard deviation.

(1516 mg kg1) in clay reported by Luo et al. (2007). So, the

households use the LFC mixed with HFCL as their domestic energy
for cooking, heating and baking foodstuffs.
On the basis of classication for coal quality (GAQS and IQPRC,
2004), total S content in the middle and high S coal is 1.5e3.0%,
high S coal with >3.0% and low S coal with <0.9%. The used re coal
in the present household in study areas is the middle and high S
coal, with an average of 2.36% (Table 2).
3.2. The outdoor gaseous uoride and SO2 pollution

The popularization test on reducing uorine and sulfur in

uorosis areas was done in Yujiawan Village, Zhaotong City
(Fig.A.2). First, dolomitic siliceous limestone near experimental
villages was calcined into powder (CDSL) in lime factory, and then
transported to experimental households. Experimental groups
(EGs) (Fig.A.6) substituted local CDSL for clay (Fig.A.7) mixed with
low-uorine coal. The mixing ratio of CDSL to coal was 3:7, namely,
there had 30 kg CDSL and 70 kg coal in 100 kg mixed re coal
(Fig.A.8). But the contrast groups (CGs) (Fig.A.1) still did cooking
and baked the food with the traditional mixed re coal-lowuorine coal mixed with high-uorine clay.

The time for hanging lime lter paper in outdoor air was from
October 30th or 31st, 2010 to November 8th, 2010 in Yujiawan
Village, Mangbu Township, Zhenxiong County, Zhaotong City. And
the time was from November 19th or 20th, 2010 to December 3rd
or 4th, 2010 in Group 22, Xiaomi Village, Zhaoyang District. The
exposed time of lime lter paper exceeded 7 days.
Table 3 shows that the gaseous uoride concentration in outdoor air in Yujiawan Village, Zhenxiong County is maximum of
1.1 mg dm2,day, with an average of 0.5 mg dm2,day. The gaseous
uoride concentration in outdoor air in Group 22, Xiaomi Village,
Zhaoyang District is maximum of 5.9 mg dm2,day, with an average
of 2.7 mg dm2,day. Mean values are both lower than the ambient
air standard (3 mg dm2,day). But some are higher than the
ambient air standard.
An excess of SO2 will form acid rain, damage ecotope and threaten
human health (An et al., 1995). The uorosis areas in Zhaotong City
are the coal-burning endemic uorosis areas (Ye et al., 2004a, 2004b,
2005a, 2005b; Luo et al., 2007). So, SO2 would be produced during
the coal burning. Therefore, monitoring the SO2 pollution in the
ambient air is very important to evaluate the residents health.
Table 3 shows that the one-hour average of SO2 concentration in
outdoor air is below detection line (<0.05 mg m3), and is much
lower than the ambient air quality standard (0.7 mg m3).

3. Results and analysis

3.3. The gaseous uoride and SO2 pollution in the kitchen

3.1. Fluoride and total S content in solid

The time of hanging lime lter paper in the kitchen was from
October 30th, 2010 to November 8th, 2010 in Yujiawan Village,
Zhenxiong County. There are 7 households with improved coal
stove and 7 households with open furnace in Yujiawan Village,
Zhenxiong County.
The function of improved coal stove is that the soot and coal ash
emitted by coal-burning is discharged from the chimney in the
kitchen. The gaseous uoride pollution in the kitchen had been
decreased since households using the improved coal stove (Wang

2.3.2. Conversion formula of sulfur dioxide

The conversion formula of sulfur dioxide is:

mg m3 M=22:4  ppm  273=273 T  Ba=101325

M: Molecular weight of SO2 (64 g mol1); T: temperature values
( C); Ba: the values of atmospheric pressure (Pa).
2.4. Experimental methods for popularization test on reducing
uorine and sulfur

F and total S content in ne coal, coal slime (coal slime: it is the

residue through coal washing technology), clay and CDSL are listed
(Table 2). The Table 2 shows that the F content in ne coal is
maximum of 124.5 mg kg1, with average of 96.9 mg kg1, which is
slightly higher than the Chinese average of 82 mg kg1 (Luo et al.,
2004). And the F content in clay (Fig.A.7) is maximum of
2422 mg kg1, with average of 1327 mg kg1, which is close to that

Fig. 5. The gaseous uoride (a) and SO2 (b) concentration in the traditional ue-curing barn air in EGs and CGs in Yujiawan Village.

Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

731

Fig. 6. Comparison of experimental results between in Guiding, Guizhou Province (GG) and in Zhaotong City, Yunnan Province.

et al., 2001; Ye et al., 2004b). Therefore, through determining the

gaseous uoride and SO2 pollution level before and after
improvement, the uorine and sulfur removal effect (Fig.4) of the
improved coal stove was studied.
Daily average of gaseous uoride concentration in the kitchen
with open furnace was 11.5 mg m3 (Fig.4(a)) (reference value (Liang
et al., 1992) is 10 mg m3). One-hour average of SO2 concentration in
the kitchen with open furnace was 14.8 mg m3 (Fig.4(b)) that was
much higher than indoor SO2 standard (0.5 mg m3). After
improving the stove, the daily average of gaseous uoride concentration in the kitchen with improved coal stove was 3.7 mg m3, with
one-hour average of SO2 concentration of 0.94 mg m3. Comparing
before and after improvement, the average value of gaseous uoride
concentration in the kitchen air was decreased by 68.3% and was
within the reference value (10 mg m3) (Fig. 4(a)). The average value
of SO2 concentration in the kitchen air was decreased by 93.7% and
was still higher than the standard value (0.5 mg m3) (Fig.4(b)).
Although the SO2 concentration in the kitchen air had decreased
markedly, the SO2 concentration in the kitchen with improved coal
stove was still higher than the indoor air standard (0.5 mg m3).
Hence, decreasing the SO2 concentration in indoor air must be come
into notice. From the above, the improved coal stove with chimney
greatly improved the indoor and outdoor air quality.
3.4. The gaseous uoride and SO2 pollution in the traditional uecuring barn
The time for hanging lime lter paper in the traditional uecuring barn was from October 30th or 31st, 2010 to November
8th, 2010 in Yujiawan Village, Zhenxiong County. The time was
from November 19th or 20th, 2010 to December 3rd or 4th, 2010 in
Group 22, Xiaomi Village, Zhaoyang District. The exposed time of
lime lter paper exceeded 7 days.
For the most part, the traditional ue-curing barn (Fig.1) in Zhaotong City, Yunnan Province is separate and do not connect with other
rooms. But hitherto, there is no report on gaseous uoride and sulfur
dioxide indoor pollution level in the traditional ue-curing barn.
Table 4 showed that gaseous uoride and SO2 indoor pollution
in the traditional ue-curing barn was very serious. So, the gaseous
uoride, SO2 and other harmful elements polluted the corn and
chili in the traditional ue-curing barn. Luo et al. (2011) have also
investigated the stove-improving effects in Zhenxiong County,
Zhaotong City, Yunnan Province in 2011 and again indicated that
the dental uorosis (Fig.A.9) rate of children was still high (82.7%) in
the coal-burning uorosis areas in Zhaotong City after improving
the stove. The main reason is that the residents use open furnace to
bake corn and chili in the traditional ue-curing barn in the harvest
season.

Consequently, in order to solve the coal-burning endemic uorosis in Zhaotong areas radically, the gaseous uoride, SO2 and
other toxic substance pollution in the traditional ue-curing barn
must be reduced dramatically.
4. Effectiveness evaluation for reducing uorine and sulfur
4.1. Study areas
There are 150 total households and 673 total populations in
Yujiawan Village (elevation of 1600 m), Zhenxiong County and 80
total households and 280 total populations in Group 22 (elevation of
2076 m), Xiaomi Village, Zhaoyang District. The area is the serious
uorosis areas (Ye et al., 2004a, 2005a, 2005b). There are 21 experimental groups (EGs) and 19 contrast groups (CGs) in Yujiawan Village,
Zhenxiong County. The experimental time which was the harvest
season of corn is from October 20th, 2010 to December 6th, 2010.
4.2. The F and SO2 pollution in the traditional ue-curing barn
Fig.5(a) shows that the F release has been decreased after
substituting CDSL for clay mixed with coal in Yujiawan Village,
Zhenxiong County. The gaseous uoride concentration (5.5 mg m3)
in the traditional ue-curing barn air in EGs in Yujiawan Village is
45.27% less than that (10.1 mg m3) in CGs. It proved that the
gaseous uoride pollution in the traditional ue-curing barn had
been reduced markedly. The SO2 concentration (1.3 mg m3) in the
traditional ue-curing barn air (Fig.5(b)) in EGs in Yujiawan Village
is 91% less than that (14.4 mg m3) in CGs.
Comparison of experimental results between in Guiding County,
Guizhou Province (Yang et al., 2010) and in Zhaotong City, Yunnan
Province (Fig.6), the indoor gaseous uoride concentration
(1.4 mg m3) in EGs in Guiding County, Guizhou Province was lower
than that (5.5 mg m3) in the traditional ue-curing barn in Yujiawan Village, Zhaotong City (Fig.6(a)). The indoor SO2 concentration
(0.17 mg m3) in EGs in Guiding County, Guizhou Province was
lower than that (1.3 mg m3) in the traditional ue-curing barn in
Yujiawan Village, Zhaotong City (Fig.6(a)). The indoor gaseous
uoride (3.6 mg m3) concentration in CGs in Guiding County,
Table 5
F content (mg kg1) in fresh and roasted corn in 2010.
Study areas

Sample
properties

Fresh

Baked
(in EGs)

Baked
(in CGs)

Yujiawan, Mangbu
Town
Group 22, Xiaomi
Village

Corn
Chili
Corn
Chili

1.1
0.8
1.7
2.5

5.1
9.0
4.7
43.7

10.2
35.2
10.5
144.1

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Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

Fig. 7. The F content in the baked corn (A) and chili (B) of 2009 and 2010 in uorosis area.

Guizhou Province was lower than that in the traditional ue-curing

barn air in Yujiawan Village, Zhaotong City (10.1 mg m3) (Fig.6(b)),
and SO2 (0.45 mg m3) concentration was also lower than that in
Yujiawan Village, Zhaotong City (14.4 mg m3) (Fig.6(b)). The F
content in the bitumite, anthracite, clay and lime in Guiding County,
Guizhou Province was 2170 mg kg1, 231 mg kg, 2098 mg kg1 and
850 mg kg1, respectively (Yang et al., 2010). The F content in ne
coal, coal slime, clay and CDSL in Zhaotong City, Yunnan Province
was 91 mg kg1, 154 mg kg1, 1327 mg kg1 and 108 mg kg1,
respectively. The reason for this difference was different ventilated
conditions. All houses in Guiding County, Guizhou Province had an
attic above the cooking/living and sleeping rooms, used for food
drying and storage (He et al., 2005; Yang et al., 2010). So, there was
no separate traditional ue-curing barn in Guiding County, Guizhou
Province. Therefore, the indoor ventilation in Guiding County,
Guizhou Province was very well and that was benecial to gaseous
uoride and SO2 dispersion. But the traditional ue-curing barn in
Zhaotong City, especially in Mangbu Township, Zhenxiong County,
was separate and did not connect with other rooms, and the volume of traditional ue-curing barn was small (9e18 m3). So, the
building structure of ue-curing barn was not benecial to gaseous
uoride and SO2 dispersion. It is clear that the gaseous uoride and
SO2 pollution in the traditional barn in Zhaotong City had great
inuence on F and S content in corn and chili (Table 5; Fig. 8).
4.3. Fluoride and sulfur content in baked foodstuffs
Table 5 shows F content in corn and chili. The F content in
roasted corn and chili in the CGs using clay as binder was 2e4 times

higher than that of EGs using CDSL as binder. Luo et al. (2010) reported that the F content (3.0 mg kg1) in the roasted corn in
Muxuan Township, Zhaotong City which was the non-uorosis area
was higher than the permitted level of uoride content in foods
(1.5 mg kg1) (NSPRC, 1984). But there was not dental and skeletal
uorosis. Luo et al. (2010) made the safety line (less than
4.0 mg kg1) of uoride content in roasted corn in coal-burning
uorosis areas. The F content (Table 5) in corn baked by coal
mixed with CDSL was close to the safe line of 4 mg kg1 (Luo et al.,
2010). The F content (Table 5) in chili baked by coal mixed with
CDSL was still much higher than the safe line of 4 mg kg1, but
signicantly lower than that of CGs using clay as binder. Therefore,
the gaseous uoride pollution in the traditional ue-curing barn
was reduced markedly after CDSL instead of clay as binder.
Local residents in the uorosis areas in Zhaotong largely eat the
baked corn and chili of last year before harvesting fresh corn and
chili. Fig. 7 showed that the F content in the baked corn of 2009 was
obviously higher than that of 2010 (Fig.7(A)). But the F content in
the baked chili of 2009 had no signicant difference as compared
with that of 2010 (Fig.7(B)).
Sulfur (S) that constitutes the cell protein, tissue uid, and various
important component of coenzyme is an essential human chemical
element. But excessive intake of S would increases lipid peroxidation
and may cause damage to the visual system (Parcell, 2002; Ozturk
et al., 2011). Fig. 8 showed S content in corn and chili. The S content (Fig. 8) in roasted corn (mean: 0.28  102) and chili (mean:
0.45  102) in the CGs using clay as binder was much higher than
fresh corn (mean: 0.14  102) and fresh chili (mean: 0.4  102).
The mixture of clay and middle and high sulfur coal, which is

Fig. 8. The S content in the baked corn and chili of 2009 and 2010 in uorosis area.

Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

produced by local mines, is used as a main household energy to bake

the foodstuffs. Because of this traditional baking method, the corn
and chili are contaminated by the SO2 emitted during the coal
burning. The S content (Fig. 8) in roasted corn (mean: 0.14  102)
and chili (mean: 0.35  102) in the EGs using CDSL as binder was
much lower than roasted corn (mean: 0.28  102) and roasted chili
(mean: 0.45  102) in the CGs using clay as binder, and they was
equivalent to the S content in fresh corn and fresh chili. Therefore, the
SO2 pollution in the traditional ue-curing barn was reduced markedly after CDSL instead of clay as binder.
The S content in the baked corn (mean: 0.34  102) and chili
(mean: 0.6  102) of 2009 was higher than that in the baked corn
(mean: 0.28  102) and chili (mean: 0.45  102) of 2010. As the
grain is stored with long time, the corn and chili continue to adsorb
the sulde emitted during the coal burning.

733

markedly, it is still higher (0.94 mg m3) than indoor SO2 quality

standard (0.5 mg m3). So, reducing the SO2 pollution in the
kitchen with improved coal stove is main direction from now
on. The epidemiological survey should be carried out.
3) Based on the above explained experiments for uorine and
sulfur reducing, the indoor gaseous uoride and SO2 pollution
in traditional ue-curing barn have obvious decrease after
CDSL instead of clay as binder. Therefore, the food adsorption
capacity to uorine and sulfur is reduced.
4) The mean uorine content in clay is 1327 mg kg1, yet in the
CDSL is less than 100 mg kg1, which suggests that the overall
uorine content in the system of coal plus 30% of this low
uorine CDSL is far less than that in coal with ordinary clay.
Therefore, abandoning the hundreds of years traditional way
of mixed clay with coal will make the gaseous uoride concentration in indoor air greatly reduced.

5. Conclusions
Based on the systematic study of the gaseous uoride and SO2
pollution level in outdoor environment, the kitchen and the
traditional ue-curing barn, as well as the experiment for uorine
and sulfur retention, main conclusions in this study have been
summarized as follows:
1) Mean value of gaseous uoride in outdoor air in Yujiawan Village,
Zhenxiong County (0.51 mg dm2 day) and in Group 22, Xiaomi
Village, Zhaoyang District (2.7 mg dm2 day) was both lower than
the ambient air quality standard (3 mg dm2 day). But some were
higher than the ambient air standard. So, to some extent, the
outdoor air was polluted by uoride emitted by coal-burning.
2) The households in Zhaotong City use LFC mixed HFCL as domestic energy. By comparing before and after improving coal
stove, the gaseous uoride and SO2 concentration in the kitchen
air has been declined markedly. The gaseous uoride concentration (3.7 mg m3) in the kitchen air is much lower than
ambient air quality (7 mg m3) and reference value (10 mg m3).
Although the SO2 concentration in the kitchen air has decreased

The cost of adding calcined dolomitic siliceous limestone

instead of clay as a binder for briquette-making.
The calcined dolomitic siliceous limestone has some cohesiveness and can be used as a binder for ne coal burning in Zhaotong
City. The calcined dolomitic siliceous limestone in the residential
coal combustion is not only a binder, but also sulfur-xing agent and
combustion improver. If the calcined dolomitic siliceous limestone
is added into the residential coal combustion, the cost of 1000 kg
coal will increase 5e10 (1e2 US$) Yuan (RMB). Also, about 4000 kg
coals are burned every year by people living in uorosis area in
Southeast China for baking food, half of them are lump coal, whose
price is twice of ne coal, 100 Yuan (RMB) (14 US $) more than ne
coal. Thus, increased cost of the briquettes is offset by using less or
no lump coal. Actually, the cost of baking foodstuffs does not increase by using the calcined dolomitic siliceous limestone.
This method is simple, and drawing the carbonate material in
local is very easy, but let local people substitute the calcined carbonate for the clay, which added in the coal for hundreds of years is
not easy. Therefore, the promotion of this method needs time and
depends on the vigorous propaganda and support of government.

Fig. A.1. Corns and chilies (corns are placed in the attic) are baked by the mixture of coal and clay, and improved coal stove is treated as open furnace.

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Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

Fig. A.2. Carbonate rocks widely distributing in coal-burning endemic uorosis area in Zhaotong.

Fig. A.3. Edibility method of baked corn.

Fig. A.4. Sampling method of indoor gaseous uoride.

Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

Fig. A.5. Sampling method of indoor SO2.

Fig. A.6. Corn and chili are baked by the mixture of coal and calcined dolomitic siliceous limestone.

Fig. A.7. The outcrop of re-resistant clay around Group 22 in Xiaolongdong Township.

735

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Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

Fig. A.8. The mixture of coal and calcined dolomitic siliceous limestone in the EGs.

Fig. A.9. A child suffering dental uorosis in Yuqing Village in Zhenxiong County
(10 years old).

Acknowledgments
This work is supported by the National High-Tech R&D Program
(863 Program) (Nos. 2004AA601080 and 2006AA06Z380) and National Natural Science Foundation of China (No. 40872210,
41172310). Special thanks are given to Science and Technology
Bureau of Zhaotong and local personnel for their support in sampling and collection of clay, calcined dolomitic siliceous limestone
and coal samples. We thank Dr. Huijie Li for their seless help in
sampling. Many thanks are also given to Dr. Yongxin Xu and Ms.
Wulan Tan for their help in the uorine and sulfur determinations.
Thank Ms Yuling Zhang for crushing samples.
References
An, D., He, G.H., Wang, Q.D., Hu, X.Q., 1995. Indoor pollution by coal smoke containing sulphur, arsenic and uorine and their inuence on humans health.
Journal of Environment and Health 12 (4), 167e169.
Ando, M., Tadano, M., Asanuma, S., Tamura, K., Matsushima, S., Watanabe, T.,
Kondo, T., Sakurai, S., Ji, R.D., Liang, C.K., Cao, S.R., 1998. Health effects of indoor
uoride pollution from coal burning in China. Environmental Health Perspectives 106 (5), 239e244.
Ando, M., Tadano, M., Yamamoto, S., Tamura, K., Asanuma, S., Watanabe, T.,
Kondo, T., Sakurai, S., Ji, R.D., Liang, C.K., Chen, X.Q., Hong, Z., Cao, S.R., 2001.
Health effects of uoride pollution caused by coal burning. The Science of the
Total Environment 271, 107e116.
Cao, S.R., 1992. Indoor air pollution of residents in uorosis prevalence area caused
by coal burning. Journal of Hygiene Research 21 (2), 75e79.
Cao, Z.P., 2001. Prevention review of endemic uorosis in Zhaotong City. Chinese
Journal of Endemiology 20 (2), 158.

Chen, C.G., Li, P., Wu, D.S., Wang, W.Y., Zheng, B.S., Xiao, H.Y., Wang, P., 2009.
Fluoride pollution control of honeycomb briquette combustion. Chinese Journal
of Environmental Engineering 3 (1), 131e136.
Dai, S.F., Ren, D.Y., Ma, S.M., 2004. The cause of endemic uorosis in western
Guizhou Province, Southwest China. Fuel 83, 2095e2098.
Finkelman, R.B., Belkin, H.E., Zheng, B.S., 1999. Health impacts of domestic coal use
in China. Proceedings of the National Academy of Sciences of the United States
of America 96 (3), 3427e3431.
Feng, F.J., Liu, X.P., Yu, J.P., Wang, W.Y., Luo, K.L., 2004. Determination of uoride in
the environmental samples by combustion-hydrolysis-ion selective electrode
method. Journal of Hygiene Research 33, 288e291.
General Administration of Quality Supervision (GAQS), Inspection and Quarantine
of the Peoples Republic of China (IQPRC), 2007. Determination of Total Sulfur in
Coal (GB/T214-2007).
General Administration of Quality Supervision (GAQS), Inspection and Quarantine
of the Peoples Republic of China (IQPRC), 2004. Classication for Coal QualityPart2: Sulfur Content (GB/T 15224.2e2004).
He, G.L., Ying, B., Liu, J., Gao, S.R., Shen, S.L., Balakrishnan, K., Jin, Y.L., Liu, F., Tang, N.,
Shi, K., Baris, E., Ezzati, M., 2005. Patterns of household concentrations of multiple
indoor air pollutants in China. Environmental Science & Technology 39, 991e998.
Jin, Y.L., M, X., Chen, X.N., Cheng, Y.B., Baris, E., Ezzati, M., 2006. Exposure to indoor
air pollution from household energy use in rural China: the interactions of
technology, behavior and knowledge in health risk management. Social Science
& Medicine 62, 3161e3176.
Li, H.B., Dong, X.H., Rao, S.Q., Chen, Q.P., Li, L., 1989. Applicability of lime lter paper
method for monitoring uoride in air. Chinese Journal of Endemiology 4 (6),
377e382.
Liang, C.K., He, Z.L., Cao, H.G., Min, D., Li, Y.P., Zhou, M., Chen, Y.X., Ma, F., Wu, Y.H.,
1993a. Study on the joint effect of uoride and sulphur dioxide from indoor coal
burning on experimental animal through natural inhalation. Journal of Hygiene
Research 22 (3), 148e151.
Liang, C.K., Li, W.H., Ma, F., 1993b. Study on hygienic standards of uoride in corn for
coal smoke uorosis areas. Journal of Environment and Health 10 (4), 158e160.
Liang, C.K., Li, W.H., Ma, F., 1992. Study on hygienic standard of uoride in indoor air
for coal smoke uorosis areas. China Journal of Public Health 11 (6), 325e327.
Li, H.Q., Xu, S.Y., Wang, M., 1995. The uoride content and distribution in clay used
for coal combustion in Zhenxiong County. Chinese Journal of Endemiology 14
(5), 290e291.
Lisle, L., Lefroy, R., Anderson, G., Blair, G., 1994. Methods for the measurement of
sulphur in plants and soil. Plants and Soils 164, 243e250.
Liu, C., Wu, F.Z., Tang, L.Y., Yu, W., 1991. The Study on evaluation of the effects for air
pollution of uorine on production environment of mulberry and silkworm.
Journal of Agro-Environmental Science 10 (2), 52e55.
Liu, D., Sakai, Y., Yamamoto, M., Sadakata, M., 2006. Behavior of uorine in the
combustion of Chinese coal in small furnaces. Energy & Fuels 20, 1406e1410.
Luo, K.L., Li, H.J., Chen, T.B., Wang, W.Z., Bi, S.G., Wu, X.Z., Li, W., Wang, L.H., 2008.
Content of arsenic, selenium, mercury in the coal, food, clay and drinking water
in the Zhaotong uorosis area, eastern Yunnan Province. Journal of China Coal
Society 33 (3), 289e294.
Luo, K.L., Li, H.J., Feng, F.J., Chen, T.B., Xiong, M.H., Wang, W.Z., Liao, X.Y., Wang, L.H.,
2007. Content and distribution of uorine in rock, clay and water in uorosis
area Zhaotong, Yunnan Province. Journal of China Coal Society 32 (4), 363e368.
Luo, K.L., Li, H.J., Niu, C.X., 2010. Fluorine and Arsenic pollution route of grain in
Yunnan-Guizhou coal-burning endemic uorosis area. Geological Review 56
(2), 289e298.
Luo, K.L., Li, L., Zhang, S.X., 2011. Coal-burning roasted corn and chili as the cause of
dental uorosis for children in southwestern China. Journal of Hazardous Materials 185, 1340e1347.
Luo, K.L., Ren, D.Y., Xu, L.R., Dai, S.F., Cao, D.Y., Feng, F.J., Tan, J.A., 2004. Fluorine
content and distribution pattern in Chinese coals. International Journal of Coal
Geology 57, 143e149.
Ministry of Environmental Protection of the Peoples Republic of China, 2003.
Methods for Chemical Analysis of Air and Exhausted Gas, fourth ed. Science
Press of China, Beijing, pp. 150e153.
National standards of the Peoples Republic of China (NSPRC), 1984. Permitted Level
of Fluorine in Foods, GB4809e84.
Ozturk, N., Yargicoglu, P., Derin, N., Akponar, D., Agar, A., Aslan, M., 2011. Dosedependent effect of nutritional sulte intake on visual evoked potentials and
lipid peroxidation. Neurotoxicology and Teratology 33 (2), 244e254.
Parcell, S., 2002. Sulfur in human nutrition and applications in medicine. Alternative Medicine Review 7 (1), 22e44.
Ren, D.Y., Zhao, F.H., Dai, S.F., Zhang, J.Y., Luo, K.L., 2006. Geochemistry of Trace
Elements in Coal. Science Press, Beijing, pp. 101e105.
Sinton, J.E., Smith, K.R., Peabody, J.W., Liu, Y.P., Zhang, X.L., Edwards, R., Gan, Q.,
2004. An assessment of programs to promote improved household stoves in
China. Energy for Sustainable Development 8 (3), 33e52.
Sun, Y.Z., 2005. Geochemical study advance about uorine in coal and coalburning endemic uorosis from Western Guizhou. Bulletin of Mineralogy
Petrology and Geochemistry 24 (4), 350e356.
Swaine, D.J., 1990. Trace Elements in Coal. Butterworth, London, pp. 73e74.
The State Bureau of Technology of the Peoples Republic of China (SBTPRC), 1997.
Determination of Fluoride in Coal (GB/T4633-1997).
Wang, M., Wang, X.R., Jia, M., 2001. Monitoring results and analysis of endemic
uorosis in Qinggangling Village in 2000. Chinese Journal of Endemiology 16
(6), 361e362.

Y. Liu et al. / Atmospheric Environment 77 (2013) 725e737

Wu, X.P., 1982. Determination of the uoride content in air-lime lter paper
method. Environmental Monitoring of China 1, 30e304.
Yamada, K., Sorimachi, A., Wang, Q.Y., Yi, J., Cheng, S.Q., Zhou, Y.R., Sakamoto, K.,
2008. Abatement of indoor air pollution achieved with coalebiomass household briquettes. Atmospheric Environment 42, 7924e7930.
Yan, B.W., 1996. Associated disease with coal-burning endemic uorosis. Foreign
Medical Sciences (Section of Med Geography) 17 (1), 15e16.
Yang, J.L., Chen, D.G., Li, S.M., Yue, Y.L., Jin, X., Zhao, B.C., Ying, B., 2010. Fluorinexing efciency on calcium-based briquette: pilot experiment, demonstration
and promotion. Chinese Medical Journal 123 (3), 361e364.
Ye, F., Yang, G.R., Peng, H.B., Wang, A.W., Yang, C.G., 2004a. Investigation result and
analysis of endemic coal-burning uorosis in Zhaotong City, Yunnan Province in
2002. Endemic Disease Bulletin 19 (2), 63e64.
Ye, F., Yang, G.R., Peng, H.B., Ma, X.W., Zhou, Z.Z., Cao, Z.P., Meng, J.H., Zhang, Y.K., Chen, Z.S.,
Wang, A.W., 2004b. Key-point investigation result and analysis of endemic coalburning uorosis in Zhenxiong County. Endemic Disease Bulletin 19 (1), 41e42.

737

Ye, F., Wang, A.W., Yang, C.G., Peng, H.B., Ma, X.W., Zhou, Z.Z., Cao, Z.P., Meng, J.H.,
Cai, Z.H., Yin, J.Z., Zhou, R.F., Sun, J.F., 2005a. Summary of the surveillance of
endemic coal-burning uorosis in Zhaoyang District in 2002 and 2003. Chinese
Journal of Endemiology 24 (5), 561e563.
Ye, F., Wang, A.W., Peng, H.B., Ma, X.W., Zhou, Z.Z., Zhou, R.F., Sun, J.F., 2005b.
Monitoring report of endemic coal-burning uorosis in Zhaoyang District,
Zhaotong City in 2003. Chinese Journal of Endemiology 24 (1), 109.
Zhao, B.C., 1992. Effect on xing uorine and sulphur in the stove-improving
areas of endemic coal-burning uorosis. Journal of Hygiene Research 21
(2), 79e82.
Zhang, J.F., Smith, K.R., 2007. Household air pollution from coal and biomass fuels in
China: measurements, health impacts, and interventions. Environmental
Health Perspectives 115 (6), 848e855.
Zhang, S.X., Qi, Q.J., Liu, J.Z., Zhou, J.H., Cao, X.Y., Chen, K.F., 2002. Pore structure
characters of limestone and inuence upon uoride retention. Journal of Fuel
Chemistry and Technology 30 (4), 311e315.