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. 2021 Apr 15;16(4):e0249913. doi: 10.1371/journal.pone.0249913

Risk assessment of workers’ exposure to BTEX and hazardous area classification at gasoline stations

Sunisa Chaiklieng 1,*
Editor: Antonio Peña-Fernández2
PMCID: PMC8049477  PMID: 33857202

Abstract

Vaporization of benzene, toluene, ethylbenzene, and xylene (BTEX) compounds pollutes the air and causes health hazards at gasoline stations. This study revealed the risk of BTEX exposure according to the hazardous area classification at gasoline stations. The risk assessment of gasoline workers from a representative group of 47 stations, which followed the United States Environmental Protection Agency-IRIS method of assessing BTEX exposure, was expressed as the hazard index (HI). A result of matrix multipliers of the hazardous exposure index and fire possibility from flammable gas classified hazardous area-I and area-II at the fuel dispensers. BTEX concentrations were actively sampled in ambient air and a flammable gas detector was used to measure the flammability level. Results showed that the BTEX concentrations from ambient air monitoring were in the range of 0.1–136.9, 8.1–406.0, 0.8–24.1 and 0.4–105.5 ppb for benzene, toluene, ethylbenzene, and xylene, respectively, which exceeded the NIOSH exposure limit of 100 ppb of benzene concentration. The risk assessment indicated that five stations reached an unacceptable risk of worker exposure to BTEX (HI>1), which correlated with the numbers of gasoline dispensers and daily gasoline sold. The risk matrix classified hazardous area-I at 4 meters and hazardous area-II at 4–8 meters in radius around the fuel dispensers. This study revealed the hazardous areas at gasoline stations and suggests that entrepreneurs must strictly control the safety operation practice of workers, install vapor recovery systems on dispenser nozzles to control BTEX vaporization and keep the hazardous areas clear of fire ignition sources within an eight-meter radius of the dispensers.

Introduction

Exhaust fumes from refueling vehicles at gasoline stations lead to a poor quality of ambient air due to volatile organic solvent evaporation of BTEX compounds (benzene, toluene, ethylbenzene, and xylene). A previous report confirmed that the annual average concentration of volatile organic compounds (VOCs) from fuel evaporation of oil and gas stations in Northwest China was 21.5±1.0% [1]. That is one reason for the induction of hazardous conditions with contributions from fuel vapor pollution [2]. Gasoline workers and clients exposed to BTEX while refueling are affected by adverse health effects. Benzene is a human carcinogen which also affects the human hematopoietic and reproductive systems [3]. Ethylbenzene and xylene have caused abnormal respiratory and neurological effects [4]. Gasoline workers had health risks from BTEX chronic exposure and some workers had a higher than acceptable risk of BTEX exposure [5, 6]. It was also shown that the lifetime cancer risk of exposure to benzene in Thai gasoline workers exceeded the acceptable limit [5, 7, 8] and this risk was similar to that found in the studies in Malaysia [9, 10]. The health risks of working in hazardous zones at gasoline stations related to BTEX exposure are still not clear with regard to the contribution from sources of vaporization.

In Thailand, maximum concentrations of 222, 527, 26 and 114 ppb were found for benzene, toluene, ethylbenzene, and xylene, respectively, at the gasoline stations of Bangkok [11]. The mean concentration of benzene was found to be 45.36 ppb at the gasoline stations in the northeast of Thailand [12]. With regard to other countries [13, 14], the concentrations found there were lower compared to Thai gasoline stations, such as in the gasoline stations of Brazil, where BTEX concentrations were 9.30, 12.7, 5.4 and 11.42 ppb for benzene, toluene, ethylbenzene and xylene, respectively [14]. Gasoline station workers in Kuwait were exposed to concentrations in excess of the NIOSH exposure limits [15]. The number of gasoline stations has risen by an average of 4–5 percent a year to 28,753 stations in Thailand [16] and they have been controlled by the Ministry of Energy. The level of benzene in fuel was reduced from 3.5% by volume to 1% by volume in 2012 [17]. Vapor recovery systems (VRS) have been installed at gasoline stations in Bangkok and its surrounding areas since 2007, according to a policy that did not cover other regions of Thailand.

The hazardous area classification related to human health risk and fire risk at gasoline stations was not adequately studied in the previous research. This study aimed to classify complex hazardous areas according to the health risk indications of gasoline workers and flammable gas evaporation during the refueling of vehicles.

Materials and methods

Sample size

This study was conducted at 47 gasoline stations. The representative sample size of the gasoline stations was calculated using Cochran [18] under the known number of a total of 64 stations located on both sides of Mittraphap Road, the main highway in Khon Kaen province, Thailand [16]. There were three inclusion criteria for the gasoline stations: 1) they had to be located in an area along either side of or within 5 km of Mittraphap Road, the main highway connecting Khon Kaen province to Bangkok, the capital city of Thailand, 2) they had to have more than eight dispenser nozzles and gasoline dispenser nozzles; and 3) they had to have more than 8 hours of daily operation time. This study was approved by Khon Kaen University’s Ethics Committee for Human Research (No. HE612102). All participants from the gasoline stations gave written informed consent prior to taking part in the study and workers aged under 18 years were not included.

Data collection

A gasoline station survey form was used to collect the characteristics of 47 gasoline stations and answers to questions regarding workers’ characteristics, i.e. working hours per day and number of work days per week, were collected from the fueling workers. The BTEX concentrations were measured by active sampling with a charcoal tube at a flow rate of 0.2 L/min, as described in NIOSH method 1501 [19]. The exposure to BTEX was monitored during each working shift; this monitoring covered the peak service hours for 4 hours of sampling and all charcoal tubes were kept at 4°C while being transported to the laboratory. Each tube was extracted with carbon disulfide (CS2), and analyzed by gas chromatography (GC) with flame ionization detector (FID) (Varian, CP3800), CP 52 wax column (30 m x 0.25 μm x 0.25 mm) of Hewlett Packard 1996, Germany, and a limit of detection (LOD) which was < 0.001 ppm and < 0.003 ppb for toluene and benzene and < 0.05 ppb for ethyl- benzene and xylene. The results of the BTEX concentrations were used to estimate the human health risk of exposure to BTEX.

A flammable gas detector was used to measure the total emission of VOCs with a photo ionization detector (PID) sensor (detection range of 0 to 1000 ppm) and a lower explosive limit—upper explosive limit (LEL-UEL) with Non-Dispersive Infrared (NDIR) combustible sensors (range of 0–100%LEL) at a distance of 0.15 meters from the fuel emission point during the refueling of vehicles. The wind velocity average was recorded on the day of BTEX collection and VOCs and flammable gas measurements.

The samples were collected between June and July 2018, at times when the temperature was 28.08 ±1.58°C, humidity was 78.51±8.89%, and wind velocity was 10.0 ±2.82 m/min.

Human health risk assessment

The health risk assessment for non-cancer effects was calculated by using the hazard quotient (HQ), which followed the United States Environmental Protection Agency-Integrated Risk Information System (EPA-IRIS) [20] according to HQBTEX = EC/RfC, where EC represents exposure concentration via inhalation intake in μg/m3, and RfC is the reference concentration of daily exposure to BTEX in μg/m3 (30 μg/m3 of benzene, 5,000 μg/m3 of toluene, 1,000 μg/m3 of ethylbenzene, and 100 μg/m3 of xylene) [21, 22]. A resulting HQ of ≥1 was considered as “adverse non-cancer health effects of concern,” and a HQ of <1 was considered an “acceptable level”. The health risk was expressed as the hazard index (HI), which was determined by the summation of all HQ values of BTEX in the same area (HI = ∑HQBTEX). The exposure level (EC) was calculated by following USEPA [22] as in the formula of EC = (CA x ET x EF x ED) / AT, where CA represents contaminant concentration in μg/m3, EF represents exposure frequency in days/year (324 days/year; 6 days/week x 54 weeks/year from on-site interviews), ET represents exposure time in hours/day (9–11 hours/day from on-site interviews), ED represents exposure duration (25 years; 324 days/year) and AT represents average time (219,000 hours; 25 year x 365 days/year x 24 hour/day).

Hazardous area classification at gasoline stations

Hazardous area (HZ) classification was determined according to emission of VOCs from the result of matrix multipliers of the hazardous exposure index (HzI) and fire possibility (flammability limit; %LEL-UEL) based on exposure which simulated distance from a source along the horizontal plane in the wind direction in meters (m) (x; distance 0.15–10 m). OSHA [23] and the AS/NZS 4360:2004 risk management standard [24] were applied as per the following equation and matrix table (Table 1);

HZ=HzIxP

where HZ represents hazardous area, HzI represents the subsequent hazardous exposure index (4 levels, 4 scores) and P represents possibility (flammability limit level; 2 levels; 2 scores). The hazardous area (HZ) was divided into two areas, i.e. hazardous area-I and hazardous area-II. The scores of hazardous BTEXemission exposure risk were calculated according to distance from the point sources and BTEXemission (BTEXemiss) concentration was converted from the total concentration of VOCs.

Table 1. Risk matrix multipliers for hazardous area classification (area I, II).

Hazardous exposure index (HzI) Flammability limit (%LEL-UEL)
Out-range of 1.3–7.4% (1) In-range of 1.3–7.4% (2)
HzI >2 (4) hazardous area-I (score of 4) hazardous area-I (score of 8)
HzI = >1–2 (3) hazardous area-I (score of 3) hazardous area-I (score of 6)
HzI = 0.5–1.0 (2) hazardous area-II (score of 2) hazardous area-I (score of 4)
HzI <0.5 (1) hazardous area–II (score of 1) hazardous area-II (score of 2)

The criteria of the hazardous areas were estimated from the results of the risk assessment scores (out of 8 points), which were divided into two groups: a score of 3–8, which was classified as “hazardous area-I” and a score of 1–2, which was classified as “hazardous area-II”, as shown in Table 1.

The hazardous exposure index (HzI) was calculated as the summary hazard quotient (HQ) of BTEXemiss exposure according to the equation of HzI = ∑HQBTEXemiss. The hazardous exposure index (HzI) was estimated from the hazard index of gasoline station workers’ exposure to BTEXemiss at a distance from the fuel vapor point source. It was considered that there were potentially adverse non-carcinogenic effects of concern based on distance from source along the horizontal plane in the wind direction in meters (x). The criteria of HzI was divided by the 95th percentile of HzI. A HzI result of <0.5 was considered to be “a score of 1”, a HzI of 0.5–1.0 was considered to be “a score of 2”, a HzI of >1–2 was considered to be “a score of 3”, and a HzI of >2 of HzI was considered to be “a score of 4”.

Concentrations of VOCs were converted to BTEXemiss concentrations by using gasoline emission factors of EPA (AP-42) [25]. The BTEXemiss concentration was calculated according to the following equation; BTEXemiss = (VOCs x EFBTEX)/120 ppm, where BTEXemiss represents benzene, toluene, ethylbenzene, and xylene concentrations (ppm), VOCs is the concentration from a flammable gas detector (ppm), EFBTEX is the gasoline emission factors of benzene, toluene, ethylbenzene, and xylene, which were 7.7, 70.7, 14.2 and 70.7 ppb, respectively.

The BTEXemiss concentrations at different distances were estimated according to exposure distance by an air pollution model; the Gaussian dispersion model detailed below;

c(x,y,z)=Q2πμσyσzexp-(y22σy2)exp{(zH)22σz2+(z+H)22σz2}

where C (x,y,z) represents the BTEXemiss concentration based on exposure distance (mg/m3), Q represents the emission rate from source (average 0.17 g/s); σy represents the dispersion coefficient of BTEXemiss on the x axis in meters (0.15–10 meters in distance); σz represents the dispersion coefficient of BTEXemiss on the y axis in meters (1.5 meters; breathing zone); μ represents a velocity of wind at a source above ground level (average 10 m/s); H represents the net high plume: hs+Δhi (meters), where hs represents the air pollution source of the high plume, and hi represents the plume rise, the plume high after emission; x represents a distance from the source along the horizontal plane in the wind direction (meters); y represents a distance from the source along the level perpendicular to the wind direction (meters); and z represents the height of the source from the ground (breathing zone = 1.5 meters).

The possibility (P) of fire ignition was determined according to the flammability limit (percentage of the Lower Explosive Limit and Upper Explosive Limit (%LEL-UEL)). It was divided into two groups, which were the out-of-range and in-range %LEL-UEL of flammable gas and vapor. The criteria of the flammability level were divided by the 95th percentile of values to be compared to the range of 1.3–7.4% as specified in the fire ignition or explosion range [26]. A result outside the range of %LEL-UEL was considered “a score of 1” and a result in the range of %LEL-UEL was considered “a score of 2”.

Statistical analysis

This work was analyzed by using STATA version 10 software. Descriptive statistics were used for gasoline station characteristics and health risk assessment. The Chi-squared test was done for the association of factors with the hazard index. The statistical significance was identified at a p-value of ≤ 0.05.

Results

Characteristics of gasoline stations

There were 10.6% of gasoline stations located in urban areas, 80.9% in suburban areas and 8.5% in rural areas. A total of 27 (57.5%) stations were open 16 hours per day (06.00 am—22.00 pm) and 20 (42.6%) stations were open 24 hours for service. There was an average of 23±12 fuel nozzles per station (min: max = 8:48) and there were no VRS installed on the dispensers. There was an average safe distance of 20.4 meters (min: max = 6:45) between the fuel dispenser and service building, while five stations (10.6%) had a safe distance of less than 8 meters.

The average daily amount of gasoline sold was 3,382.8±2,382.9 liters. The gasoline stations were classified according to service type; 14 stations (29.8%) were type IV (fuel dispenser house, oil storage tanks, office, maintenance store, minimart, coffee shop, and food court), 21 stations (44.7%) were type III (fuel dispenser house, oil storage tanks, office, maintenance store, minimart, and coffee shop), six stations (12.8%) were type II (fuel dispenser house, oil storage tanks, office, and maintenance store) and six stations (12.8%) were type I (fuel dispenser house, oil storage tanks, and office).

The mean concentration of VOCs while refueling was 410.0±172.0 ppm (min: max = 158:810). There were 43 stations (91.5%), which had a VOC emission of more than 200 ppm. The recorded wind velocity average on-site was 10 meters/min.

BTEX concentrations and health hazard index in fuel dispenser areas

The resulting maximum BTEX concentrations measured by active air sampling were 136.9, 406.0, 24.1, and 105.5 ppb for benzene, toluene, ethylbenzene, and xylene, respectively. The benzene concentration of two stations (4.3%) exceeded the safety standard of 100 ppb, or 320 μg/m3 [19]. The health risk of adverse non-cancer effects (HI) ranged from <0.1 to 7.3, and five gasoline stations (10.6%) reached an unacceptable level of risk (HI>1) with regard to BTEX exposure, as shown in Table 2.

Table 2. BTEX concentrations and hazard index at the dispenser area (N = 47).

Parameter Air concentration HQ
μg/m3 mean(min-max) ppb (min-max) >TWA; n(%) min-max >1 n(%)
Benzene(B) 33.1(0.1–437.5) 0.1–136.9 2(4.3) 0.1–5.5 4(8.5)
Toluene(T) 142.7(30.5–1,529.7) 8.1–406.0 0 <0.1–0.1 0
Ethylbenzene(E) 14.4(3.4–104.9) 0.8–24.1 0 <0.1–0.1 0
Xylene(X) 41.3(1.7–458.3) 0.4–105.5 0 <0.1–1.7 1(2.1)
HIBTEX <0.1–7.3 5(10.6)

Regarding the correlation between the health risk based on chronic inhalation and the risk factors, the level of risk found in stations with higher amounts of daily gasoline sold (≥3,000 liters/day) was significantly higher than in those with lower volumes of gasoline sold. Likewise, higher numbers of gasoline dispensers resulted in a significantly higher risk than smaller numbers of nozzles.

When analyzing the potential inhalation intake based on the 95th percentile of BTEX concentration, according to the location (urban, suburban, rural) of the gasoline station, it was shown that the HI across all zones indicated an unacceptable risk (HI>1) at five stations which were in urban and suburban areas. There was an almost significant difference between the HI of the three zones. The service type of stations and amount of gasoline dispensers and VOC emissions led to cumulative effects on the upward trend of the hazard index. Five stations classified as type III+IV gasoline stations reached an unacceptable level of risk (HI>1). A total of more than 12 gasoline dispensers (including gasoline 95, octane 91, and octane 95) increased the impact on workers’ health. Furthermore, there was also concern that VOC emissions from dispensers (≥200 ppm) could raise health risk potential, as shown in Table 3.

Table 3. The factors correlating with the hazard index (HI) of workers’ exposure to BTEX at gasoline stations (N = 47).

Parameters HI of BTEX p-value
HI≤1, n(%) HI>1, n(%)
Location of gasoline station 0.06
 Rural (n = 4) 4(100.0) 0
 Suburban (n = 38) 34(89.5) 4(10.5)
 Urban (n = 5) 4(80.0) 1(20.0)
Daily gasoline sold (liters) 0.02*
 <3,000 (n = 23) 23(100.0) 0
 ≥3,000 (n = 24) 19(79.2) 5(20.8)
Service-zone type of station 0.16
 Type I+II (n = 12) 12(100.0) 0
 Type III+IV (n = 35) 30(85.2) 5(14.3)
Number of gasoline dispensers 0.05*
 <12 (n = 19) 19(100.0) 0
 ≥12 (n = 28) 23(82.1) 5(17.9)
Number of fuel nozzles 0.20
 <12 (n = 8) 8(100.0) 0
 ≥12 (n = 39) 34(87.2) 5(12.8)
VOC concentration (ppm) 0.47
 <200 (n = 4) 4(100.0) 0
 ≥200 (n = 43) 26(88.4) 4(11.7)

*Significant at p-value ≤ 0.05

Health hazardous zone (HHZ) and fire hazardous zone (FHZ)

The mean BTEXemiss values converted from VOCs were used to analyze the hazardous exposure index (HzI) and estimate the health hazardous zone (HHZ). It was found that two stations (4.3%) had a HzI value of more than 1 at a distance of 2 meters, with a value of 1.2 at the 95th percentile of HzI (maxHzI = 2.7). One station had been shown to have a HzI value between 0.5 to 1 at a distance of 8 meters, with a maximum HzI value of 0.53. From this finding, the area around the dispenser was divided into two health hazardous zones (HHZ), i.e. within a two-meter radius of the dispenser was classified as health hazardous zone-I (HHZ-I) and the area >2–8 meters from the dispenser was classified as health hazardous zone-II (HHZ-II), as shown in Table 4.

Table 4. Hazardous exposure index and fire possibility calculated for distances (in meters) around the dispensers at gasoline stations (N = 47).

Distance (meter) Hazardous exposure index (HzI) %LEL-UEL(1.3–7.4)
<0.5 n(%) 0.5 to 1 n(%) >1 n(%) 95th HzI max HzI Out-range n(%) In-range n(%) 95th max
0.15 11(23.4) 18(38.3) 18(38.3) 22.7 27.9 0(0) 47(100) 21.8 26.0
1 39(82.9) 0 8(17.0) 4.9 12.6 24(51.0) 23(49.0) 6.5 7.8
2 45(95.7) 0 2(4.3) 1.2 2.7 44(93.6) 3(6.4) 2.0 2.4
3 45(95.7) 2(4.3) 0 0.9 0.9 47(100) 0 0.6 0.8
5 45(95.7) 2(4.3) 0 0.4 0.8 47(100) 0 0.1 0.1
8 46(97.8) 1(2.1) 0 0.2 0.5 47(100) 0 <0.1 <0.1
10 47(100) 0 0 <0.1 0.1 47(100) 0 <0.1 <0.1

Italic and bold numbers indicate the distance in meters according to a HzI>1 (zone-I) and 0.5 to 1 (zone-II); or an in-range %LEL-UEL.

The fire hazardous zones (FHZ) were decided according to the 95th percentile of %LEL-UEL. A result outside the range of 1.3–7.4% was considered “fire hazardous zone-II; FHZ-II” and a result in the range of 1.3–7.4% was considered “fire hazardous zone-I; FHZ-I”. The results were out of the range of the flammability limit level (less than the 1.3% within a two-meter radius of the dispenser area). Therefore, fire hazardous zone-I was classified as within a two-meter radius of the dispenser and fire hazardous zone-II was classified as the area >2 meters to 8 meters from the dispenser, as shown in Table 4.

Hazardous area classification

Hazardous area (HZ) classification was determined from the results of the matrix multipliers as presented in Table 5 for “hazardous area-I: HZ-I” and “hazardous area-II: HZ-II”. As shown by the data, it was found that two stations (4.26%) out of 47 stations scored higher than 3 at up to 4 meters from the dispenser; therefore, hazardous area-I was designated as up to 4 meters from the dispenser. Based on a score of 1–2 and the safety action value of the hazardous exposure index (HzI = 0.5 to 1), hazardous area-II was initially determined as up to 8 meters from the dispenser. However, it was eventually determined as >4–8 meters because the safety action set of HzI values was found to be 0.56 at 8 meters radius from the dispenser. The graphic representation of hazardous areas discovered in this study for safety action is shown in Fig 1.

Table 5. Hazardous area classification by matrix multipliers of HzI and %LEL-UEL at the gasoline stations (N = 47).

Distance (meter) HzI %LEL-UEL Hazardous area (HZ)
95th Max 95th Max HZ-I;≥3 n(%) HZ-II;1–2 n(%)
0.15 22.7 27.9 21.8 26 47(100) 0(0)
1 4.8 12.6 6.5 7.8 8(17.0) 39(82.9)
2 1.2 2.7 2.0 2.4 2(4.3) 45(95.7)
3 0.9 0.9 0.6 0.8 2(4.3) 45(95.7)
4 0.8 0.9 0.2 0.3 2(4.2) 45(95.7)
5 0.4 0.8 <0.1 0.1 0 47(100)
6 0.4 0.7 <0.1 <0.1 0 47(100)
7 0.3 0.6 <0.1 <0.1 0 47(100)
8 0.2 0.5 <0.1 <0.1 0 47(100)
9 0.2 0.4 <0.1 <0.1 0 47(100)
10 <0.1 0.1 <0.1 <0.1 0 47(100)

Fig 1. Hazardous area-I and area-II classification (HZ) to cover HHZ and FHZ.

Fig 1

Discussion

BTEX concentrations in the ambient air of working surroundings throughout the period spent at dispensing areas were lower than in previous studies in Bangkok, Thailand [11], but benzene and toluene concentrations were higher than those of other countries [13, 14] and in excess of the NIOSH standard level (100 ppb), like in the study of gasoline station workers in Kuwait [15]. A study of a gasoline station in Malaysia [9] found that concentrations were quite lower or close to the range in our study. Moreover, it was found that the benzene concentration in the dispenser area of two stations exceeded the safety standard and was higher than the previous finding in Khon Kaen, Thailand [12]. Our previous report at the fuel storage tank areas of gasoline stations [6] showed that they had higher benzene concentrations than the dispensing areas, which explains that the fuel loading amount was related to benzene exposure, resulting in consequential adverse effects on the health of workers.

From the adverse-effect risk assessment findings on exposure to BTEX via inhaled air in working zones, it was found that there were five stations which had a high health risk value exceeding an acceptable limit (HI>1) for BTEX exposure. As a result, benzene exposure at five gasoline stations was assessed to be unacceptable with regard to human risk, which was supported by recent studies in Thailand [6] and Malaysia [9, 10], which has similar climatic conditions to Thailand. The previous findings showed that an unacceptable risk (HQ>1) of benzene exposure at gasoline stations was related to their locations, i.e. there were higher risks in urban and suburban areas in comparison to rural areas [5], as confirmed by this study, and the characteristics of the refueling service function, i.e. working close to the gasoline dispensers, could lead to a higher health risk [5].

The assessed human health risk of BTEX exposure in the dispenser areas was significantly correlated with the daily amount of gasoline sold and the number of benzene dispensers. These factors potentially caused the hazard index value to be higher than 1 (HI>1). In particular, with regard to the amount of benzene sold, this study supports previous findings in that high levels of service provision were related to higher exposure to benzene among gasoline workers [12]. Concerning the location of gasoline stations, chronic inhalation of the benzene concentrations at suburban stations resulted in a significantly higher risk than in other zones. Moreover, the gasoline station workers’ health impact was related to high VOC concentrations due to exposure during the refueling of vehicles, as shown in a previous report [5].

The findings regarding the hazardous area around fuel dispensers meant that hazardous area-I was classified as up to 4 meters in radius, and area-II was classified as up to 8 meters in radius. The hazardous area, which resulted from a risk matrix which considered appropriate concentrations of flammable gases for fire ignition and exposure to volatile organic chemicals, could meet the specifications of the defined hazardous zone of the IEC international standard [27]. According to the hazardous zones defined by the 2013 ministerial regulations in Thailand [28], zone-I is only 1 meter in radius, and zone-II is classified as 1–1.5 meters around the dispensers for safety control of fire risk. However, our study found that the hazardous areas of fire risk and health risk of workers cover an area up to 8 meters in radius around dispensers, as shown in Fig 1.

Hazardous area-I had a high potential of workers’ health risk, which was supported by the previous study of urinary tt-MA biomarker detection of benzene exposure in those working close to fuel nozzle during refueling [29]. This finding seems to be consistent and covered zones wider than the 1.5-meter radius around the dispensers of the previous study, which found that fire risk zone I had an intolerable risk in the fire risk assessment [30]. Moreover, benzene exposure was previously reported as higher in refueling workers than in those doing other jobs at gasoline service stations [5, 29].

In addition, this study found that five gasoline stations had service types which included convenience stores, minimarts, parking lots, and facilities located in hazardous area-II (up to 8 meters in radius from the dispensers), which meant that they had a hazard index higher than 0.5 (safety action point). So, entrepreneurs must strictly control hazards harmful to the health of gasoline station clients and working attendants.

Conclusions and recommendations

BTEX concentrations in the working ambient air of gasoline stations were in the range of 0.1–136.9, 8.1–406.0, 0.8–24.1 and 0.4–105.5 ppb for benzene, toluene, ethylbenzene, and xylene, respectively. There were values which exceeded the safety standard value for benzene concentration. Risk assessment of workers on BTEX exposure indicated that six stations had reached an unacceptable level of risk (HI>1), which was related to the number of gasoline dispensers and the amount of daily gasoline sold. Hazardous area-I was classified as up to 4 meters in radius around the dispenser. The suggestion is that entrepreneurs must strictly control safety operation practice methods, such as wearing personal protective equipment, and provide safety training for workers to raise awareness of protecting against BTEX exposure in addition to a health surveillance program. Above all, entrepreneurs should control BTEX vaporization by installing VRS on dispenser nozzles, and make the hazardous areas clear by marking a safety line and informing clients that hazardous area-II is up to 8 meters in radius around the dispensers.

Supporting information

S1 File. Survey form English.

(PDF)

S2 File. Survey form Thai.

(PDF)

Data Availability

All relevant data are within the manuscript and its Supporting Information files.

Funding Statement

This study was partially supported by research funding from The National Research Council of Thailand (NRCT610007). No additional external funding received for this study.

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Decision Letter 0

Antonio Peña-Fernández

21 Jan 2021

PONE-D-20-27491

Risk assessment on workers’ exposure to BTEX and hazardous area classification at gasoline stations

PLOS ONE

Dear Dr. Chaiklieng,

Thank you for submitting your manuscript to PLOS ONE. After careful consideration, we feel that it has merit but does not fully meet PLOS ONE’s publication criteria as it currently stands. Therefore, we invite you to submit a revised version of the manuscript that addresses the points raised during the review process.

Thank you for your manuscript. I agree with the comments provided by the reviewers, and consider that the manuscript needs major revision. Please could you consider them and submit a revised version addressing the comments and feedback provided by the reviewers and by myself?

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We look forward to receiving your revised manuscript.

Kind regards,

Antonio Peña-Fernández, PhD

Academic Editor

PLOS ONE

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2. Please include additional information regarding the survey or questionnaire used in the study and ensure that you have provided sufficient details that others could replicate the analyses. For instance, if you developed a questionnaire as part of this study and it is not under a copyright more restrictive than CC-BY, please include a copy, in both the original language and English, as Supporting Information.

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3.Thank you for stating the following in the Acknowledgments Section of your manuscript:

"This study was financially supported by the National Research Council of Thailand (NRCT6100007)."

We note that you have provided funding information that is not currently declared in your Funding Statement. However, funding information should not appear in the Acknowledgments section or other areas of your manuscript. We will only publish funding information present in the Funding Statement section of the online submission form.

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Please include your amended statements within your cover letter; we will change the online submission form on your behalf.

Additional Editor Comments:

Dear author,

Thank you for your manuscript. I agree with the comments provided by the reviewers, and consider that the manuscript needs major revision. The manuscript should be carefully reviewed, re-written and improved for consideration for publication. The revised version should also provide more information (and updated) on the toxicological aspects of BTEX compounds. More information is also required about on the quality controls undertaken in the laboratory for the analysis of the samples. This section needs comprehensive revision. Thus, Author should explain the quality controls undertaken for the quantification of BTEX in the samples, and the reference materials used or quality controls, so the results are reliable. The author should explain what ppbs stands for, i.e. are they in µg/m3?, and indicate the limits of detection for each substance. All the measures were higher than the LoD? The author should indicate when the samples were collected. I agree with the comments provided by the second reviewer, that author should compare the data found with other similar studies performed in their country and in the recent literature. Lines 71-72 should be rewritten for clarity.

Best wishes

Antonio

[Note: HTML markup is below. Please do not edit.]

Reviewers' comments:

Reviewer's Responses to Questions

Comments to the Author

1. Is the manuscript technically sound, and do the data support the conclusions?

The manuscript must describe a technically sound piece of scientific research with data that supports the conclusions. Experiments must have been conducted rigorously, with appropriate controls, replication, and sample sizes. The conclusions must be drawn appropriately based on the data presented.

Reviewer #1: Yes

Reviewer #2: Yes

**********

2. Has the statistical analysis been performed appropriately and rigorously?

Reviewer #1: Yes

Reviewer #2: Yes

**********

3. Have the authors made all data underlying the findings in their manuscript fully available?

The PLOS Data policy requires authors to make all data underlying the findings described in their manuscript fully available without restriction, with rare exception (please refer to the Data Availability Statement in the manuscript PDF file). The data should be provided as part of the manuscript or its supporting information, or deposited to a public repository. For example, in addition to summary statistics, the data points behind means, medians and variance measures should be available. If there are restrictions on publicly sharing data—e.g. participant privacy or use of data from a third party—those must be specified.

Reviewer #1: Yes

Reviewer #2: Yes

**********

4. Is the manuscript presented in an intelligible fashion and written in standard English?

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Reviewer #1: Yes

Reviewer #2: Yes

**********

5. Review Comments to the Author

Please use the space provided to explain your answers to the questions above. You may also include additional comments for the author, including concerns about dual publication, research ethics, or publication ethics. (Please upload your review as an attachment if it exceeds 20,000 characters)

Reviewer #1: This is a relevant study on workers exposure to BTEX, a worlwide problem. The study describes well the methodology followed and how the exposure and risk have been estimated. Results are well described. The authors may consider to expand on possible solutions or exposure controls to prevent workers exposure.

Specific comments:

Title: Risk assessment "of" workers´s exposure (delete "on").

Lines 31-32. "radius around the fuel dispensers" (delete "in")

Line 93-94: "as described in NIOSH method 1501 [15]" delete "which followed NIOSH number 1501 [15] methodology

Line 95: "monitored" not "monitoring"

Line 103: describe the acronym LEL-UEL

Line 171-176: the terms Ox, Oy are not represented in the formula. It is not clear what terms in the formula the refer to.

Reviewer #2: General comment

The manuscript discusses the risk assessment of workers’ exposure to BTEX and hazardous area classification at gasoline stations in Thailand. The results show the concentration of Benzene exceeds the limit of 100 ppb. Risk assessment of workers on BTEX exposure indicated that six stations had reached an unacceptable risk (HI>1) which was related to the number of gasoline dispensers and the amount of daily gasoline sold. Overall the study is interesting. Nevertheless, the author still needs to improve the writing with the inclusion of references to strengthen the introduction of the manuscript. The methodology needs to be improved with information on sampling and QA/QC.

Detail Comment

1. Abstract: Include the full name of EPA-IRIS

2. Safe standard of benzene (100 ppb): Include name of the agency on country suggest the value of concentration.

3. In term of comparison with previous studies, I suggested the author include previous similar studies conducted in Thailand such as:

Dacherngkhao, T., Chaiklieng, S., 2019. Risk assessment on BTEX exposure at fuel storage tank area in the gasoline station. Indian Journal of Public Health Research and Development 10, 2281-2286.

Kitwattanavong, M., Prueksasit, T., Morknoy, D., Tunsaringkarn, T., Siriwong, W., 2013. Health Risk Assessment of Petrol Station Workers in the Inner City of Bangkok, Thailand, to the Exposure to BTEX and Carbonyl Compounds by Inhalation. Human and Ecological Risk Assessment 19, 1424-1439.

Tunsaringkarn, T., Siriwong, W., Rungsiyothin, A., Nopparatbundit, S., 2012. Occupational exposure of gasoline station workers to BTEX compounds in Bangkok, Thailand. International Journal of Occupational and Environmental Medicine 3, 117-125.

The authors also compared other similar studies on BTEX from motor vehicles conducted in Thailand.

4. Interm comparison with other countries I suggest the author to consider similar studies conducted in Southeast Asian countries which have similar weather condition such as:

Latif, M.T., Abd Hamid, H.H., Ahamad, F., Khan, M.F., Mohd Nadzir, M.S., Othman, M., Sahani, M., Abdul Wahab, M.I., Mohamad, N., Uning, R., Poh, S.C., Fadzil, M.F., Sentian, J., Tahir, N.M., 2019. BTEX compositions and its potential health impacts in Malaysia. Chemosphere 237.

5. Provide detail information on BTEX sampling procedures. What is the specific time for 4 hours of BTEX measurement? Provide information on replications and QA/QC including the method detection limit for BTEX measurement.

6. The characteristics of sampling stations can be included in the Methodology section rather than the Results section.

7. Compare the concentration of BTEX record in this study to previous similar studies.

**********

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Reviewer #1: No

Reviewer #2: No

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PLoS One. 2021 Apr 15;16(4):e0249913. doi: 10.1371/journal.pone.0249913.r002

Author response to Decision Letter 0


21 Mar 2021

PONE-D-20-27491

Risk assessment on workers’ exposure to BTEX and hazardous area classification at gasoline stations

Dear PLOS ONE Academic Editor,

According to the comments of reviewers and editor, we author appreciated all suggestions to improve the paper presentation and all correction and clarifications are the following;

Reviewer Comments Answers and additional comments Location

Academic Editor Ensure that your manuscript meets PLOS ONE's style requirements, including those for file naming Format was rechecked and approved

Include additional information regarding the survey or questionnaire used in the study and ensure that you have provided sufficient details that others could replicate the analyses. Questionnaire was included to one uploaded attached file; Gasoline station data survey form

Remove any funding-related text from the manuscript Financial disclosure was deleted from an acknowledgement, and updated the funding statement

provide more information (and updated) on the toxicological aspects of BTEX compounds Added more referenced of Thai gasoline workers exceeded the acceptable limit [5,7,8] and similar to the studies in Malaysia [9, 10] on comment of reviewer #2

required about on the quality controls undertaken in the laboratory for the analysis of the samples QC and analysis of samples were edited to provide more information in the methodology section. Data collection;

A flammable gas detector was used to measure the total VOCs emission (Photo ionization detector (PID) sensor (detection range of 0 to 1000 ppm) and the lower explosive limit - upper explosive limit (LEL-UEL) with Non-Dispersive Infrared (NDIR) combustible sensors (range of 0-100%LEL)

when the samples were collected. Sample collected in the season was stated Data collection;

The samples were collected between June and July 2018 June and July 2018, at times when the temperature was 28.08 ±1.58 °C, humidity was 78.51±8.89%, and wind velocity was 10.0 ±2.82 m/min

Reviewer #1 1. Title: Risk assessment "of" workers´ exposure (delete "on"). Revised; Title: Risk assessment "of" workers´ exposure (delete "on"). Title ..of…

2. Lines 31-32. "radius around the fuel dispensers" (delete "in") Revised; “radius around the fuel dispensers” Abstract;

The risk matrix classified …radius around the fuel dispensers

3. Line 93-94: "as described in NIOSH method 1501 [15]" delete "which followed NIOSH number 1501 [15] methodology Revised; "as described in NIOSH method 1501 [15]" Data collection;

The BTEX concentrations were measured… as described in NIOSH method 1501…

4. Line 95: "monitored" not "monitoring" Revised; "monitored" Data collection;

The exposure to BTEX was monitored

5. Line 103: describe the acronym LEL-UEL Revised; “describe the acronym LEL-UEL “ Data collection;

A flammable gas detector … lower explosive limit - upper explosive limit (LEL-UEL)…

6. Line 171-176: the terms Ox, Oy are not represented in the formula. It is not clear what terms in the formula the refer to. Revised; Changed the symbol “σy, σz” to match the equation. Hazardous area classification at gasoline stations;

The BTEXemiss concentrations at different distances were σy σz ..

Reviewer #2 1. Abstract: Include the full name of EPA-IRIS Revised; Added full name of EPA-IRIS in abstract (however, it caused abstract to be more than 250 word). Abstract;

The risk assessment of gasoline workers at … US. Environmental Protection Agency-IRIS

2. Safe standard of benzene (100 ppb): Include name of the agency on country suggest the value of concentration. Revised; “NIOSH exposure limits of 100 ppb benzene concentration” Abstract;

Results showed that the BTEX concentrations… of the NIOSH exposure limit of 100 ppb of benzene concentration.

3. In term of comparison with previous studies, I suggested the author include previous similar studies conducted in Thailand Revised; comparison with previous studies in introduction and discussion. Introduction;

It was also shown that the lifetime cancer risk…8]

Discussion;

…and was higher than the previous finding in Khon Kaen, Thailand [12]

4. In term comparison with other countries I suggest the author to consider similar studies conducted in Southeast Asian countries which have similar weather condition Revised; comparison with previous studies in Southeast Asian countries in introduction and discussion. Introduction;

It was also shown that the lifetime cancer risk… and similar to the studies in Malaysia [9, 10].

Discussion;

.. like in gasoline station of Kuwait study [15]. The finding of concentration at gasoline station in Malaysia [9] was quite lower or closed to the range in our study.

5. Provide detail information on BTEX sampling procedures. What is the specific time for 4 hours of BTEX measurement? Provide information on replications and QA/QC including the method detection limit for BTEX measurement. Revised;

1. the information of 4 hours measurement was calculated to be 8 hour exposure to compare to the standard limit of working period, which were added to the method.

2. Added the limit of detection (LOD) of all BTEX

and the VOCs measured by gas detector

Data collection;

1. The exposure to BTEX was monitored… covered the high service hours for 4 hours sampling.

2. Each tube was extracted with… and limit of detection (LOD) was < 0.001 ppm and < 0.003 ppb for toluene and benzene and < 0.05 ppb for ethyl benzene and xylene.

……measure the total VOCs emission (Photo ionization detector (PID) sensor (detection range of 0 to 1000 ppm) and the lower explosive limit - upper explosive limit (LEL-UEL) with Non-Dispersive Infrared (NDIR) combustible sensors (range of 0-100%LEL).

6. The characteristics of sampling stations can be included in the Methodology section rather than the Results section. Revised;

- Added sample inclusion criteria; gasoline dispenser nozzles, and gasoline stations operation time in the methodology section. Sample size;

There were two inclusion criteria… and gasoline dispenser nozzles; and 3) they had to have more than 8 hours of daily operation time.

7. Compare the concentration of BTEX record in this study to previous similar studies

Revised;

1. BTEX comparison on in discussion section.

2. HQ and HI comparison in discussion Discussion

1. BTEX concentrations in the ambient… and accessed of the NIOSH standard level (100 ppb) like in gasoline station of Kuwait study [15]. The finding of concentration at gasoline station in Malaysia [9] was quite lower or closed to the range in our study.

2. From the adverse effect risk… in Thailand [6] and Malaysia [9, 10], where had the similar climatic conditions to Thailand. The study showed that… study [5] as confirmed by this study and the characteristic of a function as refueling service working closed to the gasoline dispensers could exhibit the higher health risk [5].

Attachment

Submitted filename: Response to Reviewers -170321.docx

Decision Letter 1

Antonio Peña-Fernández

29 Mar 2021

Risk assessment of workers’ exposure to BTEX and hazardous area classification at gasoline stations

PONE-D-20-27491R1

Dear Dr. Chaiklieng,

We’re pleased to inform you that your manuscript has been judged scientifically suitable for publication and will be formally accepted for publication once it meets all outstanding technical requirements.

Within one week, you’ll receive an e-mail detailing the required amendments. When these have been addressed, you’ll receive a formal acceptance letter and your manuscript will be scheduled for publication.

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Kind regards,

Antonio Peña-Fernández, PhD

Academic Editor

PLOS ONE

Additional Editor Comments (optional):

Thank you for addressing the different comments provided and congratulations on your manuscript.

Reviewers' comments:

Acceptance letter

Antonio Peña-Fernández

6 Apr 2021

PONE-D-20-27491R1

Risk assessment of workers’ exposure to BTEX and hazardous area classification at gasoline stations

Dear Dr. Chaiklieng:

I'm pleased to inform you that your manuscript has been deemed suitable for publication in PLOS ONE. Congratulations! Your manuscript is now with our production department.

If your institution or institutions have a press office, please let them know about your upcoming paper now to help maximize its impact. If they'll be preparing press materials, please inform our press team within the next 48 hours. Your manuscript will remain under strict press embargo until 2 pm Eastern Time on the date of publication. For more information please contact onepress@plos.org.

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Thank you for submitting your work to PLOS ONE and supporting open access.

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PLOS ONE Editorial Office Staff

on behalf of

Dr. Antonio Peña-Fernández

Academic Editor

PLOS ONE

Associated Data

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    Supplementary Materials

    S1 File. Survey form English.

    (PDF)

    S2 File. Survey form Thai.

    (PDF)

    Attachment

    Submitted filename: Response to Reviewers -170321.docx

    Data Availability Statement

    All relevant data are within the manuscript and its Supporting Information files.


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