BTEX Atmospheric Levels and Health Risk in an Urban Site in Ciudad

del Carmen, Campeche

RAMÍREZ-LARA E.1, CERÓN-BRETÓN J. G.2, CERÓN-BRETÓN R. M.2,

LÓPEZ-CHUKEN U. J.1, VICHIQUE-MORALES A.2, UC-CHI M. P.2,

HERNÁNDEZ-LÓPEZ G.2, SOLIS-CANUL J. A.2, LARA-SEVERINO R. C.3,

RANGEL-MARRÓN M.2, ROBLES-HEREDIA J. C.2

1Universidad Autónoma de Nuevo León, Facultad de Ciencias Químicas, Av. Universidad s/n,

Ciudad Universitaria, C.P. 66455, San Nicolás de los Garza, Nuevo León,

MEXICO

2Universidad Autónoma del Carmen, Facultad de Química, Calle 56 No. 4, Esq. Ave. Concordia,

C.P. 24180, Ciudad del Carmen, Campeche,

MEXICO

3Universidad Autónoma del Carmen, Facultad de Ciencias de la Salud, Av. Central s/n, Mundo

Maya, Ciudad del Carmen, Campeche,

MEXICO

Abstract: Benzene, toluene, ethylbenzene, and xylenes (BTEX) were measured in ambient air in an urban site

of Ciudad del Carmen, Campeche during spring 2022. Samples were collected during the morning (from 07:00

to 08:00 h), midday (from 14:00 to 15:00 h) and afternoon (from 18:00 to 19:00 h) using glass tubes packed

with activated carbon, at a controlled air flow of  . Samples were analyzed by gas chromatography

with flame ionization detection. The relative abundance in ambient air of BTEX was the following: benzene

(



) > toluene (



) > xylenes (



) > ethylbenzene (



). The

statistical analysis revealed that BTEX compounds had strong correlations between each other, indicating that

they were originated from common sources. From the meteorological analysis, it was found that the prevailing

winds blew from the east and southeast, indicating that vehicular emissions coming from avenues located in

these directions may have contributed to the BTEX levels in the study site. Principal component analysis and

BTEX ratios (T/B and X/Ebz) revealed that vehicular emissions and fresh local air masses influenced the

BTEX concentrations during the study period. From the health risk analysis, cancer risk coefficients exceeded

the acceptable level (1  10 -6), thus exposed population may be at a possible risk of developing cancer in the

lifetime due to the inhalation of BTEX at the measured concentrations. These results will be a useful tool for

local authorities in order to establish control measures focused on the reduction of BTEX emissions and the

improvement of the air quality in the study area.

Key words: BTEX, gas chromatography, correlations, health risk.

Received: May 29, 2022. Revised: November 2, 2022. Accepted: December 2, 2022. Published: December 31, 2022.

1 Introduction

Air pollution has become a topic of interest for the

scientific community and society due to different

studies have related a poor air quality with

harmful health effects such as respiratory diseases

and some types of cancer, [1].

Common factors such as the use of fossil fuels and

coal-fired power plants, dependence on private

transport motor vehicles, inefficient use of energy

in buildings, and the use of biomass for cooking

and heating, produce so-called Volatile Organic

Compounds (VOCs), [2]. There is a sub-group of

compounds within the VOCs group called BTEX,

which includes Benzene and their alkyl-

derivatives: Toluene, Ethylbenzene and Xylenes.

These compounds can be used as markers of

damage to human health, considering both

carcinogenic and non-carcinogenic effects

(respiratory and cardiovascular diseases). In

addition, BTEX is key compounds due to they

provide information on the degree of exposure of

the human body to the harmful effects of VOCs

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Ramírez-Lara E., Cerón-Bretón J. G.,

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and they are precursors of the reactions that lead

to the generation of tropospheric ozone (under

appropriate meteorological conditions), [3].

Benzene is a highly toxic compound, becoming

myelotoxic and inducer of leukemia in humans,

besides that it has been identified as a human

carcinogen by the International Agency for

Research on Cancer, so the WHO and the United

States Environmental Protection Agency (EPA) do

not recommend any safe level of exposure, [4].

Considering the risks and consequences of

exposure to these pollutants, it is important to

include the monitoring of atmospheric BTEX in

order to assess air quality present in the

atmosphere of urban areas. However, in Mexico,

most of the monitoring stations of the air quality

monitoring network do not measure BTEX levels

in ambient air, except in some sites of Mexico

City. In addition, there is no Mexican standard

that regulates the maximum permissible levels in

ambient air of BTEX compounds. The present

study is focused on determining the levels of

BTEX in ambient air in an urban site in Ciudad

del Carmen, Campeche during the spring 2022

and the potential risk (cancer and non-cancer) to

health in the exposed population.

2 Methodology

2.1 Site Description

Ciudad del Carmen is an island of sedimentary

origin located in the southeast of Mexico within

an area named Sonda de Campeche located in the

south of the Mexican Gulf. This city is an

important center of processing and distribution of

oil and gas in Mexico. The sampling was carried

out within the facilities of the Autonomous

University of Carmen located in the downtown

area at 18.645502° N and -91.817140° W, during

the spring season (from June 6 to 10, 2022). This

period was selected due to it corresponds to the

dry season, when the lowest wind speeds usually

occur, so that the dispersion of pollutants is

limited and it may result in higher concentrations

of these air pollutants and a greater risk in the

population. Three samples were collected per day,

the first sampling period was performed during the

morning (from 07:00 to 8:00 h), the second one

during the midday (from 14:00 to 15:00 h) and the

third sampling period was carried out during the

afternoon (from 18:00 to 19:00 h). Temperature,

pressure, wind direction, solar radiation and

relative humidity were registered during each

sampling period.

2.2 BTEX Sampling in Ambient Air

Samples were collected from June 6 to 10, 2022 to

determine BTEX concentrations (benzene,

toluene, ethylbenzene and p-xylene) in ambient air

by active sampling by passing air through glass

tubes packed with activated carbon (226-01

Anasorb CSC), at a constant and controlled flow

of 1.5 L/min by means of an SKC vacuum pump

model PCXR4 [4]. The sampling lasted 1.0 hours

for each sample considering three different

periods according to the population activity

observed in the city: during the morning (B1:

07:00 to 08:00 h), noon (B2: 14:00 to 15:00),

afternoon (B3: 18:00 to 19:00 h).

2.3 Gas Chromatography - Flame

Ionization Detection Analysis (GC-FID).

Collected samples were desorbed with 1 mL of

chromatographic grade carbon disulfide. The

samples were analyzed based on the method

"Determination of aromatic hydrocarbons

(benzene, toluene, ethylbenzene, p-xylene) in air-

Adsorption method in activated carbon/gas

chromatography MTA/MA-030/A92, of the

National Institute of Safety and Hygiene of Spain.

The chromatographic analysis of the collected

samples was carried out in the Gas

Chromatography Research Laboratory of the

Chemistry Faculty of the Autonomous University

of Carmen. A Thermoscientific brand gas

chromatograph, model TRACE GC Ultra Gas

Chromatographs was used in splitless mode in

order to analyze the desorbed samples. This

system was coupled to a flame ionization detector

using extra dry air and ultra-high purity hydrogen.

Ultra-pure nitrogen was used as a carrier gas and a

30 m x 0.32 mm ID capillary column was used to

carry out the separation ( fused silica methyl type

and with a film thickness of 0.5 μm).

2.4 Statistical Analysis

Normality analyses were performed to determine

whether parametric or non-parametric statistics

were applicable. Hypothesis tests were applied to

determine if there were significant differences in

BTEX concentrations at different sampling

periods (Levine Test and Bartlett Test). A

bivariate analyses (Pearson correlation analysis)

was carried out in order to find relations between

the measured variables. A multivariate analysis

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(Principal Component Analysis: PCA) was carried

out in order to explain the variance and for

uncovering the structure of the data set. This

method is commonly used in environmental

studies in order to identify patterns in data. A PCA

analysis let us to create new variables (principal

component) which are linear combinations of the

original variables. The results of PCA are resumed

as scores and loading vectors usually represented

as bi-plots of the two principal components,

revealing relations among the observations

(measured variables). The software used was

XLSTAT for Excel version 2016.

2.5 Meteorological Analysis

The analysis of the frequency of occurrence of the

winds (direction and speed) was carried out per

day during the sampling period. The daily wind

roses were constructed using the Wind Rose

statistical tool from NOAA (Air Resource

Laboratory: ARL). Figure 1 shows a typical wind

rose representative of the sampling period. It can

be observed that the prevailing winds blew from E

and SE, with wind speed ranging from 1 to 4 m/s,

indicating that sources located in these directions

could contribute to the measured BTEX levels. An

important avenue with high vehicular flow (the

Peripheral Avenue) is located to the east, which

communicates the city (Carmen Island) with the

mainland towards the State of Tabasco. On the

other hand, to the southeast is 31st Avenue, which

crosses the city from east to west, being the main

transportation route on the island. Both avenues

constitute two of the main ways of population

mobility with heavy vehicular traffic during the

peak hours (during the morning when the

population moves to their workplaces, and during

the afternoon when the flow of vehicles is towards

homes.

Fig. 1: Wind rose representative for the sampling

period at the study site.

2.6 Health Risk Analysis

The carcinogenic potential of benzene is widely

known, [5]. The European Union recommends an

annual limit of 5 μg/m for benzene in ambient air

and the Minimal Risk Level (MRL of 1 in

10,000), while the EPA sets a value of 4.0 ppbv

for this pollutant, [6]. This study used the

methodology proposed by EPA, [5] in order to

determine the daily exposure (E), the lifetime

cancer risk and the non-cancer potential risk

coefficients, LTCR and HQ, respectively. The

individual's daily inhalation exposure can be

calculated as :

      



(1)

Where: E = is the daily inhalation exposure in

mg/kg per day, C = is the average concentration of

benzene in mg/m3, IRa = is the inhalation rate for

an adult (0.83 m3/h.), Da = is the duration of

exposure in an outdoor ambient according to the

typical activities (being 24 and 16 hr/day, for

adults and children, respectively), [5-6]. BW = is

the weight of the body (being 65 and 36 kg for

adults and children, respectively). The lifetime

cancer risk (LTCR) is calculated as:

    

(2)

Where: LTCR = is the lifetime cancer risk, SF = is

the slope factor (kg day/mg). The slope factor of

the inhalation unit risk for toxic substances when

the exposure-carcinogenic effect is considered

linear, being 2.98 E−02. kg day/mg for benzene,

[6]. The determined values were compared with

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the permissible limit values established by the

EPA (1 x10-6) and the WHO (1 x10-5).

The non-carcinogenic risk of BTEX was

calculated as a hazard quotient (HQ) according to

the following equation:

   



(3)

Where C is the average daily received

concentration and RfC represents the inhalation

reference concentration of specific air pollutants:

0.03, 5, 1 and 0.1 mg/m3 for benzene, toluene,

ethylbenzene and p-xylene, respectively. An HQ >

1.0 indicates that long term exposure may cause

adverse non-cancer health effects (respiratory and

cardiovascular diseases). An HQ < 1.0 is

considered as acceptable level according to the

recommended values established by EPA and

OMS.

3 Results and Discussion

3.1 BTEX Concentrations in Ambient Air

at the Study Site

Figures 2 and 3 show the parametric statistics and

boxplot BTEX at the study site during the summer

season. The relative abundance of BTEX in

ambient air was the following: benzene (9.197

µg/m3) > toluene (8.953 µg/m3) > xylenes (7.789

µg/m3) > ethylbenzene (7.538 µg/m3). According

to figures 2 and 3 it can be seen that the BTEX

had a diurnal pattern, showing higher

concentration values during the midday and

afternoon and with lower concentration values

during the morning. This behavior was expected,

since the greatest mobility of the population in this

area occurs during these periods, since

commercial areas, banks and restaurants are

located in this zone. The results are comparable to

those obtained at other study sites (Table 1). As

can be seen, benzene and ethylbenzene showed

higher concentrations than those registered in the

study site during 2012, [8]. Toluene and xylenes

showed a decrease in their levels compared to

those obtained 10 years earlier, [8]. Benzene

concentrations in this study were comparable to

the values reported in Beijing, China, [11] but

higher than those reported for León, [9] and

Mexico City, [10] (Table 1). Toluene presented

lower values than those reported in León, [9] and

Mexico City, [10] according to Table 1.

Ethylbenzene presented concentrations higher

than Beijing, China, [11] but lower than reported

for the city of León, Guanajuato, [9]. Finally,

xylenes in this study presented higher

concentrations than those reported for the cities of

Beijing, [11] and León in Guanajuato, [9] (Table

1).

Fig. 2: Parametric statistics and boxplot for

benzene and toluene concentrations at the study

site during the summer season.

B1: sampling period from 07:00 to 08:00 h; B2:

sampling period from 14:00 to 15:00 h; B3: sampling

period from 18:00 to 19:00 h. + is the mean value, -

represents maximum and minimum values, the central

horizontal bars are the medians. The lower and upper

limits of the box are the first and third quartiles.

Fig. 3: Parametric statistics and boxplot for

ethylbenzene and xylenes concentrations at the

study site during the summer season.

B1: sampling period from 07:00 to 08:00 h; B2:

sampling period from 14:00 to 15:00 h; B3: sampling

period from 18:00 to 19:00 h. + is the mean value, -

represents maximum and minimum values, the central

Benzene B1

Benzene B2

Benzene B3

Toluene B1

Toluene B2

Toluene B3

Concentration benzene and

to lu en e ( µ g/ m 3)

Ethylbenze

ne B1

Ethylbenzene

Ethylbenze

ne B3

Xylenes B1

Xylenes B2

Xylenes B3

Concentrations of

ethylbenzene and xylenes

( µ g / m 3)

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horizontal bars are the medians. The lower and upper

limits of the box are the first and third quartiles.

Table 1. Comparison of results found for BTEX in

Ciudad del Carmen with other studies

Place

Benzene





Toluene





Etilbenceno





Xylenes





Reference

Ciudad del

Carmen,

2022

9.19

8.95

7.55

7.78

This

study

Ciudad del

Carmen,

2012

5.42

11.23

3.97

8.32

Cerón et

al. [8]

Leon,

Guanajuato,

2018

1.73

11.85

11.86

3.31

Cerón et

al. [9]

Mexico

City, 2002

3.67

17.63

Baez et

al. [10]

Beijing,

China,

2012

9.2

1.39

0.42

1.27

Zhang et

al. [11]

The highest concentrations of benzene and

ethylbenzene were observed during the midday

period (B2) with average concentration values of

11.836 and 9.820 µg/m3, respectively. While

toluene and xylenes showed higher average

concentration values during the afternoon period

(B3) with values of 11.675 and 10.097 µg/m3,

respectively. The lowest average concentration

values for BTEX were found during the morning

sampling period (B1) with values of 3.977, 3.956,

2.978 and 3.201 for benzene, toluene,

ethylbenzene and xylenes, respectively.

The BTEX concentrations showed a normal

distribution, which was confirmed by applying the

Shapiro-Wilk (W) test. For this reason, it was

decided to apply parametric statistics to the data

set. Although a diurnal pattern was observed in

BTEX concentrations (with higher average values

during midday and afternoon), after applying the

Levene (F) and Bartlett (Chi square) tests, it was

confirmed that these differences were not

significant at a significance level of alpha = 0.05.

This allows us to infer that BTEX levels at the

study site were homogeneously distributed, with

influence from local sources (vehicular traffic).

The Pearson correlation matrix (Table 2) shows

that all BTEX had positive linear correlations

(correlation coefficients >0.97), indicating that

they could be originated from the same sources.

Table 2. Pearson Correlation Matrix of the

measured variables

EBZ

0.986

EBZ

0.995

0.971

0.997

0.976

0.999

0.252

0.279

0.222

0.237

-0.240

-0.279

-0.221

-0.235

-0.703

0.239

0.271

0.232

0.238

0.425

-0.923

0.495

0.551

0.478

0.312

-0.408

0.459

-0.184

-0.186

-0.188

-0.432

0.821

-0.808

-0.077

Bold values are different from 0 with a significance level alpha=0.05; B: Benzene; T: Toluene;

EBZ: Ethylbenzene; X: Xylenes; DV: wind direction, TE: temperature, RH: relative

humidity, P: atmospheric pressure, SR: solar radiation.

A significant moderate correlation was found

between toluene and atmospheric pressure (0.551),

indicating that this compound could be influenced

by high pressure systems in the study site. A

significant linear correlation was found between

temperature and solar radiation (0.821).

Significant negative correlations were recorded

between relative humidity and temperature (-

0.923) and between relative humidity and solar

radiation (-0.808), indicating that increases in

moisture content result in decreases in the

temperature and are also associated with a

reduction in solar radiation levels due to greater

cloud cover.

Figure 4 and Table 3 show the results of the

Principal Component Analysis (PCA). From the

PCA applied to the data set, two principal

components, F1 and F2 were obtained, which

together contributed with 82.555% to the total

variability of the data. Figure 4 shows the bi-plot

of the main components F1 and F2, observing a

strong relationship between the BTEX measured

(see the vectors located at the upper right

quadrant). A strong correlation was also observed

between temperature and solar radiation (see

vectors located at the upper left quadrant) and

strong negative correlations were observed

between the pair’s temperature-solar radiation and

wind direction-relative humidity (see vector

located diametrically opposed in the bi-plot).

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Fig. 4: Bi-plot of the principal components found

from the PCA Analysis.

Note: DV: wind direction; TE: temperature; RH,

relative humidity; P, atmospheric pressure; SR: solar

radiation

Table 3 shows the factor loadings for the

measured variables and it was possible to identify

three groups of correlated variables: F1, F2 and

F3. F1 shows a first group of interrelated

variables, which includes benzene, toluene,

ethylbenzene, and xylenes. F2 shows a second

group of variables highly correlated, which

includes temperature, relative humidity, and solar

radiation. F3 only included Wind Direction. This

variable was not correlated with the rest of

variables, indicating that the air pollutants in the

study site were only influenced by local sources

and that the regional transport was negligible.

Table 3. PCA Factor loadings for the measured

variables.

BENZENE

0.804

0.182

0.012

0.001

TOLUENE

0.824

0.154

0.002

0.000

ETHYLBENZENE

0.784

0.191

0.018

0.000

XYLENES

0.794

0.184

0.017

0.001

0.264

0.227

0.063

0.444

0.400

0.580

0.001

0.000

0.370

0.494

0.000

0.108

0.419

0.000

0.480

0.085

0.249

0.509

0.185

0.008

Note: The bold values correspond for each variable to

the factor for which the square cosine is the largest DV:

wind direction, TE: temperature, RH: relative humidity,

P: atmospheric pressure, SR: solar radiation.

3.2 BTEX Ratios

BTEX Ratios are commonly used to infer the

emission sources (vehicular, area or industrial

sources) and to know the grade of photochemical

processing of the air masses that contain BTEX.

So, from the BTEX ratios, it is possible to

determine if the emissions come from mobile

sources or from area or industrial sources (T/B

ratio) and if BTEX come from fresh or aged air

masses (X/E ratio). The T/B ratios are used as

indicators of vehicular traffic emissions, due to

benzene and toluene are commonly constituents of

gasoline (toluene content is 3 to 4 times higher

than the benzene content), for this reason during

the combustion process they are emitted into the

atmosphere by the exhausts of motor vehicles.

Values of T/B ratio between 2 and 3 or lower have

been reported in various urban areas of the world.

Values of this ratio >3 indicate that BTEX levels

can be associated with sources beyond vehicular,

for example: industrial facilities, area sources

such as evaporative emissions, automotive paint

shops, food cooking processes, screen printing

workshops, dry cleaners, among many others,

[12]. The xylene/ethylbenzene ratio (X/Eb) is

commonly used as an indicator of the

photochemical age of air masses at a given site.

Values greater than 3.8 indicate that BTEX comes

from old air masses and values less than 3.8

indicate that BTEX comes from fresh air masses

(recent emissions), [13]. This reason is related to

the atmospheric lifetime of these pollutants in the

air. Low values of this ratio indicate that air

masses are fresh (recent emissions), whereas, high

values of this ratio are an indicator that the air

masses are aged (with a high grade of

photochemical processing). Values for X/Eb

between 3.8 and 4.4 have been reported for fresh

gasoline emissions, [14, 15]. The T/B ratio

showed values ranging from 0.892 to 1.126 with

an average value of 0.976, indicating that BTEX

levels at the study site were under the influence of

vehicular-type emissions. On the other hand, the

concentration ratio (X/Eb) showed values in a

range from 0.974 to 1.129 with an average value

of 1.043. The values obtained indicate that the air

masses containing BTEX at the study site were

fresh emissions (recent emissions from local

sources).

3.3 Health Risk Assessment

Table 4 shows the carcinogenic and non-

carcinogenic risk coefficients (LTCR and HQ,

BENZENE

TOLUENE

ETHYLBENZENE

XYLENES

-1

-0,75

-0,5

-0,25

0,25

0,5

0,75

-1 -0,75 -0,5 -0,25 0 0,25 0,5 0,75 1

F2 (28.02 %)

F1 (54.54 %)

Variables (axes F1 y F2: 82.56 %)

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respectively) to which the population may be

exposed by inhalation of BTEX at the measured

concentrations. It can be observed that the LTCR

values exceeded the permissible limits established

by the EPA and WHO (1 x10-6 and 1 x10-5,

respectively), being this level of risk higher in

children. The non-cancer (HQ) risk coefficients

did not exceed the maximum permissible level

established by EPA and WHO (1.0), indicating

that the risk of developing respiratory and

cardiovascular diseases due BTEX inhalation at

the study site is low.

Table 4. Cancer and non-cancer risk coefficients

for concentrations measured at the study site.

Cancer Risk Coefficient: LTCR for Adult population

Pollutant

Average

Benzene



Cancer Risk Coefficient: LTCR for Child population

Pollutant

Average

Benzene



Non-cancer risk coefficients (HQ)

Pollutant

Average

Benzene

0.3070

Toluene

0.0017

Ethylbenzene

0.0075

Xylenes

0.0079

4 Conclusions

The dominant BTEX in the ambient air of the

study site was benzene (9.197 µg/m3) followed by

toluene (8.953 µg/m3). All measured BTEX

showed a clear diurnal pattern with higher

concentration values during the midday and

afternoon sampling periods, due to greater

mobility by the population in the study area,

resulting in higher vehicular-type emissions. From

the Pearson correlation and Principal Component

Analysis, it was possible to confirm that all BTEX

were probably originated from common sources,

since they showed strong correlations between

each other. From the meteorological analysis it

was found that the prevailing winds blew from the

E and SE, indicating that vehicular emissions from

avenues located in these directions could

contribute to the levels of BTEX measured. The

T/B and X/Eb ratios showed that BTEX

concentrations were influenced by vehicular-type

emissions and local fresh air masses. From the

health risk assessment, it was found that there is a

possible risk of developing cancer in the lifetime

at the measured concentrations, being more

critical for the child population. The level of risk

of developing cardiovascular and respiratory

diseases from BTEX inhalation is low. It is

important that environmental authorities in

Mexico considering the inclusion of BTEX within

the National emissions inventory, in order to

identify the main sources of hydrocarbons,

considering industrial, natural, mobile and area

sources, with the aim of developing control

measures of BTEX emissions that improve the air

quality in the study area. This work provides

information about BTEX concentration

distribution in an urban area of Ciudad del

Carmen, Campeche. However, it is necessary to

include more monitoring points in this area that

considering a more extensive sampling period that

covers the different seasons along the year (dry

season, rainy season and the Norths season), as

well as, the monitoring of other air pollutants such

as ozone, sulphur dioxide, nitrogen oxides, PM10,

PM2.5, among others.

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WSEAS TRANSACTIONS on ENVIRONMENT and DEVELOPMENT

DOI: 10.37394/232015.2022.18.126

Ramírez-Lara E., Cerón-Bretón J. G.,

Cerón-Bretón R. M. et al.

E-ISSN: 2224-3496

1339

Volume 18, 2022