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Sustainable Cities and Society 56 (2020) 102005

Contents lists available at ScienceDirect

Sustainable Cities and Society


journal homepage: www.elsevier.com/locate/scs

Characteristics and health effects of volatile organic compound emissions T


during paper and cardboard recycling
Ramin Nabizadeha,b, Armin Sorooshianc,d, Mahdieh Delikhoone, Abbas Norouzian Baghania,*,
Somayeh Golbaza, Mina Aghaeia, Abdullah Barkhordarif
a
Department of Environmental Health Engineering, School of Public Health, Tehran University of Medical Sciences, Tehran, Iran
b
Center for Air Pollution Research (CAPR), Institute for Environmental Research (IER), Tehran University of Medical Sciences, Tehran, Iran
c
Department of Chemical and Environmental Engineering, University of Arizona, Tucson, Arizona, USA
d
Department of Hydrology and Atmospheric Sciences, University of Arizona, Tucson, Arizona, USA
e
Department of Occupational Health Engineering, School of Public Health, Isfahan University of Medical Sciences, Isfahan, Iran
f
Department of Occupational Health, School of Public Health, Shahroud University of Medical Sciences, Shahroud, Iran

ARTICLE INFO ABSTRACT

Keywords: Urbanization generates increased amounts of solid wastes in cities and as a consequence leads to high air pol-
Paper and cardboard recycling lution levels. As a result of these trends, the subject of air quality management for sustainable concept of cities
Pollution characteristics has received increasing attention. This work characterized volatile organic compound (VOC) emissions and
VOCs health effects at different processing stages in a recycling facility for waste paper and cardboard. The highest
Carcinogenic and non-carcinogenic
total VOC levels were observed in the conveyor belt line one (5.23 ± 0.33 mg/m3), followed by a baling ma-
Exposure indices
Sustainable
chine (1.38 ± 0.07 mg/m3), conveyor belt line two (1.34 ± 0.08 mg/m3), tipping floor line one
(1.22 ± 0.07 mg/m3), and manual separation line one (1.20 ± 0.06 mg/m3). Hence, exposure to VOCs lead to
high health risks in this PCSWRF, especially at the manual separation stage (HQ = 2.7–3 and lifetime cancer
risks (LTCRs) = 1.11 × 10−4 - 1.03 × 10−4), and strategies such as adjustment of the factory to enclose the
conveyors, designing proper ventilation and air conditioning systems, minimization of VOC-contaminated waste
generation (pre-treatment), and using personal protective equipment should be considered to eliminate pollu-
tants and to protect workers from the non-carcinogenic and carcinogenic effects.

1. Introduction Hence, one of the main factors for attaining the sustainability of cities is
rooted in environmental management in the form of waste and recycling
Improper management of municipal solid waste (MSW) in the most management and air quality conservation (Des, 2013; Heidari,
cities of developing countries has become a global problem (Ahmed & Ali, Yazdanparast, & Jabbarzadeh, 2019; Rada, 2014). Managing air quality is
2004; Shao, Weng, Liou, Lo, & Jiang, 2019). In addition, the im- central to the sustainability of all cities (Maitra, 1998; Rada, 2014; WHO,
plementation of suitable municipal solid waste management (MSWM) 2019). On a global perspective, not paying attention to this issue promotes
plays a significant role in the sustainable development of cities (Durán & major socioeconomic, health, and climate-relevant issues in cities around
Messina, 2019; Mesjasz-Lech, 2014). Furthermore, rapid urbanization and the world (Rada, 2014; WHO, 2019).
industrialization generates increased amounts of various solid wastes such A major constituent emitted from such wastes and their processing
as municipal and industrial solid waste (MSW and ISW) in urban areas is volatile organic compounds (VOCs), stemming from sites such as the
creating thousands of tons of solid waste a day (Des, 2013; Norouzian landfill or processing such as recycling (An et al., 2014; Ghosh et al.,
Baghani et al., 2016; Norouzian Baghani, Dehghani, Farzadkia, Delikhoon, 2019; He et al., 2015; Liu et al., 2017; Nie, Zheng, Shao, Yang, & Chen,
& Emamjomeh, 2017; Putthakasem, Limphitakphong, & Chavalparit, 2018; Norouzian Baghani et al., 2016; Palmiotto et al., 2014; Sánchez-
2018; Ramachandra, Bharath, Kulkarni, & Han, 2018). Chemical char- Monedero, Fernández-Hernández, Higashikawa, & Cayuela, 2018;
acteristics of these wastes and emissions include hazardous air pollutants Urase, Okumura, Panyosaranya, & Inamura, 2008). Recycled waste
that need significant resources and infrastructure for minimization of includes paper and cardboard, organic wastes, and plastics, which are
emissions and mitigation of health effects (Durán & Messina, 2019). the main sources of VOCs in MSW facilities (He et al., 2015; He, Tang


Corresponding author at: Department of Environmental Health Engineering, School of Public Health, Tehran University of Medical Sciences, Tehran, Iran.
E-mail address: abbas.jj.norozi@gmail.com (A.N. Baghani).

https://doi.org/10.1016/j.scs.2019.102005
Received 2 June 2019; Received in revised form 30 November 2019; Accepted 8 December 2019
Available online 05 February 2020
2210-6707/ © 2019 Elsevier Ltd. All rights reserved.
R. Nabizadeh, et al. Sustainable Cities and Society 56 (2020) 102005

et al., 2012; Jackson, 2015; Komilis, Ham, & Park, 2004). Komilis et al. 2.2. Sampling and analysis
(2004) and Jackson (2015) reported that mixed paper with food waste
and fresh waste were the main sources of VOCs in landfill and recycled Sampling of VOCs species was carried out based on the U.S.EPA
centers, in addition to composting facilities (Jackson, 2015; Komilis TO-15 method (Durmusoglu, Taspinar, & Karademir, 2010; He et al.,
et al., 2004). Furthermore, Duan, Lu, Li, and Wang (2014) and Mustafa 2015; He, Tang et al., 2012; Mcclenny & Holdren, 1999). According to
et al. (2017) reported that the main sources of toluene in solid waste the EPA sampling guideline (EPA, 2006), sampling was carried out
can be papers and cardboard, plastics, and food waste (Duan et al., every six days from 22 December 2017 to 20 February 2018 using
2014; Mustafa et al., 2017). Air pollution, especially VOCs, generated active sampling (SKC 222 Series Low Flow Pump) with a charcoal
from MSW, ISW and waste sorting processing can pose health risks to glass tube at a flow rate of 0.2 L/min for two hours. For the 10 sam-
factory workers and nearby dwellers (An et al., 2014; Dehghani, pling sites (Fig. S1), a total of 100 VOC samples were collected be-
Sorooshian, Nazmara, Baghani, & Delikhoon, 2018; Gladding & tween December and February. During sampling, the sampler was
Coggins, 1997; Gladding & Gwyther, 2017; He et al., 2015; Li et al., located at breathing zone of the workers (at a height of 1.5 m above
2013; Villavert, Nadal, Figueras, & Domingo, 2009). Health effects as- the ground) (Baghani, Rostami, Arfaeinia, Hazrati, Fazlzadeh,
sociated with exposure to VOCs can be categorized as carcinogenic and Delikhoon, Safety et al., 2018).
non-carcinogenic (Baghani, Rostami, Arfaeinia, Hazrati, Fazlzadeh, Seventeen VOCs were examined using gas chromatography–mass
Delikhoon et al., 2018; Dehghani, Fazlzadeh, Fazlzadeh et al., 2018; spectrometry (GC–MS) (GC 7890 N, AGILENT- MS 5975C, MODE
Delikhoon et al., 2018a; Golkhorshidi et al., 2019). In other words, EI.MS), including benzene, toluene, ethylbenzene, m,p xylene, o-xy-
exposure to VOCs emitted from solid waste can lead to diseases such as lene, decane, 1-ethyl-3-methyl benzene, 1,2,3-trimethyl benzene, 1,3,5-
hypochromic anemia, headaches, loss of coordination and nausea, re- trimethyl benzene, 1,2,4-trimethyl benzene, 1,2-diethyl benzene, 1-
spiratory issues, central nervous system problems, allergic skin reac- ethyl-2-methyl benzene, limonene, 1,4 diethyl benzene, butyl benzene,
tions, emesis, epistaxis, narcosis, fatigue, asthma, dizziness, defatting 2-methyl nonane, and nonane. An HP- 5MS column (60 m ×0.32 mm
dermatitis, bronchitis, and cancers of the brain, blood, kidney, and ×0.25 μm, Agilent Technologies, USA) was used. Helium was the car-
lungs (Baghani, Rostami, Arfaeinia, Hazrati, Fazlzadeh, Delikhoon rier gas at 1.2 mL per min. The temperature of the GC–MS oven at first
et al., 2018; Domingo & Nadal, 2009; Golkhorshidi et al., 2019; Hu, Liu, was programed to be at 35 °C for five minutes, and then increased to
Zhang, Xue, & Wang, 2018; Marzouni et al., 2017; Phillips et al., 1999; 150 °C at a rate of 5 °C per minute. Finally, the oven temperature
Romagnoli, Barboni, Santoni, & Chiaramonti, 2014; Rumchev, Spickett, reached 250 °C at a rate of 15 °C per minute and held for two minutes.
Bulsara, Phillips, & Stick, 2004; U.S.EPA, 2018). For instance, benzene The MS line delivery line temperature, scan mode and ionizing energy
negatively impacts the blood-forming system and contributes to leu- were 290 °C, 45–260 (m/e) and 70 eV, respectively. In addition, tem-
kemia and hematological disorders and lymphoma cancer (Moolla, perature (°C) and relative humidity (%) were quantified with a portable
Curtis, & Knight, 2015; Smith, 2010), while toluene impacts the re- instrument (Preservation Equipment Ltd, UK and Campbell Scientific,
productive and neurobehavioral health (Foo, Jeyaratnam, & Koh, 1990; Inc., USA).
Greenberg, 1997; Tunsaringkarn et al., 2012). Generally, the con-
centration profile of VOCs is a helpful indicator of the potential for
harmful effects due to exposure to solid waste emissions (Dehghani, 2.3. Quality assurance/quality control (QA/QC)
Fazlzadeh et al., 2018; He, Tang et al., 2012; He et al., 2015; He, Li
et al., 2012). These issues motivate a health risk assessment (HRA) on In this work, two parts of tubes were analyzed individually for the
the workers exposed to VOCs in waste processing facilities. Character- potential of breakthrough for samples. There were no signs of VOC
ization of VOCs and a HRA of VOCs on the workers in a paper and contamination in the second sections of tube. Six samples were gath-
cardboard solid waste recycling factory (PCSWRF) has yet to be per- ered as blank samples and concentrations of VOC species in these tubes
formed. Hence, controlling air pollution created by MSW, especially at were limited to between 0.00 - 0.0032 (μg/m3). A mean recovery of 97
PCSWRFs, is as important factor for the sustainability of cities and this % (92–110 %) was acquired for VOC species with standard deviations
activity can indirectly impact public health and socioeconomic aspects (SDs) less than 5.00 %.
related to the sustainability of cities (Heidari et al., 2019; Zhu, Hao, Lu,
Wu, & Ran, 2019).
The goal of this work is to 1) study the concentration of VOCs 2.4. Statistical analysis
species in different areas of a PCSWRF, 2) identify VOC species and the
percentage of VOC species in different areas of a PCSWRF, 3) determine Analysis was performed by the statistical program R (version 3.0.1
interrelationships between VOCs species and meteorological condi- (2013-05-16)) (Team, 2013). The Fligner-Killeen test was applied to
tions, 4) investigate occupational exposure limits (OLE) for workers in assess for homogeneity of variance. If the p-value obtained from the
different areas of a PCSWRF, and 5) estimate health risk assessment of Fligner-Killeen test exceeded 0.05, the ANOVA test was performed for
workers (carcinogenic and non-carcinogenic) exposure to VOCs in dif- further analysis. But, if the p-value was less than 0.05, the Kruskal-
ferent areas of a PCSWRF. Wallis test was applied for further analysis. Furthermore, if the Krus-
kal–Wallis test was significant, the Kruskal-Wallis post-hoc test (Kruskal
2. Materials and methods Mac) was carried out to show that levels of the independent variable
vary from other levels. For comparison, VOC concentrations between
2.1. Descriptions of study area the two lines of the tipping floor and conveyor belt in the PCSWRF were
assessed using the Mann-Whitney-Wilcoxon test, while a paired t-test
This work was carried out in a paper and cardboard solid waste was used for comparison of VOC concentraions between the two lines of
recycling factory (PCSWRF) located in Tehran, Iran (35°32′42″N, manual separation. The relationship between VOC concentrations and
51°23′35″E) (Fig. 1). This factory has two lines of separation processes meteorological conditions (i.e., temperature, relative humidity) were
for paper and cardboard, including a tipping floor (line one and two), quantified using Spearman's rho correlation coefficient. In addition,
conveyor belt (line one and two), hand picking/manual separation (line occupational exposure indices (Ei) were determined for workers for
one and two), and finally a baling machine (Fig. 2). Sampling locations emitted VOCs in the PCSWRF. In the end, HRA was calculated for es-
were positioned at the tipping floor (line one and two), conveyor belt timating the hazard quotient (HQ) and the lifetime cancer risk (LTCR)
(line one and two), manual separation area (line one and two), baling for VOC species. Figures were drawn using GraphPad Prism 7 and R
machine, storage area, office area, and a background area (Fig. 2). Statistical Software version 3.0.1.

2
R. Nabizadeh, et al. Sustainable Cities and Society 56 (2020) 102005

Fig. 1. Map of the study area and air monitoring stations.

2.5. Occupational exposure limits (OEL) and health risk assessment (HRA) that Ei not exceed the value 1 (Mo et al., 2009). Hence, Ei < 1 de-
for workers monstrates that the potential health risk cannot be important for the
workers in the PCSWRF (Mo et al., 2009).
2.5.1. Occupational exposure limits (OEL)
According to American Conference of Industrial Hygienists (ACGIH) 2.5.2. Health risk assessment (HRA)
and International Organization for Standardization (ISO), OELs were With regard to the recycling of paper and cardboard performed by
determined for humans for some harmful VOC species (Acgih, 2001; He workers, it is essential to evaluate the carcinogenic and non-carcino-
et al., 2015; Romagnoli et al., 2014). The ACGIH determined threshold genic health effects of VOCs. In this work, the hazard quotient (HQ)
limit values (TLV) based on the short-term exposure limit (STEL) and parameter was used for calculating non-carcinogenic health effects of
time weighted average (TWA). The Threshold Limit Value-Time- VOCs, which is expressed as the ratio of chronic daily intake (CDI) (mg/
Weighted Average (TLV-TWA) indicates whether an employee's exposure kg-day) and the reference dose (RfD) (mg/kg-day) (Table S1) (Baghani,
may not surpass the time-weighted average in an eight hour workday or Rostami, Arfaeinia, Hazrati, Fazlzadeh, Delikhoon, Safety et al., 2018;
forty hour work week (Verma, 2000; Zhang et al., 2018). According to Cao et al., 2018; Delikhoon et al., 2018b; Jiang, Duan, Yu, Zhang, &
the measured VOCs in this work and TLV-TWA in Table S1, the occu- Wang, 2018; Shuai et al., 2018; Zhu & Liu, 2014):
pational exposure indices (Ei) for emitted VOCs are determined as fol-
lows (He et al., 2015; He, Tang et al., 2012; Mo et al., 2009): HQ = CDI/ RfD (2)

n mg Hazard quotients exceeding one (1 ≤ HQ) indicate unsafe risk


Ei = Concentrations of VOCs / Threshold limit value time (harmful health effects) (Durmusoglu et al., 2010; Zhang et al., 2018).
i m3
mg In addition, McCarthy, O’Brien, Charrier, and Hafner (2009); He et al.
weighted average (TLV TWA) ( 3 ) (2015) and Ramírez, Cuadras, Rovira, Borrull, and Marcé (2012) re-
m (1)
ported that HQ values from 0.1 to 1 still exposes workers to risks (He
In this study, Ei > 1 indicates that the potential health risk can be et al., 2015; McCarthy et al., 2009; Ramírez et al., 2012).
important for the workers in the PCSWRF (He et al., 2015; He, Li et al., Furthermore, the lifetime cancer risk (LTCR) was applied to esti-
2012; Mo et al., 2009). According to Mo et al. (2009), it is necessary mate carcinogenic health effects of VOCs, which is specified as the

3
R. Nabizadeh, et al. Sustainable Cities and Society 56 (2020) 102005

Fig. 2. A map of operational units (processes units) in the PCSWRF.

product of chronic daily intake (CDI (mg/kg-day) and cancer slope conveyor belt line two (1.34 ± 0.08) > tipping floor line one
factor (CSF (mg/kg-day)−1) (Table S1) using the following equation (1.22 ± 0.07) > manual separation line one (1.20 ± 0.06) > manual
(Baghani, Rostami, Arfaeinia, Hazrati, Fazlzadeh, Delikhoon et al., separation line two (1.06 ± 0.05) > tipping floor line two (0.54 ±
2018; Golkhorshidi et al., 2019; Li et al., 2013; Zhang et al., 2018): 0.02) > office (0.69 ± 0.04) > background (0.43 ± 0.02) > storage
(Table S1) (0.09 ± 0.01). Among the steps of operational units, inclined conveyor
belt one (5.23 ± 1.20 mg/m3) had the most emissions of TVOCs. During
LTCR = CDI (mg/kg-day) × CSF (mg/kg-day)−1) (3)
the PCSW recycling processes, 17 VOCs were identified and quantified in
CDI = (C (pollutant concentrations (μg/m3)) × ET (exposure time operational units (Fig. 2). The mean ( ± SD) concentration of TVOCs
(40 h/week or 8 h/days) × EF (exposure frequency (48 weeks/year or (mg/m3) in different operational units is shown in Fig. 3. Accordingly,
240 days/year)× ED (exposure duration (30 year)) × IR (human in- the maximum concentrations of m,p-xylene (1.2 ± 0.11), 1,2,4-tri-
halation rate (0.83 m3/h / BW body weight 70 kg × AT the average methyl benzene (0.82 ± 0.05) and 1-ethyl-3-methyl benzene
lifetime 365 × 30 10,950 days (4) (0.69 ± 0.05) were measured in the conveyor belt line one. In contrast,
He et al. (2015) reported that the predominant concentrations of VOCs
Based on the United States Environmental Protection Agency (U. S. isolated from the air of in the poly (acrylonitrile-butadiene styrene)
EPA), the IR and BW values for adults are 0.83 m3/h and 70 kg, re- (ABS) recycling process in Southern China were styrene
spectively (EPA, 2011; Moya et al., 2011). According to Sexton, Linder, (6.3 ± 2.1 × 102 mg/m3), ethylbenzene (1.5 ± 0.5 × 102 mg/m−3),
Marko, Bethel, and Lupo (2007), Durmusoglu et al. (2010) and Li et al. xylene (54 ± 22 mg/m3), toluene (31 ± 14 mg/m3) and i-pro-
(2013), if the lifetime cancer risk (LTCRs) exceeds 1 × 10−4, ranges pylbenzene (28 ± 9 mg/m3) (He et al., 2015). In addition, Urase et al.
from 1 × 10−5 to 1 × 10−4, is between 1 × 10−5 and 1 × 10−6, or is (2008) observed that the main VOCs emitted from the landfill gas into
less than 1 × 10−6, it indicates as definite, probable, possible, and the ambient air were benzene, toluene, ethylbenzene, and xylene (BTEX),
negligible risk, respectively (Durmusoglu et al., 2010; Li et al., 2013; trimethyl benzenes and low levels of chlorinated compounds (Urase
Sexton et al., 2007). For calculating health risks of VOC species, the et al., 2008). Wu et al. (2018) reported that the major VOCs species at
equations above were applied separately to compute risks of species MSW landfills in Beijing, China were BTEX, styrene, propylbenzene,
and finally the risks for all of them combined together. The product of naphthalene, and 1,3,5-trimethylbenzene (Wu et al., 2018). Scaglia et al.
the above equations gave an indication of the total health risk. (2011) reported that the main emitted VOCs from MSW in the North Italy
were p-xylene, o-xylene, styrene, benzene, 1 ethyl 4 methyl benzene, 1
3. Results and discussion methyl 2 (1 methylethyl) benzene, 1 ethyl 4(1 methylethyl) benzene, 1
methyl 3(1 methylethyl) benzene, 2 ethyl 1,3 dimethyl benzene, 1,2,3
3.1. VOCs emissions trimethyl benzene, and 1 methoxy 4 methyl 2(1methylethyl) benzene
(Scaglia et al., 2011). Hence, the main reasons for difference in emitted
In this work, all of locations that included operational units (tipping VOCs from various studies could be explained by differences in sampling
floor line one and two, baling machine, hand picking line one and two, sites (landfill/disposal, composting, during waste collection, and in-
and inclined conveyor belt line one and two), storage, and offices emitted dustrial process), composition of waste (only paper and cardboard or
VOCs to the air. The mean concentrations ± (SD) of VOCs emitted from mixed municipal solid waste (MMSW) and thermal degradation of dif-
operational units, storage areas, office areas, and the outdoor area ferent types of plastic wastes (He et al., 2015; Pagans, Font, & Sánchez,
(background) are described in Table 1. The mean concentrations ± (SD) 2006; Scaglia et al., 2011; Shen et al., 2018; Urase et al., 2008). In ad-
of TVOCs emitted from PCSWRF were in the following order: conveyor dition, the findings of this work revealed that VOC concentrations in the
belt line one (5.23 ± 0.33 mg/m3) > baling machine (1.38 ± 0.07) > operational units in the PCSWR ranged between 1.10 ± 0.23 and

4
R. Nabizadeh, et al.

Table 1
The mean ± standard deviation (SD) of VOCs (mg/m3) in different sampling locations in the PCSWRF.
pollutant Tipping floor line Tipping floor line Conveyor belt line Conveyor belt line Manual separation line Manual separation line Baling machine Storage Office Background
one two one two one two

Benzene 0.030 ± 0.004 0.027 ± 0.003 0.065 ± 0.009 0.047 ± 0.004 0.059 ± 0.004 0.070 ± 0.008 0.017 ± 0.001 0.007 ± 0.001 0.076 ± 0.005 0.010 ± 0.001
Toluene 0.069 ± 0.005 0.075 ± 0.008 0.095 ± 0.007 0.073 ± 0.008 0.078 ± 0.010 0.071 ± 0.006 0.106 ± 0.010 0.065 ± 0.005 0.106 ± 0.010 0.061 ± 0.005
Ethylbenzene 0.030 ± 0.003 0.008 ± 0.001 ND 0.031 ± 0.002 0.066 ± 0.006 0.037 ± 0.003 0.021 ± 0.002 0.011 ± 0.001 0.040 ± 0.005 0.003 ± 0.000
M,P-xylene 0.208 ± 0.018 0.078 ± 0.006 1.195 ± 0.118 0.276 ± 0.023 0.200 ± 0.014 0.109 ± 0.011 0.267 ± 0.030 0.012 ± 0.002 0.171 ± 0.014 0.082 ± 0.010
O-xylene 0.095 ± 0.011 0.033 ± 0.003 0.557 ± 0.047 0.116 ± 0.014 0.096 ± 0.011 0.056 ± 0.005 0.124 ± 0.016 0.011 ± 0.001 0.048 ± 0.005 0.027 ± 0.003
Decane 0.031 ± 0.003 0.014 ± 0.002 0.184 ± 0.023 0.030 ± 0.002 0.036 ± 0.004 0.025 ± 0.003 0.054 ± 0.007 0.011 ± 0.001 0.015 ± 0.001 0.016 ± 0.001
1-ethyl-3-methyl 0.152 ± 0.021 0.013 ± 0.002 0.687 ± 0.049 0.145 ± 0.020 0.151 ± 0.011 0.135 ± 0.012 0.036 ± 0.005 0.005 ± 0.001 0.079 ± 0.008 0.010 ± 0.001
benzene
1,2,3-trimethyl 0.034 ± 0.004 0.041 ± 0.005 0.187 ± 0.018 0.027 ± 0.002 0.032 ± 0.004 0.028 ± 0.003 0.153 ± 0.017 0.011 ± 0.001 0.015 ± 0.001 0.035 ± 0.005

5
benzene
1,3,5-trimethyl 0.045 ± 0.004 0.013 ± 0.001 0.286 ± 0.023 0.035 ± 0.004 0.044 ± 0.006 0.055 ± 0.004 0.025 ± 0.002 0.011 ± 0.002 0.021 ± 0.002 0.011 ± 0.002
benzene
1,2,4-trimethyl 0.168 ± 0.017 0.067 ± 0.009 0.821 ± 0.094 0.161 ± 0.018 0.139 ± 0.010 0.113 ± 0.011 0.028 ± 0.002 0.012 ± 0.001 0.071 ± 0.008 0.013 ± 0.001
benzene
1,2-diethyl benzene ND 0.011 ± 0.001 0.081 ± 0.007 0.065 ± 0.007 0.014 ± 0.001 0.013 ± 0.001 ND ND ND 0.034 ± 0.003
1-ethyl-2-methyl 0.018 ± 0.002 0.010 ± 0.001 0.201 ± 0.023 ND 0.038 ± 0.005 0.036 ± 0.003 0.136 ± 0.013 0.013 ± 0.002 0.015 ± 0.001 0.008 ± 0.001
benzene
Limonene 0.265 ± 0.019 0.081 ± 0.010 0.485 ± 0.034 0.264 ± 0.026 0.170 ± 0.012 0.215 ± 0.021 0.212 ± 0.027 0.012 ± 0.001 0.012 ± 0.001 0.064 ± 0.005
1,4-diethyl benzene 0.034 ± 0.004 0.041 ± 0.004 0.187 ± 0.021 0.027 ± 0.002 0.032 ± 0.004 0.038 ± 0.004 0.153 ± 0.017 0.014 ± 0.003 0.015 ± 0.001 0.035 ± 0.004
Butyl benzene 0.031 ± 0.003 0.014 ± 0.002 0.184 ± 0.014 0.030 ± 0.003 0.036 ± 0.005 0.051 ± 0.006 0.054 ± 0.005 ND 0.015 ± 0.001 0.016 ± 0.002
2-methyl nonane 0.011 ± 0.001 0.005 ± 0.002 0.013 ± 0.001 0.013 ± 0.001 0.005 ± 0.002 0.009 ± 0.001 ND ND ND 0.008 ± 0.003
Nonane ND 0.008 ± 0.003 0.007 ± 0.001 0.006 ± 0.002 0.005 ± 0.003 0.006 ± 0.001 ND ND ND 0.003 ± 0.002
TVOCs 1.220 ± 0.079 0.541 ± 0.027 5.234 ± 0.335 1.346 ± 0.086 1.202 ± 0.060 1.066 ± 0.054 1.386 ± 0.078 0.097 ± 0.018 0.696 ± 0.047 0.430 ± 0.024

ND - Not Detectable.
Sustainable Cities and Society 56 (2020) 102005
R. Nabizadeh, et al. Sustainable Cities and Society 56 (2020) 102005

3.2. Frequency of occurrence of VOCs species

The percentage of measured VOCs during operational units in


PCSWRF were in the following order: conveyor belt line one (43.64
%) > baling machine (11.55 %) > conveyor belt line two (11.22
%) > tipping floor line one (10.17 %) > hand picking line one (10.01
%) > hand picking line two (8.88 %) > tipping floor line two (4.50 %).
As mentioned above, the line one was polluted than line two. In addi-
tion, the percentage of emitted VOCs in storage, office and background
compared with operational units were 0.39, 0.77 and 0.12 %. Reasons
for conveyor belt line one being highest in concentration in this work
could be linked to proper moisture content and higher temperature as
compared to different units, and severe mechanical stirring of solid
waste by front-end loaders for easier separation of paper and cardboard
as compared to manual separation (Chiriac, Carre, Perrodin, Fine, &
Letoffe, 2007; He, Tang, Zhang, Zeng, & Shao, 2010; Laitinen et al.,
2016).
The percentage of detected VOCs based on frequency in different
sampling sites were simplified in Fig. S2. As shown in Fig. S2 b and c,
the four main species of VOC identified in the indoor air of tipping floor
(line one vs. line two) were m,p-xylene (21.76 vs. 15.05 %), limonene
Fig. 3. The mean ( ± SD) concentration of TVOCs (mg/m3) in all operational (17.05 vs. 14.51 %), 1,2,4-trimethyl benzene (13.80 vs. 12.32 %), and
units. toluene (5.65 vs. 13.91 %). In addition, according to Figs. S2 d and e,
the five dominant species of VOCs in conveyor belt line one were m,p-
xylene (22.84 %), 1,2,4-trimethyl benzene (15.68 %), 1-ethyl-2-methyl
5.30 ± 1.20 mg/m3, which is consistent with the results of the previous benzene (13.31 %), o-xylene (10.63 %), and limonene (9.26 %), while
studies by Lehtinen, Tolvanen, Nivukoski, Veijanen, and Hänninen in conveyor belt line two the prcentage of these species were 20.52 %
(2013) in the optic sorting plant in Hämeenlinna and the waste trans- for m,p-xylene, 11.95 % for 1,2,4-trimethyl benzene, 10.74 % for 1-
ferring plant in Hyvinkää in Finland (Lehtinen et al., 2013). ethyl-2-methyl benzene, 8.56 % for o-xylene, and 19.61 % for limo-
The main VOCs emitted from the processing hall in the optic sorting nene. Moreover, Figs. S2 f and g revealed the following differences
plant in Hämeenlinna were ethylbenzene, p-xylene, p-cymene, propyl between line one and line two: m,p-xylene (16.64 vs. 10.20 %), limo-
benzene, C3-alkyl benzene, and limonene, each of which ranged be- nene (14.17 vs. 20.15 %), 1-ethyl-2-methyl benzene (12.55 vs. 12.69
tween 0.04–1.20 mg/m3. The same study showed that the concentra- %), and 1,2,4-trimethyl benzene (11.57 vs. 10.59 %).
tions of limonene (1.20 mg/m3) exceeded other components (Lehtinen In addition, the results of this work showed that the major pollu-
et al., 2013), which is in agreement with the findings of the present tants measured in the air of the baling machine were m,p-xylene (19.24
study. Another study examining urban waste wheel containers for VOCs %), limonene (15.30 %), 1,2,3-trimethyl benzene (11.01 %), and 1-
in Athens, Greece showed that the most abundant VOCs included de- ethyl-2-methyl benzene (9.83 %) (Fig. S2 h) and the chief reason why
cane, limonen, nonane, and benzene with median concentrations ran- the concentrations of VOCs were lower than other operational units
ging from 212.6 to 694.9 μg/m3 (Statheropoulos, Agapiou, & Pallis, could be described by the recycled materials (paper and cardboard)
2005). Some VOCs such as styrene, toluene, ethylbenzenes, m,p-xylene, were packaged. The main measured VOCs species in storage were to-
and o-xylene have been emitted from plain paper, especially in the luene (66.87 %), limonene (12.83 %), benzene (7.24 %), and 1-ethyl-2-
presence of toner, in aged/old books (109 VOCs identified) and pro- methyl benzene (5.53 %) (Fig. S2 i). Surprisingly, the percentage of
cessed paper from photocopying machines (Betha, Selvam, Blake, & toluene was the first highest VOCs (66.87 %) with a mean value of
Balasubramanian, 2011; Gaspar, Santana, Lopes, & Diniz, 2010; Knight 0.21 ± 0.07 mg/m3, which might be generated by devices such as a
& Horie, 2007; Henschel, Fortmann, Roache, & Liu, 2001; Horie, 2020; liftruck and trucks (fresh emissions) during loading bales and waste
Kumar et al., 2014; Pagans et al., 2006; Wolkoff, Wilkins, Clausen, & materials that includes VOCs (fresh waste/ mixed paper with food
Larsen, 1993). Furthermore, paper and cardboard production im- wastes) (Chiriac et al., 2007; Conte et al., 2018; Dehghani, Fazlzadeh
pregnated with oil and grease was another source of VOCs (Banou et al., et al., 2018; Hoque, Khillare, Agarwal, Shridhar, & Balachandran, 2008;
2016; Pagans et al., 2006; Propst, 2010). Generally, several parameters Jackson, 2015; Komilis et al., 2004; Nie, Zheng, Shao, Yang, & Chen,
could lead to emissions of VOCs into the air of operational units in this 2018; Termonia & Termonia, 1999). The major VOCs emission from the
PCSWRF including biodegradation of organic solid wastes, proper office building included m,p-xylene (24.52 %), toluene (15.61 %),
moisture content and temperatures higher than 30 °C in the waste, benzene (10.88 %), and o-xylene (6.84 %), while the main VOCs
polystyrene plastic waste, an old ink or toner cartridge, processed paper emitted in ambient background air (outdoor) were m,p-xylene (19.19
from photocopying machines, paper and cardboard production im- %), limonene (14.81 %), toluene (14.25 %), and 1,2,3-trimethyl ben-
pregnated with petroleum products, and in old books. The mean con- zene (8.13 %) (Figs. S2 j and a). For contrast, the findings of this work
centrations of TVOCs in the indoor microenvironment of the PCSWRF were opposite to other studies in that the main VOCs discharged into
was about 5–19 times higher than indoor microenvironments (re- the air of plastic solid waste recycling workshops (PSW) with pyrolysis
sidential and workplace) in EXPOLIS-Helsinki, Finland (Edwards, of plastics were BTEX and styrene (He et al., 2015; Mehta, Biederman,
Jurvelin, Saarela, & Jantunen, 2001), and the mean TVOC concentra- & Shivkumar, 1995). In this work the main factors leading to emisions
tions in the indoor microenvironment in office of PCSWRF was 19 times of VOCs into the air were the materials that included VOCs (fresh waste
lower than in the largest office building in Jahra City since Jahra's large and mixed paper with food wastes) and some processes such as fer-
office is located near of oil fields (Al-Khulaifi, Al-Mudhaf, Alenezi, Abu- mentation of paper and cardboard (Arshadi & Gref, 2005; Gaspar et al.,
Shady, & Selim, 2014). In addition, the mean emitted TVOCs in the 2010; He et al., 2010; Jackson, 2015; Komilis et al., 2004; Zhu, Chai, &
operational units in PCSWRF were 2.5–150 times lower than the mean Dhasmana, 1998), while the main source of discharged VOCs into the
TVOCs concentrations in the melting extrusion process of various air of PSW workshops was thermal degradation of different types of
plastic solid waste recycling workshops (He et al., 2015). plastics at high tempreture (more than 160 °C) (He et al., 2015; Mehta

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R. Nabizadeh, et al. Sustainable Cities and Society 56 (2020) 102005

et al., 1995). was used to compare normally distributed variables for more than two
Generally, the main species of VOCs in the different processes of the groups (Kruskal-Wallis test). Hence, the results of Kruskal-Wallis test on
indoor microenvironment were m,p-xylene, limonene and 1,2,4-tri- VOCs concentrations in different processes described that the chi-
methyl benzene. Furthermore, the predominant VOC species in the square test statistic was 14.45, which was significant at a level of 0.05.
PCSWRF were m,p-xylene, limonene, 1,2,4-trimethyl benzene, 1-ethyl- Therefore, it is safe to say that there were significant difference between
3-methyl benzene, and toluene. Finally, the VOC concentrations de- the concentration of VOCs in different operational units (p < 0.05).
creased from the tipping floor to the baling machine, and were lowest in Consequently, the results of the Kruskal-Wallis post-hoc test (Kruskal
the storage site. Mac) showed that the mean concentrations of VOCs between two dif-
ferent operating units of baling machine - tipping floor line two, con-
3.3. Statistical analysis of VOCs in PCSWRF veyor belt line one - conveyor belt line two, conveyor belt line one -
manual separation line, conveyor belt line one -tipping floor line one,
3.3.1. Interrelationships between VOCs species and meteorological conveyor belt line one - tipping floor line two, and manual separation
conditions line -tipping floor line two were significantly different
Table S2 summarizes Pearson's correlations among VOC con- (p < 0.05).However, there was not a significant difference between
centrations based on mean concentrations and meteorological para- the mean concentrations of VOCs in other operating units (p > 0.05).
meters for all sites in the PCSWRF. Accordingly, the correlation coef-
ficients (r) for VOC species in most places of the PCSWRF were higher 3.4. Occupational exposure limits (OEL) assessment for workers in
than 0.679. In addition, significant positive correlations were among PCSWRF
among VOCs species. These results showed that VOC species had si-
milar sources and the recycled materials that included VOCs (fresh VOCs with high levels could lead to chronic and acute health effects
waste and mixed paper with food wastes) were the major sources of for those in the PCSWRF. Therefore, based on emitted VOCs, we can
VOCs in the PCSWRF (Jackson, 2015; Komilis et al., 2004). The max- calculate occupational exposure limits (OEL) for the workers. A threshold
imum correlation coefficient (r = 0.999, p < 0.01) was obtained be- limit value-time-weighted average (TLV-TWA) of 10 out of 17 measured
tween 1,2,3-trimethyl benzene and 1,4-diethyl benzene. VOCs were valuated for health effects of the workers in this work (Table
A significant correlation was observed between VOCs species with S1). According to TWA–TLV the exposure indices (Ei) for 10 emitted
either relative humidity or temperature (p < 0.01) except for benzene, VOCs from the PCSWRF in different sites are shown in Fig. S4. As can be
toluene, ethylbenzene, and nonane. Hence, the results of this work seen, the Ei for TVOCs in all of sites in PCSWRF were higher than one
shows that concentrations of VOC species were not related to fresh except for the background and storage areas. This indicates that people in
emissions except for storage site where liftruck and trucks (fresh this factory might suffer from health effects of VOCs from different sites
emissions) can generate VOCs species. In general, these findings are and that workers should pay attention to the health effects of VOCs.
highly indicative of the recycled materials that include VOCs species Moreover, the highest sum of Ei for TVOCs in this work revealed the
(fresh waste and mixed paper with food wastes) as the main source of following order of abundance: hand picking line two (4.5) > conveyor
VOCs species in the air of PCSWRF. belt line one (4.2) > hand picking line one (3.5) > hand picking line one
(3.8) > conveyor belt line two (3.1) > tipping floor line one
3.3.2. Statistical analysis of VOCs in different sampling location (1.9) > tipping floor line two (1.7) > baling machine (1.1) > back-
Fig. S3 displays a box plot of VOC concentrations in different ground (0.63) > storage (0.45). In this work, benzene with the highest
sampling locations (storage, office, process and background). The average Ei of 3 accounted for more than 85 % of TVOC Ei in the PCSWRF
output of the Fligner-Killeen test showed that p-value for VOC con- since TLV-TWA for benzene (1.7 × 10−3 mg/m3) was lower than the
centrations in different sampling stations was lower than 0.05 other compounds (Table S1). The the mean Ei of nonane (TLV-
(p < 0.05). This indicates that the difference between the variances in TWA = 1.1 × 103 mg/m3) was lower than 0.001, and accounted for
different processes were significant (p < 0.05). Therefore, analysis of lower than 0.002 % of TVOC Ei. In addition, the mean Ei of TVOCs for
variance was used to compare normally distributed variables for more background and storage areas were lower than one. Generally, the Ei for
than two groups (Kruskal-Wallis test). The results of the Kruskal-Wallis TVOCs in different sites was more than one, and so using personal pro-
test on VOC concentrations in different sampling stations was sig- tective equipment (PPE) such as respirators and gloves can help workers
nificant at a level of 0.05. Consequently, the results of the Kruskal- decrease exposure to emitted VOCs in this WPCRF.
Wallis post-hoc test (Kruskal Mac) showed that the mean concentra-
tions of VOCs between two different sampling locations of background 3.5. Health risk assessment (HRA) for VOCs
– storage, background - process and office – storage were significantly
different (p < 0.05). All of 17 measured VOCs were evaluated based on the RfD values
for non-carcinogenic effects (Table S1). According to concentrations of
3.3.3. Statistical analysis in different processes VOCs (Table 1), the HQ of VOCs are summarized in Fig. S5. The highest
The results of the Mann-Whitney-Wilcoxon test showed that there sum of HQs with a value of 5.8 for the examined VOCs was acquired in
was no statistically significant difference between VOC concentrations the conveyor belt line one, followed by hand picking line two (3), hand
in tipping floor line one and two (p ≤ 0.001) and conveyor belt line one picking line one (2.7), conveyor belt line two (2.6), office (1.6), tipping
and two (p ≤ 0.001), while the results of the paired t-test showed that a floor line one (1.1), baling machine (0.88), tipping floor line two (0.72),
statistically significant difference was observed between concentrations background (0.64), and storage (0.17). With the HQ more than one,
of VOCs in manual separation line one and two (p = 0.112). Hence, non-carcinogenic risk could be introduced to the workers by VOCs
VOCs concentrations of manual separation line one and two were discharged from the conveyor belt line one, where the top three com-
combined together as a defined manual separation line (Fig. 4). Box pounds for HQs were 1,3,5-trimethyl benzene (1.78), nonane (1.4) and
plot of VOCs concentrations based on mg/m3 in different processes benzene (1.06), accounting for 30.79 %, 23.48 % and 17.56 % of the
(operational units) is shown in Fig. 4. Accordingly, the output of the cumulative HQ, respectively. Furthermore, the HQ of conveyor belt line
Fligner-Killeen test showed that p-value for VOCs in different processes one was two times higher than line two so the non-carcinogenic risk of
(tipping floor line one and two, conveyor belt line one and two, manual line one is two times larger than line two. In the conveyor belt line two,
separation line, and baling machine) was lower than 0.05 (p < 0.05). the only compound that affects non-carcinogenic risk of workers was
This indicates that the difference between the variances in different nonane (HQ = 1.29), which supports the 48.98 % of total hazard
processes were significant (p < 0.05). Therefore, analysis of variance quotient (2.6). In addition, the HQs for manual separation line two

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R. Nabizadeh, et al. Sustainable Cities and Society 56 (2020) 102005

Fig. 4. Box plot of VOC concentrations in different processes (operational units) in winter.

exceeded one, representing a non-carcinogenic risk for residents; ben- LTCRs for ethylbenzene in office, manual separation line one and two
zene (41.22–42.91%) and nonane (34.74–36.38%) had the highest HQs were calculated, respectively 9.38 × 10−6 (7.76 % of total LTCRs),
for line two. Moreover, the total HQs in the office area was 1.6 and 8.56 × 10−6 (7.70 % of total LTCRs) and 1.53 × 10−5 (14.88 % of total
benzene is the main pollutant that the residents were exposed to LTCRs). Durmusoglu et al. (2010) reported that compounds with LTCRs
(HQ = 1.18), contributing 75.14 % of the total non-cancer risk. As for from 1 × 10−5 to 1 × 10−6 can be categorized as a “possible risk”
the other sites, the total HQ was lower than one, indicating a non- (Durmusoglu et al., 2010), which is ethylbenzene in this work. Li et al.
carcinogenic risk of VOC species. (2013) reported that ethylbenzene (8.95 × 10−6), dichloropropane
McCarthy et al. (2009), He et al. (2015) and Ramírez et al. (2012) (9.50 × 10−6) and trichloromethane (7.36 × 10−6) discharged from the
reported that HQ values from 0.1 to 1 could make the site workers MSW compression transfer station during periods when the compressor
vulnerable to health risks (He et al., 2015; McCarthy et al., 2009; was working were identified as a “possible risk” (Li et al., 2013b). In
Ramírez et al., 2012). The HQs for benzene in the indoor micro- addition, in plastic solid waste recycling workshops (PSW) in southern
environments of the PCSW such as tipping floor line two, conveyor belt China, 1,2-dichloromethane was a probable risk for workers with LTCR
line two, manual separation (line one and two), background, baling more than10−5 (contributing 51.5–55.9% of the LTCR) (He et al., 2015).
machine, and storage ranged from 0.1 to 0.73, describing 24–65% of the Furthermore, the study by Ramírez et al. (2012) in the ambient air of a
total non-carcinogenic risk. Furthermore, 1,3,5-trimethyl benzene large Mediterranean industrial site showed that ethylbenzene
(HQs = 0.13 to 0.34) also accounted for 8.31–18.11% of the sum non- (3.5 × 10−6) and tetrachloroethylene (2.3 × 10−6) were identified as a
carcinogenic risk in the indoor air of tipping floor line one, conveyor belt probable risk for workers (Ramírez et al., 2012). Finally, benzene (Group
(line two), hand picking (line one and two), and baling machine. Fur- 1) and ethylbenzene (group 2B) can promote cancers such as those of the
thermore, 1,2,4-trimethyl benzene (HQs = 0.1 to 0.73) contributed brain, lungs, liver, and kidneys for workers at office, manual separation
3.36–12.7% of the total HQs of PCSW recycling factory, especially for line one and two in PCSWRF, which is consistent with former findings
indoor air of tipping floor line one, conveyor belt (line one and two), (Durmusoglu et al., 2010; He et al., 2015; Huff, Chan, & Melnick, 2010;
hand picking (line one and two). Moreover, the HQ for 1,2,3-trimethyl Lehtinen et al., 2013). Hence, exposure to VOCs leads to high risk in the
benzene was limited between 0.19 and 0.23, which contributes 4–21.8% PCSWRF, especially at hand picking line two (HQ = 3 and LTCRs =
of the total HQ of VOCs for the PCSW recycling factory, especially for 1.11 × 10−4), hand picking line one (HQ = 2.7 and LTCRs = 1.03 ×
indoor air of conveyor belt line one and baling machine. Finally, in the 10−4), office (HQ = 1.6 and LTCRs = 1.21 × 10−4) and strategies
indoor microenvironment of conveyor belt line one, o-xylene was also should be considered to eliminate pollutants and to keep workers im-
the main non-carcinogenic risk for residents (estimating for 3 % of total mune from the non-carcinogenic and carcinogenic effects.
HQs) with the HQ of 0.17. Based on the International Agency for Re-
search on Cancer (IARC), two of the measured VOCs were benzene 3.6. Control methods for VOCs
(group 1) and ethylbenzene (group 2B) that are categorized as a human
carcinogen and probable human carcinogen, respectively (Dehghani, The different levels of VOCs are released from various municipal
Fazlzadeh et al., 2018; International Agency for Research on Cancer, waste management practices such as recycling, composting, incinera-
2014; Lim et al., 2014). Fig. S6 describes the LTCRs of the carcinogenic tion, and landfilling (Xin and Tsuda, 2017; Sarkhosh et al., 2017).
VOCs in PCSWRF. The highest total of LTCRs (1.21 × 10−4) occurred in Controlling VOC emissions from waste paper and cardboard recycling
the indoor microenvironment of the office, followed by manual separa- factories is important for the sake of improving the general health of
tion line two (1.11 × 10−4), manual separation line one (1.03 × 10−4), workers and inhabitants in locations with these operations, in addition
conveyor belt line one (9.74 × 10−5), conveyor belt oute two to improving air quality. Generally, current VOCs control strategies at
(7.64 × 10−5), tipping floor line one (5.06 × 10−5), tipping floor line PCSWRFs can be categorised into three methods including pre-treat-
two (4.19 × 10−5), baling machine (3.02 × 10−5), background ment (reduction) of VOC-contaminated waste, and also in situ and post-
(1.51 × 10−5), and storage (1.05 × 10−5). It should be noted that the treatment methods (Shen & Sewell, 1988). With pre-treatment methods
workers in the office and manual separation process (line one and two) of such as steam-stripping, air-stripping, and carbon adsorption, VOCs can
the PCSW recycling factory have been exposed to cancer risks. In the be eliminated from paper and cardboard before it enters to the PCSWRF
former three sites, the total of LTCRs was mostly provided by benzene (Babar & Shareefdeen, 2014; Li, Yuan, & Jie, 2018). In addition, se-
(participating for 92.24 %, 92.30 % and 85.12 % of the sum of LTCRs, paration of paper and cardboard production impregnated with oil and
respectively) whose LTCRs values transcended a level of 1 × 10−4 grease, especially at tipping floor sites, can reduce emissions of VOCs in
(Durmusoglu et al., 2010; Li et al., 2013; Sexton et al., 2007b). Besides, PCSWRF (Banou et al., 2016; Pagans et al., 2006; Propst, 2010). In situ

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R. Nabizadeh, et al. Sustainable Cities and Society 56 (2020) 102005

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