Distribution and Risk Assessment of Phthalate Esters in Refuse Dumpsite

Soils of Obafemi Awolowo University, Ile-Ife, Nigeria

Omolara Josephine Fagbemi1, Aderemi Okunola Ogunfowokan², John Adekunle O.

Oyekunle², Francis Cheng3, Leo Deobald3, Ruth Olubukola A. Adelagun4
1
Department of Industrial Chemistry, Faculty of Science, University of Ilesa, Ilesa,
Nigeria.
2
Department of Chemistry, Faculty of Science, Obafemi Awolowo University, Ile-Ife,
Nigeria.
3
Department of Chemistry, University of Idaho, Moscow, USA
4
Department of Chemical Sciences, Federal University Wukari, Nigeria

Corresponding author: Omolara Josephine Fagbemi ([Link]@[Link])

Abstract

The levels, seasonal variation, lateral and vertical migration of PAEs in refuse dumpsite

soils of Obafemi Awolowo University, Ile-Ife, Nigeria was investigated in this research.

This was done to calculate the health hazards linked n to contact with these soils. Soil

samples were collected using soil auger during dry and wet season at varying soil depths

and different intervals of 50, 100, and 117 m between dumpsite and the receiving stream.

Microwave extraction method was optimized to extract PAEs from soil samples.

Chromatographic quantifications were done using Gas Chromatography connected to a

quadrupole Mass Spectrometer. Di(2-ethylhexyl phthalate) possessed the most significant

concentration of 49.83 ± 0.49 mg kg -1 in December. The cumulative levels of butylbenzyl

phthalate and di (2-ethylhexyl phthalate) accounted for more than 90% of total PAEs in

dumpsite soils. Dimethyl phthalate, diethyl phthalate and dibutyl phthalate had higher

levels during wet season as opposed to the high levels of butylbenzyl phthalate and di

(2-ethylhexy phthalate) during dry season. The PAEs exhibited a potential to affect

groundwater quality based on their vertical distribution. Plastic pollution was identified as

the primary source of the PAEs in the dumpsite soils. The health risk evaluation indicated

that there were no non-carcinogenic and carcinogenic health risks linked to exposure to the

1
aforementioned phthalates. Stringent measures should be enforced to avoid the

introduction of increased levels of these priority pollutants into the environment.

Key words: human health; phthalate esters; refuse dumpsite; risk assessment; soil

1. Introduction

Phthalate acid esters (PAEs) are environmental hormones which are highly toxic, semi-

volatile, and have bioaccumulative tendencies [1]. They possess the ability to act as

endocrine disruptors, entering directly into the human body via diet, skin contact, and

breathing [2]. They can cause interference with the body's hormonal balance and thus

result in endocrine disorder, decrease in sperm quantity, breast cancer, and reproductive

diseases [ 3 ] . More attention has been focused on PAEs in recent times due to an upsurge

in its prevalent use. While they do not dissolve in water, they exhibit significant solubility

in specific organic solvents and often very difficult to volatilize [4,5].They find extensive

use in the production of pesticides, detergents, plastics, and cosmetics. A large percentage

of them have also been used as plasticizers in polyvinyl chloride in a bid to improving

softness and ductility [6,7].

The widespread presence of PAEs in environmental matrices (soil, sediments, water, and

air) and biota have been documented in previous studies [8-13]. While the incorporation of

PAEs into materials tends to be obviously advantageous,it poses potential toxicity to

both human and environmental health. The higher boiling point, environmental

persistence, lower vapor pressure, and low Henry constant makes them adsorb strongly to

environmental matrices [14]. Their weak electrostative force with materials is a solid reason

why they are continuously released into the environment after production [14]. Consequent

upon the knowledge that PAEs are substances that can cause harm to the development and

reproductive systems, six of them namely dimethyl phthalate (DMP), diethyl phthalate (DEP),

di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBP), di-n-octyl phthalate (DnOP), and

2
di(2-ethylhexyl)phthalate (DEHP) have been classified as priority pollutants by the United

States Environmental Protection Agency (USEPA 2011).

Owing to the fact that soils possess a high capacity for absorption, they act as final reservoir

for many environmental toxicants including PAEs [ 1 2 ] . The contamination of the food

chain which might pose severe threats to human life is a possibility due to the existence of

PAEs within soil [ 9 ] . The need therefore arises to study the extent of soil pollution

accrued to PAE levels. The uncontrolled disposal of waste and its handling in Nigeria

has emerged as a significant environmental issue. It is presumed that the presence of trace

organics such as phthalate acid esters, polycyclic aromatic hydrocarbons,

polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins, polychlorinated

dibenzofurans and polybrominated diphenyl ethers, which might be released from the open-

air incineration of wastes, poses potential devastating effects. In the past, studies carried

out on the pollution status of the study area include: trace metals assessment [15,16] and

polybrominated diphenyl contained in the soil of the dumpsite and sediments of the

adjoining stream [17,18]. However, no study has been carried out on the phthalate esters

content of samples obtained from the current study area. Thus, the present study was

therefore set to evaluate the levels of phthalate esters in the dumpsite soils of Obafemi

Awolowo University, Ile-Ife, Nigeria.

2. Materials and Methods

2.1 Description of the Study area

A topographical map of the Obafemi Awolowo University, lle-Ife dumpsite area is shown

in Figure 1. Obafemi Awolowo University campus is located at the north western outskirt of

lle-Ife, Osun state. The altitude of lle-Ife varies from 15 meters to 457 meters above the sea

level. Geographically, the research site is situated within the basement complex of

southwestern Nigeria, which is a component of the African crystalline shield. This

3
shield predominantly comprises dolerites, apitite, microgranite genesis, granite genesis,

ultrasonic rocks, mica schists, and banded genesis. The sampled dumpsite which lies within

latitudes 07°31994"N - 07°32058'N and longitudes 004°31470°E - 004°31490"E at 318 m

above sea level which started operation in 1971. It serves as the final destination for

several thousands of plastic product wastes alongside with other forms of waste

collected within the university community. The amount of this waste has increased over

time because of increase in population of the University community over the years and the

refuse are subjected to open air incineration at regular interval.

2.2 Reagents,Standards and Equipment

Sodium chloride, hydrochloric acid was purchased from Aldrich-Sigma, South Africa

through their Nigerian based vendors. Ethyl acetate, acetonitrile, acetone, dichloromethane,

sodium tetraoxosulphate, hexane, phthalate standard stock solutions (1000 mg/L), butyl

benzoate (internal standard), silica gel (Kieselgel, 60, 230-400 mesh) and others were

acquired from Aldrich-Sigma,Merck, Fisher and WVR Scientific Chemicals, USA. All

solvents used were of high-performance liquid chromatography(HPLC) grade, while other

chemicals utilized were of analytical grade. A working phthalate ester standard mix

containing 2000 mg/mL (of each phthalate of interest) standard solution formulated from

USEPA phthalate esters mix (4S8231) which was purchased from Supelco Analytical

(Philadelphia, PA, USA) was made by moving 500 μL out of a stock solution into a 5 mL

teflon capped graded amber glass vial and filled up tc the desired volume with

[Link] working standard solutions were prepared on a monthly basis and

stored at 4°C. Calibration standard solutions at concentrations of 1, 1.5, 3.0, 6.0, 12.0,

24.00 and 50 mg/L were prepared freshly on the day of analysis by diluting the working

standard in dichloromethane. Microwave Biotage initiator classic (MAE) and Gas

Chromatography – Mass Spectrophotometry (GC-MS) -Hewlett-Packard 6890 with Hewlett-

4
Packard 5973 Mass Selective Detector available at the University of Idaho, USA, was used

for this study.

2.3 Sample Collection and pre-treatment

Sample collection took place throughout the wet season,spanning from June to September

a n d the dry season,which extends from October to February. Soil samples were collected

randomly at ten different locations on the dumpsite,and were mixed thoroughly to form

a composite sample. Soil samples were collected at two different depths: 0-15 cm and 15-30

cm, respectively. Similarly, soil samples were collected at regular intervals of 50, 100, and

117 meters from the dumpsite towards the direction of the receiving stream. The collected

soil samples were wrapped in aluminium foil,air-dried within five days of collection, ground

and subsequently sieved using a 500-micron stainless steel sieve, and preserved in

airtight aluminiun foil at 4C in a refrigerator until the time of analysis. As a quality

control measure, it was ensured that no plastic apparatus was used during sampling.

2.4 Microwave-Assisted Extraction (MAE) of Phthalate Esters from Soil Samples

United State Environmental Protection Agency (USEPA) method 2546 (USEPA 2007) as

explained by Liang et al. [19] was adopted. The parameters that were optimized includes

temperature (60, 80, 100, 120, 149, 160°C), time (5, 10, 15, 20, 30 mins.), solvent and

solvent mixture (DCM; Acetonitrile; ethyl acetate; Acetone (2:1,1:1) : DCM), volume of

solvent and sample ratio (5 mL/2.5 g, 10 mL/5.0 g). Spiked and unspiked reference soil

sample, which was used for the optimization process,was dried using air and then passed

through a sieve with a pore size of 0.50 μm. 5 g was spiked with 2 mL of 2.5 mg/L of each

of the phthalates standards in a mixture and 12.5 mg/L of the internal standard (benzyl

benzoate). The extraction solvent was introduced into the microwave-assisted extraction

(MAE) vessel, which already contained a specified volume of the soil sample. The vessel

was tightly sealed and vigorously shaken for several seconds before being inserted into the

5
microwave sample preparation system. Extraction was conducted with pre-stirring for a

duration of 10 seconds. Following the extraction process, the vessel was taken out from

the microwave and left to cool down to room temperature. Subsequently, the extract was

transferred to a centrifuge bottle and subjected to centrifugation at a speed of 3000 rpm. The

residue was rinsed three times using 5 mL of the extraction solvent during each washing

cycle. The collected aliquots of solvent were combined and subjected to evaporation, using

a gentle stream of nitrogen, until they reached a state of near dryness. The resulting

residue was dissolved again using 2 mL of dichloromethane (DCM) for the purpose of

chromatography clean up. Qualitative identification and qualitative estimation of the

analytes of interest was done using GC-MS.

2.5 Column Chromatographie Clean-up for the Extracts

The soil extract (reconstituted in 2 mL of DCM) was introduced onto silica gel

chromatographic column (250 mm x 10 mm i.d.) to remove interference molecules. To

prepare the column, a small piece of glass wool was placed at the base, followed by 2 g

of sand and 5 g of silica gel slurry (prepared with 20 mL of n-hexane). Additionally, a

layer of 2 cm of anhydrous sodium sulfate was added on top of the silica gel.

Subsequently, the packed column was rinsed with 10 mL of ethyl acetate,and the extract

was introduced into the column. Elution was performed in a sequential manner using 20 mL

of n-hexane to eliminate the hydrocarbons. Next, the phthalate compound was eluted from

the column using 20 mL of ethyl [Link] ethyl acetate eluate was subjected to gentle

nitrogen stream evaporation until it dried. Subsequently, it was reconstituted with 2 mL of

a solution containing 12.5 mg/L of benzyl benzoate (used as an internal standard) in n-

hexane and transferred to a glass vial for GC-MS analysis.

2.6 Instrumental Analysis

6
The validation of phthalate analysis in soil samples using GC-MS was conducted following

the quality management guidelines of Institute Bachema AG, which is certified by ISO

17025. (Institute Bachema, 2004; 2006). The instrumental analysis was performed using

GC-MS equipment at the Mass Spec Core Lab, Renfrew Hall, Room 30, University of Idaho,

USA. Phthalate calibration standards were prepared in methylene chloride across a range

of 0 -50 mg/L; the calibration standards contained five phthalates. The identification of

analytes was accomplished by comparing their retention times with those of reference

standards. Quantification was conducted by measuring the peak area of the targeted

compounds utilizing the intemal standard technique. The amount of each compound was

determined by calculating the ratio of the peak response of the phthalate standards to the

peak response of the internal standard, employing a multipoint calibration curve.

2.7 Health Risk Assessment

The non-dietary exposure to PAEs in the soils was evaluated. The exposure routes include

ingestion,inhalation and dermal pathways [10]. The non-carcinogenic health risks associated

with these exposure pathways is given by the estimated daily intake and it is calculated as

follows:

C × IRS × EF × ED
ED I ing = ×CF
BW × AT

C × SA × AF ×|×| EF × ED
ED I derm= ×CF
BW × AT

C × EF × ED × I j 3
ED I inh = × 10
PEF × AT

Where EDI = estimated daily intake, C = concentration of PAE in soil, IRS = soil ingestion

rate (100 mg day-1), EF = exposure frequency (350 days year), ED = exposure duration (24

years), CF = conversion factor (10⁶), BW = body weight (70 kg), AT = average lifetime

exposure (365 × ED), SA = soil surface area (5700 cm² day-1), AF = soil adherence factor

7
(0.07 mg cm-2), ABS = fraction of pollutant absorbed dermally from soil (0.1), PEF = particle

emission factor (1.36E09 m3 kg-1), Ij = respiratory rate (13.5 m3 day-1) [20-22].

The hazard quotient (HQ) was calculated as follows:

EDI
HQ=
RfD

Where RfD = oral reference dose (DMP = 10, DEP = 0.8, DBP = 0.1, BBP = 0.2, DEHP = 0.02

mg kg-1 day-1) [22].

The hazard index (HI), a cumulative sum of the hazard quotients emanating from the three

exposure pathways was calculated as follows:

HI =H Qing + H Qderm+ H Qinh

The carcinogenic risks (CR) associated with the PAEs was calculated as follows:

CR=EDI × SF

Where SF = cancer slope factor (BBP = 0.019, DEHP = 0.014) [23]

3. Results and Discussion

3.1 Optimization Extraction Method for Soil Sample

The percentage recoveries for the studied five phthalates - DMP, DEP, DBP, BBP, and DEHP

using Soxhlet, sonication, and microwave methods of extraction from spiked reference soil

samples were calculated and presented in Table 1. The highest percentage recoveries for

the studied phthalates were recorded when 2.5 g of the reference soil was extracted with

5 mL acetonitrile at a temperature of 120 ℃, a pressure of 8 barr and within a time

frame of 20 minutes. Recovery using Soxhlet extraction ranged between 62 and 71%,

while recovery using sonication method of extraction ranged between 49 and 68%.

Maximum recovery ranging between 71 and 113% was observed using microwave method

of extraction. This validates the reliability of the results presented in this study.

3.2 Seasonal Variation in Levels (mg/kg) of PAEs in Refuse Dumpsite Soils

8
The seasonal variation in the levels of phthalate esters in refuse dumpsite soils is presented

in Table 2. Wet season in the study area is between June and September while dry season is

between November and February. During the wet season, the concentration of DMP ranged

from below the detection limit (BDL) to 0.29 ± 0.05 mg/kg, whereas it was below the

detection limit (BDL) during the dry season. During the dry season, DEP was below the

detection limit (BDL), whereas during the wet season, it ranged from below the detection

limit (BDL) to 0.19 ± 0.11 mg/kg. For DBP, during the wet season, its levels ranged from

0.07±0.39 to 6.11±0.27 mg/kg, while during the dry season, it ranged from 0.03±0.39 to

1.19±0.19 mg/kg. The levels of BBP during the wet season varied from 0.11±0.21 to

2.09±0.17 mg/kg, while during the dry season, they ranged from 0.21±0.80 to 3.16±0.35

mg/kg. DEHP levels ranged from 6.98±0.08 to 31.72±0.28 mg/kg in wet season while it

ranged from 4.17±0.52 to 49.83±0.49 mg/kg during dry season. The relative upsurge

observed in the levels of DEHP of the dumpsite soils could be as a result of its common

and extensive use in the manufacturing of plastic products [24]. As shown in Figure 2,

On average, the levels of DMP, DEP, and DBP were comparatively higher during the wet

season, while the levels of BBP and DEHP were relatively higher during the dry season.

The observed high levels of DMP, DEP, and DBP during the wet season could be due to

the fact that they have short alkyl chains,which have a tendency to be easily transformed

in the environment. Particularly, under the influence of rainfall, they could be easily

released from the plastic wastes from the dumpsite into the soils. However, the long alkyl

chains BBP and DEHP do not undergo degradation easily, hence their persistence

and accumulation in the soils, which explains their upsurge during the dry season [25].

Over 90% of the total PAEs found in the refuse dumpsite soils originated from the

combined concentrations of BBP and DEHP,thus signifying their predominant use in the

studied areas. The concentrations of PAEs observed in the investigated soils are greater than

9
those reported by Song et al. [26], Zhang et al. [27] and Ma et al. [28]. This variation

could be due to a low or high favorable natural condition that aids organic pollutant

degradation and/or differences in contamination sources [29].

3.3 Vertical Distribution of PAEs in Refuse Dumpsite Soils

Table 3 presents the distribution of PAEs in the refuse dumpsite soils based on soil depths

of 0 - 15 cm and 15-30 cm. ∑5PAEs in the studied refuse dumpsite soils were relatively

lower at depth 0-15 cm in June, August, and January. Nevertheless, at a depth of 15-30 cm,

the total concentration of the five PAEs (referred to as ∑5PAEs) was comparatively lower

during the months of July, September, October, November, December, and February. The

comparatively higher ∑5PAEs levels at depths 15-30 cm is an indication of the migration of

PAEs downwards as they percolate the soil profile. This could also indicate the

possibility of non-equilibrium transport by preferential flow which showed that the PAEs

could pass through the soil barrier through sorption related processes. A devastating

ramification of the observed vertical distribution is a potential impact of the studied PAEs on

the quality of ground water.

3.4 Lateral Migration of PAEs away from Dumpsite to the Receiving Stream

The study examined the lateral migration of PAEs from the dumpsite at distances of 50, 100,

and 117 m, both during the wet and dry seasons. The corresponding findings are presented

in Tables 4 and 5, respectively. In both seasons, irregularity existed in ∑5PAEs at the

different distances. The irregularity in distribution pattern might be due to the differences in

refuse components and the nature of soil as it moves closer to the receiving stream.

3.5 Source Identification of PAEs in Refuse Dumpsite Soils

The possible sources of PAEs in refuse dumpsite soils were identified using principal

component analysis. As shown in the component plot in Figure 3, two major principal

components were retained. Principal component 1 (accounting for 61.212% of total data

10
variance) showed strong factor loadings of 0.918, 0.921, and 0.850 for DMP, DEP, and

DBP respectively while principal component 2 (accounting for 21.753% of total data

variance) had strong factor loadings of 0.851 and 0.796 for BBP and DEHP respectively.

The former belongs to a group of short-chain PAEs with a characteristic high-water

solubility and susceptibility to degradation. They find extensive application in various areas

such as coatings, products for personal care, adhesives, and aerosol insecticides, among

others [27]. Microbial decomposition of large esters might have led to the presence of

residual short-chain PAEs in the soils of the dumpsite under investigation [13]. The latter

group comprising of BBP and DEHP represents the major plasticizers used in plastic

products. Their resistance to degradation would result in increased adsorption and

enrichment in the soils [13].

3.6 Health Risk Assessment of PAEs in Refuse Dumpsite Soils

The health risk assessment of phthalate esters emanating from the ingestion, inhalation

and dermal contact with the refuse dumpsite soils is presented in Table 6. The non-dietary

exposure to the phthalates in the dumpsite soils were evaluated. The hazard quotient

of the studied phthalates upon exposure via inhalation, ingestion or dermal contact were

less than 1. The cumulative sum of the three exposure pathways, known as the hazard

index, is also below 1 for the phthalates examined in the study. These findings suggest

that exposure to the phthalates present in the dumpsite soils does not pose non-carcinogenic

health risks. In terms of non- carcinogenic risk,the order of significance was observed to

be inhalation > ingestion > dermal, indicating that inhalation is the primary route of

exposure to the phthalates analyzed in the study. BBP and DEHP are classified as possible

carcinogens. The CR values obtained for BBP and DEHP are 7.08E-08 and 8.72E-07

respectively, both of which are less than the tolerable limit of 1E-06 set by USEPA [22].

Based on the findings, it can be inferred that exposure to the studied phthalates does not

11
pose any carcinogenic health risks. The health risk calculations cast doubt on the presence of

potential carcinogenic and non-carcinogenic health risks associated with the studied

substances. It is however important to exercise caution in order to prevent the

bioaccumulation of these phthalates as they progress through the food chain [30,31]. Long-

term exposure to these phthalates should also be avoided.

4. Conclusion

This study focused on examining the seasonal, lateral, and vertical distribution of PAEs

(phthalate esters) in soils found in refuse dumpsites. The results indicated that DMP (dimethyl

phthalate), DEP (diethyl phthalate), and DBP (dibutyl phthalate) levels were higher during the

wet season, while BBP (butyl benzyl phthalate) and DEHP (di(2-ethylhexyl) phthalate) levels

were higher during the dry season. The latter, referring to BBP and DEHP, consituted more

than 90% of the total PAEs detected in the soils of the dumpsite. Plastic pollution represented

the predominant source of these phthalates in the soils. The health risk assessment indicated

that there were no apparent non-carcinogenic or carcinogenic health risks associated with

exposure to the PAEs. Inhalation exposure route was found to be the major exposure pathway

to the PAEs. It is imperative to implement effective measures to prevent the lateral migration

12
of PAEs into the receiving stream. More stringent regulations should also be enforced to avert

the introduction of these PAEs into the environment.

Ethical approval
Not applicable

Consent to participate
Not applicable

Consent to publication
Not applicable

Competing interests
The authors declare no competing interests.

13
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(PAEs) and biological macromolecule: A review. Chemosphere, 138578.

27. Yang, Y., Wang, H., Chang, Y., Yan, G., Chu, Z., Zhao, Z., & Wu, T. (2020).

Distributions, compositions, and ecological risk assessment of polycyclic aromatic

hydrocarbons and phthalic acid esters in surface sediment of Songhua river,

China. Marine Pollution Bulletin, 152, 110923.

28. Zeng, H.H., Zhang, H.X., Wu, X., Gu, H.X., Zhang, L.Z., Liu, Y.Y., Zhao, X.F. and

Li, J.H., 2017. Pollution levels and health risk assessment of particulate phthalic acid

esters in arid urban areas. Atmospheric Pollution Research, 8(1), pp.188-195.

29. Zhang, B., Zhang, T., Duan, Y., Zhao, Z., Huang, X., Bai, X., & Sun, H. (2019).

Human exposure to phthalate esters associated with e-waste dismantling: exposure

levels, sources, and risk assessment. Environment international, 124, 1-9.

30. Zhao, H.M., Du, H., Xiang, L., Chen, Y.L., Lu, L.A., Li, Y.W., Li, H., Cai, Q.Y. and

Mo, C.H., 2015. Variations in phthalate ester (PAE) accumulation and their formation

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 mechanism in Chinese flowering cabbage (Brassica parachinensis L.) cultivars grown

on PAE-contaminated soils. Environmental pollution, 206, pp.95-103.

31. Zhou, Q., Zheng, Z., Xiao, J., Fan, H., & Yan, X. (2016). Determination of phthalate

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18
Тable 1: Percentage Recoveries of PAE Congeners usng Difeгепt Ехtгасйоп ТесПпйдиеб

Phthalates Soxhlet extraction Sonication extraction Microwave extraction % RSD

(ME) for ME
DMP 71.34 49.00 93.02 3.61
DEP 62.45 59.09 85.37 2.53

DBP 67.65 60.78 91.00 5.40

BBP 70.01 62.67 113.24 7.00

DEHP 71.21 68.23 108.87 4.50

Table 2: Seasonal Variation of Phthalate Esters (mg/kg) in Dumpsite Soils

Year Month DMP DEP DBP BBP DEHP ∑5PAEs

2014 JUNE 0.01±0.1 0.16±0.13 0.20±0.65 0.11±0.21 9.09±0.07 9.57±1.25

9

JULY BDL BDL 0.62±0.48 0.19±0.27 12.13±0.16 12.94±0.91

AUGUST 0.29±0.0 0.19±0.11 6.11±0.27 2.09±0.17 31.72±0.28 40.40±0.88

5

SEPTEMBER BDL BDL 0.07+0.39 0.14±0.45 6.98±0.26 7.19±1.10

NOVEMBER BDL BDL 0.03±0.39 0.21±0.80 6.54±0.08 6.78±1.27

DECEMBER BDL BDL 1.19±0.19 1.57±0.21 49.83±0.49 52.59±0.89

2015 JANUARY BDL BDL 0.61±0.39 3.16±0.35 10.26±0.19 14.03±0.93

FEBRUARY BDL BDL 0.74±0.31 0.35±0.31 4.17±0.52 5.26±1.14

 BDL = below detection limit

19
Table 3: Vertical Distribution of Phthalate Esters (mg/kg) in Dumpsite Soils

Year Month Depth(cm) DMP DEP DBP BBP D

2014 JUNE 0-15 0.01±0.19 0.18±0.21 0.32±1.14 0.11±0.06 5.6

15-30 BDL 0.15±0.04 0.09±0.15 0.10±0.08 12.5
JULY 0-15 BDL BDL 0.32±0.84 0.15±0.23 14.3
15-30 BDL BDL 0.91±0.11 0.24±0.09 9.9
AUGUST 0-15 0.34±0.50 0.21±0.06 8.39±0.13 1.79±0.26 26.7
15-30 0.23±0.71 0.18±0.15 3.82±0.40 2.38+029 36.7
SEPTEMBER 0-15 BDL BDL 0.12±0.27 0.16±0.29 8.7
15-30 BDL BDL 0.02±0.52 0.11±0.23 5.2
NOVEMBER 0-15 BDL BDL 0.02±0.16 BDL 6.8
15-30 BDL BDL 0.03±0.62 BDL 6.2
DECEMBER 0-15 BDL BDL 0.85±0.22 1.66±0.59 50.3
15-30 BDL BDL 1.55±0.17 1.47±0.39 49.3
2015 JANUARY 0-15 BDL BDL 0.63±0.61 2.37±0.17 7.6
15-30 BDL BDL 0.59±0.18 3.93±0.21 12.9
FEBRUARY 0-15 BDL BDL 0.44±0.33 0.45±0.14 5.3
15-30 BDL BDI 1.04±0.28 0.24±0.89 2.9
 BDL = below detection limit

20
Тablе 4: Lateral Мigгatiоn of Phthlate Esters (mg/kg) аway fгоm Dumpsite to the receiving stream

Year Month Location DMP DEP DBP BBP DEHP

2014 JUNE 2A BDL 0.09±0.77 0.03±0.02 0.15±0.17 2.74±0.07

2B BDL BDL 6.44±0.17 3.34±0.14 42.37±0.62
3A BDL 0.09±0.04 0.27±0.01 0.26±0.09 2.69±0.01
3B BDL 0.09±0.60 0.60±0.27 1.02±0.06 27.99±0.07
4A BDL 0.13±0.26 0.04±0.05 0.12±0.75 17.67±0.44
4B BDL BDL 0.26+0.03 0.09±0.15 48.16+0.27
JULY 2A BDL BDI 0.74±1.23 BDL 46.91±0.36
2B BDL BDL 1.11±1.47 BDL 42.37±0.52
3A BDL BDL 0.05±0.79 0.22±1.54 2.69±0.76
3B BDL BDL 0.26±0.56 0.18±2.74 9.75±0.16
4A BDL BDL 0.02±0.28 0.17±1.77 9.28±0.24
4B BDL BDL 0.15±0.55 0.15±0.04 11.23±0.08
AUGU 2A BDL BDL 0.55±0.19 0.23±0.28 6.83±0.05
ST
2B BDL BDL 0.93±0.12 0.14±0.55 5.79±0.13
3A BDL BDL 0.02±0.95 0.04±0.28 0.76±0.11
3B BDL BDL 0.13±0.03 0.07±0.12 0.90±0.21
4A BDL BDL 0.24±0.31 0.18±0.02 1.76±0.13
4B BDL BDL 0.13±0.11 0.18±0.18 1.92±0.08

21
 SEPTEMBER 2A BDL BDL 1.75±0.14 0.02±0.97 5
2B BDL BDL 0.69±0.28 0.12±0.78 4
3A BDL BDL 0.16±0.13 0.16±0.54 1
3B BDL BDL 0.01±0.27 9.33±0.00 5
4A BDL BDL 0.01±0.33 0.13±0.01 2
4B BDL BDL 0.18±0.11 0.19±0.57 9
 BDL = below detection limit

22
Тablе 5: Lateral Мigгatiоn of Phthlate Esters (mg/kg) аway fгоm Dumpsite to the receiving stream

Year Month Location DMP DEP DBP BBP D

2014 NOVEMBER 2A BDL BDL 1.75±0.14 0.08±0.91 40.

2B BDL BDL 0.69±0.28 0.14±0.01 81.
3A BDL BDL 0.16±0.38 BDL 67.
3B BDL BDL 0.01±0.20 BDL 12.
4A BDL BDL 0.01±0.3 0.09±0.46 23.
4B BDL BDL 0.19±0.11 3.19±0.17 62.
DECEMBER 2A BDL BDL 15.99±1.67 13.03±0.95 65.
2B BDL BDL 6.15±0.17 16.03±0.75 72.
3A 0.09±0.66 BDL 13.75±0.17 18.30±1.75 38.
3B BDL 2.11±0.84 20.74±0.43 45.58±0.28 45.
4A 0.13±0.81 BDL 12.01±0.54 25.37±1.18 37.
4B BDL BDL 3.98±0.34 55.17±1.63 25.
JANUARY 2A BDL 0.11±1.37 1.52±0.24 7.41±0.47 8.8
2B BDL BDL 0.89±0.08 7.32±0.26 0.6
3A 0.02±1.02 0.08±1.95 0.07±0.02 0.17±0.16 0.6
3B BDL BDL 0.01±0.08 0.19±0.38 2.8
4A BDL BDL 0.05±0.23 0.26±1.13 7.2
4B BDL BDL 1.19±0.55 6.63±1.47 3.6

23
 FEBRUARY 2A BDL BDL 0.35±0.26 0.41±0.88
2B BDL BDL 4.81±0.15 1.18±0.24
3A BDL BDL 0.30±0.21 0.17±0.24
3B BDL BDL 0.89±0.68 0.21±1.07
4A BDL BDL 0.21±0.62 0.21±0.67
4B BDL 0.06±0.76 0.18±0.42 0.12±1.66
 BDL = below detection limit

24
 Table 6: Health Risk Assessment of PAEs in Refuse Dumpsite Soils

PAEs EDI(ing) EDI(derm) EDI(inh) RfD HQ(ing) HQ(derm) HQ(inh) HI SF CR

DMP 2.05E-07 8.19E-08 1.42E-06 10 2.05E-08 8.19E-09 1.42E-07 1.72E-07

DEP 2.39E-07 9.56E-08 1.66E-06 0.8 2.99E-07 1.19E-07 2.08E-06 2.50E-06

DBP 1.63E-06 6.53E-07 1.13E-05 0.1 1.63E-05 6.53E-06 1.13E-04 1.37E-04

BBP 1.33E-06 5.34E-07 9.30E-06 0.2 6.69E-06 2.67E-06 4.65E-05 5.59E-05 0.019 7.08E-08

DEHP 2.23E-05 8.93E-06 1.55E-04 0.02 1.11E-03 4.46E-04 7.77E-03 9.34E-03 0.014 8.72E-07

EDI = estimated daily intake, RfD = oral reference dose, ing = ingestion, derm =

dermal,
inh = inhalation, HQ = hazard quotient, HI = hazard index, SF = slope factor, CR =
carcinogenic risk

25
26
Figure 2: Mean Seasonal Variation in PAEs of Refuse Dumpsite Soils

27
Figure 3: Component Plot of PAEs in Refuse Dumpsite Soils

28