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Econ. Environ. Geol. 2023; 56(1): 75-85

Published online February 28, 2023

https://doi.org/10.9719/EEG.2023.56.1.75

© THE KOREAN SOCIETY OF ECONOMIC AND ENVIRONMENTAL GEOLOGY

Plant Leave as an Indicator for Pollution by Hydrocarbons and Heavy Metals in Al-Zubair City, Southern Iraq

Sajjad W. Jaafar1,*, Sattar J.Al.Khafaji2

1Department of Geology, College of Science, University of Basrah ,Basrah, Iraq
2Department of Geology, College of Science, University of Basrah ,Basrah, Iraq

Correspondence to : *Sajadwafaa2@gmail.com

Received: January 11, 2023; Revised: February 15, 2023; Accepted: February 15, 2023

This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided original work is properly cited.

Abstract

The potential sources and spatial distribution of heavy metals and polycyclic aromatic hydrocarbons (PAHs) were investigated in the leaf plants of Al-Zubair city. A total of 14 samples of conocarpus lancifolius plant leaf were collected and analyzed for their heavy metals and PAHs content using inductively coupled plasma mass spectrometry (ICP-MS) and a 7890 Agilent capillary gas chromatograph (GC) respectively. Bioaccumulation factor calculation revealed the highest pollution of heavy metals , due to the activity of a petrochemical in the area. The diagnostic ratio of Ant/(Phe+Ant), BaA/BaA+Chr), In/(In+BghiP), Flu/Pyr, FlA/FlA+Pyr), ΣLMW/ΣHMW are commonly used for determining the origin and source of PAHs in various environmental media. The diagnostic ratio indicated the anthropogenic origin. PAHs with five-to-six membered rings were dominant in the plant leaf, which likely results from anthropogenic activities. The leaves of C. lancifolius have a preponderance of high molecular weight PAHs compared to low molecular weight PAHs, indicating a combustion origin (car exhaust, petroleum emissions, and fossil fuel). C. lancifolius leaves are a reliable indication of atmospheric PAHs absorption. The background level of heavy metals in the city (or the near environment) is in the order of Fe > Cu > Ni > Cr. On the other hand, the bioaccumulation in plant leaves showed greater tendencies as follows: Co>Cd>Zn=As>Cu>Mn>Ni>Pb>Cr>Fe. Cobalt showed high bioaccumulation, indicating strong uptake of Co by plant leaves. These findings point to human activity and car emissions as the primary sources of roadside vegetation pollution in Al-Zubair city.

Keywords Al-Zubair , PAHs, Conocarpus lancifolius, pollution, Bioaccumulation factor

  • Gaseous emissions resulting from fuel combustion can be reduced through the use of technologies in the upstream stage of combustion, including what is applied after the combustion stage and before leaving the chimney

  • Avoid constructing oil refineries and refining facilities close to cities and densely populated areas

  • Conducting health and epidemiological studies of the population around the study area for the purpose of estimating the incidence of diseases carcinogenic and non-carcinogenic caused by toxic toxic elements

Pollution that resulting from cars is a big problem all over the world. (Deubner et al. 2004) note that advanced measurements of air quality such as regulatory and technical innovations like unleaded gasoline, catalytic converters, and fuel-efficient engines have often been negated by an increase in vehicle traffic. Numerous pollutants are contaminating the environment near roads (Unger and Prinz 1997). Fuels, gasoline tank walls, engine components, vehicle components, catalytic converters, tires, brake pads, and road surface materials can all include heavy metals. Incomplete fuel combustion and abrasion of road surfaces both release polycyclic aromatic hydrocarbons (PAHs) into the environment (Unger and Prinz 1997).

In urban areas, polycyclic aromatic hydrocarbons (PAHs) are generated from a variety of sources, including vehicle emissions, fossil fuel combustion, painting, wood and garbage burning, solvent application, and asphalt pavement operations at small factories and workshops (Essumang et al., 2006). Changes in weather patterns and the chemical and physical properties of each PAHs contribute to modifications to the compounds' overall concentrations. Vapor and/or particle-bound PAHs are found in the air and can be deposited on vegetation, trees, soil, and water through both wet and dry deposition. Plants absorb PAHs in the vapor phase through stomata or outer circular lamellae, whereas particle-bound PAHs have accumulated on the leaf surface (Franzaring, 1997). Anthracene is a good example of a PAH that can cross the epicuticle wax and leaf cuticle to enter the cytoplasm of the epidermal cells (Wild et al., 2004). This suggests that the accumulated PAHs are swiftly transferred to the wax layer of the leaf. PAHs are a type of organic pollutant that may be found just about anywhere but are more prevalent in urban and industrial settings due to the prevalence of waste incineration, vehicle traffic, and residential heating systems. Ratios of the distinct PAHs have been proposed to differentiate between different origins with using ratio of PAHs in Table 3. (Yunker et al., 2002; Ravindra et al., 2008), although it is generally accepted that PAHs can arise from petrogenic, pyrolitic, and diagenetic sources. Al-Zubair cities have rapid population growth, coupled with the pollution from nearby oil and gas fields, electrical, petrochemical, and fertilizer sector plants, has led to the deposition of substantial volumes of atmospheric pollution in recent years. The primary goal of this research is to assess the pollution in Al-Zubair city by using the C. lancefolius leaves and identifying their content and source of heavy metals and PAHs as an indicator for pollution.

Table 3 . PAHs diagnostic ratio analysis for Al-Zubair C.lancifolius leave

PAH ratiosAnt/(Phe+Ant)BaA/BaA+Chr)In/(In+BghiP)Flu/PyrFlA/FlA+Pyr)ΣLMW/ΣHMW
Boundary valuesPetrogenic<0.1<0.2<0.2<1<0.5>1
Pyrogenic>0.1>0.2>0.5>1>0.5<1
Al-Jumhuria Al-awlaaNDNDNDNDND0
Mahlat Al-Arab Al-awlaaNDND0.82720.01830.01790
Kut Al-MarkazND0.20080.83460.03640.03510.0055
Al-DrahmiaNDNDNDNDND0
Al-Faraha and Al-ThoahratND0.1568NDNDND0.0031
Al-AmeerND0.41700.39520.03180.01090.0154
MazraeaNDND0.18130.01100.01090.0214
Hay Al-AskaryNDNDND0.18090.15320
Near Al-Al-Shuaiba RefineryNDNDNDNDND0
Main Waste AreaNDND0.9575NDND0.0198
Al-HussainND0.56660.30880.13940.12230
Al-ThobatND0.21430.92170.00170.00170.0015
AL-ShuhdaaNDND0.31700.08590.07910
MeanND0.11960.36480.03890.03320.0051
ND-Not detected

2.1. Study Area

The study area is located in the Al-Zubair district, it is located within a longitude (47° 40'-47° 44' E) and a latitude (30° 20'-30° 24' N). the spatial boundaries of the area at the southwestern part of Basrah Governorate, west of Safwan sub-district, and south of Umm Qasr and Khor Al-Zubair sub-district, with an area of about 1134 km², it is surrounded by many oil and gas fields, State Company for Petrochemical Industry and Fertilizer industry plants. The city consists of (23) residential neighborhoods Fig. 1, (Al Zubair Municipality Directorate, 2015).

Fig. 1. Sample locations in studied area.

Leave plants samples were taken from 14 different stations namly; (Al-Jumhuria Al-awlaa, Mahlat Al-Arab Al-awlaa, Kut Al-Markaz, Al-Drahmia, Al-Faraha and Al-Thoahrat, Al-Ameer, Mazraea, Hay Al-Askary, Near Al-Al-Shuaiba Refinery, Main Waste Area, Al-Hussain, Al-Shuaiba Houses, Al-Thobat and AL-Shuhdaa, Fig. 1.

The information of each sample was written on the plastic bags and then transferred to the laboratory. Samples were collected under stable weather conditions during September 2021, fieldwork was carried out in the urban district inside of AL-Zubair city include green space, open space traffic roadsides and industrial area The samples were taken by scissors and the highest height was 2 meters. A number of open leaves were taken and in the direct direction of the road and the oil facility. The old parts were taken, not the new shoots. They were taken to the laboratory to dry in the atmosphere of the laboratory. Then the leaves were grinded without washing and transferred to the analysis laboratory at the University of Basrah, College of Marine Sciences, Department of Chemistry.

Sixteen PAHs specified were extracted by using Soxhlet apparatus according to method of Wang et al. (2011), including Benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(123cd)pyrene and dibenzo(ah)anthracene Naphthalene (NAP), 2-Methylnaphthalne (2-METH), Acenapthylene (ACY), Acenapthene (ACE), Flourene (FLU), Phenanthrene (PHE), Anthracene (ANT), Flouranthene (FLUA), Pyrene (PYR), Benz[a] anthracene (B[a]A), Chrysene (CHR), Benzo[b]flouranthene (B[b]F), Benzo[k]flouranthene (B[k]F), Benzo[a]pyrene (B[a]P), Benzo[ghi]perylene (B[ghi]P), Indeno[1,2,3-cd]pyren (Ind p). then PAHs compounds were identified in the laboratories of Basrah oil company by using 7890 Agilent capillary Gas Chromatography (GC), For heavy metals analysis, the sample was grinded without washing and transferred to the analysis laboratory. Ten of heavy metals (Pb, Zn, Ni, Mn, Fe, Co, Cd, Cu, Cr and AS) were determined in Conocarpus lancifolius using Inductively coupled plasma-mass spectrometry (ICP-MS) in Iran.

4.1 Polycyclic Aromatic Hydrocarbons

The results showed that the mean values for PAHs compounds in C. lancefolius leaves have the following orders: Pyr(498.07 ng/g)>Indo(26.73 ng/g)>Ben(A)Ant(23.13 ng/g)>Ben(15.84 ng/g)>Ben(A)(13.10 ng/g)>Flu(12.67 ng/g)>Ben(K)(3.82 ng/g)>Chr(3.14 ng/g). The mean content of LMW PAHs is 3.7 ng/g, whereas the mean content of HMW PAHs is 598.98 ng/g (Table 1), (Fig. 2, 3). The total mean of carcinogenic aromatic compound concentration is 544.25 ng/g. The maximum total PAHs content was recorded at Kut Al-Markaz (2034.56 ng/g), whereas the minimum value was recorded at Near Al-Shuaiba Refinery (20.03 ng/g). The PAHs accumulation in C. lancefolius leaves was influenced by the traffic volume according to results at the sampling location and the high concentration of PAHs emitted by vehicles on the road.

Table 1 . PAHs concentration in C. lancifolius leaves (ng/g)

StationsAromatic ringAl-Jumhuria Al-awlaaMahlat Al-Arab Al-awlaaKut Al-MarkazAl-DrahmiaAl-Faraha and Al-ThoahratAl-AmeerMazraeaHay Al-AskaryNear Al-Shuaiba RefineryMain Waste AreaAl-HussainAl-ThobatAL-ShuhdaaMeanMinMaxAC
PAHS Compounds
LMWNAPHTHALENE2NDNDNDNDNDNDNDNDNDNDNDNDND000ND
2-METHYLNAPHTHALNE2NDND2.42NDNDNDNDNDND5.76NDNDND0.622.425.76ND
ACENAPHTHYENE3NDND6.42NDND1.96NDNDND2.69NDNDND0.851.966.42ND
ACENAPHTHNEN3NDNDNDNDND3.432.97NDNDNDNDNDND0.492.973.43ND
FLUORENE3NDNDNDNDND5.382.63NDNDNDNDNDND0.612.635.38ND
PHENANTHRENE3NDNDNDNDNDNDNDNDNDNDND1.99ND0.151.991.99ND
ANTHRACENE3NDND2.33ND2.246.052.94NDNDNDNDNDND1.042.246.05ND
HMWFLUORANTHENE4ND9.2762.12NDND24.513.954.25NDND32.072.1926.3612.672.1962.129.27
PYRENE4265.28506.231702.9133.49655.94770.71356.3923.50ND385.40229.971238.50306.59498.0723.501702.91506.23
CHRYSENE4NDND8.43ND8.794.95NDNDNDND7.6111.09ND3.144.9511.09ND
BENZO(A)ANTHRACENE4NDND2.12ND1.633.5413.15255.1212.21ND9.963.02ND23.131.63255.12ND
BENZO(B)FLUORANTHENE5NDND7.49ND10.522.95NDND4.08ND1.86ND3.662.351.8610.52ND
BENZO(K)FLUORANTHENE51.032.021.23ND4.6024.83ND2.723.722.052.262.832.413.821.0324.832.02
BENZO(A) PYRENE5NDND24.07ND8.82109.809.462.84NDND3.073.318.9813.102.84109.80ND
INDENO(1,2,3-CD)PYRENE+DIBENZO(A,H)ANTHRACENE6ND15.40179.435.5516..4859.383.035.69ND36.464.8130.487.2426.733.03179.4315.40
BENZO(G,H,I)PERYLENE611.283.2135.54ND21.1590.8313.72NDND1.6110.772.5815.6015.871.6190.833.21
ΣLMW0011.1702.2416.848.5611008.4501.9900011.17
ΣHMW277.59536.152023.3939.04711.481091.55399.73294.1420.03425.54302.421294.04370.87277.59536.152023.39
ΣCar266.31517.531786.6633.49683.74837.58376.45285.6020.03387.45283.761257.65339.03266.31517.531786.66
PAHs277.59536.152034.5639.04713.721108.39408.29294.1420.03433.99302.421296.03370.87ΣPAHs277.59536.15

*Σ16-PAHs: means concentration of 16 kinds of PAHs. *ΣCar-PAH: means concentrations of carcinogenic PAHs, including Benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(123cd)pyrene and dibenzo(ah)anthracene (USEPA 2002b). ΣLMW sum of 7 Low Molecular Weight Polycyclic aromatic hydrocarbons :Naphthalene (NAP), 2-Methylnaphthalne (2-METH), Acenapthylene (ACY), Acenapthene (ACE), Flourene (FLU), Phenanthrene (PHE), Anthracene (ANT), Flouranthene, ΣHMW sum of 9 High Molecular weight polycyclic aromatic hydrocarbons : (FLUA), Pyrene (PYR), Benz[a]anthracene (B[a]A), Chrysene (CHR), Benzo[b]flouranthene (B[b]F), Benzo[k]flouranthene (B[k]F), Benzo[a]pyrene (B[a]P) Benzo[ghi]perylene (B[ghi]P), Indeno[1,2,3-cd]pyren (Ind p). ND, not detected. ΣCar sum of 7 Carcinogenic polycyclic aromatic hydrocarbons:BaA,chr,BbF,BkF,BaP,InP and BghiP Ac: Acceptable concentration Netherlands Ministry of Housing and environment (1994)


Fig. 2. Distribution of LMW PAHs and HMW PAHs in C. lancifolius leaves.
Fig. 3. Heavy metal concentration (ppm) in roadside c. lancifolius plant leaves.

One major and effective uptake method in plant leaves is the inhalation of volatile PAHs from the environment (Simonich and Hites 1994a). Vapor-phase PAHs are typically taken in through the leaf cuticle rather than through the stomata (Barber et al., 2004). After penetrating the cuticle, these PAHs may be taken into the body. At room temperature, low molecular weight polycyclic aromatic hydrocarbons (LMW PAHs) with fewer than four rings are more likely to condense as a vapor and deposit on plants in the troposphere. Subsequently, the deposited PAHs could enter cells via diffusion.

4.2. Heavy Metals

Heavy metal concentrations in C. lancifolius leaves are listed in Tables 2. It is reported that the amount of Ni is higher than the normal value in leaf tissue (0.1–5 ppm) according to Kabata-Pendias (2011), with the maximum concentration at Mahlat Al-Arab Al-Awlaa (6 ppm) (Fig. 3). This is associated with heavy traffic and industrial pollutants, the highest concentration of Cu (14 ppm) is detected at Al-Drahmia. This is significantly higher than background concentration reported by Kabata-Pendias (2011). Because of traffic and industrial pollution, levels of Fe in the leaves' tissues are abnormally high (308.28 ppm) compared to the normal value (20–100 ppm) at Mahlat Al-Arab Al-Awlaa (709 ppm).

Table 2 . Heavy metal concentration (ppm) in conocarpus lancifolius leaves of study area and comparison with other studies

Sample locationPbNiZnMnFeCuCrCoCdAs
Al-Jumhuria Al-awlaa122116208510.90.2<1
Mahlat Al-Arab Al-awlaa2636327091140.90.1<1
Kut Al-Markaz3429225621130.40.2<1
Al-Drahmia1324132381410.70.1<1
Al-Faraha and Al-Thoahrat121927300510.50.2<1
Al-Ameer1441315761030.60.3<1
Mazraea121516125610.70.1<1
Hay Al-Askary141619200710.40.3<1
Near Al-Al-Shuaiba Refinery111912395520.20.4<1
Main Waste Area13929170410.60.1<1
Al-Hussain1169112310.50.2<1
Al-Shuaiba Houses111810216420.30.3<1
Al-Thobat131114393520.10.1<1
AL-Shuhdaa11118112410.30.3<1
Min11118112410.10.1<1
Max3641327091440.90.4<1
Mean1.212.6419.6418.42308.286.711.710.500.20<1
1Normal Values5-100.1-527-15030-30020-1005-300.1-0.50.02-10.05-21-1.7
2 Basrah city3.2520.6132.6422.56266.5413.9618.521.160.512.36
3Ramadi city6.99±0.447.71±0.1862.95±2.9649.64±3.23-14.03±0.847.26±0.412.13±0.080.93±0.18-
4Permissible value6.49±0.217.55±0.1955.02±2.0345.23±1.42-12.49±0.496.37±0.262.04±0.050.57±0.09-

1Kabata-pendias and pendias (2011)

2Al-Khafaji and Jalal (2020)

3Al-Heety et al.(2021)

4FAO/WHO (2007)

- Not detected



The maximum value of Cr was at Mahlat Al-Arab Alawlaa (4 ppm), whilst the minimum values detacted Al-Jumhuria Al-awlaa (1 ppm). The high Cr content is associated with industrial emissions from the oil field around the research area. The main sources of Cu in the study area are oil oxidation, abrasion of tires on vehicles, and industrial waste, all of which are easily transported via air and deposited on plant leaves (Celik et al., 2005). The high concentrations of Fe found in all plant samples can be attributed to the fact that plant roots can take up large quantities of Fe from the soil and store it mostly in the leaves (Gholami et al., 2013).

Although zinc (Zn) is essential to all living things, the excess of Zn it can be toxic to plants, and too little can induce leaf development (Bucher and Schenk, 2000). The high concentrations of Zn were in normal range except in Al-Ameer, Mahlat Al-Arab Al-Awlaa, and Kut Al-Markaz, which were (41 ppm), (36 ppm), and (29 ppm), respectively, which are located close to a manufacturing facility and highway.

Overall, the data indicate that a variety of discrete inputs associated with human activities—including automobiles, industrial pollution, fossil fuel combustion, garages, and garbage dumps—had a significant impact on Al-Zubair flora.

5.1. PAHs Diagnostic Ratios

Diagnostic ratios of PAHs are commonly used for determining the origin and source of PAHs in various environmental media (Bucheli et al., 2004; Yunker et al., 2002). Several researchers have found this method to be an effective way to identify the origins of PAHs at particular places, such as areas near point sources and the soil around industrial districts (Christensen and Bzdusek 2005). As a result, the diagnostic ratio was employed in this investigation as a suggestive method of providing information regarding the origins of PAHs. A ratio of Ant/ (Ant + Phe) 0.1 indicates petroleum, while a ratio greater than 0.1 indicates combustion dominance (Bucheli et al., 2004). Yunker et al. (2002) proposed that a Fla/(Fla + Pyr) ratio of 0.5 denotes a coal, wood, or grass combustion source, and a BaA/(BaA + Chr) ratio of 0.35 denotes a biomass combustion source. According to the literature (Mannino and Orecchio 2008), the value of Ind/(Ind + Bghip) >0.5 indicates grass, coal, or wood combustion sources, while a ratio between 0.20 and 0.50 implies fuel combustion sources (vehicles and crude oil). The ratio of specific PAHs was determined to identify potential sources. Typically, a value of one for high molecular weight (HMW) or one for low molecular weight (LMW) PAHs indicates that they are primarily derived from a petrogenic source, while a value of one for HMW/LMW PAHs indicates that they are primarily derived from a pyrogenic source (Soclo et al., 2000; Zakaria et al., 2002). A flu/pyr ratio of one indicates that the PAHs are petrogenic. Table 3 shows that the mean of LMW/HMW indicates the pyrogenic sources, as BaA/(BaA + Chr) indicates the petrognic sources, and Flu/Pyr shows the petrognic sources. The FlA/(FlA + Pyr) ratio indicates the presence of petrol emission sources. The results were compared with previous studies, Table 4.

Table 4 . Total PAHs concentrations in the C. lancifolius leave from different locations around the world

LocationTotal PAHs (ng/g1)-1Plant SpeciesReferences
Nanling Mountains646Hypnum plumaeformaeLiu et al. (2005)
Szulborze Poland2373Hylocomium splendenWang et al. (2009b)
Ny-Ålesund Arctic Circle217MossOrliński (2002)
Liaoning, China Industrial area550Pinus thunbergiiTian et al. (2009)
Barcelona Natural75Pinus pineaRatola et al. (2006)
Al-Zubair city (Current) study , Iraq602C.lancifoliusThis study


5.2. Bioaccumulation Factor

Bioaccumulation factor (BF) was determined as an indication of metal accumulation in plants. BF value greater than 1.0 indicates a high metal accumulation Dowdy & McKone (1997). BF was calculated to determine the amount of metals accumulated by the plant using the formula shown in equation 1.

Cp/Cs=BioaccumulationFactor

where Cp is the concentration of metals in plants and CS is the concentration of metals in soil according to the concentration of metals in soil that was suggested by Kabata-Pendias (2011).

According to the results, the mean of heavy metal bioaccumulation in leaves follows the order: Co>Cd>Zn=As>Cu>Mn>Ni>Pb>Cr>Fe. Cobalt showed high bioaccumulation, indicating strong uptake of Co by plant leaves. Table show that Pb, Fe, and Cr showed low bioaccumulation (0.063), (0.037), and (0.057), respectively, indicating that this element has relatively low availability, while Ni, Zn, Mn, Cu, Cd, and As showed median bioaccumulation (0.125), (0.489), (0.128), (0.440), (0.746), and (0.484), respectively.

Table 5 . Bioaccumulation factor values of heavy metals in C.lancifolius leaves

Sampling locationPbNiZnMnFeCuCrCoCdAs
Al-Jumhuria Al-awlaa0.0430.0710.3380.1040.0220.2940.0284.510.2
Mahlat Al-Arab Al-awlaa0.0760.4610.6100.2780.11210.1812.250.250.5
Kut Al-Markaz0.1110.0970.1900.110.0370.50.0540.5710.2850.2
Al-Drahmia0.0580.20.5580.1200.0320.2910.05710.25
Al-Faraha and Al-Thoahrat0.0450.0900.0410.2640.0410.5550.0352.511
Al-Ameer0.0430.1680.2660.2280.0630.4670.0931.8750.9370.294
Mazraea0.0370.0740.1480.0530.0130.1360.0292.3330.3330.333
Hay Al-Askary0.0830.0861.3330.0780.0140.6360.0101.33310.25
Near Al-Al-Shuaiba Refinery0.0710.0760.7910.1210.0450.50.0760.510.5
Main Waste Area0.0320.1570.8180.1280.0270.50.0471.50.50.5
Al-Hussain0.10.0340.4610.0540.0130.3330.0272.50.51
Al-Shuaiba Houses0.0530.0370.5590.0480.0230.2430.0460.9370.9370.416
Al-Thobat0.0710.1420.3230.1170.0500.4160.0600.3330.21
AL-Shuhdaa0.0660.0620.4070.0890.0210.2850.0580.751.50.333
Min0.0320.0340.0410.0480.0130.1360.0100.3330.20.2
Max0.1110.4611.3330.2780.11210.18171.51
Mean0.0630.1250.4890.1280.0370.440.0572.0630.7460.484

High concentrations of Co, Ni, Cr, Fe, Cu and Cd were found in C. lancifolius leaf samples taken at several locations inside Zuabir city. In addition, they are a useful indicator for the absorption of Co, since Co is taken up so readily by the root system and the leaves in direct correlation with its concentration in the surrounding environment. C. lancifolius leaves can bioaccumulate substantial levels of heavy metals, particularly Co, according to BF findings. The BF results indicate that the leave of C.lancifolius can accumulate high-level of heavy metals especially Co and Cd showed high bioaccumulation. The BF value in C.lancifolius were followed the order : Co>Cd>Zn=As>Cu>Mn>Ni>Pb>Cr>Fe. HMW PAHs compounds were dominant in C. lancifolius leaves. The sources of PAHs compounds in C. lancifolius leave were pyrogenic and petrogenic, effected by diesel and fuel oil combustion deriving from vehicle exhausts, can be PAHs transport by the air particles the deposited on the leaf surface.

Generally, plants of the study area are considered contaminated with heavy metals, effected by heavy traffic and vehicle exhaust emission. The leaves of C. lancifolius tended to be rich in HMW PAHs compounds. Diesel and fuel oil combustion from vehicle exhausts are potential sources of pyrogenic and petrogenic PAHs in C. lanceolatus leaves, which are then transported by air particles and deposited on the leaf surface. Heavy metals and polycyclic aromatic hydrocarbons (PAHs) released by human activities like oil and industrial activities and vehicle exhaust emissions within Al-Zubair city are thought to be reflected in the plant leaves of the research area.

Firstly I thank and pray to Allah for what I have achieved so far. Secondly, I would like to gratefully acknowledge the help, support and encouragement of my supervisor, Assist. Prof. Dr. Sattar J. Al-Khafaji; I am extremely thankful for his suggestion of research project and his supervision and guidance through all aspects of this study, his ideas are estimable and their presence is indelible.

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Article

Research Paper

Econ. Environ. Geol. 2023; 56(1): 75-85

Published online February 28, 2023 https://doi.org/10.9719/EEG.2023.56.1.75

Copyright © THE KOREAN SOCIETY OF ECONOMIC AND ENVIRONMENTAL GEOLOGY.

Plant Leave as an Indicator for Pollution by Hydrocarbons and Heavy Metals in Al-Zubair City, Southern Iraq

Sajjad W. Jaafar1,*, Sattar J.Al.Khafaji2

1Department of Geology, College of Science, University of Basrah ,Basrah, Iraq
2Department of Geology, College of Science, University of Basrah ,Basrah, Iraq

Correspondence to:*Sajadwafaa2@gmail.com

Received: January 11, 2023; Revised: February 15, 2023; Accepted: February 15, 2023

This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided original work is properly cited.

Abstract

The potential sources and spatial distribution of heavy metals and polycyclic aromatic hydrocarbons (PAHs) were investigated in the leaf plants of Al-Zubair city. A total of 14 samples of conocarpus lancifolius plant leaf were collected and analyzed for their heavy metals and PAHs content using inductively coupled plasma mass spectrometry (ICP-MS) and a 7890 Agilent capillary gas chromatograph (GC) respectively. Bioaccumulation factor calculation revealed the highest pollution of heavy metals , due to the activity of a petrochemical in the area. The diagnostic ratio of Ant/(Phe+Ant), BaA/BaA+Chr), In/(In+BghiP), Flu/Pyr, FlA/FlA+Pyr), ΣLMW/ΣHMW are commonly used for determining the origin and source of PAHs in various environmental media. The diagnostic ratio indicated the anthropogenic origin. PAHs with five-to-six membered rings were dominant in the plant leaf, which likely results from anthropogenic activities. The leaves of C. lancifolius have a preponderance of high molecular weight PAHs compared to low molecular weight PAHs, indicating a combustion origin (car exhaust, petroleum emissions, and fossil fuel). C. lancifolius leaves are a reliable indication of atmospheric PAHs absorption. The background level of heavy metals in the city (or the near environment) is in the order of Fe > Cu > Ni > Cr. On the other hand, the bioaccumulation in plant leaves showed greater tendencies as follows: Co>Cd>Zn=As>Cu>Mn>Ni>Pb>Cr>Fe. Cobalt showed high bioaccumulation, indicating strong uptake of Co by plant leaves. These findings point to human activity and car emissions as the primary sources of roadside vegetation pollution in Al-Zubair city.

Keywords Al-Zubair , PAHs, Conocarpus lancifolius, pollution, Bioaccumulation factor

Research Highlights

  • Gaseous emissions resulting from fuel combustion can be reduced through the use of technologies in the upstream stage of combustion, including what is applied after the combustion stage and before leaving the chimney

  • Avoid constructing oil refineries and refining facilities close to cities and densely populated areas

  • Conducting health and epidemiological studies of the population around the study area for the purpose of estimating the incidence of diseases carcinogenic and non-carcinogenic caused by toxic toxic elements

1. Introduction

Pollution that resulting from cars is a big problem all over the world. (Deubner et al. 2004) note that advanced measurements of air quality such as regulatory and technical innovations like unleaded gasoline, catalytic converters, and fuel-efficient engines have often been negated by an increase in vehicle traffic. Numerous pollutants are contaminating the environment near roads (Unger and Prinz 1997). Fuels, gasoline tank walls, engine components, vehicle components, catalytic converters, tires, brake pads, and road surface materials can all include heavy metals. Incomplete fuel combustion and abrasion of road surfaces both release polycyclic aromatic hydrocarbons (PAHs) into the environment (Unger and Prinz 1997).

In urban areas, polycyclic aromatic hydrocarbons (PAHs) are generated from a variety of sources, including vehicle emissions, fossil fuel combustion, painting, wood and garbage burning, solvent application, and asphalt pavement operations at small factories and workshops (Essumang et al., 2006). Changes in weather patterns and the chemical and physical properties of each PAHs contribute to modifications to the compounds' overall concentrations. Vapor and/or particle-bound PAHs are found in the air and can be deposited on vegetation, trees, soil, and water through both wet and dry deposition. Plants absorb PAHs in the vapor phase through stomata or outer circular lamellae, whereas particle-bound PAHs have accumulated on the leaf surface (Franzaring, 1997). Anthracene is a good example of a PAH that can cross the epicuticle wax and leaf cuticle to enter the cytoplasm of the epidermal cells (Wild et al., 2004). This suggests that the accumulated PAHs are swiftly transferred to the wax layer of the leaf. PAHs are a type of organic pollutant that may be found just about anywhere but are more prevalent in urban and industrial settings due to the prevalence of waste incineration, vehicle traffic, and residential heating systems. Ratios of the distinct PAHs have been proposed to differentiate between different origins with using ratio of PAHs in Table 3. (Yunker et al., 2002; Ravindra et al., 2008), although it is generally accepted that PAHs can arise from petrogenic, pyrolitic, and diagenetic sources. Al-Zubair cities have rapid population growth, coupled with the pollution from nearby oil and gas fields, electrical, petrochemical, and fertilizer sector plants, has led to the deposition of substantial volumes of atmospheric pollution in recent years. The primary goal of this research is to assess the pollution in Al-Zubair city by using the C. lancefolius leaves and identifying their content and source of heavy metals and PAHs as an indicator for pollution.

Table 3 . PAHs diagnostic ratio analysis for Al-Zubair C.lancifolius leave.

PAH ratiosAnt/(Phe+Ant)BaA/BaA+Chr)In/(In+BghiP)Flu/PyrFlA/FlA+Pyr)ΣLMW/ΣHMW
Boundary valuesPetrogenic<0.1<0.2<0.2<1<0.5>1
Pyrogenic>0.1>0.2>0.5>1>0.5<1
Al-Jumhuria Al-awlaaNDNDNDNDND0
Mahlat Al-Arab Al-awlaaNDND0.82720.01830.01790
Kut Al-MarkazND0.20080.83460.03640.03510.0055
Al-DrahmiaNDNDNDNDND0
Al-Faraha and Al-ThoahratND0.1568NDNDND0.0031
Al-AmeerND0.41700.39520.03180.01090.0154
MazraeaNDND0.18130.01100.01090.0214
Hay Al-AskaryNDNDND0.18090.15320
Near Al-Al-Shuaiba RefineryNDNDNDNDND0
Main Waste AreaNDND0.9575NDND0.0198
Al-HussainND0.56660.30880.13940.12230
Al-ThobatND0.21430.92170.00170.00170.0015
AL-ShuhdaaNDND0.31700.08590.07910
MeanND0.11960.36480.03890.03320.0051
ND-Not detected

2. Materials and Methods

2.1. Study Area

The study area is located in the Al-Zubair district, it is located within a longitude (47° 40'-47° 44' E) and a latitude (30° 20'-30° 24' N). the spatial boundaries of the area at the southwestern part of Basrah Governorate, west of Safwan sub-district, and south of Umm Qasr and Khor Al-Zubair sub-district, with an area of about 1134 km², it is surrounded by many oil and gas fields, State Company for Petrochemical Industry and Fertilizer industry plants. The city consists of (23) residential neighborhoods Fig. 1, (Al Zubair Municipality Directorate, 2015).

Figure 1. Sample locations in studied area.

3. Sampling and Sample Preparation

Leave plants samples were taken from 14 different stations namly; (Al-Jumhuria Al-awlaa, Mahlat Al-Arab Al-awlaa, Kut Al-Markaz, Al-Drahmia, Al-Faraha and Al-Thoahrat, Al-Ameer, Mazraea, Hay Al-Askary, Near Al-Al-Shuaiba Refinery, Main Waste Area, Al-Hussain, Al-Shuaiba Houses, Al-Thobat and AL-Shuhdaa, Fig. 1.

The information of each sample was written on the plastic bags and then transferred to the laboratory. Samples were collected under stable weather conditions during September 2021, fieldwork was carried out in the urban district inside of AL-Zubair city include green space, open space traffic roadsides and industrial area The samples were taken by scissors and the highest height was 2 meters. A number of open leaves were taken and in the direct direction of the road and the oil facility. The old parts were taken, not the new shoots. They were taken to the laboratory to dry in the atmosphere of the laboratory. Then the leaves were grinded without washing and transferred to the analysis laboratory at the University of Basrah, College of Marine Sciences, Department of Chemistry.

Sixteen PAHs specified were extracted by using Soxhlet apparatus according to method of Wang et al. (2011), including Benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(123cd)pyrene and dibenzo(ah)anthracene Naphthalene (NAP), 2-Methylnaphthalne (2-METH), Acenapthylene (ACY), Acenapthene (ACE), Flourene (FLU), Phenanthrene (PHE), Anthracene (ANT), Flouranthene (FLUA), Pyrene (PYR), Benz[a] anthracene (B[a]A), Chrysene (CHR), Benzo[b]flouranthene (B[b]F), Benzo[k]flouranthene (B[k]F), Benzo[a]pyrene (B[a]P), Benzo[ghi]perylene (B[ghi]P), Indeno[1,2,3-cd]pyren (Ind p). then PAHs compounds were identified in the laboratories of Basrah oil company by using 7890 Agilent capillary Gas Chromatography (GC), For heavy metals analysis, the sample was grinded without washing and transferred to the analysis laboratory. Ten of heavy metals (Pb, Zn, Ni, Mn, Fe, Co, Cd, Cu, Cr and AS) were determined in Conocarpus lancifolius using Inductively coupled plasma-mass spectrometry (ICP-MS) in Iran.

4. Results and Discussion

4.1 Polycyclic Aromatic Hydrocarbons

The results showed that the mean values for PAHs compounds in C. lancefolius leaves have the following orders: Pyr(498.07 ng/g)>Indo(26.73 ng/g)>Ben(A)Ant(23.13 ng/g)>Ben(15.84 ng/g)>Ben(A)(13.10 ng/g)>Flu(12.67 ng/g)>Ben(K)(3.82 ng/g)>Chr(3.14 ng/g). The mean content of LMW PAHs is 3.7 ng/g, whereas the mean content of HMW PAHs is 598.98 ng/g (Table 1), (Fig. 2, 3). The total mean of carcinogenic aromatic compound concentration is 544.25 ng/g. The maximum total PAHs content was recorded at Kut Al-Markaz (2034.56 ng/g), whereas the minimum value was recorded at Near Al-Shuaiba Refinery (20.03 ng/g). The PAHs accumulation in C. lancefolius leaves was influenced by the traffic volume according to results at the sampling location and the high concentration of PAHs emitted by vehicles on the road.

Table 1 . PAHs concentration in C. lancifolius leaves (ng/g).

StationsAromatic ringAl-Jumhuria Al-awlaaMahlat Al-Arab Al-awlaaKut Al-MarkazAl-DrahmiaAl-Faraha and Al-ThoahratAl-AmeerMazraeaHay Al-AskaryNear Al-Shuaiba RefineryMain Waste AreaAl-HussainAl-ThobatAL-ShuhdaaMeanMinMaxAC
PAHS Compounds
LMWNAPHTHALENE2NDNDNDNDNDNDNDNDNDNDNDNDND000ND
2-METHYLNAPHTHALNE2NDND2.42NDNDNDNDNDND5.76NDNDND0.622.425.76ND
ACENAPHTHYENE3NDND6.42NDND1.96NDNDND2.69NDNDND0.851.966.42ND
ACENAPHTHNEN3NDNDNDNDND3.432.97NDNDNDNDNDND0.492.973.43ND
FLUORENE3NDNDNDNDND5.382.63NDNDNDNDNDND0.612.635.38ND
PHENANTHRENE3NDNDNDNDNDNDNDNDNDNDND1.99ND0.151.991.99ND
ANTHRACENE3NDND2.33ND2.246.052.94NDNDNDNDNDND1.042.246.05ND
HMWFLUORANTHENE4ND9.2762.12NDND24.513.954.25NDND32.072.1926.3612.672.1962.129.27
PYRENE4265.28506.231702.9133.49655.94770.71356.3923.50ND385.40229.971238.50306.59498.0723.501702.91506.23
CHRYSENE4NDND8.43ND8.794.95NDNDNDND7.6111.09ND3.144.9511.09ND
BENZO(A)ANTHRACENE4NDND2.12ND1.633.5413.15255.1212.21ND9.963.02ND23.131.63255.12ND
BENZO(B)FLUORANTHENE5NDND7.49ND10.522.95NDND4.08ND1.86ND3.662.351.8610.52ND
BENZO(K)FLUORANTHENE51.032.021.23ND4.6024.83ND2.723.722.052.262.832.413.821.0324.832.02
BENZO(A) PYRENE5NDND24.07ND8.82109.809.462.84NDND3.073.318.9813.102.84109.80ND
INDENO(1,2,3-CD)PYRENE+DIBENZO(A,H)ANTHRACENE6ND15.40179.435.5516..4859.383.035.69ND36.464.8130.487.2426.733.03179.4315.40
BENZO(G,H,I)PERYLENE611.283.2135.54ND21.1590.8313.72NDND1.6110.772.5815.6015.871.6190.833.21
ΣLMW0011.1702.2416.848.5611008.4501.9900011.17
ΣHMW277.59536.152023.3939.04711.481091.55399.73294.1420.03425.54302.421294.04370.87277.59536.152023.39
ΣCar266.31517.531786.6633.49683.74837.58376.45285.6020.03387.45283.761257.65339.03266.31517.531786.66
PAHs277.59536.152034.5639.04713.721108.39408.29294.1420.03433.99302.421296.03370.87ΣPAHs277.59536.15

*Σ16-PAHs: means concentration of 16 kinds of PAHs. *ΣCar-PAH: means concentrations of carcinogenic PAHs, including Benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(123cd)pyrene and dibenzo(ah)anthracene (USEPA 2002b). ΣLMW sum of 7 Low Molecular Weight Polycyclic aromatic hydrocarbons :Naphthalene (NAP), 2-Methylnaphthalne (2-METH), Acenapthylene (ACY), Acenapthene (ACE), Flourene (FLU), Phenanthrene (PHE), Anthracene (ANT), Flouranthene, ΣHMW sum of 9 High Molecular weight polycyclic aromatic hydrocarbons : (FLUA), Pyrene (PYR), Benz[a]anthracene (B[a]A), Chrysene (CHR), Benzo[b]flouranthene (B[b]F), Benzo[k]flouranthene (B[k]F), Benzo[a]pyrene (B[a]P) Benzo[ghi]perylene (B[ghi]P), Indeno[1,2,3-cd]pyren (Ind p). ND, not detected. ΣCar sum of 7 Carcinogenic polycyclic aromatic hydrocarbons:BaA,chr,BbF,BkF,BaP,InP and BghiP Ac: Acceptable concentration Netherlands Ministry of Housing and environment (1994).


Figure 2. Distribution of LMW PAHs and HMW PAHs in C. lancifolius leaves.
Figure 3. Heavy metal concentration (ppm) in roadside c. lancifolius plant leaves.

One major and effective uptake method in plant leaves is the inhalation of volatile PAHs from the environment (Simonich and Hites 1994a). Vapor-phase PAHs are typically taken in through the leaf cuticle rather than through the stomata (Barber et al., 2004). After penetrating the cuticle, these PAHs may be taken into the body. At room temperature, low molecular weight polycyclic aromatic hydrocarbons (LMW PAHs) with fewer than four rings are more likely to condense as a vapor and deposit on plants in the troposphere. Subsequently, the deposited PAHs could enter cells via diffusion.

4.2. Heavy Metals

Heavy metal concentrations in C. lancifolius leaves are listed in Tables 2. It is reported that the amount of Ni is higher than the normal value in leaf tissue (0.1–5 ppm) according to Kabata-Pendias (2011), with the maximum concentration at Mahlat Al-Arab Al-Awlaa (6 ppm) (Fig. 3). This is associated with heavy traffic and industrial pollutants, the highest concentration of Cu (14 ppm) is detected at Al-Drahmia. This is significantly higher than background concentration reported by Kabata-Pendias (2011). Because of traffic and industrial pollution, levels of Fe in the leaves' tissues are abnormally high (308.28 ppm) compared to the normal value (20–100 ppm) at Mahlat Al-Arab Al-Awlaa (709 ppm).

Table 2 . Heavy metal concentration (ppm) in conocarpus lancifolius leaves of study area and comparison with other studies.

Sample locationPbNiZnMnFeCuCrCoCdAs
Al-Jumhuria Al-awlaa122116208510.90.2<1
Mahlat Al-Arab Al-awlaa2636327091140.90.1<1
Kut Al-Markaz3429225621130.40.2<1
Al-Drahmia1324132381410.70.1<1
Al-Faraha and Al-Thoahrat121927300510.50.2<1
Al-Ameer1441315761030.60.3<1
Mazraea121516125610.70.1<1
Hay Al-Askary141619200710.40.3<1
Near Al-Al-Shuaiba Refinery111912395520.20.4<1
Main Waste Area13929170410.60.1<1
Al-Hussain1169112310.50.2<1
Al-Shuaiba Houses111810216420.30.3<1
Al-Thobat131114393520.10.1<1
AL-Shuhdaa11118112410.30.3<1
Min11118112410.10.1<1
Max3641327091440.90.4<1
Mean1.212.6419.6418.42308.286.711.710.500.20<1
1Normal Values5-100.1-527-15030-30020-1005-300.1-0.50.02-10.05-21-1.7
2 Basrah city3.2520.6132.6422.56266.5413.9618.521.160.512.36
3Ramadi city6.99±0.447.71±0.1862.95±2.9649.64±3.23-14.03±0.847.26±0.412.13±0.080.93±0.18-
4Permissible value6.49±0.217.55±0.1955.02±2.0345.23±1.42-12.49±0.496.37±0.262.04±0.050.57±0.09-

1Kabata-pendias and pendias (2011).

2Al-Khafaji and Jalal (2020).

3Al-Heety et al.(2021).

4FAO/WHO (2007).

- Not detected.



The maximum value of Cr was at Mahlat Al-Arab Alawlaa (4 ppm), whilst the minimum values detacted Al-Jumhuria Al-awlaa (1 ppm). The high Cr content is associated with industrial emissions from the oil field around the research area. The main sources of Cu in the study area are oil oxidation, abrasion of tires on vehicles, and industrial waste, all of which are easily transported via air and deposited on plant leaves (Celik et al., 2005). The high concentrations of Fe found in all plant samples can be attributed to the fact that plant roots can take up large quantities of Fe from the soil and store it mostly in the leaves (Gholami et al., 2013).

Although zinc (Zn) is essential to all living things, the excess of Zn it can be toxic to plants, and too little can induce leaf development (Bucher and Schenk, 2000). The high concentrations of Zn were in normal range except in Al-Ameer, Mahlat Al-Arab Al-Awlaa, and Kut Al-Markaz, which were (41 ppm), (36 ppm), and (29 ppm), respectively, which are located close to a manufacturing facility and highway.

Overall, the data indicate that a variety of discrete inputs associated with human activities—including automobiles, industrial pollution, fossil fuel combustion, garages, and garbage dumps—had a significant impact on Al-Zubair flora.

5. Assessment and Quantify of Plants Pollution

5.1. PAHs Diagnostic Ratios

Diagnostic ratios of PAHs are commonly used for determining the origin and source of PAHs in various environmental media (Bucheli et al., 2004; Yunker et al., 2002). Several researchers have found this method to be an effective way to identify the origins of PAHs at particular places, such as areas near point sources and the soil around industrial districts (Christensen and Bzdusek 2005). As a result, the diagnostic ratio was employed in this investigation as a suggestive method of providing information regarding the origins of PAHs. A ratio of Ant/ (Ant + Phe) 0.1 indicates petroleum, while a ratio greater than 0.1 indicates combustion dominance (Bucheli et al., 2004). Yunker et al. (2002) proposed that a Fla/(Fla + Pyr) ratio of 0.5 denotes a coal, wood, or grass combustion source, and a BaA/(BaA + Chr) ratio of 0.35 denotes a biomass combustion source. According to the literature (Mannino and Orecchio 2008), the value of Ind/(Ind + Bghip) >0.5 indicates grass, coal, or wood combustion sources, while a ratio between 0.20 and 0.50 implies fuel combustion sources (vehicles and crude oil). The ratio of specific PAHs was determined to identify potential sources. Typically, a value of one for high molecular weight (HMW) or one for low molecular weight (LMW) PAHs indicates that they are primarily derived from a petrogenic source, while a value of one for HMW/LMW PAHs indicates that they are primarily derived from a pyrogenic source (Soclo et al., 2000; Zakaria et al., 2002). A flu/pyr ratio of one indicates that the PAHs are petrogenic. Table 3 shows that the mean of LMW/HMW indicates the pyrogenic sources, as BaA/(BaA + Chr) indicates the petrognic sources, and Flu/Pyr shows the petrognic sources. The FlA/(FlA + Pyr) ratio indicates the presence of petrol emission sources. The results were compared with previous studies, Table 4.

Table 4 . Total PAHs concentrations in the C. lancifolius leave from different locations around the world.

LocationTotal PAHs (ng/g1)-1Plant SpeciesReferences
Nanling Mountains646Hypnum plumaeformaeLiu et al. (2005)
Szulborze Poland2373Hylocomium splendenWang et al. (2009b)
Ny-Ålesund Arctic Circle217MossOrliński (2002)
Liaoning, China Industrial area550Pinus thunbergiiTian et al. (2009)
Barcelona Natural75Pinus pineaRatola et al. (2006)
Al-Zubair city (Current) study , Iraq602C.lancifoliusThis study


5.2. Bioaccumulation Factor

Bioaccumulation factor (BF) was determined as an indication of metal accumulation in plants. BF value greater than 1.0 indicates a high metal accumulation Dowdy & McKone (1997). BF was calculated to determine the amount of metals accumulated by the plant using the formula shown in equation 1.

Cp/Cs=BioaccumulationFactor

where Cp is the concentration of metals in plants and CS is the concentration of metals in soil according to the concentration of metals in soil that was suggested by Kabata-Pendias (2011).

According to the results, the mean of heavy metal bioaccumulation in leaves follows the order: Co>Cd>Zn=As>Cu>Mn>Ni>Pb>Cr>Fe. Cobalt showed high bioaccumulation, indicating strong uptake of Co by plant leaves. Table show that Pb, Fe, and Cr showed low bioaccumulation (0.063), (0.037), and (0.057), respectively, indicating that this element has relatively low availability, while Ni, Zn, Mn, Cu, Cd, and As showed median bioaccumulation (0.125), (0.489), (0.128), (0.440), (0.746), and (0.484), respectively.

Table 5 . Bioaccumulation factor values of heavy metals in C.lancifolius leaves.

Sampling locationPbNiZnMnFeCuCrCoCdAs
Al-Jumhuria Al-awlaa0.0430.0710.3380.1040.0220.2940.0284.510.2
Mahlat Al-Arab Al-awlaa0.0760.4610.6100.2780.11210.1812.250.250.5
Kut Al-Markaz0.1110.0970.1900.110.0370.50.0540.5710.2850.2
Al-Drahmia0.0580.20.5580.1200.0320.2910.05710.25
Al-Faraha and Al-Thoahrat0.0450.0900.0410.2640.0410.5550.0352.511
Al-Ameer0.0430.1680.2660.2280.0630.4670.0931.8750.9370.294
Mazraea0.0370.0740.1480.0530.0130.1360.0292.3330.3330.333
Hay Al-Askary0.0830.0861.3330.0780.0140.6360.0101.33310.25
Near Al-Al-Shuaiba Refinery0.0710.0760.7910.1210.0450.50.0760.510.5
Main Waste Area0.0320.1570.8180.1280.0270.50.0471.50.50.5
Al-Hussain0.10.0340.4610.0540.0130.3330.0272.50.51
Al-Shuaiba Houses0.0530.0370.5590.0480.0230.2430.0460.9370.9370.416
Al-Thobat0.0710.1420.3230.1170.0500.4160.0600.3330.21
AL-Shuhdaa0.0660.0620.4070.0890.0210.2850.0580.751.50.333
Min0.0320.0340.0410.0480.0130.1360.0100.3330.20.2
Max0.1110.4611.3330.2780.11210.18171.51
Mean0.0630.1250.4890.1280.0370.440.0572.0630.7460.484

6. Conclusion

High concentrations of Co, Ni, Cr, Fe, Cu and Cd were found in C. lancifolius leaf samples taken at several locations inside Zuabir city. In addition, they are a useful indicator for the absorption of Co, since Co is taken up so readily by the root system and the leaves in direct correlation with its concentration in the surrounding environment. C. lancifolius leaves can bioaccumulate substantial levels of heavy metals, particularly Co, according to BF findings. The BF results indicate that the leave of C.lancifolius can accumulate high-level of heavy metals especially Co and Cd showed high bioaccumulation. The BF value in C.lancifolius were followed the order : Co>Cd>Zn=As>Cu>Mn>Ni>Pb>Cr>Fe. HMW PAHs compounds were dominant in C. lancifolius leaves. The sources of PAHs compounds in C. lancifolius leave were pyrogenic and petrogenic, effected by diesel and fuel oil combustion deriving from vehicle exhausts, can be PAHs transport by the air particles the deposited on the leaf surface.

Generally, plants of the study area are considered contaminated with heavy metals, effected by heavy traffic and vehicle exhaust emission. The leaves of C. lancifolius tended to be rich in HMW PAHs compounds. Diesel and fuel oil combustion from vehicle exhausts are potential sources of pyrogenic and petrogenic PAHs in C. lanceolatus leaves, which are then transported by air particles and deposited on the leaf surface. Heavy metals and polycyclic aromatic hydrocarbons (PAHs) released by human activities like oil and industrial activities and vehicle exhaust emissions within Al-Zubair city are thought to be reflected in the plant leaves of the research area.

Acknowledgment

Firstly I thank and pray to Allah for what I have achieved so far. Secondly, I would like to gratefully acknowledge the help, support and encouragement of my supervisor, Assist. Prof. Dr. Sattar J. Al-Khafaji; I am extremely thankful for his suggestion of research project and his supervision and guidance through all aspects of this study, his ideas are estimable and their presence is indelible.

Fig 1.

Figure 1.Sample locations in studied area.
Economic and Environmental Geology 2023; 56: 75-85https://doi.org/10.9719/EEG.2023.56.1.75

Fig 2.

Figure 2.Distribution of LMW PAHs and HMW PAHs in C. lancifolius leaves.
Economic and Environmental Geology 2023; 56: 75-85https://doi.org/10.9719/EEG.2023.56.1.75

Fig 3.

Figure 3.Heavy metal concentration (ppm) in roadside c. lancifolius plant leaves.
Economic and Environmental Geology 2023; 56: 75-85https://doi.org/10.9719/EEG.2023.56.1.75

Table 1 . PAHs concentration in C. lancifolius leaves (ng/g).

StationsAromatic ringAl-Jumhuria Al-awlaaMahlat Al-Arab Al-awlaaKut Al-MarkazAl-DrahmiaAl-Faraha and Al-ThoahratAl-AmeerMazraeaHay Al-AskaryNear Al-Shuaiba RefineryMain Waste AreaAl-HussainAl-ThobatAL-ShuhdaaMeanMinMaxAC
PAHS Compounds
LMWNAPHTHALENE2NDNDNDNDNDNDNDNDNDNDNDNDND000ND
2-METHYLNAPHTHALNE2NDND2.42NDNDNDNDNDND5.76NDNDND0.622.425.76ND
ACENAPHTHYENE3NDND6.42NDND1.96NDNDND2.69NDNDND0.851.966.42ND
ACENAPHTHNEN3NDNDNDNDND3.432.97NDNDNDNDNDND0.492.973.43ND
FLUORENE3NDNDNDNDND5.382.63NDNDNDNDNDND0.612.635.38ND
PHENANTHRENE3NDNDNDNDNDNDNDNDNDNDND1.99ND0.151.991.99ND
ANTHRACENE3NDND2.33ND2.246.052.94NDNDNDNDNDND1.042.246.05ND
HMWFLUORANTHENE4ND9.2762.12NDND24.513.954.25NDND32.072.1926.3612.672.1962.129.27
PYRENE4265.28506.231702.9133.49655.94770.71356.3923.50ND385.40229.971238.50306.59498.0723.501702.91506.23
CHRYSENE4NDND8.43ND8.794.95NDNDNDND7.6111.09ND3.144.9511.09ND
BENZO(A)ANTHRACENE4NDND2.12ND1.633.5413.15255.1212.21ND9.963.02ND23.131.63255.12ND
BENZO(B)FLUORANTHENE5NDND7.49ND10.522.95NDND4.08ND1.86ND3.662.351.8610.52ND
BENZO(K)FLUORANTHENE51.032.021.23ND4.6024.83ND2.723.722.052.262.832.413.821.0324.832.02
BENZO(A) PYRENE5NDND24.07ND8.82109.809.462.84NDND3.073.318.9813.102.84109.80ND
INDENO(1,2,3-CD)PYRENE+DIBENZO(A,H)ANTHRACENE6ND15.40179.435.5516..4859.383.035.69ND36.464.8130.487.2426.733.03179.4315.40
BENZO(G,H,I)PERYLENE611.283.2135.54ND21.1590.8313.72NDND1.6110.772.5815.6015.871.6190.833.21
ΣLMW0011.1702.2416.848.5611008.4501.9900011.17
ΣHMW277.59536.152023.3939.04711.481091.55399.73294.1420.03425.54302.421294.04370.87277.59536.152023.39
ΣCar266.31517.531786.6633.49683.74837.58376.45285.6020.03387.45283.761257.65339.03266.31517.531786.66
PAHs277.59536.152034.5639.04713.721108.39408.29294.1420.03433.99302.421296.03370.87ΣPAHs277.59536.15

*Σ16-PAHs: means concentration of 16 kinds of PAHs. *ΣCar-PAH: means concentrations of carcinogenic PAHs, including Benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(123cd)pyrene and dibenzo(ah)anthracene (USEPA 2002b). ΣLMW sum of 7 Low Molecular Weight Polycyclic aromatic hydrocarbons :Naphthalene (NAP), 2-Methylnaphthalne (2-METH), Acenapthylene (ACY), Acenapthene (ACE), Flourene (FLU), Phenanthrene (PHE), Anthracene (ANT), Flouranthene, ΣHMW sum of 9 High Molecular weight polycyclic aromatic hydrocarbons : (FLUA), Pyrene (PYR), Benz[a]anthracene (B[a]A), Chrysene (CHR), Benzo[b]flouranthene (B[b]F), Benzo[k]flouranthene (B[k]F), Benzo[a]pyrene (B[a]P) Benzo[ghi]perylene (B[ghi]P), Indeno[1,2,3-cd]pyren (Ind p). ND, not detected. ΣCar sum of 7 Carcinogenic polycyclic aromatic hydrocarbons:BaA,chr,BbF,BkF,BaP,InP and BghiP Ac: Acceptable concentration Netherlands Ministry of Housing and environment (1994).


Table 2 . Heavy metal concentration (ppm) in conocarpus lancifolius leaves of study area and comparison with other studies.

Sample locationPbNiZnMnFeCuCrCoCdAs
Al-Jumhuria Al-awlaa122116208510.90.2<1
Mahlat Al-Arab Al-awlaa2636327091140.90.1<1
Kut Al-Markaz3429225621130.40.2<1
Al-Drahmia1324132381410.70.1<1
Al-Faraha and Al-Thoahrat121927300510.50.2<1
Al-Ameer1441315761030.60.3<1
Mazraea121516125610.70.1<1
Hay Al-Askary141619200710.40.3<1
Near Al-Al-Shuaiba Refinery111912395520.20.4<1
Main Waste Area13929170410.60.1<1
Al-Hussain1169112310.50.2<1
Al-Shuaiba Houses111810216420.30.3<1
Al-Thobat131114393520.10.1<1
AL-Shuhdaa11118112410.30.3<1
Min11118112410.10.1<1
Max3641327091440.90.4<1
Mean1.212.6419.6418.42308.286.711.710.500.20<1
1Normal Values5-100.1-527-15030-30020-1005-300.1-0.50.02-10.05-21-1.7
2 Basrah city3.2520.6132.6422.56266.5413.9618.521.160.512.36
3Ramadi city6.99±0.447.71±0.1862.95±2.9649.64±3.23-14.03±0.847.26±0.412.13±0.080.93±0.18-
4Permissible value6.49±0.217.55±0.1955.02±2.0345.23±1.42-12.49±0.496.37±0.262.04±0.050.57±0.09-

1Kabata-pendias and pendias (2011).

2Al-Khafaji and Jalal (2020).

3Al-Heety et al.(2021).

4FAO/WHO (2007).

- Not detected.


Table 3 . PAHs diagnostic ratio analysis for Al-Zubair C.lancifolius leave.

PAH ratiosAnt/(Phe+Ant)BaA/BaA+Chr)In/(In+BghiP)Flu/PyrFlA/FlA+Pyr)ΣLMW/ΣHMW
Boundary valuesPetrogenic<0.1<0.2<0.2<1<0.5>1
Pyrogenic>0.1>0.2>0.5>1>0.5<1
Al-Jumhuria Al-awlaaNDNDNDNDND0
Mahlat Al-Arab Al-awlaaNDND0.82720.01830.01790
Kut Al-MarkazND0.20080.83460.03640.03510.0055
Al-DrahmiaNDNDNDNDND0
Al-Faraha and Al-ThoahratND0.1568NDNDND0.0031
Al-AmeerND0.41700.39520.03180.01090.0154
MazraeaNDND0.18130.01100.01090.0214
Hay Al-AskaryNDNDND0.18090.15320
Near Al-Al-Shuaiba RefineryNDNDNDNDND0
Main Waste AreaNDND0.9575NDND0.0198
Al-HussainND0.56660.30880.13940.12230
Al-ThobatND0.21430.92170.00170.00170.0015
AL-ShuhdaaNDND0.31700.08590.07910
MeanND0.11960.36480.03890.03320.0051
ND-Not detected

Table 4 . Total PAHs concentrations in the C. lancifolius leave from different locations around the world.

LocationTotal PAHs (ng/g1)-1Plant SpeciesReferences
Nanling Mountains646Hypnum plumaeformaeLiu et al. (2005)
Szulborze Poland2373Hylocomium splendenWang et al. (2009b)
Ny-Ålesund Arctic Circle217MossOrliński (2002)
Liaoning, China Industrial area550Pinus thunbergiiTian et al. (2009)
Barcelona Natural75Pinus pineaRatola et al. (2006)
Al-Zubair city (Current) study , Iraq602C.lancifoliusThis study

Table 5 . Bioaccumulation factor values of heavy metals in C.lancifolius leaves.

Sampling locationPbNiZnMnFeCuCrCoCdAs
Al-Jumhuria Al-awlaa0.0430.0710.3380.1040.0220.2940.0284.510.2
Mahlat Al-Arab Al-awlaa0.0760.4610.6100.2780.11210.1812.250.250.5
Kut Al-Markaz0.1110.0970.1900.110.0370.50.0540.5710.2850.2
Al-Drahmia0.0580.20.5580.1200.0320.2910.05710.25
Al-Faraha and Al-Thoahrat0.0450.0900.0410.2640.0410.5550.0352.511
Al-Ameer0.0430.1680.2660.2280.0630.4670.0931.8750.9370.294
Mazraea0.0370.0740.1480.0530.0130.1360.0292.3330.3330.333
Hay Al-Askary0.0830.0861.3330.0780.0140.6360.0101.33310.25
Near Al-Al-Shuaiba Refinery0.0710.0760.7910.1210.0450.50.0760.510.5
Main Waste Area0.0320.1570.8180.1280.0270.50.0471.50.50.5
Al-Hussain0.10.0340.4610.0540.0130.3330.0272.50.51
Al-Shuaiba Houses0.0530.0370.5590.0480.0230.2430.0460.9370.9370.416
Al-Thobat0.0710.1420.3230.1170.0500.4160.0600.3330.21
AL-Shuhdaa0.0660.0620.4070.0890.0210.2850.0580.751.50.333
Min0.0320.0340.0410.0480.0130.1360.0100.3330.20.2
Max0.1110.4611.3330.2780.11210.18171.51
Mean0.0630.1250.4890.1280.0370.440.0572.0630.7460.484

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KSEEG
Apr 30, 2023 Vol.56 No.2, pp. 115~215

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