Research Article

Environmental and health risks of metal‑contaminated soil

in the former tannery area of Hazaribagh, Dhaka
Al‑Mizan1 · Md Ariful Islam Juel1,2 · Md Shahin Alam3 · John Pichtel3 · Tanvir Ahmed4

Received: 9 July 2020 / Accepted: 13 October 2020 / Published online: 28 October 2020
© Springer Nature Switzerland AG 2020

Abstract
Soil and plant samples collected from Hazaribagh, the former tannery area in Dhaka, Bangladesh, were analyzed for
heavy metals (Cr, Pb, Ni, Zn, Cd, and Cu). The pollution and health risks of the metals were assessed with commonly used
indicators. The mean soil Cr concentration was 4321 mg/kg (range 294–23,148 mg/kg). Most sites had a moderate to high
degree of contamination and were classified as extremely polluted (Pollution Load Index > 1). The non-carcinogenic haz-
ard index was greater than 1 for Pb and Cr for both children and adults, which indicates considerable non-cancer health
risk. The combined cancer risks for Pb and Cr exceeded the allowable range of 1 × 10−6–1 × 10−4 for most sites (8 out of 11
sites in the case of adults, all sites in the case of children) with Cr being the dominant contributor and oral ingestion the
primary pathway. The cancer and non-cancer risks for children were 26- and 3-fold higher, respectively, than for adults.
Among all heavy metals, Pb and Zn were the most susceptible to leaching and becoming mobilized in groundwater.
Concentrations of Pb, Cr, and Zn in edible parts of vine spinach (Basella alba) exceeded safe limits. However, Pb and Cu
showed significant accumulation in plants (Mean Transfer Factor of 1.064 and 0.94, respectively, for Pb and Cu), while
Cr exhibited relatively lower bioavailability. The spatial distribution of heavy metal contamination and associated risks
presented in this study will allow policymakers to pinpoint areas of intervention for remediation.

Keywords Cancer risk · Chromium · Non-carcinogenic risk · Risk assessment · Soil pollution

1 Introduction disposal, battery recycling and oil refining have been

responsible for emissions of heavy metals to various envi-
Heavy metal contamination of soil is a significant hazard ronmental compartments [5–10].
and can impart adverse impacts on human health and In Bangladesh, tannery industries have been at the fore-
the environment [1, 2]. Both natural and anthropogenic front of environmental pollution for decades. The hub of
sources contribute to heavy metal pollution [3, 4]. Natu- tanning industries was established in Hazaribagh, Dhaka,
ral sources such as volcanic eruptions and weathering about 70 years ago, prior to establishment of relevant
of rocks enrich and mobilize heavy metals on the earth’s environmental regulations. Approximately 185 tanneries
surface. However, anthropogenic activities, especially over operated in the area, which discharged untreated liquid
the past few decades, have been documented as the key effluent and generated hazardous solid waste without
contributor to increased concentrations of heavy metals requirements for effluent treatment and waste manage-
in soil and water. Chemical industries, tanneries, mining ment [11].
and smelting, iron and steel industries, agriculture, waste

* Al‑Mizan, almizan@[Link]; almizanbcsir@[Link] | 1Department of Leather Engineering, Khulna University of Engineering

and Technology, Khulna 9203, Bangladesh. 2Department of Civil and Environmental Engineering, The University of North Carolina
at Charlotte, Charlotte, NC 28223, USA. 3Department of Environment, Geology and Natural Resources, Ball State University, Muncie,
IN 47306, USA. 4Department of Civil Engineering, Bangladesh University of Engineering and Technology, Dhaka 1000, Bangladesh.

SN Applied Sciences (2020) 2:1915 | [Link]

Vol.:(0123456789)
Research Article SN Applied Sciences (2020) 2:1915 | [Link]

A wide range of chemicals is required for leather pro- spaces, along with medical and educational institutions
cessing; those of greatest concern are chromium sulfate, and other facilities [13]. Those living and working in this
tannins, pigments, dyes, lime, salt of ammonia, bacteri- area may experience accidental exposure to heavy metals
cides, and fungicides [12–14]. During leather processing at via ingestion, inhalation, or dermal contact. Therefore, the
the Hazaribagh tanning industries, large quantities of solid current state of heavy metal contamination and its asso-
and liquid wastes were generated. It is estimated that, on ciated risks need to be assessed in order to formulate a
average, about 22,000 m3 of highly toxic effluents were reclamation strategy and for mitigating adverse human
discharged daily into low-lying areas, lagoons and canals, health effects and environmental damage.
which ultimately entered the Buriganga River [14, 15]. The primary objective of this study is to assess the
In addition, 1.25 metric tonnes of chromium were gen- present status of heavy metal contamination in the Haz-
erated daily by these industries, from which 0.35 metric aribagh area and its potential impact on the local envi-
tonnes may have settled into the surrounding low-lying ronment. We used indices such as ecological risk factor
areas of Hazaribagh [15]. Besides tanneries, over 70 paint (Er), ecological risk index (RI), pollution load index (PLI),
and glue industries were located in Hazaribagh, discharg- contamination factor (CF), geo-accumulation index (Igeo),
ing 504,000 m3 of untreated effluents annually, further degree of contamination (Cdeg), transfer factor (TF), and
aggravating local environmental conditions [12]. The estimated non-carcinogenic and carcinogenic risks to
Bangladesh Government has only recently relocated the understand the hazard posed by heavy metal accumula-
scattered tanneries from Hazaribagh to a separate indus- tion to the surrounding environment and human health.
trial estate in Savar, Dhaka, where specialized facilities The extent of potential leaching of heavy metals was
have been designed to treat liquid effluents and manage assessed for predicting groundwater pollution. An assess-
solid waste. However, uncontrolled discharge into water ment of human health risks via the consumption of veg-
bodies, canals, and open spaces in Hazaribagh over sev- etables grown on the contaminated sites was also done.
eral decades have likely enriched the pollutants in soil
and vegetation and still poses a risk to human health and
the local environment [12]. Heavy metals can accumulate 2 Materials and methods
and become immobilized via chemical precipitation and
adsorption reactions and occur as highly resistant com- 2.1 Study area and sampling
pounds in soil [3]. In certain circumstances, heavy metals
may be transported from soil to surface water and ground- The study area is the former tannery campus of Hazarib-
water through runoff or percolation. Metals can also be agh, located in southwestern Dhaka (Fig. 1). The campus
taken up by plants, accumulate, and eventually enter into encompasses an area of 0.55 km2 and has a population
the human body [4, 16]. density of 32,856 per ­k m2 [24]. Untreated heavy metal-
Recent studies have revealed that 90% of heavy metal enriched solid waste had been disposed and stored in and
intake in the human body is attributed to the consumption adjacent to the former Hazaribagh tannery estate for sev-
of plants [4, 17]. Excessive exposure and accumulation of eral decades. Effluent discharged from the tannery were
heavy metals in the body can result in acute and chronic sometimes temporarily stored in ponds before being con-
health problems including cardiovascular disease, bone veyed to the Buriganga River [12]. The soil of Hazaribagh
damage, kidney dysfunction, cancer as well as gastroin- is basically non-calcareous alluvium having a silty texture
testinal, muscular, reproductive, neurological and genetic [22]. The major elements (in terms of oxides) in the topsoil
damages [1, 6, 18]. (0–0.5 m) are S­ iO2 (22.9%), CaO (20%), S­ O3 (7%), and A
­ l 2O 3
Research has been conducted in the Hazaribagh district (6.8%), where the S­ iO2 fraction increases more than two-
to assess heavy metal contamination of water, soil, and fold in the deeper strata [25].
sediment of the Buriganga River, which flows adjacent to Eleven soil sampling locations were selected in the Haz-
the area [2, 19–21]. Few studies, however, have assessed aribagh, Dhaka (Fig. 1). All soil samples were collected to
heavy metal content in plants occurring on the embank- a depth of 0 to 20 cm and placed in clean plastic bags.
ment or the effluent discharge channels to the river Three replicate samples were collected from each site. Vine
Buriganga [22, 23]. Earlier work has highlighted soil and spinach (Basella alba) samples were collected from three
groundwater pollution within the tannery establishment representative sampling sites (Table 1). Vine spinach is the
[11, 13, 15]. However, contact with contaminated soil may most commonly cultivated vegetable in the study area and
pose direct risks to human health, and a holistic picture of was therefore selected as an indicator species for metal
the risks of the area is yet to be developed. This area has uptake assessment.
been earmarked for residential development with green

Vol:.(1234567890)
SN Applied Sciences (2020) 2:1915 | [Link] Research Article

Fig. 1  Map of the study area and soil sampling locations

Table 1  Coordinates of the soil and plant sampling locations was added and kept overnight. The sample was refluxed
Sample site Geographical location Soil Vegetable
for 2 h, diluted in distilled water to 500 ml, and filtered
through 0.45 µm filter paper. The filtrate was collected
L1 23°44′16.0″N 90°21′41.8″E √ × in clean plastic bottles for heavy metal (Cr, Pb, Cu, Zn, Ni,
L2 23°44′13.8″N 90°21′50.7″E √ × and Cd) determination using direct air/acetylene mixture
L3 23°44′10.2″N 90°21′52.9″E √ × by flame atomic absorption spectrophotometry (FAAS). A
L4 23°44′01.3″N 90°21′51.1″E √ √ linear calibration was performed with standard solutions
L5 23°44′00.1″N 90°21′48.6″E √ × before each analysis in an Atomic Absorption Spectro-
L6 23°43′57.3″N 90°21′51.1″E √ × photometer (Shimadzu AA6800). All elemental analysis
L7 23°44′05.2″N 90°21′59.1″E √ √ via FAAS was performed following Standard Method 3111
L8 23°44′09.3″N 90°22′02.6″E √ × [28]. The minimum detection limit of the instrument was
L9 23°44′08.5″N 90°22′03.2″E √ × 0.001 mg/L for Cr, Cu, Zn, and Cd and 0.01 mg/L for Pb and
L10 23°44′09.2″N 90°22′03.4″E √ √ Ni. The mean and standard deviation of three replicates for
L11 23°43′59.7″N 90°22′08.0″E √ × each sampling location is reported in this study. Analyzed
heavy metal concentrations were compared with China
and Finland maximum permissible limits.
2.2 Digestion of soil samples
2.3 Digestion of plant samples
Soil samples were digested following ISO 11466 Standard
Method [26] with slight modification [27]. Soil material Plant samples were digested following Standard Method
was oven-dried and lightly ground in an agate mortar 3030 [29]. Washed spinach plants (edible parts only) were
and pestle. Five grams soil was transferred to a beaker and oven-dried at 105 °C in an aluminum bowl. Two g of dried
10 mL of 65% (w/v) ­HNO3 and 37% (w/v) HCl in a 1:3 ratio pulverized plant tissue was placed in a flask followed by

Vol.:(0123456789)
Research Article SN Applied Sciences (2020) 2:1915 | [Link]

addition of 2–3 mL distilled water, and 25 mL of 65% (w/v) soil [3, 31, 32]. Four categories express the contamination
­HNO3, and the mixture was stored for 24 h. The flask was factor: CFi< 1 indicates a low contamination factor, i.e., low
subsequently heated to boiling for 2 h. After cooling, soil contamination; 1 ≤ CFi< 3 is moderate contamination;
10 mL of 70% (w/v) perchloric acid was added to the flask 3 ≤ CFi< 6 is considerable contamination; and 6 ≤ CFi stands
and heated again to boiling for 1 h. The digestion was con- for very high contamination [33, 34].
sidered complete when the color of the solution turned Degree of contamination (Cdeg): This value assesses the
yellow. If the solution remained dark in color, then 2–3 mL concentration of multi-metal contamination in soil, where
of 65% (w/v) ­HNO3 was added and heat was re-applied. the contamination factor accounts for the concentration of
The process was repeated until the yellow color appeared. a single metal [3, 33]. The value embraces the total metal
The digested solution was filtered through a 0.45 µm filter contamination at a sampling point. The equation is:
and collected in plastic bottles for determination of Cr, Pb, ∞
Cu, Zn, Ni, and Cd by FAAS following Standard Method
∑
Cdeg = CF i (2)
3111 [28]. i=1

2.4 Leaching test where CFi is the contamination factor of the metal in the
study area. According to Hakanson [33], Cdeg < 8 represents
For evaluating the risks from leaching of heavy metals, a low degree of contamination; 8 ≤ Cdeg < 16 represents
the Toxicity Characteristics Leaching Procedure (TCLP) moderate contamination; 16 ≤ Cdeg < 32 represents con-
was used in accordance with USEPA Method 1311 [30]. siderable contamination; and 32 ≤ Cdeg represents a very
Dried and pulverized soil samples which passed through high degree of contamination.
a 9.5 mm mesh standard sieve were placed into a glass cyl- Pollution load index (PLI): The PLI, proposed by Tomlin-
inder. An acetic acid solution (0.57% v/v) was added to the son [35], is used to assess the extent of pollutants (heavy
samples in a 20:1 ratio. The pH of the extraction fluid was metals in this case) of a particular location [3]. PLI is cal-
adjusted to 2.88 ± 0.05. After rotating the cylinder for 18 h culated by obtaining the n-th root of the product of CFs
at 30 ± 2 rpm, the leachate was filtered through a 0.45 µm obtained for n number of metals as follows:
filter, and ­HNO3 added to maintain filtrate pH at less than √
(3)
n
PLI = CF 1 × CF 2 × CF 3 × ⋯ × CF n
2. The extracts were analyzed for Cr, Pb, Zn, Cu, and Ni by
FAAS (Shimadzu AA 6800). A site is designated as polluted when the PLI value > 1.
Geoaccumulation index (Igeo): The index of geoaccu-
2.5 Data analysis mulation, first proposed by Muller [36] is used to assess
the degree of soil contamination of the selected area; it
Heavy metal spatial distribution maps were generated compares the measured heavy metal content against the
using ArcGIS 10.6.1™ employing an Inverse Distance background concentrations of that element:
Weighted (IDW) interpolation method. Pairwise correla-
Cn
[ ]
tion of heavy metal concentrations was performed using Igeo = log2 (4)
1.5 × B n
Microsoft Excel.
where Cn is the measured metal concentration of the soil
2.6 Factors for ecological risk analysis sample and Bn is the standard background concentra-
tion of element n. The numerical factor 1.5 is applied to
Contamination factor (CFi): The estimate of heavy metal account for possible variations in background values of a
contamination and enrichment of metal in soil was metal due to the lithological differences as well as anthro-
assessed by the contamination factor (CFi), denoted as: pogenic influences. Igeo is classified into seven categories:
Igeo ≤ 0 represents unpolluted; 0 < Igeo ≤ 1 slightly polluted;
Ci
CF i = (1) 1 < Igeo ≤ 2 moderately polluted; 2 < Igeo ≤ 3 moderately to
Bi
severely polluted; 3 < Igeo ≤ 4 severely polluted; 4 < Igeo ≤ 5
where Ci is the metal concentration of the soil sample severely to extremely polluted; and 5 < Igeo ≤ 6 extremely
and Bi is the standard background concentration of the polluted [3, 34, 36].
i-th element. In this study, the standard background value Ecological risk factor (Eri): The ecological risk factor (Eri) is
was derived from the average of three different, widely used to determine the ecological risk of an area contami-
accepted background values: (1) the average concentra- nated with heavy metals [3]. This risk assessment method
tion in shale; (2) the average crustal content of the earth; has been widely used to determine the impact of heavy
and (3) the worldwide mean concentration of the metal in metal contamination [37, 38] and is expressed by:

Vol:.(1234567890)
SN Applied Sciences (2020) 2:1915 | [Link] Research Article

(5) CS × SA × AF × ABSd × IngR × EF × ED

Er i = T i × CF i CDIdermal = × CF
BW × AT
where Ti is the toxic response factor of the metal, and CFi (9)
is the contamination factor of the metal. The Ti value of CS × InhR × EF × ED
Pb, Cr, Zn, Cu, and Ni are, respectively, 5, 2, 1, 5, and 5, CDIinh = × CF (10)
BW × AT
as evaluated by Hakanson [33]. The risk factor has five
categories: Eri< 40 represents a low potential ecologi- CDI
cal risk; 40 ≤ Eri< 80 a moderate potential ecological risk; HQ = (11)
RfD
80 ≤ Eri< 160 a considerable potential ecological risk;
160 ≤ Eri< 320 a high potential ecological risk, and Eri ≥ 320 ∑
a very high ecological risk. HI = HQ = HQing + HQdermal + HQinh
Ecological risk index (RI): The RI is the summation of risk CDIing CDIdermal CDIinh (12)
factors (Eri) for the location. RI is used to represent the tox- = + +
RfDing RfDdermal RfDinh
icity of the heavy metal and the environmental response
of Cr, Zn, Cu, Pb, and Ni in the study area [34]: where, CS represents heavy metal concentration in soil.
∞ The other parameters, units, and standard values used for
evaluating non-carcinogenic risks appear in Table 2. Cal-
∑
RI = Er i (6)
i=1 culation of HQ was performed by dividing the CDI with
the corresponding reference doses (RfD) of different met-
RI < 150 represents low ecological risk; 150 ≤ RI < 300 als (Pb, Cr and Cu) (Table 2). A value of HQ lower than 1
moderate ecological risk; 300 ≤ RI < 600 considerable eco- indicates no significant human health risk, and HQ greater
logical risk; and RI ≥ 600 very high ecological risk [34]. than 1 indicates a potentially serious health risk. Cumu-
Transfer Factor (TF): The transfer factor is used to assess lative non-cancer hazard HI was calculated by summing
heavy metal uptake by plants. In this study, the transfer the HQ of ingestion, dermal, and inhalation. When the
factor of five metals was determined from the edible part value of HI exceeds unity it indicates an extreme health
of plants grown in contaminated soil. The following equa- risk. Increasing trends of HI raise the probability of non-
tion is used to calculate TF [39]: carcinogenic risks accordingly [46].
Concentration of metal in edible part Carcinogenic risk analysis for adults and children: Deter-
TF = (7) mination of carcinogenic risk to humans was calculated by
Concentration of metal in soil
Eqs. 13–16 [40, 43–45]:

2.7 Human exposure and health risk assessment CRing =

CS × AF × IngR × EF × ED × CF × CSFing
(13)
BW × AT
Non-carcinogenic health risk assessment method: Human
exposure and health risk assessment is a multi-step pro- CS × SA × AF × ABSd × EF × ED × CF × CSFing × ABSGI
cess that includes determination of chronic daily intake CRdermal =
BW × AT
(CDI), Hazard quotient (HQ), Hazard index (HI), Carcino- (14)
genic Risk (CR), and risk characterization [40]. In this case, CS × ET × EF × ED × IUR
we estimated the exposure due to the intrusion of heavy CRinh = × 103 (15)
PEF × 24 × AT
metal from the soil through various pathways. Heavy metal
entry into the human body can occur via oral ingestion ∑
Total carcinogenic risk (CRtotal ) = Risk = CRing + CRdermal + CRinh
(CDIing), absorption through exposed skin (CDIdermal), and
(16)
inhalation (CDIinh) [41]. Ingestion of Pb, Cr, Cu, Cd, and Ni
from soil is considered the main human exposure path- where CRing, CRdermal and CRinh represent cancer risk via
way [42]. Both non-carcinogenic and carcinogenic risks ingestion, dermal contact and inhalation from soil, succes-
were calculated for adult and child residents of the study sively. The total cancer risk (CRtotal) posed by heavy metals,
area. For assessing non-carcinogenic risks of human health as indicated by Eq. 16, is the summation of risks posed by
(adult and child), Eqs. 8–12 were used [40, 43–45]. the three pathways. Opinions are divided as to what con-
stitutes ‘acceptable risk’ for carcinogenic effects. A cancer
CDIing =
CS × IngR × EF × ED
× CF (8) risk (CRtotal) lower than 1 × 10−6 (1 in 10,00,000 probability
BW × AT of developing cancer) indicates negligible risk, and CRtotal
greater than ­10−6 is considered unacceptable by many
international health regulatory bodies [41, 43]. Other

Vol.:(0123456789)
Research Article SN Applied Sciences (2020) 2:1915 | [Link]

Table 2  Parameters for human Parameters Units Value (Resident) References

exposure and health risk
assessment of contaminated Adult Child
soil of former tannery areas
−1
Ingestion rate (IngR) mg ­d 100 200 [40]
Exposure frequency (EF) d ­yr−1 350 350 [40]
Exposure duration (ED) Yr 30 6 [40]
Average body weight (BW) Kg 70 15 [49]
Average time (AT = 365xED) Yr 10950 2190 [40]
Conversion factor (CF) kg ­mg−1 10−6 10−6 [50]
2
Exposure skin area (SA) cm 5700 1600 [49]
Adherence factor (AF) mg ­cm−2 0.07 0.2 [40]
Dermal absorption factor ­(ABSd) Unitless 0.001 for all metals except [49]
As
Inhalation rate (InhR) m3d−1 20 [44]
Chronic oral slope factor ­(CSFing) (mg kg−1 ­d−1)−1 Pb = 0.0085 [40]
Cr = 4.1
Gastrointestinal absorption factor ­(ABSGI) Unitless Pb = 1 [49]
Cr = 0.013
Particle emission factor (PEF) soil to air m3 ­kg−1 1.36 × 109 [40], [49]
Chronic inhalation unit risk (IUR) (μg m−3)−1 Pb = 0.000012 [40]
Cr = 0.012
Exposure time (ET) h ­d−1 24 [40]
Reference dose (RfD) for ingestion, inhala- mg ­kg−1 ­d−1 Cr = 0.003 [40], [50]
tion and dermal Pb = 0.0035
Cu = 0.04

studies have indicated the range 1 × 10−6 < CR ≤ 1 × 10−4 to 3.2 Spatial distribution of heavy metals
be an acceptable level for carcinogenic risk [47, 48] though
CRtotal = 10−6 is considered unacceptable by USEPA [49]. For The relative abundance and spatial distribution of Pb, Cr,
risk assessment of heavy metal contamination in Hazari- Zn, Cu, Ni, and Cd in Hazaribagh are shown in Table 3 and
bagh soil, we assumed a less conservative threshold – we Fig. 2. We compared heavy metal concentrations with the
considered CRtotal < 1 × 10−4 to be an acceptable level of soil contaminant thresholds of Finland and China [51,
risk. 52]. The Ministry of Environment (MoE) of Finland recom-
mends contaminant remediation when one or more harm-
ful substances in the soil exceeds the threshold concentra-
3 Results and Discussion tion. All sites except L5, L8, and L11, were contaminated
with high concentrations of chromium ranging from 294
3.1 Soil properties to 23,148 mg/kg, which exceeded the maximum per-
missible concentration (MPC) for both Finland (100 mg/
Soil pH averaged 7.6 (range 6.9-8.3) (Table 3). The alka- kg) and China (200 mg/kg). The average Cr concentra-
line pH of the topsoil may be a consequence of the dis- tion in the study area was 4321 mg/kg (Table 3), which is
posal of spent lime liquor used in the liming operations approximately 22- and 43-fold higher than the restriction
of leather processing. The high pH of sites L5-L10 is likely limit set by China and Finland, respectively. Location L1
the result of dumping of limed fleshing (a portion of hides (23,148 mg/kg) and L6 (12682 mg/kg) are the most con-
and skins containing lime solution separated after fleshing taminated with respect to Cr among all other locations.
operation) in these areas for storage and final disposal. This may be due to the use of these areas as dumping
Other studies have shown similar pH values in Hazaribagh grounds for chrome shaving scraps, trimmings and buff-
soil [15, 25]. The organic matter content varied from 3 to ing dust. Additionally, the canal that flowed beside these
12%. Solid waste containing organic matter from leather sites and carried untreated effluent overflowed frequently
industries and untreated tannery effluents is the probable during periods of heavy rain when production was at full
source of this high-soil organic content. capacity. Sites L2, L7,and L10 also had significantly high-
Cr concentrations (2440–2900 mg/kg) due to proximity to
effluent discharge points. L1, L2, and L6 were previously

Vol:.(1234567890)
SN Applied Sciences (2020) 2:1915 | [Link] Research Article

Table 3  pH, organic content (OC) (%) and heavy metal concentrations (mg/kg) of soils in Hazaribagh
Sample pH OC Pb Cr Zn Cu Ni Cd

L1 7.4 11.5 52.4 ± 1.1 23,148 ± 48.6 558.9 ± 2.75 66.3 ± 0.2 4.05 ± 0.07 n.d
L2 7.0 7.3 59.6 ± 1.1 2438.9 ± 10.8 193.7 ± 1.13 271.8 ± 0.28 19.9 ± 0.42 n.d
L3 7.7 12 70.6 ± 1.1 1458 ± 3.67 250.9 ± 1.34 115 ± 0.28 8.65 ± 0.21 n.d
L4 7.5 10.7 61.25 ± 1.2 1834.8 ± 3.67 304 ± 1.2 58.25 ± 7.40 8.45 ± 0.49 n.d
L5 7.8 11 61.5 ± 0.1 34.85 ± 2.19 327.1 ± 2.67 323.2 ± 0.56 9 ± 0.56 n.d
L6 8.2 9.5 23.95 ± 0.77 12,682 ± 51.56 53.75 ± 1.76 35.9 ± 0.14 3 ± 0.42 n.d
L7 7.9 11.4 130 ± 0.77 2492.6 ± 10.8 1034 ± 14.56 301 ± 0.07 12.25 ± 0.21 n.d
L8 8.3 7.8 16.75 ± 0.77 115.8 ± 5.25 77.8 ± 2.26 32.5 ± 0.28 6.6 ± 0.14 n.d
L9 7.8 6.7 15.7 ± 1.5 294.6 ± 10.88 20 ± 1.2 30 ± 0.12 5.55 ± 0.07 n.d
L10 6.9 8.6 62.9 ± 0.42 2888.9 ± 0.2 210.35 ± 0.77 75.5 ± 0.42 9.85 ± 0.35 n.d
L11 7.1 3.1 41.9 ± 0.42 145.45 ± 7.28 127.5 ± 32.4 133.05 ± 2.1 9.25 ± 0.92 n.d
Mean 7.6 9.1 54 4321 287 131 9 –
Background value [3] – – 19.66 ± 5.50 90.66 ± 44.73 75.66 ± 17.21 38 ± 21.3 35.33 ± 28.30 1.56 ± 1.35
China limit [51] – – 120 200 250 100 100 0.3
MoE, Finland [52] – – 60 100 200 100 50 1

n.d: not detected; detection limit of Cd is > 0.001 mg/l

storage locations for Cr-rich solid wastes, which were used was reported by researchers in India [55], Pakistan [5], and
to make glue and gelatine. Previous studies found similar Italy [56]. Heavy metal concentration several orders of
levels of Cr (1000–30,000 mg/kg) in soil near discharge magnitude over established background levels as well as
canals and solid waste disposal sites and indicated the high spatial variation indicate the consequences of anthro-
possibility of Cr leaching to groundwater [11, 15, 25, 53]. pogenic activities modulating the local environment. In
Almost all Cr accumulated in the soils occurred as Cr(III) the Hazaribagh former tannery area, there were localized
[54], and only insignificant quantities of Cr were available discharges of heavy metal-containing wastes, both con-
as Cr(VI) [25]. The soil of the Hazaribagh area had insig- tinuous and sporadic. Therefore, in addition to the overall
nificant quantities of MnO (0.1–0.08%) which does not high-concentration heavy metals, hotspots having high
change appreciably with depth [25]. This indicates that concentrations of Cr, Pb, Cu, and Zn were found (Fig. 2).
catalytic oxidation of Cr(III) to Cr(VI) by MnO may not be
occurring, and Cr(III) remains the dominant form of Cr. 3.3 Correlation among heavy metals
Soil Cu concentrations were highest in locations L2,
L3, L5, L7, and L11, exceeding both Finland and China A significant positive correlation was detected among
regulatory limits of 100 mg/kg (Fig. 2). Additionally, Cu soil Pd, Zn, Cu, and Ni (Table 4). Cadmium was excluded
concentrations in all the sites except L6, L8, and L9 were from analysis as concentrations were below detection lev-
higher than background values. Soil Zn distribution is simi- els. Chromium was negatively correlated with all metals
lar to those of Cu; locations L1 (559 mg/kg), L3 (251 mg/ except Zn, which may imply that Cr and the other metals
kg), L4 (304 mg/kg), L5 (327 mg/kg), and L7 (1034 mg/kg) (Pb, Cu, and Ni) may not originate from the same source.
exceeded the Finland and China standards (Table 3). Soil This supports the suggestion that the abundance of Cr
Pb concentration ranged from 16 to 130 mg/kg with a in soil is due to specific anthropogenic activities such as
mean of 54 mg/kg (Table 3). Soil L3 (71 mg/kg), L4 (61 mg/ chrome tanning and re-tanning operations during leather
kg), L5 (62 mg/kg), L7 (130 mg/kg), and L10 (63 mg/kg) processing. Sources of soil Pb, Zn, Cu, and Ni are primarily
exceeded the Finland standard. Except for L7 (130 mg/kg) anthropogenic activities (battery disposal, alloy making)
all concentrations were below the MPC of China, though other than the tanning operations, though Pb and Zn can
significantly higher than the standard background value. arise from pigments used in tanning [15]. In addition, salts
Similar concentration ranges of Pb have been determined of Cu and Ni are used for dye mordanting (a process where
in previous studies [25]. The impact of Ni and Cd is consid- metal salt form metal complexes in dye molecule to act as
ered negligible as their concentrations were far below the a link between leather and dye thus modifying the final
international benchmark for background values. Spatial color of the dye) and thereby used in leather dyeing when
variation of heavy metals in soil of tannery industrial areas the desired color is expected [57]. This practice is currently

Vol.:(0123456789)
Research Article SN Applied Sciences (2020) 2:1915 | [Link]

Fig. 2  Spatial distribution of Cr, Cu, Zn, Pb, and Ni in the soil of Hazaribagh

Table 4  Pearson correlation coefficient for heavy metals in soil applied with lower frequency in tannery industries, lead-
(Correlation is significant at p < 0.05) ing to negligible Cu and Ni contributions from tanneries.
Pb Cr Zn Cu Ni
3.4 Contamination factor
Pb 1
Cr −0.078 1
The contamination factor (CFi) values indicate that all
Zn 0.884 0.220 1
sites were enriched in metals (Table 5). The CF value of
Cu 0.676 −0.283 0.539 1
Cr for locations L1, L2, L3, L4, L6, L7, and L10 exceeded
Ni 0.490 −0.444 0.210 0.692 1
6, indicating very high contamination. During leather

Vol:.(1234567890)
SN Applied Sciences (2020) 2:1915 | [Link] Research Article

Table 5  Contamination factor Samples Pb Cr Zn Cu Ni

(CFi) and Geoaccumulation
index (Igeo) of metals in soils L1 2.67 (0.83) +++
255.33** (7.41 ) 7.39** (2.30) 1.74 (0.22) 0.11 (−3.71)
of Hazaribagh tannery area
L2 3.03* (1.02) 26.90** (4.16++) 2.56 (0.77) 7.15** (2.25) 0.56 (−1.41)
(values in parentheses indicate
Igeo value) L3 3.59* (1.26) 16.08** (3.42+) 3.32* (1.14) 3.03* (1.01) 0.24 (−2.62)
L4 3.12* (1.05) 20.24** (3.75+) 4.02* (1.42) 1.53 (0.03) 0.24 (−2.65)
L5 3.13* (1.06) 0.38 (−1.96) 4.32* (1.53) 8.51** (2.50) 0.25 (−2.56)
L6 1.22 (−0.30) 139.89** (6.54+++) 0.71 (−1.08) 0.94 (−0.67) 0.08 (−4.14)
L7 6.61** (2.14) 27.49** (4.20++) 13.67** (3.19+) 7.92** (2.40) 0.35 (−2.11)
L8 0.85 (−0.82) 1.28 (−0.23) 1.03 (−0.54) 0.86 (−0.81) 0.19 (−3.01)
L9 0.80 (−0.91) 3.25 (1.12) 0.26 (−2.50) 0.79 (−0.93) 0.16 (−3.26)
L10 3.20* (1.09) 31.87** (4.41++) 2.78 (0.89) 1.99 (0.41) 0.28 (−2.43)
L11 2.13 (0.51) 1.60 (0.10) 1.69 (0.17) 3.50* (1.22) 0.26 (−2.52)

*Considerable contamination (3 ≤ CF i< 6); **Very high contamination (6 ≤ CFi); +Severely polluted
(3 < Igeo ≤ 4); ++Severely to extremely polluted (4 < Igeo ≤ 5); +++Extremely polluted (5 < Igeo ≤ 6)

processing, wastewater containing about 40–50% basic than for Cr. Six sites fall into the moderately polluted cat-
chromium sulfate was discharged in surrounding low-lying egory for Pb (Igeo = 1.02–2.14). Five sites are designated
areas and lagoons, resulting in Cr enrichment [15]. Most as moderately to severely polluted for Zn (Igeo = 1.14-3.19).
sampling points show moderate to considerable Pb con- The level of contamination for Cu is found to be some-
tamination, while L7 possesses very high contamination. what lower (Igeo = 1.01-2.50). The Igeo value obtained for
The Pb enrichment may originate from small-scale paint Ni is less than 0, which implies that it imparts no signifi-
or coating factories, workshops, battery recycling and dis- cant health hazard. Based on Igeo values, the major con-
posal, and glazing of ceramics in the study area [25]. Lead taminants in Hazaribagh soil are arranged in the order:
contamination may also occur from the use of pigments Cr > Zn > Cu > Pb > Ni. A similar order of contaminants was
in tanning. Five sites have moderate to very high con- observed by Karim et al. [15].
tamination with Zn and Cu, while the remainder exhibit
low to moderate contamination. Zinc may have origi- 3.6 Ecological risk factor and risk index
nated from galvanization of automobiles and use in zinc
alloy factories, whereas Cu may have resulted from wire Average and maximum ecological risk (Er) values for
disposal and its use in various machine parts and alloys. Pb, Zn, and Ni were under 40 (Eq. 5), indicating low
None of the study locations were enriched with Ni. The potential ecological risk for all sites. The maximum
order of heavy metal contamination in the soils is ranked Er value for Cu exceeded 40, indicating a moderate
as Cr > Zn > Cu > Pb > Ni. risk. On the other hand, the average Er of Cr was more
than 95, which denotes considerable risk for the study
3.5 Pollution load index, degree of contamination area. More than half the sites of the eleven sampling
and geo‑accumulation index locations exhibited low to very high ecological risk
posed by Cr (maximum Er of Cr is 511). The higher
The degree of contamination (Cdeg) ranged from 4 to 267 ecological risk from Cr is due to its elevated concen-
(Fig. 3a), indicating low to a very high degree of contami- tration in soil.
nation by metals. Five sampling locations (L1, L2, L6, L7, The ecological risk index (RI) for most sites was below
and L10) exhibited a very high degree of contamination 150, which indicates low ecological risk (Fig. 4). Location
(Cdeg> 32). This suggests that soil in these sites pose a risk L6 has a moderate risk (RI = 292) and L1 possesses con-
to local inhabitants and surrounding flora and fauna. The siderable risk (RI = 541), indicating a potentially toxic envi-
PLI values for all sites except L8 and L9 were greater than 1 ronment for residents. The main contributors to the high
(Fig. 3b), indicating that most of the sampling sites in the for- RI are Cr and Cu as indicated by Er values. The risk posed
mer tannery estate of Hazaribagh are polluted with heavy by heavy metals in Hazaribagh soil, as shown by RI, is of
metals. Table 5 delineates the geoaccumulation index (Igeo) concern for the area. This is because the city authority is
of metals for the study area. The value of Igeo for Cr is greater planning for residences, hospitals, educational institutions,
than 3 for 7 out of 11 sites, indicating severe pollution. and recreational facilities in the area. The current residents
Those sites polluted by Cr are also affected by Pb also live near the old establishments. Therefore, exposure
(Table 5), although the level of pollution is less severe

Vol.:(0123456789)
Research Article SN Applied Sciences (2020) 2:1915 | [Link]

Fig. 3  Degree of contamina- (a)

tion a and pollution load index
b of 11 sampling sites in the
Hazaribagh tannery area

(b)

Vol:.(1234567890)
SN Applied Sciences (2020) 2:1915 | [Link] Research Article

Fig. 4  Ecological risk index (RI) 600

of heavy metals in soil of the
Hazaribagh tannery area
450 Considerable Risk

RI
300

Moderate Risk

150
Low Risk

0
L1 L2 L3 L4 L5 L6 L7 L8 L9 L10 L11
Sampling sites

to these soils through ingestion or inhalation may result the exposure pathways is ­C R ing (1.70 × 10 −3) > CR inh
in harm to current and future residents [9]. (3.66 × 10−5) > CRdermal (1.26 × 10−6) for adults and C ­ Ring
(4.53 × 10−2) > CRinh (3.66 × 10−5) > CRdermal (4.71 × 10−6) for
3.7 Non‑carcinogenic and carcinogenic risks children. This indicates that oral ingestion of metals is the
from soil metals dominant exposure pathway for both adults and children
(97.82% and 99.91% contribution, respectively), which
The non-carcinogenic hazard index (HI) was estimated for concur with other research [58, 59]. The order of Pb contri-
ingestion, dermal contact and inhalation of metal- (Pb, bution for children and adults was: ­CRing > CRdermal > CRinh
Cr and Cu) contaminated soil using Eq. 12 (Table 6). The (Table 7). Therefore, dermal contact and inhalation had a
order and intensity of non-carcinogenic hazard (expressed minimal contribution to cancer risk for both adults and
as HQ) posed by all heavy metals through the exposure children in the affected area.
pathways is HQing (18.66) > HQdermal (5.97) > HQinh (1.86) for The carcinogenic risk value (Cr and Pb combined)
children and HQdermal (7.98)  > HQing (2.0) > HQinh (0.4) for ranges from 4.66 × 10−5 to 9.30 × 10−3 (mean 1.74 × 10−3)
adults. The cumulative HI in eleven sampling sites ranges for adults and from 3.67 × 10 −4 to 2.43 × 10 −1 (mean
from 0.68-140 (mean = 26.5) for children and 0.27-55 4.53 × 10−2) for children; this implies that risks to children
(mean = 10.37) for adults. These values, being far greater are 26-fold higher than that for adult populations (Fig. 5b,
than unity, signify a significant non-carcinogenic threat for Table 7). Chromium constituted the maximum carcino-
both child and adult health. The non-carcinogenic risk to genic risk (99.98% contribution compared to 0.02% from
children is almost three times that of adults (Fig. 5a), which Pb). Most of the computed carcinogenic values for Cr are
is consistent with studies conducted elsewhere [58, 59]. greatly in excess of the threshold limit of 1 × 10−4, whereas
The contribution by Cr, Pb, and Cu to non-carcinogenic the carcinogenic risk posed by Pb rarely exceeds 1 × 10−6.
health risk is 98.71%, 1.06% and 0.23%, respectively, for This indicates that Cr should be prioritized in risk manage-
both children and adults. The oral ingestion route posed ment measures in Hazaribagh former tannery area.
the maximum contribution (70%) to non-carcinogenic risk
for adults, whereas dermal contact had the greatest contri- 3.8 Mobility of heavy metals in soil
bution (77%) for children. The contribution by inhalation
was minimal (7% for adults, 4% for children). The average TCLP concentrations of Cr, Pb, Zn, Cu, and
Both US EPA [50] and WHO [60] categorized Cr as Ni were 0.05, 0.09, 0.37, 0.06 and 0.01 mg/l, respectively
human carcinogen (group A), and Pb as probable human (Table 8). No metal tested in this study exceeded the EPA
carcinogen (group B). Other metals (Cu, Zn) do not pose regulatory limit for maximum concentration of contami-
a cancer risk. Although Ni contributes to some carcino- nants for toxicity. The TCLP concentration of Cr comprised
genic risk, soil Ni concentrations were far below all MPCs. only 0.03% of the total Cr obtained from H ­ NO3/HCl extrac-
Therefore, only the carcinogenicity of Cr and Pb were tion. Therefore, although Cr is present in very high con-
investigated. Table 7 shows the individual and combined centrations in soil, only a small fraction may be mobilized
cancer risk to both adults and children for Cr and Pb via by rainwater and result in groundwater contamination.
ingestion, dermal and inhalation pathways. The order Karim et al. [15] found similar leaching behavior for soil
and intensity of carcinogenic risks posed by Cr through Cr in the Hazaribagh area. Among all metals, Zinc was the

Vol.:(0123456789)
Vol:.(1234567890)
Research Article

Table 6  Hazard Index (HI) of heavy metals via ingestion, dermal contact, and inhalation of soil
Sampling site Group Cr HICr Pb HIPb Cu HICu HItotal (Cr + Pb + Cu)
HQing HQdermal HQinh HQing HQdermal HQinh HQing HQdermal HQinh

L1 Adult 10.570 42.174 2.114 54.858 0.021 0.082 0.004 0.107 0.002 0.009 0.000 0.011 54.976
Child 98.652 31.569 9.865 140.086 0.191 0.061 0.019 0.271 0.021 0.007 0.002 0.030 140.387
L2 Adult 1.114 4.443 0.223 5.780 0.023 0.093 0.005 0.121 0.009 0.037 0.002 0.048 5.949
Child 10.394 3.326 1.039 14.759 0.218 0.070 0.022 0.310 0.087 0.028 0.009 0.124 15.193
L3 Adult 0.666 2.656 0.133 3.455 0.028 0.110 0.006 0.144 0.004 0.016 0.001 0.021 3.620
Child 6.214 1.988 0.621 8.823 0.258 0.083 0.026 0.367 0.037 0.012 0.004 0.053 9.243
L4 Adult 0.838 3.343 0.168 4.349 0.024 0.096 0.005 0.125 0.002 0.008 0.000 0.010 4.484
Child 7.820 2.502 0.782 11.104 0.224 0.072 0.022 0.318 0.019 0.006 0.002 0.027 11.449
L5 Adult 0.016 0.063 0.003 0.082 0.024 0.096 0.005 0.125 0.011 0.044 0.002 0.057 0.264
Child 0.149 0.048 0.015 0.212 0.225 0.072 0.022 0.319 0.103 0.033 0.010 0.146 0.677
L6 Adult 5.791 23.106 1.158 30.055 0.009 0.037 0.002 0.048 0.001 0.005 0.000 0.006 30.109
Child 54.048 17.295 5.405 76.748 0.087 0.028 0.009 0.124 0.011 0.004 0.001 0.016 76.888
L7 Adult 1.138 4.541 0.228 5.907 0.051 0.203 0.010 0.264 0.010 0.041 0.002 0.053 6.224
Child 10.623 3.399 1.062 15.084 0.475 0.152 0.047 0.674 0.096 0.031 0.010 0.137 15.895
L8 Adult 0.053 0.211 0.011 0.275 0.007 0.026 0.001 0.034 0.001 0.004 0.000 0.005 0.314
Child 0.494 0.158 0.049 0.701 0.061 0.020 0.006 0.087 0.010 0.003 0.001 0.014 0.802
L9 Adult 0.135 0.537 0.027 0.699 0.006 0.025 0.001 0.032 0.001 0.004 0.000 0.005 0.736
Child 1.256 0.402 0.126 1.784 0.057 0.018 0.006 0.081 0.010 0.003 0.001 0.014 1.879
L10 Adult 1.319 5.263 0.264 6.846 0.025 0.098 0.005 0.128 0.003 0.010 0.001 0.014 6.988
Child 12.312 3.940 1.231 17.483 0.230 0.074 0.023 0.327 0.024 0.008 0.002 0.034 17.844
L11 Adult 0.066 0.265 0.013 0.344 0.016 0.065 0.003 0.084 0.005 0.018 0.001 0.024 0.452
Child 0.620 0.198 0.062 0.880 0.153 0.049 0.015 0.217 0.043 0.014 0.004 0.061 1.158
Mean Adult 1.973 7.873 0.395 10.241 0.021 0.085 0.004 0.110 0.004 0.018 0.001 0.023 10.374
Child 18.417 5.893 1.842 26.151 0.198 0.064 0.020 0.281 0.042 0.014 0.004 0.060 26.492
SN Applied Sciences (2020) 2:1915 | [Link]
SN Applied Sciences (2020) 2:1915 | [Link] Research Article

Fig. 5  a Box-whisker plot of

total Hazard Index for Cr, Pb,
and Cu in the Hazaribagh
tannery area, indicating that
children are at a higher risk of
non-carcinogenic effects due
to presence of heavy metals in
the soil; and b Total Cancer Risk
for Cr and Pb. This graph also
shows that children are more
susceptible to developing
cancer than are adults

Table 7  Carcinogenic risk (CR) of heavy metals via ingestion, dermal contact, and inhalation of soil
Sampling site Group Cr CRtotal(Cr) Pb CRtotal(Pb) CRcombined (Cr + Pb)
CRing CRdermal CRinh CRing CRdermal CRinh

L1 Adult 9.10E − 03 6.74E − 06 1.96E − 04 9.30E − 03 4.27E − 08 2.43E − 09 4.43E − 10 4.56E − 08 9.30E − 03
Child 2.43E − 01 2.52E − 05 1.96E − 04 2.43E − 01 1.14E − 06 9.11E − 09 4.43E − 10 1.15E − 06 2.43E − 01
L2 Adult 9.59E − 04 7.11E − 07 2.06E − 05 9.80E − 04 4.86E − 08 2.77E − 09 5.04E − 10 5.19E − 08 9.80E − 04
Child 2.56E − 02 2.66E − 06 2.06E − 05 2.56E − 02 1.30E − 06 1.04E − 08 5.04E − 10 1.31E − 06 2.56E − 02
L3 Adult 5.73E − 04 4.25E − 07 1.23E − 05 5.86E − 04 5.75E − 08 3.28E − 09 5.97E − 10 6.14E − 08 5.86E − 04
Child 1.53E − 02 1.59E − 06 1.23E − 05 1.53E − 02 1.53E − 06 1.23E − 08 5.97E − 10 1.55E − 06 1.53E − 02
L4 Adult 7.21E − 04 5.35E − 07 1.55E − 05 7.37E − 04 4.99E − 08 2.85E − 09 5.18E − 10 5.33E − 08 7.37E − 04
Child 1.92E − 02 2.00E − 06 1.55E − 05 1.93E − 02 1.33E − 06 1.07E − 08 5.18E − 10 1.34E − 06 1.93E − 02
L5 Adult 1.37E − 05 1.02E − 08 2.95E − 07 1.40E − 05 5.01E − 08 2.86E − 09 5.20E − 10 5.35E − 08 1.41E − 05
Child 3.65E − 04 3.80E − 08 2.95E − 07 3.66E − 04 1.34E − 06 1.07E − 08 5.20E − 10 1.35E − 06 3.67E − 04
L6 Adult 4.99E − 03 3.69E − 06 1.07E − 04 5.10E − 03 1.95E − 08 1.11E − 09 2.03E − 10 2.08E − 08 5.10E − 03
Child 1.33E − 01 1.38E − 05 1.07E − 04 1.33E − 01 5.21E − 07 4.16E − 09 2.03E − 10 5.25E − 07 1.33E − 01
L7 Adult 9.80E − 04 7.26E − 07 2.11E − 05 1.00E − 03 1.06E − 07 6.04E − 09 1.10E − 09 1.13E − 07 1.00E − 03
Child 2.61E − 02 2.72E − 06 2.11E − 05 2.62E − 02 2.83E − 06 2.26E − 08 1.10E − 09 2.85E − 06 2.62E − 02
L8 Adult 4.55E − 05 3.37E − 08 9.80E − 07 4.65E − 05 1.37E − 08 7.78E − 10 1.42E − 10 1.46E − 08 4.66E − 05
Child 1.21E − 03 1.26E − 07 9.80E − 07 1.22E − 03 3.64E − 07 2.91E − 09 1.42E − 10 3.67E − 07 1.22E − 03
L9 Adult 1.16E − 04 8.58E − 08 2.49E − 06 1.18E − 04 1.28E − 08 7.29E − 10 1.33E − 10 1.37E − 08 1.18E − 04
Child 3.09E − 03 3.21E − 07 2.49E − 06 3.09E − 03 3.41E − 07 2.73E − 09 1.33E − 10 3.44E − 07 3.09E − 03
L10 Adult 1.14E − 03 8.42E − 07 2.44E − 05 1.16E − 03 5.13E − 08 2.92E − 09 5.32E − 10 5.47E − 08 1.16E − 03
Child 3.03E − 02 3.15E − 06 2.44E − 05 3.03E − 02 1.37E − 06 1.09E − 08 5.32E − 10 1.38E − 06 3.03E − 02
L11 Adult 5.72E − 05 4.24E − 08 1.23E − 06 5.85E − 05 3.42E − 08 1.95E − 09 3.55E − 10 3.65E − 08 5.85E − 05
Child 1.52E − 03 1.59E − 07 1.23E − 06 1.53E − 03 9.11E − 07 7.29E − 09 3.55E − 10 9.18E − 07 1.53E − 03
Mean Adult 1.70E − 03 1.26E − 06 3.66E − 05 1.74E − 03 4.42E − 08 2.52E − 09 4.59E − 10 4.72E − 08 1.74E − 03
Child 4.53E − 02 4.71E − 06 3.66E − 05 4.53E − 02 1.18E − 06 9.43E − 09 4.59E − 10 1.19E − 06 4.53E − 02

most mobile with a relatively higher concentration in the (0.09 mg/l), which corresponds to a 6.13% mobilized frac-
leaching test (0.37 mg/L), and also a higher mobilized frac- tion. Previous studies have also reported Zn and Pb to
tion (4.98%) compared to the acid extraction concentra- be highly mobile metals [61]. These results indicate that
tion. Similarly, high TCLP concentration was found for Pb Pb and Zn pose a potential threat for groundwater pollu-
tion. According to leaching potential, the order of heavy

Vol.:(0123456789)
Research Article SN Applied Sciences (2020) 2:1915 | [Link]

Table 8  Leaching of Cr, Pb, Zn, Heavy metals Average (mg/l) Standard Leaching (%) (relative to USEPA regula-
Cu and Ni from TCLP leaching deviation ­HNO3/HCl extraction) tory ­limita
(mg/l)

Cr 0.05 0.02 0.03 5

Pb 0.09 0.04 6.13 5
Zn 0.37 0.31 4.98 –
Cu 0.06 0.04 1.64 –
Ni 0.01 0.01 4.41 –
a
Environmental Protection Agency (EPA) 40 CFR § 261.24-Toxicity characteristic

Table 9  Heavy metal content Metals L4 L7 L10 Safe limit (FAO/ Safe limit Safe limit
of edible part of vine spinach WHO) [63] (India) [64] (China)
grown on Hazaribagh soil (All [65]
quantities in mg/kg)
Cr 6.1 ± 0.09 178.45 ± 0.80 10.1 ± 0.14 5 20 0.5
Pb 18.6 ± 0.15 14.2 ± 0.23 8.8 ± 0.09 5 2.5 0.3
Zn 66.9 ± 0.10 556.45 ± 1.10 72.6 ± 0.49 60 50 –
Cu 13.2 ± 0.42 27.25 ± 0.28 10.3 ± 0.07 40 30 –
Ni 1.9 ± 0.07 3.5 ± 0.05 1.7 ± 0.03 20 1.5 –

metals can be ranked as: Zn > Pb > Ni > Cu > Cr for the Table 10  Transfer factor of heavy metals in vine spinach grown on
Hazaribagh soil. contaminated soil
Sampling TF
3.9 Heavy metals in plants location
Cr Pb Zn Cu Ni

Heavy metal concentrations in edible parts of spinach L4 0.003 0.304 0.220 0.227 0.225
were variable, with tissue from L7 having the highest con- L7 0.072 0.109 0.538 0.091 0.286
centration (Table 9). The concentration of heavy metals in L10 0.046 2.780 0.409 2.503 0.787
vegetables correlates positively to corresponding concen- Mean 0.040 1.064 0.389 0.940 0.433
trations in soil in the sampling locations (Table 3). Concen-
trations of Pb, Cr, and Zn in plant tissue were several orders
of magnitude in excess of safe limits. Although the soil Zn high concentration in plants could be a result of histori-
concentration is within acceptable limits, the high con- cal accumulation that has occurred over the years. Dur-
centration in vine spinach (66.9–556.45 mg/kg) supports ing our sampling, soil pH was in the range 6.9–8.3, but
earlier findings that Zn bioavailability and mobility is high. there is evidence that soil pH was less than 4 when the
Tissue Cu and Ni concentrations were generally below tanneries were operational [25]. Highly acidic wastes dis-
FAO/WHO acceptable limits, with only Ni exceeding the charged in the environment, and microbial decomposi-
Indian limit (1.5 mg/kg). These results show that, although tion of organic matter could have resulted in low pH in the
soil metal concentrations are within acceptable limits, veg- soil and mobilized Pb, resulting in increased plant uptake.
etables grown on the same soil may accumulate them to Other studies have found high transfer of Pb to plants
levels beyond safe edible limits. Therefore, consuming grown on contaminated soil, and that leafy vegetables
vegetables grown in the study area may impart harmful accumulated higher quantities of Pb than did fruit plants
impacts on human health. Amount of metal uptake and [16, 62]. Copper was the second most mobile metal, with
accumulation is likely to vary with plant species. a maximum TF of 2.503 (mean value = 0.940). On the other
Transfer of metals from soil into different plant parts hand, Cr had the lowest bioavailability (mean TF = 0.040).
can be assessed using the transfer factor (TF). The high- This may be due to the tendency of Cr to bind strongly
est value of TF for Pb was 2.780 (Mean TF = 1.064), indi- with soil colloids [39]. The tendency of metal transfer from
cating that it is the most mobile among all heavy metals soil to plants follows the order: Pb > Cu > Ni > Zn > Cr. These
tested (Table 10). Although it is typically reported that Pb trends are similar to investigations elsewhere [39]. Based
is scarcely soluble in soil, especially at basic pH values, the on the results of this study, it is strongly recommended

Vol:.(1234567890)
SN Applied Sciences (2020) 2:1915 | [Link] Research Article

that inhabitants of Hazaribagh, Dhaka should avoid cul- References

tivating any edible plants in the soil to reduce exposure.
1. Chen HY, Teng YG, Lu SJ, Wang YY, Wang JS (2015) Contamina-
tion features and health risk of soil heavy metals in China. Sci
Total Environ 512–513:143–153. https​://[Link]/10.1016/[Link]​
4 Conclusions tenv.2015.01.025
2. Whitehead PG, Bussi G, Peters R, Hossain MA, Softley L, Shawal
Decades of unregulated industrial activities by tanneries S, Jin L, Rampley CPN, Holdship P, Hope R, Alabaster G (2019)
in the Hazaribagh area of Dhaka have taken a significant Modelling heavy metals in the Buriganga river system, Dhaka,
Bangladesh: impacts of tannery pollution control. Sci Total Envi-
toll on the surrounding environment. In this study, using ron 697:134090. https:​ //[Link]/10.1016/[Link]​ env.2019.13409​
environmental and health indices such as CF, Cdeg, PLI, 0
and Igeo, it was shown that more than half of the area was 3. Joy OC, Uchenna AP (2017) Accumulation and risk assessment
highly or moderately contaminated with Cr, Pb, Zn, and of heavy metal contents in school playgrounds in Port Harcourt
Metropolis, Rivers State, Nigeria. J Chem Health Safety 24:11–22.
Cu. Significant enrichment of Cr occurred presumably due https​://[Link]/10.1016/[Link]​.2017.01.002
to the operation of tanning industries. High soil Cr and 4. Pajević S, Arsenov D, Nikolić N, Borišev M, Orčić D, Župunski M,
Cu concentrations pose a significant ecological risk. The Dukić NM (2018) Heavy metal accumulation in vegetable spe-
total cancer risk for Cr and Pb exceeded the universally cies and health risk assessment in Serbia. Environ Monit Assess
190(459):1–14. https​://[Link]/10.1007/s1066​1-018-6743-y
recognized safe limits (1 × 10−4), rendering the area unsafe 5. Ali Z, Malik RN, Shinwari ZK, Qadir A (2015) Enrichment, risk
for habitation. The potential for leaching of Pb and Zn to assessment, and statistical apportionment of heavy metals in
groundwater is also a major concern. The concentrations tannery-affected areas. Int J Environ Sci Technol 12:537–550.
of Pb, Cr, and Zn in edible parts of spinach exceeded safe https​://[Link]/10.1007/s1376​2-013-0428-4
6. Shao M, Zhu Y, Hao R, Yu Z, Song M (2018) The health hazards
limits, indicating the potential for significant enrichment of potentially toxic metals in the daily diets of adults and chil-
in the food chain. There is a general perception that the dren from a mining and smelting region (Hezhang County) in
Hazaribagh area has been ‘cleaned’ since the tanneries southwestern China. Environ Monit Assess 190:432. https​://doi.
have been relocated; this may be partly due to the slightly org/10.1007/s1066​1-018-6816-y
7. Juel MAI, Chowdhury ZUM, Mizan A, Alam MS (2016) Toxicity
higher dissolved oxygen levels recently observed in the and environmental impact assessment of metals contaminated
adjacent Buriganga river [66]. In this study, analysis of soil of Hazaribagh Tannery Area. In: International conference on
soil has confirmed that this might not be the case, and advances in civil engineering, pp 21–23
mitigation measures are necessary in order to render the 8. Barrett HA, Ferraro A, Burnette C, Meyer A, Krekeler MPS (2012)
An investigation of heavy metal content from disposable batter-
area safe for living. Soil remediation measures must be ies of non-U.S. origin from Butler County, Ohio: an environmen-
undertaken before initiating residential and commercial tal assessment of a segment of a waste stream. J Power Sources
development projects. Some cost-effective, environment- 206:414–420. https​://[Link]/10.1016/[Link]​our.2012.01.008
friendly remediation techniques include phytoremedia- 9. Kabir E, Ray S, Kim KH, Yoon HO, Jeon EC, Kim YS, Cho YS, Yun
ST, Brown RJC (2012) Current status of trace metal pollution in
tion (with or without chelating agents), immobilization of soils affected by industrial activities. Sci World J. https​://doi.
heavy metals by applying chemical agents, and soil wash- org/10.1100/2012/91670​5
ing using chemical solutions [62]. The spatial distribution 10. Hassan S, Hakimeh O, Daryoush A, Effatosadat AM (2012) Lead
of heavy metal contamination and associated risks pre- contamination in soil and vegetation of areas surrounding dif-
ferent mining activity zones in Kerman province of Iran. African
sented in this study will allow policymakers to pinpoint J Biot 11:14146–14152. https​://[Link]/10.5897/AJB11​.3613
areas of intervention for remediation. 11. Zahid A, Balke KD, Hassan MQ, Flegr M (2006) Evaluation of aqui-
fer environment under Hazaribagh leather processing zone of
Acknowledgement The authors acknowledge Ehosan Habib of the Dhaka city. Environ Geol 50:495–504. https​://[Link]/10.1007/
Department of Civil Engineering and the staff of the Environmen- s0025​4-006-0225-1
tal Engineering Laboratory of BUET for their assistance in analyzing 12. Bhuiyan MAH, Suruvi NI, Dampare SB, Islam MA, Quraishi
samples. The authors also wish to thank the three reviewers for their SB, Ganyaglo S, Suzuki S (2011) Investigation of the possible
useful comments and suggestions. sources of heavy metal contamination in lagoon and canal
water in the tannery industrial area in Dhaka, Bangladesh. Envi-
ron Monit Assess 175:633–649. https​://[Link]/10.1007/s1066​
Compliance with ethical standards 1-010-1557-6
13. Alam MS, Han B, Mizan A, Pichtel J (2019) Assessment of soil
Conflict of interest The author(s) declare that they have no compet- and groundwater contamination at a former Tannery district
ing interests. in Dhaka, Bangladesh. Environ Geochem Health. https​://doi.
org/10.1007/s1065​3-019-00457​-6
14. Mizan A, Zohra FT, Ahmed S, Nurnabi M, Alam MZ (2016) Low
cost adsorbent for mitigation of water pollution caused by tan-
nery effluents at Hazaribagh. Bangladesh J Sci Ind Res. 51:215–
220. https​://[Link]/10.3329/bjsir​.v51i3​.29433​

Vol.:(0123456789)
Research Article SN Applied Sciences (2020) 2:1915 | [Link]

15. Karim MR, Manshoven S, Islam MR, Gascon JA, Ibarra M, Diels 30. USEPA (1992) Toxicity Characteristic Leaching Procedure (TCLP).
L, Rahman MM (2013) Assessment of an urban contaminated Publication SW846. Method 1311, US Environmental Protection
site from tannery industries in Dhaka city, Bangladesh. J Hazard Agency, Washington D.C
Toxic Radioact Waste 17:52–61. https​://[Link]/10.1061/(ASCE) 31. Turekian KK, Wedepohl KH (1961) Distribution of the elements
HZ.2153-5515.00001​39 in some major units of the earth’s crust. Bull Geol Soc Am
16. Muchuweti M, Birkett JW, Chinyanga E, Zvauya R, Scrimshaw MD, 72:175–192
Lester JN (2006) Heavy metal content of vegetables irrigated 32. Kabata-Pendias A, Pendias H (2001) Trace elements in soils and
with mixtures of wastewater and sewage sludge in Zimbabwe: plants, 3rd edn. CRC Press, Boca Raton
implications for human health. Agric Ecosyst Environ 112:41–48. 33. Hakanson L (1980) An ecological risk index for aquatic pollution
https​://[Link]/10.1016/[Link].2005.04.028 control. a sedimentological approach. Water Res 14:975–1001.
17. Chang CY, Yu HY, Chen JJ, Li FB, Zhang HH, Liu CP (2014) Accu- https​://[Link]/10.1016/0043-1354(80)90143​-8
mulation of heavy metals in leaf vegetables from agricultural 34. Mugoša B, Đurović D, Nedović-Vuković M, Barjaktarović-Labović
soils and associated potential health risks in the Pearl River S, Vrvić M (2016) Assessment of ecological risk of heavy metal
Delta, South China. Environ Monit Assess 186:1547–1560. https​ contamination in coastal municipalities of montenegro. Int J
://[Link]/10.1007/s1066​1-013-3472-0 Environ Res Public Health 13:393. https​://[Link]/10.3390/ijerp​
18. Beyersmann D, Hartwig A (2008) Carcinogenic metal com- h1304​0393
pounds: recent insight into molecular and cellular mecha- 35. Tomlinson DL, Wilson JG, Harris CR, Jeffrey DW (1980) Problems
nisms. Arch Toxicol 82:493–512. https​://[Link]/10.1007/s0020​ in the assessment of heavy-metal levels in estuaries and the
4-008-0313-y formation of a pollution index. Helgoländer Meeresuntersu-
19. Uddin ANMM, Ahmed SA (2018) Heavy metal contamination of chungen. 33:566–575. https​://[Link]/10.1007/BF024​14780​
soil and health hazards among the residents of tannery indus- 36. Muller G (1969) Index of geoaccumulation in sediments of the
trial area. Anwer Khan Mod Med Coll J. 9:39–43. https​://doi. Rhine River. Geo J 2:108–118
org/10.3329/akmmc​j.v9i1.35823​ 37. Shakeri A, Shakeri R, Mehrabi B (2016) Contamination, toxicity
20. Rahaman A, Afroze JS, Bashar K, Ali MF, Hosen MR (2016) A com- and risk assessment of heavy metals and metalloids in sedi-
parative study of heavy metal concentration in different layers ments of Shahid Rajaie Dam, Sefidrood and Shirinrood Rivers,
of tannery vicinity soil and near agricultural soil. Am J Analy Iran. Environ Earth Sci 75:679. https​://[Link]/10.1007/s1266​
Chem 7:880–889. https​://[Link]/10.4236/ajac.2016.71207​5 5-016-5461-4
21. Latif SA, Afroj D, Hossain SM, Uddin MS, Islam MA, Begum K, 38. Xie Z, Jiang Y, Zhang H, Wang D, Qi S, Du Z, Zhang H (2016)
Oura Y, Ebihara M, Katada M (2009) Determination of toxic trace Assessing heavy metal contamination and ecological risk in
elements in foodstuffs, soils and sediments of Bangladesh using Poyang Lake area, China. Environ Earth Sci 75:549
instrumental neutron activation analysis technique. Bull Envi- 39. Gebrekidan A, Weldegebriel Y, Hadera A, Bruggen BV (2013) Toxi-
ron Contam Toxicol 82:384–388. https​://[Link]/10.1007/s0012​ cological assessment of heavy metals accumulated in vegeta-
8-008-9621-4 bles and fruits grown in Ginfel river near Sheba Tannery, Tigray,
22. Mondol MN, Asia A, Chamon AS, Faiz SMA (2017) Contamination Northern Ethiopia. Ecotoxicol Environ Saf 95:171–178. https​://
of soil and plant by the Hazaribagh tannery industries. J. Asiat [Link]/10.1016/[Link]​v.2013.05.035
Soc. Bangladesh Sci. 43:207–222 40. USDOE (2011) The risk assessment information system (RAIS).
23. Khan FE, Jolly YN, Islam GMR, Akhter S, Kabir J (2014) Contamina- U.S. Department of Energy’s Oak Ridge Operations Office (ORO)
tion status and health risk assessment of trace elements in food- 41. Luo XS, Ding J, Xu B, Wang YJ, Li HB, Yu S (2012) Incorporating
stuffs collected from the Buriganga River embankments, Dhaka, bioaccessibility into human health risk assessments of heavy
Bangladesh. Int J Food Contam 1:1–8. https​://[Link]/10.1186/ metals in urban park soils. Sci Total Environ 424:88–96. https​://
s4055​0-014-0001-z [Link]/10.1016/[Link]​tenv.2012.02.053
24. BBS (Bangladesh Bureau of Statistics), (2011) Bangladesh popu- 42. Proshad R, Kormoker T, Islam SM, Hanif MA, Chandra K (2018)
lation and housing census Chronic exposure assessment of toxic elements from agricul-
25. Shams KM, Tichy G, Sager M, Peer T, Bashar A, Jozic M (2009) Soil tural soils around the industrial areas of Tangail district, Bangla-
contamination from tannery wastes with emphasis on the fate desh. Arch Agri Environ Sci 3:317–336. https:​ //[Link]/10.26832​
and distribution of tri- and hexavalent chromium. Water Air Soil /24566​632.2018.03040​1
Pollut 199:123–137. https:​ //[Link]/10.1007/s11270 ​ -008-9865-y 43. USEPA (1989) Risk assessment guidance for Superfund. Volume
26. ISO 11466, International Standard (1995) Soil quality— extrac- I: human health evaluation manual (Part A), Interim Final. U.S.
tion of trace elements soluble in Aqua Regia. International Environmental Protection Agency, Office of Emergency and
Organization for Standardization, Genève Remedial Response. EPA/540/1-89/002
27. Choudhury MR, Islam MS, Ahmed ZU, Nayar F (2015) Phytore- 44. USEPA (1997) Exposure factors handbook. Washington, DC: U.S.
mediation of heavy metal contaminated buriganga riverbed Environmental Protection Agency, Office of Research and Devel-
sediment by indian mustard and marigold plants. Environ Prog opment. EPA/600/P-95/002Fa
Sustain Energy 35:117–124. https​://[Link]/10.1002/ep.12213​ 45. USEPA (2001) Risk assessment guidance for superfund: volume
28. APHA (1992) Standard Methods 3111, Metals by atomic III - part A, process for conducting probabilistic risk assessment,
absorption spectrometry. Standard methods for the examina- 20460. Washington, DC: U.S. Environmental Protection Agency,
tion of water and wastewater, American Public Health Asso- Office of Emergency and Remedial Response. EPA 540-R-02-002
ciation, American Water Works Association/Water Environment 46. Zheng N, Liu JH, Wang QC, Liang ZZ (2010) Health risk assess-
Federation ment of heavy metal exposure to street dust in the zinc smelting
29. APHA (2017) Standard Methods 3030, Preliminary treatment of district. Northeast China Sci Total Environ. 408:726–733. https:​ //
samples, standard methods for the examination of water and [Link]/10.1016/[Link]​tenv.2009.10.075
wastewater. American Public Health Association/American 47. Huang YN, Dang F, Li M et al (2019) Environmental and
Water Works Association, Water Environment Federation. https​ human health risks from metal exposures nearby a Pb–Zn–Ag
://[Link]/10.2105/smww.2882.041 mine. Sci Total Environ China. https​://[Link]/10.1016/[Link]​
tenv.2019.13432​6

Vol:.(1234567890)
SN Applied Sciences (2020) 2:1915 | [Link] Research Article

48. Cao S, Duan X, Zhao X, Ma J, Dong T, Huang N, Sun C, He B, Wei a case study in North China. Sci Total Environ 631–632:348–357.
F (2014) Health risks from the exposure of children to As, Se, Pb https​://[Link]/10.1016/[Link]​tenv.2018.03.011
and other heavy metals near the largest coking plant in China. 59. Zeng S, Ma J, Yang Y, Zhang S, Liuc GJ, Chen F (2019) Spatial
Sci Total Environ 472:1001–1009 assessment of farmland soil pollution and its potential human
49. USEPA (2011) Screening Levels (RSL) for chemical contaminants health risks in China. Sci Total Environ 687:642–653. https​://doi.
at superfund sites. U.S. Environmental Protection Agency org/10.1016/[Link]​tenv.2019.05.291
50. USEPA (2002) Supplemental guidance for developing soil 60. WHO (2011) Agents classified by the iarc monographs. World
screening levels for superfund sites. U.S. Environmental Protec- Health Organization, International Agency for Research on Can-
tion Agency. pp 4–24. OSWER 9355 cer (IARC)
51. Ministry of Environmental Protection of the People’s Republic of 61. Rahman SH, Khanam D, Adyel TM, Islam MS, Ahsan MA, Akbor
China, (2018). Soil environmental quality, risk control standard MA (2012) Assessment of Heavy Metal contamination of agri-
for soil contamination of agricultural land standard (GB15618- cultural soil around dhaka export processing zone (DEPZ), Bang-
2018), China ladesh: implication of seasonal variation and indices. Appl Sci
52. Ministry of the Environment, Finland, (2007). Government 2:584–601. https​://[Link]/10.3390/app20​30584​
Decree on the Assessment of Soil Contamination and Reme- 62. Wuana RA, Okieimen FE (2011) Heavy metals in contaminated
diation Needs, 214 soils: a review of sources, chemistry, risks and best available
53. Abedin MJ, Akter S, Arafin SAK (2015) Chromium toxicity in soil strategies for remediation. Int Schol Res Notices. https​://doi.
around tannery area, Hazaribagh, Dhaka, Bangladesh, and its org/10.5402/2011/40264​7
impacts on environment as well as human health. Int J Inno Res 63. FAO/WHO (1999) Expert committee on food additives, summary
Adv Eng (IJIRAE) 2(4):119 and conclusions. In: 53rd Meeting, Rome, 1–10
54. Saha GC, Ali MA (2001) Groundwater contamination in Dhaka 64. Awasthi SK (2000) Prevention of food adulteration Act No. 37
city from tannery waste. J Civ Eng Inst Eng Bangladesh of 1954. Central and State rules as amended for 1999 (3rd ed.).
29:151–165 Ashoka Law House, New Delhi
55. Paul D, Choudhary B, Gupta T, Jose MT (2015) Spatial distribu- 65. Chinese national food standards (2017) National Food Safety
tion and the extent of heavy metal and hexavalent chromium Standard for Maximum Levels of Contaminants in Foods (GB
pollution in agricultural soils from Jajmau, India. Environ Earth 2762-2017), China
Sci 73:3565–3577. https​://[Link]/10.1007/s1266​5-014-3642-6 66. Rashedul Islam MR (2018) Effects of relocation of tannery indus-
56. Bini C, Maleci L, Romanin A (2008) The chromium issue in soils of tries from Hazaribagh on water quality of Buriganga river. Dis-
the leather tannery district in Italy. J Geochem Explor 96(2):194– sertation, Bangladesh University of Engineering and Technology
202. https​://[Link]/10.1016/[Link]​o.2007.03.008
57. Covington AD (2009) Tanning chemistry the science of leather. Publisher’s Note Springer Nature remains neutral with regard to
Royal Society of Chemistry, UK, 1st edition, 372–380 jurisdictional claims in published maps and institutional affiliations.
58. Ma W, Tai L, Qiao Z, Zhong L, Wang Z, Fu K, Chen G (2018) Con-
tamination source apportionment and health risk assessment
of heavy metals in soil around municipal solid waste incinerator:

Vol.:(0123456789)