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Environ Geochem Health

https://doi.org/10.1007/s10653-019-00388-2 (0123456789().,-volV)
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ORIGINAL PAPER

Heavy metals contamination in soil, surface water, crops,


and resident blood in Uthai District, Phra Nakhon Si
Ayutthaya, Thailand
Sumana Kladsomboon . Chakkaphop Jaiyen . Chalisa Choprathumma .
Thitaporn Tusai . Amara Apilux

Received: 2 April 2019 / Accepted: 8 August 2019


Ó Springer Nature B.V. 2019

Abstract This study evaluates the heavy metal (As, consumption of local crops were assessed using target
Cd, Cu, Hg, Pb, and Zn) contamination in soil, surface hazard quotients (THQs) and hazard indices (HIs).
water, and crops in Uthai District, Ayutthaya Pro- The former values of the crops varied. 100.0% for As,
vince, Thailand, an agricultural area located near an 40% for Cd, 60% for Cu, 20% for Pb, and 30% for Zn
industrial park. Further, the blood levels of these of the analyzed samples had THQs above 1. This
metals in residents living in the study area are indicated that consumers were probably exposed to
investigated. The concentrations of the six metals in some non-carcinogenic health risk (except for Hg
soil were below the values permitted under the Soil which was 0%). Of greater concern, the HI values of
Quality Standard, Thailand. In contrast, the concen- each consumed crop were [ 1, indicating obvious risk
trations of As and Hg in surface water exceeded the of adverse health effect. Finally, the heavy metal
permissible limits. For the crops, all heavy metal levels in blood from a sample of local residents
values in eggplant, kale, and rice were at safe levels. (n = 16) were assessed along with blood chemistry
However, in basil, both Hg and Cu levels exceeded the tests. The levels of all heavy metals were within the
permissible limits, and in coriander, Hg content normal ranges. Nevertheless, heavy metal contamina-
exceeded the permissible limit. Additionally, the tion in both the environment and food crops raise
potential health risks of heavy metal exposure through concerns of health risks to the residents of this area.

Keywords Heavy metal  Phra Nakhon Si


S. Kladsomboon Ayutthaya  Food crops  Environment  Human
Department of Radiological Technology, Faculty of health  Risk assessment
Medical Technology, Mahidol University, 999
Phutthamonthon 4 Road, Salaya, Nakhon Pathom 73170,
Thailand

C. Jaiyen  C. Choprathumma  T. Tusai Introduction


Community Health Care Service, Faculty of Medical
Technology, Mahidol University, 2 Wang Lang Road
Siriraj, Bangkok-Noi, Bangkok 10700, Thailand Rapid population growth is linked to the expansion of
industrial and agricultural development. Recently,
A. Apilux (&) heavy metals have been widely used in industrial and
Department of Clinical Chemistry, Faculty of Medical
agricultural activities. Arsenic (As), copper (Cu),
Technology, Mahidol University, 999 Phutthamonthon 4
Road, Salaya, Nakhon Pathom 73170, Thailand cadmium (Cd), lead (Pb), mercury (Hg), and zinc
e-mail: amara.apl@mahidol.edu (Zn) are frequently used in various industrial

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Environ Geochem Health

activities, including electronics, automotive machin- (2019) reported that the levels of Hg and As in crop
ery, and paints (Kumar Sharma et al. 2007). The heavy samples exceed the permissible limits set by the
metals-related industrial facilities can lead to contam- Ministry of Public Health, Thailand (Notification of
ination of surrounding environments. Importantly, Ministry of Public Health 1986) and Codex; (FAO/
because these elements are not biodegradable, they WHO 2015), respectively. Contamination by these
can accumulate in soil and surface water and enter metals may cause health problems for entire local
food chains. The yearly usage of fertilizers and population.
pesticides in Thailand is about 3,920,000 (Economics The Uthai District in Phra Nakhon Si Ayutthaya
2011) and 198,000 (Economics 2017) tonnes, respec- (Ayutthaya) Province is an important agricultural area
tively. The use of these chemicals in agricultural which also includes two industrial estates. Because
production increases the supply of nutrients within this area may be exposed to heavy metals from
soils, protects crops, and controls disease. However, multiple sources, it is important to evaluate for
unpurified fertilizers and pesticides usually contain contamination. Mingkhwan and Worakhunpiset
several impurities, especially heavy metals. As, Cu, (2018) investigated the levels of Cd, Cr, Cu, Ni, Mn,
Cd, Pb, and Zn are reported to be major impurities in Pb, and Zn in river and stream water, sediment, and
fertilizers. Cd, Pb, and Zn are found in high levels in fish collected from the area around the industrial
pesticides and herbicides (Gimeno-Garcı́a et al. 1996; estates in the Uthai and Bangpa-in Districts of Phra
Kuziemska et al. 2016). Hg is a major component of Nakhon Si Ayutthaya Province. Their results revealed
organomercuric fungicides (Turull et al. 2018). In that Mn levels in water exceeded Thailand’s surface
some developing countries, phosphate fertilizers are water quality standards. However, more data are
found to be major sources of As (Jayasumana et al. needed in this on contamination by heavy metals in the
2015). Thus, accumulation of heavy metals in the environment, crops, and humans in this area. There-
environment may occur when chemicals are repeat- fore, the levels of heavy metals in agricultural soil,
edly applied during agricultural activities (Ning et al. surface water, and crops grown in the district [basil
2017). (Ocimum basilicum Linn.), coriander (Coriandrum
Human exposure of heavy metals via occupation, sativum L.), eggplant (Solanum melongena L.), kale
environment or diet can cause both acute and chronic (Brassica alboglabra) and rice (Oryza sativa L.)], and
adverse health effects as summarized in Table 1. Cu blood of residents were investigated. The health risks
and Zn are essential trace elements for the human from heavy metals in consumed crops were evaluated.
body, however too much exposure to them can cause The concentrations of five elements (As, Cd, Cu, Pb,
adverse health effects (Tchounwou et al. 2012). As, and Zn) were determined using inductively coupled
Cd, Hg, and Pb are classified as toxic heavy metals and plasma mass spectrometry (ICP-MS) for environmen-
considered among the top ten most hazardous chem- tal and crop samples, and atomic absorption spec-
icals of public health concern by the World Health troscopy (AAS) for blood specimens. Hg was
Organization (WHO 2010a). They can cause serious quantitated using cold-vapor atomic absorption spec-
illness or death to humans even with small exposures. troscopy (CV-AAS) for both types of specimens. The
Despite this, heavy metals (Cu, Cd, Pb, Hg, and Zn) findings provided useful information on the levels of
are widely used in industry. Also, As, Cu, Zn, Cd, Hg, heavy metal contamination of the environment and
and Pb are normally contained in chemical fertilizers, food crops, and potentially on the health of workers
pesticides, and fungicides. Use of these products and local residents.
allows entry of these toxic substances into the
environment, and contamination of soil, surface water,
and vegetables. Materials and methods
Although, Thailand is an agricultural country, the
presence of heavy metals over permissible limits have Chemicals and reagents
been found in soil (Netpae and Phalaraksh 2009;
Kayee et al. 2018), water (Wongsasuluk et al. 2013; Hydrochloric acid, nitric acid, and hydrogen peroxide
Choo-In et al. 2013), rivers (Veschasit et al. 2012) and were purchased from Merck (Darmstadt, Germany).
agricultural products. Moreover, Choprathumma et al. Mercury standard was purchased from SCP (Science

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Environ Geochem Health

Table 1 Potential sources and toxicities of As, Cd, Cu, Hg, Pb, and Zn
Metal Sources Chronic exposure Acute exposure

As (Vlotman et al. 2018; Jayasumana Processing of glass, Abdominal pain, and skin Vomiting, abdominal pain,
et al. 2015; Smith et al. 2012; pigments, paper, textiles, lesions and diarrhea
WHO 2010b) and smelters Cancers of lung, bladder, Neurological problems, and
Use of pesticides, prostate, and kidney cardiovascular disease
fungicides and phosphate Cancers of bladder, lung,
fertilizers prostate, and skin
Cd (Chunhabundit 2016) Processing of batteries, Cancers in skeletal and Kidney damage, especially
pigments, metal coatings, respiration systems renal tubular damage
and plastics Renal damage
Use of fertilizers Diabetic nephropathy
Decrease in bone density
Cu (Netpae and Phalaraksh 2009; Electrical wiring, alloys Toxicity and damage to liver Gastrointestinal tract
Copper: Health Information and piping and kidneys distress
Summary) Use of fertilizers and Wilson’s disease Liver toxicity
(DES Environmental Health Program fungicides Destruction of red blood
2013) cells, possibly resulting in
anemia
Pb (Assi et al. 2016) Mining, smelting, and fossil Effects on bodies enzyme Storage in bone
fuels systems, vascular and cardiac Muscular weakness and
Processing of batteries, damage weight loss
paints, and soldering Brain damage, kidney
materials damage, and may even
Use of herbicides cause death
Hg (Fernandes Azevedo et al. 2012; Processing of batteries, Damage to the central nervous Toxicity to gastrointestinal
Webb et al. 2016) lamps, and dental fillings system tract, lungs, kidneys, skin,
Use of pesticides and Suppression of immune and eyes
fungicides function
Zn (Plum et al. 2010; Wuana and Biosolids such as sewage Effects on the gastrointestinal, Abnormalities of growth
Okieimen 2011) and sludge hematological, and and development
Use of fertilizers respiratory systems

Quebec, Canada). For ICP-MS, a multi-element Study area


calibration standard (containing 10 mg mL-1 of Ag,
Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ga, In, Phra Nakhon Si Ayutthaya is one of the central
K, Li, Mg, Mn, Na, Ni, Pb, Rb, Se, Sr, Ti, U, V, and provinces of Thailand. Uthai District is located in
Zn) and internal calibration standard solutions (con- south Ayutthaya with a total area of 187 km2 (Fig. 1).
taining 10 mg mL-1 of Bi, Ge, In, Li, Sc, Tb, and Y) Its population in 2011 was 50,658. Most people are
were purchased from PerkinElmer Pure Plus (Mas- farmers whose homes are located on their farms. 76%
sachusetts, USA). All standards, internal standards, of the land is agricultural though two industrial estates
control solutions, and digested sample solutions were are located in the district. The selected study area was
prepared by diluting in 0.1% (v/v) of HNO3 before located about 15 km from one of the industrial estates
analysis using ICP-MS. A standard solution for AAS (Rojana) and was a productive area for crops as well as
analysis was purchased from PerkinElmer Pure Plus. vegetables for residents.
Analytical-grade reagents and 18 MX-cm water were
used throughout these experiments.

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Environ Geochem Health

Fig. 1 Map of Thailand showing the study area, Phra Nakhon Si Ayutthaya Province

Sample collection and preparation 50 mL with Milli-Q water and stored in a refrigerator
until use.
Surface water, soil, and food crop samples were
collected on February 23, 2017, at the house of the Soil
Village Headman, Ampor Uthai (14°230 46.400 N
100°420 54.900 E). Blood and urine samples from sub- Ten topsoil samples were collected using a shovel,
jects were collected on May 22, 2018, at 14°230 46.400 N after the removal of the vegetation cover, from sites in
100°420 54.900 E. a triangular line around a total area of 90 9 40 m2 as
shown in Fig. 2. Each sample was 1 kg, collected from
Surface water a soil area of 10 cm diameter and depth less than
15 cm. The samples were kept in sealed polyethylene
Water sampling was performed at * 1 m water bags. They were dried in an oven (CRYSTE
depth, at ten points along the pond (Fig. 2) using PURIVEN, Novapro, Korea) at 60 °C for 24 h to
glass water samplers. The collected samples were reach a constant weight, then ground, and passed
stored in polyethylene bottles. All water samples were through a 2-mm mesh sieve. From each sample, 0.1 g
filtrated using Whatman filter paper No. 42 before (using a precision balance with a readability of
digestion. One milliliter of water was mixed with 0.001 g) of soil was added to a mixture of 6 mL
10 mL of 65% HNO3 and then digested in microwave 65% HNO3, 3 mL 37% HCl, and 0.25 mL 30% H2O2.
digestion (MLS-1200 MEGA of MILESTONE) for The mixed solution was digested in microwave
21 min. After that, the sample volume was adjusted to digestion for 10 min and was kept in a refrigerator
before measurement.

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Environ Geochem Health

Fig. 2 Sampling points of


surface water and soil in the
study area

Crops occupation, health status, daily food consumption, and


agricultural activities.
Crop samples of basil (O. basilicum Linn.), kale (B. Venous blood samples from each subject were
alboglabra.), coriander (C. sativum L.), eggplant (S. collected (fasting) in five tubes (two plain tubes, two
melongena L.), and rice (O. sativa L.) were randomly EDTA tubes, and one NaF tube). Plain tubes were used for
collected from the same fields where soil and surface serum biochemistry tests (liver function, lipid profile, renal
water was sampled. These samples were chopped or function) and As, Cu, and Zn analysis. EDTA tubes were
ground, and oven-dried at 80 °C for 24 h to reach a used for complete blood count tests (CBC, hemoglobin
constant weight, and then sieved through a 2-mm and hematocrit), and Cd, Hg, and Pb analysis. NaF tubes
nylon mesh to make powder (Islam and Hoque 2014). were used to determine fasting blood sugar (FBS).
0.5 g of each powdered sample underwent microwave All heavy metal testing was done at the Toxicology
digestion using 6 mL of 65% HNO3 and 2 mL of 30% Laboratory, Community Health Care Service, Mahi-
H2O2. The digested solutions were then cooled to dol University, and all biochemistry testing was done
room temperature and diluted with Milli-Q water to at the Center of Medical Laboratory Service, Faculty
50 mL. of Medical Technology, Mahidol University. In
preparation for heavy metal analysis, serum samples
Blood and urine for Cu and Zn were diluted to the ratio of 1:10 with
0.2% HNO3, while samples for As were diluted to the
The study was approved by the Ethics Committee of ratio of 1:4 with 2% Triton X100. Whole-blood
Mahidol University (Ethic: MU-CIRB samples were diluted to the ratio of 1:10 with 0.2%
2018/046.1602). Potential subjects were informed (NH4)2 HPO4 in 0.1% Triton X100. Then the samples
about the research objectives, and the requirement to were analyzed for Pb and Cd using graphite furnace
complete and sign the consent form. For eligibility, AAS. For Hg analysis, whole-blood samples were
subjects had a minimum of 10 years of residence in the mixed with 65% HNO3 and 30% H2O2 followed by
study area. For health information, study question- microwave digestion. Finally, the prepared samples
naires collected data regarding gender, age, address, were measured using CV-AAS.

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Environ Geochem Health

Analytic methods
where EF is the exposure frequency from consumption
of heavy metals-contaminated vegetables (365 days/
As, Cd, Cu, Pb, and Zn measurements.
year); ED is the exposure duration or the average
lifetime of Thai people (71.8 years for males and
Soil, surface water, and crops
78.6 years for females; Institute for Population and
Social Research 2016); FIR is the food ingestion rate
Concentrations of As, Cd, Cu, Pb, and Zn in soil,
(kg/person/day) of Thai people (268 g/person/day for
surface water, and crops were determined using an
males and 283 g/person/day for females; The Health
inductively coupled plasma mass spectrometer (Perk-
Systems Research Institute 2006); C is metal concen-
inElmer NexIONÒ 300). The optimized conditions
tration (mg/kg); RFD is the oral reference dose (As,
were 1.1 L min-1 of nebulizer gas flow, 1.35 L min-1
3 9 10-4 mg/kg/day; Cd, 1 9 10-3 mg/kg/day; Cu,
of auxiliary gas flow, 18 L min-1 of plasma gas flow,
4 9 10-2 mg/kg/day; Hg, 5 9 10-4 mg/kg/day; Pb,
and 1600 W of radio frequency (RF) in an ICP system.
4 9 10-3 mg/kg/day; Zn, 0.3 mg/kg/day respectively;
Internal quality control for accuracy and precision at
USEPA IRIS 2007); and TA is the average exposure
20 ppb was performed every 10 samples.
time for non-carcinogens (ED 9 365 days/year).
A THQ value of less than 1 means that the exposure
Blood samples
is unlikely to cause any deleterious effects to the
exposure population. A THQ value [ 1 means non-
Cu and Zn in blood samples were identified using
carcinogenic effects may occur. Additionally, chronic
Flame-AAS (Varian spectrAA flame 640, Varian,
hazard index (HI) was used to evaluate the potential
Mulgrave, Australia). As, Cd, and Pb were measured
risk to human health from multiple heavy metals found
using Graphite Furnace AAS (PerkinElmer PinAAcle
in samples. HI was obtained as the sum of all THQs
900z, PerkinElmer, Massachusetts, USA) for Cd and
calculated for individual heavy metals according to the
Pb, and Varian SpectrAA 220 (Varian, Mulgrave,
following equation.
Australia) for As.
HI ¼ THQAs þ THQCd þ THQCu þ THQHg
Hg measurement þ THQPb þ THQzn

Hg was analyzed using a cold-vapor atomic absorption


spectrometer (PerkinElmer Flow Injection Mercury
Results and Discussion
Systems 400, PerkinElmer; Wellesley, MA, USA).
Five hundred microliters of the sample solution was
Quantitative analysis of heavy metals.
prepared in a mixture of 1.1% (v/v) SnCl2 in 3% (v/v)
HCl. Standard reference materials were included in
ICP-MS
each batch run to ensure analytical quality.
In the present work, As, Cd, Cu, Pb, and Zn
Health risk assessment
concentrations in soil, surface water, and crops were
determined using ICP-MS. A three-point calibration
The potential health risks based on the non-carcino-
curve for each element was constructed for quantifi-
genic effects of heavy metal consumption through
cation of each element (at concentrations of 25, 50,
vegetables were expressed by a target hazard quotient
and 75 ppb). The correlation coefficients of standard
(THQ) and hazard index (HI) as proposed by the
curves for all heavy metals were greater than 0.9995
United States Environmental Protection Agency
(AOAC 2015), As 0.9998, Cd 0.9990, Pb 0.9995, Cu
(USEPA 2007; Zhou et al. 2016; Liang et al. 2019;
0.9999, and Zn 0.9996. Accuracy of tests were
Thummajitsakul et al. 2018). THQ was calculated
determined by using internal quality control solutions
using the following equation.
of 3 and 15 ppb in 0.1% HNO3, run after every 10
ðEF  ED FIR  CÞ samples. The results ranged from 2.72 to 5.13 ppb for
THQ ¼  103
ðRFD  WAB  TA Þ the 3 ppb solution, and 13.65 to 19.50 ppb for the

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Environ Geochem Health

15 ppb solution. The % RSDs ranged from 1.2 to 10.9, performance of the test was confirmed by the External
showing the high precision of the tests at these ppb Quality Assurer (EQA): Lead and Multielement
levels; all were in accord with the Guidelines for Proficiency Program of the Centers for Disease
Standard Method Performance Requirements of Control and Prevention, USA.
AOAC International (AOAC 2015).
Cold-vapor AAS
AAS
Hg determination was carried out using a calibration
For human samples, heavy metals were measured by curve obtained from standard Hg solutions with
AAS. As, Cu, and Zn were determined in serum with concentrations of 5, 10, and 20 ppb in 7% HCl for
GF-AAS and Flame-AAS, respectively. Cd and Pb soil, surface water, and crop samples. Internal quality
were determined in whole blood with GF-AAS. control was done for every 10 samples using standards
to insure that the CV-AAS system was working
Zinc and Copper accurately. The measured concentrations of control
solutions were 5.13 ppb and 19.5 ppb, for 3 and
A standard curve was constructed using working 15 ppb, respectively. The % RSDs were in the range of
standards at 50, 150, and 300 lg/dL, prepared from 0.34 to 0.69. The calibration curve for blood analyses
1000 mg/L in 2% HNO3 PerkinElmer Pure Plus was constructed using 10, 20, and 40 ppb Hg standards
(Massachusetts, USA). The measured concentrations (1000 lg/mL in 10% HNO3 PerkinElmer). Correla-
of control solutions were in the range of values tion coefficients were greater than 0.995 for all tests.
recommended by Seronorm Trace Elements in Serum, The accuracy of tests was assessed using in-house
Level 1 (Bilingstad, Norway) and used to evaluate the controls at three levels (level 1 = 0.6–3.0 ppb, level
accuracy of analytical data. Internal quality control 2 = 3.2–6.8 ppb, and level 3 = 11.6–17.6 ppb) which
was done for every 10 samples to monitory test confirmed to the External Quality Assurer: Lead and
accuracy. The % RSDs were \ 10. Multielement Proficiency Program of the Centers for
Disease Control and Prevention, USA.
Arsenic
Heavy metals in soil, surface water, and crops
A calibration curve was constructed using working
standards at 25 and 50 ppb, each prepared from This study aimed to assess the extent of heavy metal
1000 mg/L of standard solution, Merck (Darmstadt, contamination in an agricultural village located in
Germany). In-house controls were run every 10 Uthai District near Rojana Industrial Park, and to
samples to monitor test accuracy; controls were at provide baseline information for monitoring heavy
two levels: level 1 = 5.1–10.7 ppb and level metal levels in soil, surface water, crops, and local
2 = 6.7–15.9 ppb. The % RSDs were all \ 0. residents.

Cadmium and Lead Heavy metal content in surface water

A standard curve of Pb was prepared using in-house The use of fertilizers and pesticides in the study area
standards (at 5.1, 21, and 54 lg/dL) from 1000 mg/L can cause heavy metal contamination of surface water.
of standard solution (PerkinElmer Pure Plus, Mas- Moreover, the pond studied was connected to a canal
sachusetts, USA) in 2% HNO3. For Cd, the standard which was commonly used for agricultural activities.
curve of was prepared at concentration of 1.0, 7.0, and Therefore, heavy metal monitoring is very important.
24 lg/dL, from 1000 mg/L of standard solution Firstly, the pH of water samples was investigated. The
(PerkinElmer Pure Plus) in 2% HNO3. In order to average pH value of 10 samples was 8.14 ± 0.07
evaluate accuracy, the control solutions were tested, (mean ± SD). All values met the surface quality
and the results found to be in the range of values standard (class III, pH 5–9) of the Pollution Control
recommended by Seronorm Trace Elements in whole Department of Thailand (PCD 1992). For heavy
blood, level 1, and level 2 (Bilingstad, Norway). The metals analysis, results are shown in Fig. 3a. Six

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Environ Geochem Health

Fig. 3 Average
concentrations of heavy
metals found in a surface
water and b soil compared
with the permissible values
(solid bars). The error bar
represents the standard
deviation (SD), n = 3. c The
pH of soil at ten sampling
points. The standards for
surface water are those of
the National Thailand
Surface Water Standard:
Class 3 (WEPA 1994). The
standards for soil are those
of the Act to Promote and
Preserve the National
Environmental Quality, BE
2547 (2004), for Cu, As, Cd,
Pb, and Hg, and of the Soil
Quality Standards for
Habital and Agricultural
Purposes in Thailand (PCD
2004) for Zn

heavy metals were detected with the following order contamination of surface water may be due to
of concentration: As (75.93 ± 11.52 ppb) [ Cu chemical pesticide and fertilizer applications to the
(2.69 ± 1.17 ppb) [ Hg (2.49 ± 0.90 ppb) [ Zn fields and/or agricultural use of contaminated irriga-
(0.87 ± 0.50 ppb) [ Pb (0.59 ± 0.15 ppb) and Cd tion water (Chaoua et al. 2018; Malan et al. 2014).
(0.02 ± 0.01 ppb). The trace elements Cu and Zn
were found to be at safe levels. For non-essential toxic Heavy metals content in soil samples
elements, the results showed that Cd and Pb concen-
trations were at safe levels with respect to the National Soil is a complex mixture of organic and inorganic
Thailand Surface Water Standard: Class III (WEPA matter, minerals, water and air (Nortcliff et al. 2011).
1994). However, As and Hg levels in water samples It is an essential factor for agriculture. Recently, Thai
exceeded maximum allowable levels. The As and Hg farmers commonly apply fertilizers and pesticides

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Environ Geochem Health

containing heavy metals to their fields to increase levels in eggplant and kale were very close to the
agricultural production. Such methods can cause maximum allowable values. Importantly, coriander
accumulation of these metals in soil and is affected and basil contained Hg levels above the allowable
by factors such as moisture, pH, site hydrology, and value. Basil contained Cu concentrations above the
the behavioral characteristics of the soil (Islam et al. standard limit. The levels of Cu and Hg in crops were
2000). In this study, contamination levels of As, Cu, related to concentrations of these metals in the
Cd, Pb, Hg, and Zn in soil were investigated (Fig. 3b). associated water samples. This was likely due to the
The soil samples had acidic pHs of about 5.9 ± 0.7 plant absorption of both heavy metals from the water
(Fig. 3c) and clay texture. into their tissues. In addition, the absorption of heavy
Heavy metals were detected in soil with the metals by each plant also depends on specific transfer
following order of concentration: Cu [ Pb [ Zn [ factors of the plant itself. According to previous
As [ Hg [ Cd. Heavy metal concentrations, as research, the accumulation of Cu can be higher than
measured in soil samples, were 1.40 ± 0.26, that of Hg and Pb (Bi et al. 2018) concentrations of Cu
0.05 ± 0.01, 18.37 ± 0.64, 0.06 ± 0.05, 8.19 ± which we found in plants were probably related to high
0.46, and 3.94 ± 0.64 mg/kg for As, Cd, Cu, Hg, concentrations in the soil. Hg was found to be over
Pb, and Zn, respectively (Fig. 3b). The heavy metal permissible levels in water, basil, and coriander. This
concentrations measured in these soils were lower result is similar to that of a previous study which found
than the levels defined as critical according to the Act Hg contamination in crops which were randomly
to Promote and Preserve the National Environmental collected from the northeast region of Thailand. The
Quality, 2004, for Cu, As, Cd, Pb, and Hg, as well as Hg content in rice and yard-long beans exceeded the
the Soil Quality Standards for Habital and Agricultural permissible limit, while the Hg content found in soil
Purposes in Thailand (PCD 2004) for Zn. Soil in this from growing areas did not reach the limit for Hg in soil
area was contaminated with As, Cd, Cu, Hg, Pb, and (Zarcinas et al. 2004a, b). This suggests that food crops
Zn. These results are in agreement with the previous may receive Hg from additional sources such as water
report by Zarcinas and colleagues (2004a, b), that soils and air contaminated by factories (Joseph et al. 2016),
in southern Asian countries are often contaminated fertilizers, pesticides (Ferrante et al. 2013), and/or
with these metals. fungicides (Turull et al. 2018).

Heavy metals content in food crop samples Health risk assessment

Food crops are the source of many essential human The health risks of heavy metals through crop
nutrients (Hirschi 2009). However, the use of chemical consumption were evaluated using target hazard
fertilizers and pesticides, and being located near quotient and hazard index based on methodology
industrial estates, create risks of contamination with described by the US EPA. A THQ lower than 1
heavy metals. Crops can absorb metals via soil, water, indicates that consumers are not exposed to harmful
and air from environments, and so metals can be health effects, while values [ 1 indicate that there are
deposited in different parts of the plants (Srinivas et al. potential health risks via consumption of crops. The
2009). The concentrations of heavy metals were results, grouped by gender, are shown in Table 2.
investigated in basil, coriander, eggplant, kale, and The THQ values of the crops varied and were
rice which were all planted in the sampling area of the 1.051–3.969 for As, 0.014–4.312 for Cd, 0.220–3.447
study site. The heavy metal values were compared with for Cu, 0.066–0.320 for Hg, 0.277–1.231 for Pb, and
the permissible limits of the Ministry of Public Health 0.206–1.463 for Zn. Moreover, 100.0% for As, 40%
in Thailand (Fig. 4). The heavy metal concentrations for Cd, 60% for Cu, 0%, for Hg, 20% for Pb, and 30%
found in crops were: As (0.08–0.24 mg kg-1), Cu for Zn of the analyzed samples had target hazard
(2.26–27.96 mg kg-1), Cd (0.004–0.016 mg kg-1), quotients above 1, which indicated potential health
Hg (0.008–0.032 mg kg-1), Pb (0.29–1.00 mg kg-1), risks due to crop consumption (Table 3).
and Zn (15.90–89.00 mg kg-1). These results indi- In addition, the total THQ (TTHQ, sum of individ-
cated that the food crop samples from this area were ual metals) values of As, Cd, Cu, Hg, Pb, and Zn due to
safe in regard to As, Cd, Pb, and Zn. However, the Pb consumption for each of the crops were greater than

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Environ Geochem Health

Fig. 4 The mean concentrations of a As, b Cd, c Cu, d Hg, e Pb The horizontal lines show the limit of permissible values from
and f Zn in 4 species of vegetable and rice (mg kg-1, fresh the Ministry of Public Health in Thailand for As, Cu, Hg, Pb, and
weight). The error bars represent the standard deviations (SDs). Zn and Codex Alimentarius Guidelines for Cd, respectively

1.00, while only that of Hg only was lower than 1. health risk from heavy metals only due to consumption
These results indicated that As, Cd, Cu, Pb, and Zn of studied crops.
imposed health risks to the consumer. The sequence of Contamination is possible from both excessive
TTHQ for subjects was As (12.786) [ Cu (8.699) [ amounts of fertilizers and pesticides, and irrigation
Cd (6.417) [ Pb (4.252) [ Zn (4.064 ) [ Hg (0.976). water polluted with industrial waste. Pesticides and
Further, HI via all metal intake of crops were also fertilizers were identified as the main sources of heavy
calculated. The sequence of the HI for subjects was metal contamination of soil and water in our study
coriander [ basil [ kale [ eggplant [ rice. The val- area. Since chemical fertilizers and various pesticides
ues in each case were more than 1, and higher values are widely used in agricultural fields (Alam et al.
were observed for females than males. This meant that 2003), we suggest that regular monitoring of heavy
the health risks associated with heavy metal exposure metals in this area is essential to identify and prevent
were significant (Minolfi et al. 2018). However, it excessive buildup of these metals in the human food
should be noted that the present study estimated the chain.

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Table 2 Target hazard quotient (THQ), total target hazard quotient (TTHQ) and hazard index (HI) values (mean ± standard deviation) of heavy metals via crop consumption
THQ (Mean ± SD) HI (mean ± SD)
Samples As Cd Cu Hg Pb Zn

Male
Basil 3.134 ± 0.009 0.093 ± 0.005 2.722 ± 0.001 0.199 ± 0.039 0.581 ± 0.112 1.155 ± 0.060 7.885 ± 0.225
Coriander 2.226 ± 0.212 3.405 ± 0.018 1.562 ± 0.016 0.253 ± 0.072 0.604 ± 0.171 0.914 ± 0.025 8.964 ± 0.514
Eggplant 1.051 ± 0.005 0.553 ± 0.005 1.651 ± 0.041 0.113 ± 0.017 0.924 ± 0.011 0.277 ± 0.007 4.569 ± 0.087
Kale 1.979 ± 0.174 1.003 ± 0.003 0.714 ± 0.061 0.140 ± 0.011 0.972 ± 0.030 0.658 ± 0.019 5.466 ± 0.298
Rice 1.707 ± 0.156 0.014 ± 0.003 0.220 ± 0.004 0.066 ± 0.017 0.277 ± 0.009 0.206 ± 0.057 2.490 ± 0.245
TTHQ 10.098 ± 0.555 5.068 ± 0.034 6.870 ± 0.123 0.771 ± 0.154 3.358 ± 0.333 3.210 ± 0.169
Female
Basil 3.969 ± 0.012 0.118 ± 0.007 3.447 ± 0.001 0.251 ± 0.049 0.736 ± 0.141 1.463 ± 0.076 9.984 ± 0.285
Coriander 2.818 ± 0.268 4.312 ± 0.023 1.978 ± 0.020 0.320 ± 0.091 0.765 ± 0217 1.157 ± 0.032 11.351 ± 0.651
Eggplant 1.331 ± 0.007 0.700 ± 0.007 2.091 ± 0.052 0.143 ± 0.021 1.170 ± 0.014 0.350 ± 0.009 5.786 ± 0.110
Kale 2.506 ± 0.220 1.270 ± 0.003 0.904 ± 0.078 0.177 ± 0.014 1.231 ± 0.037 0.833 ± 0.024 6.921 ± 0.377
Rice 2.161 ± 0.197 0.017 ± 0.003 0.279 ± 0.006 0.084 ± 0.021 0.351 ± 0.011 0.261 ± 0.072 3.153 ± 0.310
TTHQ 12.786 ± 0.703 6.417 ± 0.043 8.699 ± 0.156 0.976 ± 0.195 4.252 ± 0.421 4.064 ± 0.213

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Table 3 Percentages of crops that were found below and above the permissible limit of THQ (value = 1) for each heavy metal
As (%) Cd (%) Cu (%) Hg (%) Pb (%) Zn (%)

THQ \ 1 0 60 40 100 80 70
THQ [ 1 100 40 60 0 20 30

Residents’ health condition and heavy metal Table 4 Demographic characteristics and agricultural activi-
determinations in their blood ties of the participants
Parameter Value
Heavy metals can transfer from soil to vegetables, a
process which human activities may enhance. As a Demographic characteristics
result, the accumulation of several heavy metals in Gender (%)
rural and urban soils at excessive levels can cause Male 62.5%
serious health problems in humans (Huang et al. 2018; Female 37.5%
Nedelescu et al. 2017; Rai et al. 2019). The residents’ Age (average years) 55.3 ± 18.3
health condition and heavy metal values in blood were Male 57.4 ? 22.7
determined to evaluate individual exposure to heavy Female 52.0 ± 8.5
metals. Information about demographic characteris- BMI (average) 25.17 ± 3.40
tics, occupation, health status, smoking habits, alcohol Congenital disease (%)
consumption, dietary habits, and BMI are summarized Diabetes mellitus 43.75%
in Table 4. A total of 16 subjects (10 men and 6 Hypertension 6.25%
women) participated in the study. The mean age of the No 56.25%
participants was 55.3 ± 18.3 years (range 30–75). All Smoking (%)
participants were residents who had lived in the study Smoking 25.0%
district for more than 10 years. The main occupation Non-smoking 75.0%
of the participants was farming (81.25%). None of the Alcohol consumption (%)
participants worked in factories. The average BMI was Yes 31.25%
25.17 ± 3.40. As for their health conditions, non- No 68.75%
communicable diseases were present including 6.35% Farming (%)
with diabetes mellitus and 56.25% with hypertension. Farming 81.25%
Agricultural activity information showed that chem- Non-faming 18.75%
ical pesticides and fertilizers were used by 81.25% and Agricultural activity
75.00% of the subjects, respectively. Pesticides used ( [ 5 years) (%) 75.00%
The potential risk of heavy metal exposure from Organic pesticide 0.00%
consumption was investigated (Table 5). From con- Chemical pesticide 75.00%
sumption behavior data, the percentage of subjects Insecticide 66.67%
who ‘often’ consumed vegetables, fruit, meats, grains Herbicide 41.67%
and seafood were 87.50%, 31.25%, 75.00%, 31.25%,
Fertilizer used ( [ 5 years) 81.25%
and 0%, respectively. From the clinical testing
Organic fertilizer 12.50%
(Table 6), the average values of blood glucose,
Chemical fertilizer 56.25%
cholesterol, triglyceride, LDL-C, and HDL-C were
Both organic and chemical fertilizers 12.50%
105.50 mg/dL, 192.81 mg/dL, 166.94 mg/dL,
121.06 mg/dL, and 45.43 mg/dL, respectively. The Bold indicates the largest value of the obtained data
levels of blood glucose, cholesterol, triglyceride, and
LDL-C were found in the subjects to be higher than the subjects with results lower than the reference range
normal range for 12.50%, 43.75%, 43.75%, and were found in 37.5% of subjects. For the liver and
43.75% of them, respectively. For the HDL-C, renal function tests, AST, ALT, BUN, and creatinine

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Environ Geochem Health

Table 5 Consumption behavior of the participants


Behavior Do often (%) Do moderate (%) Few (%) Don’t do (%)

Eat 3 meals a day 68.75 25.00 0.00 6.25


Consume vegetables 87.50 12.50 0.00 0.00
Consume fruits 31.25 62.50 6.25 0.00
Consume cooked meats 75.00 18.75 6.25 0.00
Consume offal, seaweed, herbal tea 0.00 18.75 50.00 31.25
Consume grains 31.25 43.75 18.75 6.25
Consume brown rice 18.75 6.25 6.25 68.75
Consume seafood 0.00 56.25 31.25 12.50
Consume canned food 0.00 25.00 50.00 25.00
Consume fried food 12.50 37.50 31.25 18.75
Consume colorful food 0.00 25.00 25.00 50.00
Consume snacks (potato chips, etc.) 6.25 31.25 12.50 50.00
Bold indicates the largest value of the obtained data

Table 6 Results of clinical Test Average Reference levels Normal (%) Abnormal (%)
laboratory tests and
urinalysis FBS (mg/dL) 105.50 70–100 87.5 12.50
Cholesterol (mg/dL) 192.81 \ 200 56.25 43.75
Triglyceride (mg/dL) 166.94 50–150 56.25 43.75
HDL-C (mg/dL) 45.43 M [ 40 62.5 37.50
F [ 50
LDL-C (mg/dL) 121.06 \ 130 56.25 43.75
AST (U/L) 21.06 M 8–46 100 0
F 7–34
ALT (U/L) 22.62 0–48 100 0
BUN (mg/dL) 13.19 10–20 100 0
Creatinine (mg/dL) 0.93 0.5–1.2 100
Urinalysis – – 100

were in the normal range with average values of concentrations were below the critical levels set by
21.06 U/L, 22.62 U/L, 13.19 mg/dL, and 0.93 mg/dL, the WHO. Levels of trace metals in blood showed the
respectively. following descending order: Cu [ Zn; for the toxic
For the heavy metal analyses, the concentrations of metals, the order of levels were Pb [ Hg [ Cd = As
heavy metals in blood (Pb, Cd, and Hg) and serum (As, (Fig. 5).
Zn, and Cu) were measured. These metals were found Although the levels of heavy metals in blood were
in the samples but the values were less than critical within normal ranges, there was contamination with
values for all elements (Fig. 5). The values of As, Cd, these metals in the local environment. As and Hg
Cu, Hg, Pb, and Zn were 1.1 ± 1.0 lg/L, concentrations in surface water, and Cu and Hg
1.1 ± 0.5 lg/L, 991 ± 111 lg/L, 3.1 ± 1.8 lg/L, concentrations in crops, each exceeded the permitted
31 ± 13 lg/L, and 608 ± 92 lg/L, respectively. values. Moreover, the HI values were above the
Regarding the health conditions of subjects, levels normal value. Regarding the questionnaire data, use of
of the trace elements, Cu and Zn, were in the normal chemical pesticides and fungicides, and consumption
range. The toxic elements, As, Cd, Hg, and Pb, were of local eating crops, each suggested that human
found in the samples from our subjects. Their health risks were posed by heavy metal exposure (Rai

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Environ Geochem Health

Fig. 5 The mean


concentrations of As, Cd,
Cu, Hg, Pb, and Zn in blood
samples of study subjects

et al. 2019; Singh et al. 2017). Therefore, a problem of Acknowledgements This project was financially supported
heavy metal contamination was shown to exist in the by Mahidol University. The authors would like to acknowledge
Professor Dr. Virapong Prachayasittikul, Mr. Lerson
studied area, and attention is needed to mitigate the Suwannathon, and Miss Aumaporn Pinyosirikul for their
problem and protect human health in the long term. assistance and suggestions about clinical analysis and health
performance, and Miss Ubonwan Somsukpiroh, Miss Jantanee
Boonprakong, Mr. Nattawut Junpetch, and Miss Pornpawee
Kaewwandee for data collection and sample collection and
Conclusions preparation.

The frequency and concentration of heavy metals (As,


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