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European Journal of Applied Sciences – Vol. 12, No. 6

Publication Date: December 25, 2024

DOI:10.14738/aivp.126.18025.

Tan, X. & Wang, Z. (2024). Trace Elements Determination in Human Scalp Hair by Inductively Coupled Plasma Mass Spectrometry

and Its Application to Health Status Assessment. European Journal of Applied Sciences, Vol - 12(6). 609-620.

Services for Science and Education – United Kingdom

Trace Elements Determination in Human Scalp Hair by

Inductively Coupled Plasma Mass Spectrometry and Its

Application to Health Status Assessment

Xijuan Tan

Laboratory of Mineralization and Dynamics, College of Earth Sciences and

Land Resources, Chang’an University, 126 Yanta Road, Xi’an, 710054, China

Zhuming Wang

Laboratory of Mineralization and Dynamics, College of Earth Sciences and

Land Resources, Chang’an University, 126 Yanta Road, Xi’an, 710054, China

ABSTRACT

In this paper, elements including Al, Cr, Mn, Fe, Cu, Zn, As, Se, Cd and Pb in scalp hair

samples from five male adults in the age of 50 – 55 were accurately quantified by

inductively coupled plasma mass spectrometry (ICP-MS). The ICP-MS quantification

results were analyzed according to the recommendation from the Trace Element

Research Council of China. It was found that the contents of Cr, As, Cd, and Pb were

within the permitted ranges, while the concentrations of Mn, Fe, and Cu

differentiated individually. It was worth noting that Fe contents in two samples

were over 200 μg·g–1, which were higher than the highest permitted value of 130

μg·g–1. Interestingly, these two specimens also exhibited relatively higher

concentrations of Mn and Cu. For Se, all five specimens showed slightly higher than

the upper permitted value of 0.6 μg·g–1. But Al far exceeded the allowed 7.0 μg·g–1,

yielding a ratio up to approximately 26-fold. It was also found that the content of Zn

in one sample was out of the permitted range, giving about 13.5% lower than the

least required concentration. It can thus be deduced that the participants having an

accumulation of Mn, Fe, Cu, Se or Al were suggested to control the daily ingestion of

these elements from foodstuff and/or medicine, while the participant showing Zn

deficiency was recommended to take a reasonable amount of Zn supplements. From

this study, all these participants were highly recommended to take a detailed check- up for the further health status assessment.

Keywords: Human scalp hair, trace element quantification, health status evaluation,

acidic digestion, ICP-MS.

INTRODUCTION

Trace elements in biochemistry are known as the dietary minerals required in minute amounts

for proper growth, development, and physiology of organs [1]. The inorganic trace elements in

human bodies have diverse roles in a range of biological activities, such as immune system

effectiveness, tissue development/maintenance, and cell metabolic rate optimization [2, 3].

Among various inorganic trace elements, some metal elements such as Zn, Cu, Fe, Mn, Cr and Se

exhibit unique physiological properties and indispensable for human, which are called essential

and/or nutrition elements [4, 5]. For example, element Zn usually functions as a cofactor for

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certain enzymes involved in metabolism and cell growth [6, 7]. It is also known that element Cu

is not only a pivotal constituent in a series of enzymes, but also helpful for bone’s

growth/formation, and the iron absorption/transferring [8, 9]. Similarly, the element Cr in form

of Cr (III) can increase enzyme activities, and show important functions in carbohydrate

metabolism, stimulation of fatty acid, and cholesterol synthesis [10, 11]. However, some other

trace elements involving As, Cd and Pb are regarded as xenobiotics due to no clear body

functions and well-known harmful effects at trace levels [12-14]. Such elements exert biological

toxicities causing health problems from neural to genetic systems [15]. For instance, Pb was

shown to result in behavior abnormalities, and learning/hearing disorders [14], while Cd can

inhibit the repairs of DNA mismatch [14, 16]. Also, the element As was found to correlates to

hyperpigmentation, keratosis, various types of cancer and vascular diseases [12, 13, 17]. The

element Al, which can cross the blood-brain barrier and accumulate into glial and neuronal cells

[18], is highly neurotoxic and thus proposed to be involved in Parkinsonism, dementia, and

Alzheimer’s disease [19]. In fact, the excessive essential/nutrition trace elements can become

toxic for body health and might cause fatal diseases [20-22]. On the other side, the deficiency of

essential/nutrition trace elements could make the involving biological functions impaired and

result in severe malfunctions [23, 24]. Islam et al. [25] comprehensively summarized the

relationships between trace elements and human health. Hence, the concentration level

evaluation of trace elements is of importance in both the identification of the excess or

deficiency of specific nutrients and the prediction of the undesired exposure to contaminants

from environment.

Trace element concentration levels in human beings are usually assessed using blood and urine.

However, both blood and urine samples reflect the xenobiotic exposure for a very short or

limited period, and the analytical results from such matrices fluctuate with any changes in

physiological or environmental condition. Human hair, which grows at a rate of approximately

1 cm per month and exhibits high affinity to most inorganic elements, has been proved to

provide a more permanent and historic record of trace elements assimilated from human

medium [26]. Furthermore, hair sample is characterized by non-invasive collection, convenient

storage, and less hazardous handling [27]. The hair matrix has thus become an attractive

biological material in studies related to pollutant exposure [28], medicine [29], forensics [30],

archaeology [31], nutrition [32], and effect of lifestyle on human health [33], etc. For example,

scalp hair as an efficient biomarker was used in the monitoring of heavy metals on large cohorts

[34], occupational exposure determination [35] and the exposure observation of local habitants

in polluted areas [36-38]. Many analytical approaches were employed to determine trace

elements in human hair samples. Atomic absorption spectrophotometry (AAS) was the most

frequently utilized technique in trace element determination of human hair samples [39-43].

Other techniques including inductively coupled plasma atomic emission spectrometry (ICP- AES) [44-46], atomic fluorescence spectrometry [47], spectrofluorimetric [48], anodic

stripping voltammetry [49], particle-induced X-ray emission [50] and X-ray fluorescence [51]

were also developed for the quantification of trace elements in hair samples. ICP mass

spectrometry (ICP-MS) is a sophisticated technique for multi-element determination at trace

levels, showing merits of low detection limits, high sensitivities, wide dynamic ranges, and

excellent element resolution [52]. By using ICP-MS technique, trace elements in human hair

samples were studied and applied to therapeutic treatment identification [53], health risk

assessment in mining affected area [36, 44, 54]/electronic waste recycling area [55], long-term

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Tan, X. & Wang, Z. (2024). Trace Elements Determination in Human Scalp Hair by Inductively Coupled Plasma Mass Spectrometry and Its Application

to Health Status Assessment. European Journal of Applied Sciences, Vol - 12(6). 609-620.

URL: http://dx.doi.org/10.14738/aivp.126.18025

safety monitoring of environmental exposure to pollutants [56, 57], and screening tests in

different diseases [58].

In this work, human scalp hair sample as a biomarker for health risk assessment was evaluated

via trace element concentration levels. The scalp hair samples from five male adults between

50 and 55 years old were decomposed by a low-pressure closed wet digestion pattern using

concentrated HNO3. Ten trace elements including Al, Cr, Mn, Fe, Cu, Zn, As, Se, Cd, and Pb, in the

scalp hair samples were then quantified by ICP-MS. The potential health risks of the

participants were discussed in detail according to the permitted values set by the Trace

Element Research Council of China (TERCC).

EXPERIMENTAL

Reagents and Standard Solutions

High purity acids and ultra-pure water were used throughout in this work. To remove metallic

or cationic impurities, the commercially available acid of HNO3 (68% v/v, AR grade) was

treated by a sub-boiling distillation system (Savillex DST-1000-PFA, USA) using a middle mode

prior to usage. Ultra-pure water with a resistivity of 18.2 MΩ·cm was obtained by passing

deionized water through a Milli-Q water purification system (Millipore, Bedford, MA, USA).

Here, five solutions containing elements Al, Cr, Mn, Fe, Cu, Zn, As, Se, Cd, and Pb (5, 20, 50, 80

and 100 ng·g–1) in 2% HNO3 (v/v), which were used as the external calibrators, were prepared

by gravimetric dilution from a Multi-element Calibration Standard solution of 10 μg·g–1 (Agilent

Technologies, Tokyo, Japan).

Instrumental Apparatus

In this work, the element quantification was carried out on a Thermofisher Scientific X series

ICP-MS instrument (Waltham, MA, USA). The configuration of this ICP-MS was described in

detail in our previous work [63]. The ICP-MS was optimized daily by mass calibration to obtain

stable and relative maximum signal intensities for elements Li, Co, In, and U by using a tuning

solution of 10 ng·mL–1. Before optimization, the mass resolution was adjusted to achieve a 10%

peak width of 0.7 – 0.8 amu. During the optimization, the ratios for oxide formation, hydroxide

formation and doubly charged species were controlled less than 2.0%. The details of parameter

optimization were discussed below. Before element determination, the pulse/analog factors of

the detector were calibrated using a multi-element tuning solution of 500 ng·mL–1. A 10 ng·mL–

1 of Rh solution, which was prepared using 1.0 mg·mL–1 of single-element standard solution

(the National Institute of Standards and Technology, Beijing, China), was aspirated online as an

internal standard element to correct any signal drift from the organic matrix effect of hair

samples. In addition, the quantification quality was controlled by repeatedly analyzing a

standard solution using an SSB (standard-sample bracketing) strategy. The typical operating

conditions and optimum instrumental parameters were summarized in TABLE 1.

Table 1: Operating parameters for the utilized Thermofisher X series ICP-MS

instrument. 1

Instrument parameters Operating conditions Instrument

parameters

Operating

conditions

Spray chamber Cone chamber at 2 oC Extraction* −561 v

Sample/skimmer cone Nickle/Xi, 1.1/0.75 mm Focus* 22 v

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Scan type Peak jumping Lens 1* −10.0 v

Output power 1250 W Lens 2* −39.2 v

Nebulizer inserting

depth*

3.0 cm Lens 3* −182.7 v

Plasma Ar* 14.5 L·min−1 D1* −36.5 v

Auxiliary Ar* 0.80 L·min−1 D2* −145 v

Nebulizer Ar* 0.80 L·min−1 DA* −35.3 v

Sampling depth* 100 Pole bias* 2.8 v

Dwell time* 10 ms Hexapole* 2.0 v

Sweeps* 20 Horizontal position* 70

Sample introduction

rate*

1.0 L·min−1 Vertical position* 400

Mass resolution Standard Analog voltage* 1950 v

Detector mode Dual Pulse counting

voltage*

2670 v

1 The parameters marked with a star are the default values that can be optimized daily.

Hair Sample Collection and Handling

Here, the study associated to hair sample collection and analysis were performed according to

the legal provisions and rules of the Hospital of Chang’an University. Informed consent was also

obtained from all the individual participants involved in this study. Additionally, the

experimental protocol of the present investigation including hair sample digestion and

application of trace elements to health status assessment was approved by the Local Ethics

Committee.

Five local male residents, who were in the age of 50 – 55, voluntarily joined this study and

declared that there had been no usage of hairspray and hair dyes at least one year before

sampling. The collected hair samples, approximately 2.0 cm, were taken from the occipital

region of the participants. After sampling, the hair samples were stored in air-tight sealed

plastic bags and transferred to a thousand-clean room in the Laboratory of Mineralization and

Dynamics, Chang’an University. The collected hair samples were thoroughly washed with

detergent and subsequent ultra-pure water to eliminate the absorbed mud and dust particles,

and then cut into 1 – 2 mm by a scissor which is made of polytetrafluoroethylene (PTFE) to

avoid potential elemental contamination. Thereafter, the hair samples were rinsed with ultra- pure water and dried at 80 °C in an oven for 4 h before subsequent digestion.

In this work, the hair samples were directly decomposed by using concentrated HNO3 via a low- pressure acidic digestion method. In brief, the samples with weight of about 0.70 g were

transferred into PTFE vessels, and the concentrated HNO3 with a volume of 5 mL was carefully

added. After been continually heated at 125 °C for 15 min, the samples in the sealed vessels

were evaporated until incipient dryness. Then, the samples were fortified with 2.0 mL of ultra- pure water and heated to reach incipient dryness again. Thereafter, 2.0 mL of 2% HNO3 (v/v)

were introduced into the samples, and the sample solutions were naturally cooled down to

ambient temperature. Finally, the digested samples were diluted using 2% HNO3 (v/v) to the

10.0-mL calibrated mark. Here, to reduce the possible effect from the decomposed proteins on

sample introduction system in particular the nebulizer device of the ICP-MS, the decomposed

sample solutions were then filtrated through the Sartorius ash-free qualitative filter paper

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Tan, X. & Wang, Z. (2024). Trace Elements Determination in Human Scalp Hair by Inductively Coupled Plasma Mass Spectrometry and Its Application

to Health Status Assessment. European Journal of Applied Sciences, Vol - 12(6). 609-620.

URL: http://dx.doi.org/10.14738/aivp.126.18025

(0.22 μm, Goettingen, Germany). Thereafter, the samples were directly taken for trace element

determination by the optimized ICP-MS.

Spiking Procedures

The repeatability of the ICP-MS detector in this work was tested with calibration procedures

carried out on three different days. The quantification precision was assessed via repetitive

measurements for all the analytes in standard solutions and digested hair samples with RSDs

studied. The standard reference material (SRM) GBW09101 was applied to accuracy evaluation

of this proposed approach. In brief, the SRM GBW09101 was decomposed as above, and known

quantities of standard solutions which contained elements Al, Cr, Mn, Fe, Cu, Zn, As, Se, Cd, and

Pb were fortified. After the mixture became homogeneous, the trace elements were then

assayed by ICP-MS, and the spiked recoveries were studied.

RESULTS AND DISCUSSION

Experimental Condition Optimization for ICP-MS

Considering the operation property of the quadrupole ICP-MS, a daily instrumental

optimization was done before any element quantification. Here, the effects of

nebulizer/plasma/auxiliary gas flow rate, and sampling depth were discussed in detail for this

utilized ICP-MS. The influence of nebulizer gas flow rate from 0.6 to 1.2 L·min–1 on oxide

formation (CeO+/Ce+), hydroxide formation (CeOH+/Ce+) and doubly charged species

(Ce2+/Ce+) was checked, with results graphically shown in FIGURE 1. It can be seen from

FIGURE 1 that the formation of oxides and hydroxides exhibited a close relationship with

nebulizer gas flow rate. Generally, the obtained ratios of CeOH+/Ce+ and CeO+/Ce+ were lower

than 1.1% with a nebulizer gas flow rate less than 0.8 L·min–1. But an exaggerating increment

of oxide formation and hydroxide formation with ratio values over 3.0% was observed. On the

other hand, the ratio of Ce2+/Ce+ first went up to 3.3% and then declined obviously with

nebulizer gas flow rate higher than 0.75 L·min–1. It was obvious that these observed phenomena

were similar with those in our previous work [59], in which the optimal nebulizer gas was 0.85

L·min–1. We assumed that such slight differentiation might come from the compromise of the

parameters of this ICP-MS configuration, or the status of the nebulizer/quartz torch devices for

human hair sample matrix.

Figure 1: The effect of nebulizer gas flow rate on analyzing the accuracy of ICP-MS [59].

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To further assure the optimal nebulizer gas flow rate, the signal intensities of low- to high-mass

elements were studied when applying 0.65 – 0.95 L·min–1 of nebulizer gas flow rate. The results

were given in FIGURE 2, where a 10 ng·mL−1 of the tuning standard solution was used. As shown

in FIGURE 2, the signal intensities from low- to high-mass including Li, Co, In, and U were found

to increase steadily with the increasing nebulizer gas flow rate up to 0.80 L·min–1. After that,

the signal intensities of Co, In, and U slightly declined, while the signal intensity of low mass

element Li presented a staggering decrement. Thus, 0.80 L·min−1 of nebulizer gas flow rate was

chosen as optima in this work. Here, the effects of plasma and auxiliary gas flow rates on the

m/z counting rate were tested within 11.0 – 16.0 and 0.60 – 0.85 L·min−1, respectively. Under

the optimized nebulizer gas flow rate, results showed that 14.5 L·min−1 of plasma gas flow rate

and 0.80 L·min−1 of auxiliary gas flow rate yielded relatively high and stable signal intensities

for Li, Co, In and U.

Figure 2: Relationship of element counting intensity versus nebulizer gas flow rate.

To enhance the signal sensitivity and improve the determination precision, the sampling depth

in a range from 80 to 120 was examined in this work, and the results were graphically given in

FIGURE 3. It was observed that the element signal sensitivities varied differently with sampling

depth. As shown in Figure 3, the signal intensity of low-mass Li increased with the increasing

sampling depth, but the signal intensity of mid-mass Co was found to increase first and then

decline from 100 of sampling depth. It was worth noting that the signal intensity of high-mass

U had small variations with the sampling depth less than 100, and then exhibited a prominent

decrement. For element In, the signal intensity presented a steady decline from 80 to 110 of

sampling depth and then became stabilized. Considering the compromise of the stability of

signal intensity and element sensitivities, a sampling depth of 100 was selected in the

subsequent work. The optimum values of nebulizer inserting depth and sample introduction

rate, and the typically default values of dwell time, sweeps, lens voltages, torch position and RF

power were collected in TABLE 1.

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Tan, X. & Wang, Z. (2024). Trace Elements Determination in Human Scalp Hair by Inductively Coupled Plasma Mass Spectrometry and Its Application

to Health Status Assessment. European Journal of Applied Sciences, Vol - 12(6). 609-620.

URL: http://dx.doi.org/10.14738/aivp.126.18025

Figure 3: The influence of sampling depth on the element counting intensity. Here, the effect of

sampling depth was studied by continuous aspirating a 10 ng·mL−1 of tuning standard solution

into the ICP-MS, with relative signal intensities of Li, Co, In and U recorded.

Repeatability and Accuracy Study of Element Analysis in Hair Sample by ICP-MS

To evaluate the repeatability of this approach, a series of standard solutions (5, 50, 100 ng·g–1)

and digested human hair samples were repetitively quantified in three consecutive days under

the proposed optimum operating conditions given in Table 3 with the determination RSDs

studied. Results showed that the RSDs for intra- and inter-day measurements were less than

4.0% (n = 5), which indicated the capability of this current method for trace element

determination in hair samples.

It is known that the accuracy of a method is typically verified by comparing quantification

results of the SRM from the proposed method and the certified values with the absolute or the

relative errors assayed. Here, the hair SRM GBW09101 was applied to the accuracy study of

this ICP-MS approach. By taking the concentration differences for the elements in this hair

standard material into consideration, 1.0 g of this hair SRM sample was digested as mentioned

above and the solution was then split into three parallel batches. For these three batches, one

was directly introduced to the ICP-MS for trace element measurement, and the other two were

diluted 10 and 102-fold before element analysis, respectively. The concentration levels of trace

elements Al, Cr, Mn, Fe, Cu, Zn, As, Se, Cd, and Pb in the SRM sample were quantified by ICP-MS

using the spiked-recovery protocol. The analytical results including RSDs, determination

recoveries, and element concentrations were collected in TABLE 2.

Table 2: Accuracy study results for SRM GBW09101 by the proposed ICP-MS

method. 1

Elements Added

ng·g–1

Found

ng·g–1

RSDs

%

Recovery

%

Content

μg·g–1

Referred value

μg·g–1

Al 20 43.5 2.7 102.5 23.0 ± 1.2 23.2 ± 2.0

30 52.6 2.8 97.1 23.5 ± 1.5

Cr 70 158.2 1.6 101.4 8.72 ± 0.25 8.74 ± 0.97

100 185.4 1.3 97.9 8.75 ± 0.24

Mn 30 68.1 2.3 100.6 3.79 ± 0.33 3.83 ± 0.38

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50 89.2 2.0 103.4 3.75 ± 0.26

Fe 100 263.4 1.6 98.4 165 ± 3.8 160 ± 16

200 361.8 1.1 97.9 166 ± 1.9

Cu 20 52.5 2.2 93.5 33.8 ± 1.2 33.6 ± 2.3

30 63.0 3.2 97.7 33.7 ± 2.0

Zn 100 292.5 2.3 105.1 189 ± 6.7 191 ± 16

200 391.6 2.5 100.8 190 ± 9.8

As 10 29.5 1.2 96.5 0.199 ± 0.011 0.198 ± 0.023

20 39.7 1.5 100.6 0.196 ± 0.060

Se 10 68.6 2.2 96.4 0.59 ± 0.06 0.59 ± 0.04

20 77.8 2.8 102.0 0.57 ± 0.04

Cd 10 17.4 1.1 103.2 0.071 ± 0.014 0.072 ± 0.010

20 27.2 1.9 99.5 0.073 ± 0.012

Pb 30 68.7 2.3 101.1 3.84 ± 0.16 3.83 ± 0.18

50 89.6 1.8 102.0 3.86 ± 0.16

1 Elements Al, Mn, Fe, Cu, and Zn were analyzed in the batch sample with a dilution index of 102; Cr, As, Se, and

Pb are analyzed in the batch sample with a dilution index of 10; Cd is analyzed in the batch sample without

further dilution. Results were given as the average of five repetitions.

Apparently, the concentration results of the studied trace elements in this hair SRM highly

agreed with the certified values, giving the determination recoveries ranging from 93.5% to

105.1% and RSDs less than 2.8% (n = 5). Hence, it can be deduced that this proposed method

was capable of accurately quantifying the trace element in hair samples.

Trace Element Determination Results in Human Scalp Hair Samples

The scalp hair samples from five male adults (50 – 55 years old) were decomposed as described

in sample handling section. Under the optimized conditions of ICP-MS system, the elements

including Al, Cr, Mn, Fe, Cu, Zn, As, Se, Cd, and Pb in the hair samples were measured with RSDs

lower than 3.2% (n = 5), and the determination results which were given in the form of 95%

confidential level were summarized in TABLE 3. It can be seen from TABLE 3 that the

concentration levels of the ten elements varied in different degrees for the studied hair samples.

It was clear that the contents of Al, Mn, and Fe for the five specimens were in a wide range of

8.45 ± 0.19 to 181.7 ± 2.1 μg·g–1, 2.74 ± 0.08 to 15.73 ± 0.28 μg·g–1, and 28.30 ± 0.57 to 230.1 ±

7.4 μg·g–1, respectively. The other seven elements including Cr, Cu, Zn, As, Se, Cr, and Pb showed

corresponding concentration ranges of 0.58 ± 0.01 ~ 1.09 ± 0.03 μg·g–1, 12.48 ± 0.52 ~ 22.88 ±

0.79 μg·g–1, 103.8 ± 2.3 ~ 151.9 ± 2.9 μg·g–1, 0.23 ± 0.01 ~ 0.61 ± 0.04 μg·g–1, 0.81 ± 0.03 ~ 0.93

± 0.08 μg·g–1, 0.05 ± 0.01 ~ 0.23 ± 0.01 μg·g–1, and 2.39 ± 0.11 ~ 7.95 ± 0.23 μg·g–1, respectively.

Table 3: Analytical results for trace elements in scalp hair samples. 1

Elements Sample 1

μg·g–1

Sample 2

μg·g–1

Sample 3

μg·g–1

Sample 4

μg·g–1

Sample 5

μg·g–1

TERCC permitted value

μg·g–1

Al 8.45 ±

0.19

17.13 ±

0.45

70.35 ±

1.6

90.25 ±

1.4

181.7 ±

2.1

≤ 7.0

Cr 0.58 ±

0.01

0.64 ±

0.05

0.82 ±

0.03

0.94 ±

0.03

1.09 ±

0.03

0.3 ~ 1.2

Mn 2.74 ±

0.08

2.79 ±

0.08

7.34 ±

0.22

10.57 ±

0.28

15.73 ±

0.28

0.8 ~ 2.8

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Tan, X. & Wang, Z. (2024). Trace Elements Determination in Human Scalp Hair by Inductively Coupled Plasma Mass Spectrometry and Its Application

to Health Status Assessment. European Journal of Applied Sciences, Vol - 12(6). 609-620.

URL: http://dx.doi.org/10.14738/aivp.126.18025

Fe 28.30 ±

0.57

46.87 ±

1.69

46.66 ±

0.61

230.1 ±

7.4

216.9 ±

8.7

20 ~ 130

Cu 16.06 ±

0.29

12.48 ±

0.52

20.62 ±

0.43

18.01 ±

0.62

22.88 ±

0.79

8.0 ~ 20

Zn 130.4 ±

2.2

148.9 ±

3.9

103.8 ±

2.3

145.2 ±

2.8

151.9 ±

2.9

120 ~ 210

As 0.46 ±

0.04

0.23 ±

0.01

0.61 ±

0.04

0.28 ±

0.03

0.54 ±

0.07

≤ 1.0

Se 0.88 ±

0.05

0.93 ±

0.08

0.81 ±

0.03

0.86 ±

0.06

0.83 ±

0.07

0.2 ~ 0.6

Cd 0.05 ±

0.01

0.09 ±

0.01

0.16 ±

0.01

0.12 ±

0.01

0.23 ±

0.01

≤ 0.6

Pb 3.90 ±

0.11

2.39 ±

0.11

7.95 ±

0.23

5.46 ±

0.13

2.65 ±

0.01

≤ 10

1 The RSDs were less than 3.2% (n = 5), and the results were given in 95% confidential level.

Assessment of Potential Health Risk Based on The Trace Element Analysis

To further evaluate the concentration levels of the studied elements in the hair samples, the

quantification results were compared to the permitted values from the TERCC which were

compiled in TABLE 3. it was found that the elements Cr, As, Cd, and Pb in the five hair samples

were well within the suggested ranges, which revealed that the daily intakes of these trace

elements were reasonable. It was also observed that the concentration levels of element Mn,

Fe, and Cu differentiated individually. For element Fe in sample 4 and sample 5, the contents

were found to reach 230.1 ± 7.4 and 216.9 ± 8.7 μg·g–1, respectively. It was clear that they were

over the highest Fe permitted value of 130 μg·g–1. Since the excess Fe can cause direct intestine

damage, oxidative stress and/or pathogen growth [60], these two participants were specifically

suggested to lower down the iron enriched foodstuff. It was worth noting that these two sample

specimens also exhibited relatively higher concentrations of Mn and Cu, which might reveal

that there existed potential health risks associated to synaptic dysfunction and interruption of

axonal transport [61]. When came to element Se, all the five specimens were found to be slightly

higher than the upper permitted value of 0.6 μg·g–1. But element Al far exceeded the allowed

7.0 μg·g–1, showing 1.2 – 26-fold higher than the upper limit. The sample 5 in particular had the

concentration of Al high up to 181.7 ± 2.1 μg·g–1, yielding a ratio to the highest suggested value

of approximately 26-fold. It can thus be deduced that there might be a slight burden of Mn, Fe,

and Cu for some participants, but a relatively heavy burden of Se and Al to different degrees for

all the five participants. Thus, the daily ingestion of these elements from foodstuff and/or

medicine should be controlled stringently, and a detailed routine check-up for these

participated males was highly recommended. For element Zn, it was found that only the content

in sample 3 was out of the permitted range, showing about 13.5% lower than the least required

concentration which demonstrated there might exist deficiency of this element. This suggested

that a reasonable intake of Zn supplements was necessary for this participant due to the

possible health risks from Zn deficiency [62].

CONCLUSION

In this paper, trace elements including Al, Cr, Mn, Fe, Cu, Zn, As, Se, Cd, and Pb in human scalp

hair samples were accurately quantified by the proposed ICP-MS approach, with determination

recoveries in a range of 93.5 – 105.1% and RSDs less than 2.8% (n = 5). The data analysis

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according to the recommendations from the TERCC revealed that elements Cr, As, Cd, and Pb in

the participants lay within the suggested ranges. However, the concentrations of Mn, Fe, and Cu

in some participants were found to be higher than the upper permitted values, which revealed

that there might be health risks such as synaptic dysfunction and interruption of axonal

transport. Furthermore, all the participants showed concentration levels of Se and Al over the

allowed highest values. It was worth noting that the content of element Al in sample 5 were 26-

fold higher than the upper limit of 7.0 μg·g–1. It can thus be deduced that there might be a

relatively heavy burden of element Al to some degree for the participated male adults, who

might have potential health risks associated to Al excess. It was also observed that element Zn

contents in the studied hair samples expect sample 3 were in the permitted concentration

range, showing there might be Zn deficiency for this participant.

By this current trace element analysis in scalp hair samples, it was highly recommended that

the routine ingestion of Al and Se from daily diet and/or medicine must be regulated strictly for

all the participants, while the daily intake of foodstuff which enrich in Mn, Fe and Cu should be

carefully controlled for some participants. Additionally, a reasonable intake of Zn supplements

was suggested for the participant who showed the deficiency of Zn. Collectively, a detailed

routine check-up for these participants was highly recommended based on the analytical

results of trace elements in scalp hair matrix. Our study clearly assured the practical value of

scalp hair as a biomarker for nutrition status and health risk evaluation via trace element

analysis, promising an alternative strategy in merits of convenience and non-invasive sampling

for mass health status investigation.

Conflicts of Interest

The authors declare no conflict of interest.

ACKNOWLEDGEMENTS

We highly appreciate constructive comments from anonymous reviewers and the editor. This

research was funded by the metal element analytical program, China (No. 220227210701). The

authors also gratefully acknowledge the instrument support from the Laboratory of

Mineralization and Dynamics, College of Earth Sciences and Land Resources, Chang’an

University.

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