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Kumasaka,1,3Gaku Ichihara,3 Masashi Kato1,3,4 1 Unit of Environmental Health Sciences, Department of Biomedical Sciences, College of Life and Health Sciences, Chubu University, Kasugai-s

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Human Nontumorigenic Keratinocytes Exposed

to a Low Level of Barium for a Long Time

Nguyen D Thang,1,2 Ichiro Yajima,1,3Shoko Ohnuma,4Nobutaka Ohgami,1,4

Mayuko Y Kumasaka,1,3Gaku Ichihara,3 Masashi Kato1,3,4

1

Unit of Environmental Health Sciences, Department of Biomedical Sciences,

College of Life and Health Sciences, Chubu University, Kasugai-shi, Aichi, 487-8501, Japan

2

Department of Biochemistry and Plant Biology, Vietnam National University, Hanoi, Vietnam

3

Department of Occupational and Environmental Health, Nagoya University Graduate School

of Medicine, 65 Tsurumai-cho, Showa-ku, Nagoya, Aichi, 466-8550, Japan

4

Voluntary Body for International Health Care in Chubu University, Kasugai,

Aichi, 487-8501, Japan

Received 14 January 2013; revised 20 May 2013; accepted 22 May 2013

ABSTRACT: We have recently demonstrated that exposure to barium for a short time (4 days) and at a

low level (5 mM 5 687 mg/L) promotes invasion of human nontumorigenic HaCaT cells, which have

charac-teristics similar to those of normal keratinocytes, suggesting that exposure to barium for a short time

enhances malignant characteristics Here we examined the effect of exposure to low level of barium for a

long time, a condition mimicking the exposure to barium through well water, on malignant characteristics

of HaCaT keratinocytes Constitutive invasion activity, focal adhesion kinase (FAK) protein expression and

activity, and matrix metalloproteinase 14 (MMP14) protein expression in primary cultured normal human

epidermal keratinocytes, HaCaT keratinocytes, and HSC5 and A431 human squamous cell carcinoma

cells were augmented following an increase in malignancy grade of the cells Constitutive invasion

activ-ity, FAK phosphorylation, and MMP14 expression levels of HaCaT keratinocytes after treatment with 5 mM

barium for 4 months were significantly higher than those of control untreated HaCaT keratinocytes Taken

together, our results suggest that exposure to a low level of barium for a long time enhances constitutive

malignant characteristics of HaCaT keratinocytes via regulatory molecules (FAK and MMP14) for invasion.

V C 2013 Wiley Periodicals, Inc Environ Toxicol 30: 161–167, 2015.

Keywords: barium; focal adhesion kinase; invasion; keratinocytes; matrix metalloproteinase; well water

INTRODUCTION

Pollution of well drinking water with toxic elements is a serious public health problem throughout the world Previ-ous studies showed that over 200 million people worldwide face the risk of exposure to highly toxic elements, including arsenic, from drinking well water (Sun et al., 2006; Wang

et al., 2010) More than 25 million patients with arsenicosis

in Bangladesh have been reported (Chowdhury et al., 2000), and about 10 million patients with arsenicosis in the Red

Correspondence to: M Kato; e-mail: katomasa@med.nagoya-u.ac.jp

Supported by: Ministry of Education, Culture, Sports, Science and Technology

(MEXT) (Grants-in-Aid for Scientific Research [B], Nos 20406003, 24390157, and

24406002; Grant-in-Aid for Challenging Exploratory Research, No 23650241;

Grant-in-Aid for Scientific Research on Innovative Areas, No 24108001); MEXT

and Chubu University (COE Project [Health Science Hills] for Private Universities,

No S0801055); Supported by: Japan Society for the Promotion of Science (JSPS

[AA Science Platform Program]); Tokyo Biochemical Research Foundation; the

Naito Foundation Natural Science Scholarship; the Uehara Memorial Foundation;

AEON Environmental Foundation; The Cosmetology Research Foundation.

Published online 26 June 2013 in Wiley Online Library

(wileyonlinelibrary.com) DOI: 10.1002/tox.21881

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River Delta and 1 million patients with arsenicosis in the

Mekong River Delta in Vietnam have been reported (Berg

et al., 2007) Moreover, epidemiological studies have

revealed increases in skin, lung, liver, prostate, and bladder

cancers in patients with arsenicosis (Smith et al., 1992)

Since experimental studies have also provided evidence that

arsenic promotes cellular malignant characteristics (Tokar

et al., 2010; Kato et al., 2011b; Singh et al., 2011), arsenic in

well water is believed to be a main cause of tumorigenesis

The skin is thought to be one of target organs of arsenic

because skin melanosis and hyperkeratosis develop in

patients with arsenicosis (Ahsan et al., 2000; Chowdhury

et al., 2000; Pimparkar and Bhave, 2010) Bowen’s disease

(carcinomain situ) and squamous cell carcinoma (SCC) are

known as representative skin cancers derived from chronic

exposure to arsenic (Chowdhury et al., 2000; Pimparkar and

Bhave, 2010) However, the evidence does not rule out the

possibility that another element as well as arsenic in well

water contributes to carcinogenesis of the skin in humans

Multistep carcinogenesis through steps including

initia-tion, promoinitia-tion, transformainitia-tion, and progression has been

proposed for various carcinomas including skin cancer

(Zoumpourlis et al., 2003; Kumasaka et al., 2010, 2013)

Ini-tiation is the first step of tumor development and is

irreversi-ble Promotion is the step of clonal expansion of the initiated

cells, resulting in formation of benign tumors (Zoumpourlis

et al., 2003) Transformation is the step of change from

benign tumors to malignant tumors Transformed cells gain

hyperproliferative and antiapoptotic characteristics, invasion

activity, and anchorage-independent growth capability (Berg

et al., 2007; Tsuji et al., 2008) Progression is the step to

gain further invasive potential for distant metastasis and

sur-vival potential of anchorage-independent growth

(Zoum-pourlis et al., 2003; Mehlen and Puisieux, 2006) The in

vitro invasion assay is a method to evaluate cellular motility

and invasion activity in transformed cells (Thang et al.,

2011) Since increased invasion is a crucial step in the

devel-opment of cancer, invasion activity is one of the hallmarks

of malignant characteristics (Kato et al., 2002; Thang et al.,

2011; Yajima et al., 2012a) Previous studies showed that

focal adhesion kinase (FAK) phosphorylation and matrix

metalloproteinase 14 (MMP14) expression levels play a key

role in invasion (Hahne et al., 2005; Kato et al., 2008; Thang

et al., 2011)

HaCaT keratinocytes, spontaneously transformed human

epithelial cells from adult skin, are immortal but remain

non-tumorigenic HaCaT keratinocytes express

differentiation-specific keratins and other markers (involucrin and filaggrin)

and exhibit normal proliferation, suggesting that HaCaT

keratinocytes are similar to normal keratinocytes (Boukamp

et al., 1988) Therefore, HaCaT keratinocytes are useful for

examining the effects of environmental factors on malignant

characteristics of human keratinocytesin vitro (Thang et al.,

2011) In fact, we showed that exposure to barium alone for

a short time (4 days) promotes invasion activity in human

nontumorigenic HaCaT keratinocytes in addition to murine nontumorigenic melanocytes and fibroblasts (Bennett et al., 1987; Boukamp et al., 1988; Kato et al., 2002; Thang et al., 2011) Moreover, a classical study in humans showed that one external application of barium and dimethyl sulfoxide to the uterine cervix resulted in the development of dysplasia and carcinoma in situ (Ayre and LeGuerrier, 1967) These results suggest that exposure to barium for a short time enhances cellular malignant characteristics in nontumori-genic cells However, there has been very limited study on the influence of exposure to barium for a long time on con-stitutive cellular malignant characteristics, despite the fact that residents of cancer-prone areas suffer form chronic exposure to barium in addition to arsenic

Previous studies showed high levels of barium in arsenic-polluted well water in Bangladesh and Vietnam (Thang

et al., 2011; Winkel et al., 2011) Since previous studies have shown increased malignant characteristics in HaCaT keratinocytes that were exposed to arsenicin vitro for a long time (Achanzar et al., 2002; Benbrahim-Tallaa et al., 2005), this study was carried out to determine the constitutive effect

of exposure to barium for a long time, at a level at which people drinking well water are exposed to, on cellular malig-nant characteristics through invasion activity

MATERIALS AND METHODS Analysis of Barium Concentration

The levels of barium in well water samples from Ho Chi Minh (n 5 33) and Mekong Delta (n 5 67) in Vietnam were measured by using an inductively coupled plasma-mass spectrophotometer (7500cx, Agilent Technologies, CA) fol-lowing the method previously described (Kato et al., 2010)

Cell Lines and Culture Conditions

Human immortalized HaCaT keratinocytes (German Can-cer Research Center “DKFZ,” Germany) (Boukamp et al., 1988; Calay et al., 2010) and human HSC5 (Health Sci-ence Research Resources Bank, Japan) and A431 (Riken Bioresource Center, Japan) SCC cells were cultured in RPMI-1640 with 10% fetal bovine serum (FBS) on collagen-coated dishes (Kato et al., 1999; Ohshima et al., 2010) Normal human epithelial keratinocytes (NHEK) purchased from Kohjin Bio were cultured following the instructions from the company Barium-treated HaCaT (BT-HaCaT) keratinocytes and barium-untreated control HaCaT (C-HaCaT) keratinocytes were developed through culture in the presence or absence of 5 mM barium (BaCl2, Wako, Osaka, Japan), respectively, for 4 months (37 pas-sages) BT-HaCaT keratinocytes were used for in vitro invasion assay and immunoblot analysis after culturing in the medium without barium for more than 2 weeks to wash out barium from the keratinocytes

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The In Vitro Invasion Assay

The in vitro invasion assay was performed according to

the method described previously (Thang et al., 2011) To

examine constitutive invasion activity in various kinds of

keratinocytic cells, the assay in this study was performed

in the condition without barium Briefly, 2 3 105 cells in

300 mL culture medium with 0.5% FBS were applied to

the Matrigel-coated upper chamber of 8 mm in diameter

(8 mm in pore size) Then the upper chambers were

placed in 24-well culture plates containing 600 mL

condi-tioned medium with 0.5% FBS to trigger invasion activity

and were incubated for 12 hours Invading cells were

stained with hematoxylin and counted under a

microscope

Immunoblot Analysis

Immunoblot analysis was performed according to the

method described previously (Kato et al., 2002) Rabbit

pol-yclonal primary antibody against anti-phosphorylated

tyro-sine 397 in FAK (Invitrogen, California, USA) and mouse

monoclonal first antibodies against anti-FAK (Millipore,

Massachusetts, USA), MMP14 (Millipore, Massachusetts,

USA) and anti-a-Tubulin (Sigma, Missouri, USA) were

used

Statistical Analysis

Statistical analysis was performed following the method pre-viously described (Kato et al., 2011a) We used the SPSS version 18 software package (SPSS Japan) for the statistical analyses, and the significance level was set atp < 0.05

RESULTS Concentrations of Barium in Well Water in Vietnam

We first measured concentrations (mean 6 SD) of barium in well water in Ho Chi Minh (129 6 62 mg/L) and Mekong Delta (281 6 133 mg/L) in Vietnam (Fig 1) The mean con-centration of barium in well water samples obtained from Mekong Delta was more than twofold higher than that in well water samples obtained from Ho Chi Minh Since the maximum level of barium in well water in Mekong Delta was 970 mg/L (57.1 mM), chronic exposure to 5 mM barium

is possible to expose

Invasion in Various Human Keratinocytic Cells

We next examined invasion activity in four kinds of kerati-nocytic cells with different malignancy grades Invasion activities of NHEK (lane 1), human nontumorigenic HaCaT keratinocytes (lane 2), and human HSC5 (lane 3) and A431 (lane 4) SCC cells are shown in Figure 2 No invading cells were observed in NHEK The ratios of invading cells in HSC5 and A431 SCC cells were about 10-fold and 14-fold higher than those in HaCaT keratinocytes, respectively

Fig 1 Levels of barium in well water samples from Vietnam.

Barium concentrations in well water samples from Vietnam

are shown Value in each sample (lanes 1 and 2) and mean

6 SD (lanes 3 and 4) are shown for samples from Ho Chi

Minh (lanes 1 and 3) and Mekong Delta (lanes 2 and 4) *,

Significantly different (p < 0.05) from the Ho Chi Minh

sam-ple by the Mann-Whitney U test.

Fig 2 Constitutive invasion activities in various human ker-atinocytic cells Ratio of constitutive invasion activities in primary cultured NHEK, nontumorigenic HaCaT keratino-cytes, and HSC5 and A431 SCC cells are shown **, Signifi-cantly different (p < 0.01) from HaCaT keratinocytes by the Mann-Whitney U test.

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These results indicated that invasion activity of HaCaT

kera-tinocytes was near that of NHEK rather than that of SCC

cells, whereas invasion activity of HaCaT keratinocytes was

intermediate between NHEK and SCC cells

We next examined phosphorylation and/or expression

levels of FAK and MMP14 in NHEK, HaCaT keratinocytes,

and HSC5 and A431 SCC cells As shown in Figure 3, level

of FAK phosphorylation and levels of FAK and MMP14

protein expression in HaCaT keratinocytes were significantly

higher than those in NHEK and were significantly lower

than those in HSC5 and A431 SCC cells Since ratios of

phosphorylated FAK (pY397/FAK) were comparable among

NHEK and HaCaT, HSC5 and A431 cells, higher levels of FAK activity in HSC5 and A431 cells than in HaCaT cells may be due to increased levels of FAK protein expression in HSC5 and A431 cells

Promoted Constitutive Activities of Invasion

in BT-HaCaT Keratinocytes

We then examined constitutive invasion activities in BT-HaCaT and C-BT-HaCaT keratinocytes As shown in Figure 4, invasion activity of BT-HaCaT keratinocytes was significantly increased compared with that of C-HaCaT keratinocytes

We finally examined constitutive levels of phosphoryla-tion and/or expression of FAK and MMP14 in BT-HaCaT and C-HaCaT keratinocytes FAK protein expression levels were comparable in BT-HaCaT and C-HaCaT keratinocytes (Figure 5) However, levels of FAK activity and MMP14 expression in BT-HaCaT keratinocytes were higher than those in C-HaCaT keratinocytes (Fig 5) Since BT-HaCaT keratinocytes were not exposed to barium in either the in vitro invasion assay or immunoblot analysis, our results sug-gest that invasion activities in BT-HaCaT keratinocytes are

Fig 3 Phosphorylation and/or expression levels of FAK and

MMP14 in various human keratinocytic cells Constitutive

tyrosine 397 (Y397) phosphorylation level in FAK

(pY397-FAK) and protein expression levels of FAK, MMP14, and

TUBULIN in primary cultured NHEK, nontumorigenic HaCaT

keratinocytes, and HSC5 and A431 SCC cells are shown.

The levels (mean 6 SD) of pY397/TUBULIN, FAK/TUBULIN,

pY397/FAK, and MMP14/TUBLIN determined by

densito-metric analyses of the bands in three independent

experi-ments are presented as graphs showing relative intensities

(multiple numbers) for HaCaT keratinocytes *, Significantly

different (p < 0.05) from control HaCaT keratinocytes by the

Mann-Whitney U test.

Fig 4 Constitutive invasion activities of BT-HaCaT and C-HaCaT keratinocytes Ratio of constitutive invasion activ-ities of BT-HaCaT and C-HaCaT keratinocytes, which were cultured in the presence or absence of 5 mM barium for 4 months, is shown *, Significantly different (p < 0.05) from C-HaCaT keratinocytes by the Mann-Whitney U test.

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constitutively increased with increased FAK activity and

MMP expression

DISCUSSION

Some elements, including manganese, iron, and zinc, for

which values were shown in the 3rd edition of WHO

health-based guidelines for drinking water were deleted in the

new-est 4th edition revised in 2011 However, the guideline value

of 700 mg/L (55.1 mM) for barium has been maintained in

the present edition of the guidelines, suggesting that toxicity

of barium is impossible to overlook In fact, increased blood pressure by vasoconstriction has been reported in mice treated with 100,000 mg/L of barium for 16 months (Nish-ioka, 1975) A significant decrease in survival rate with lymphoid depletions in the spleen, thymus, and lymph nodes has been reported in mice treated with 2,500,000 mg/L of barium for 15 months (NTP [National Toxicology Program], 1994) However, 2,000,000 mg/L of barium had no effects

on body weight, renal function, and reproduction in rats and mice (Dietz et al., 1992) Thus, the concentrations of barium used in most previous studies were much higher than the lev-els of barium to which people drinking well water are exposed to, and there has been a lack of studies showing tox-icity of low levels of barium

Recently, we have been performing studies focusing on toxicity of low levels (700 mg/L) of barium Our pervious

in vitro study showed that exposure to barium alone (2.5–100 mM) for 4 days significantly promoted invasion activity in nontumorigenic keratinocytes, melanocytes, and fibroblasts (Thang et al., 2011) Cancer toxicity of 3 mM arsenic was enhanced by coexposure to 1 mM barium for 4 days, 3 mM arsenic and 1 mM barium being about the aver-age concentrations in arsenic-polluted well drinking water in cancer-prone areas of Bangladesh (Yajima et al., 2012b) Our previous results suggest that exposure to barium for a short time (4 days) and at a low level not exceeding the value of WHO health-based guidelines promote malignant characteristics of human HaCaT keratinocytes in vitro Together with the results of another previous study by us showing acceleration of hearing loss in wild-type mice drinking 700 mg/L barium for 1 month (Ohgami et al., 2012), our previous results suggest that 700 mg/L of bar-ium exhibited toxicityin vivo and in vitro In this study, we demonstrated that invasion, FAK protein expression and activity, and MMP14 protein expression were constitutively augmented following an increase in malignancy grade in human keratinocytic cells We further demonstrated increased constitutive invasion activity with enhanced FAK phosphorylation and MMP14 expression in HaCaT keratino-cytes treated with 5 mM barium for 4 months Since FAK and MMP14 are representative signal transduction mole-cules closely linked to invasion activity (Hahne et al., 2005; Kato et al., 2008; Thang et al., 2011), our results suggest that increased FAK activity and MMP14 expression are cor-related with promoted invasion of HaCaT keratinocytes Taken together, our results suggest that malignant character-istics of HaCaT keratinocytes were increased by exposure to barium at a low concentration and for a long time from the analytical points of view of invasion However, there is no evidence showing barium-mediated cancer development in either an epidemiological study or animal experiment, despite a classical study showing development of dysplasia

in humans by external application of barium to the uterine cervix (Ayre, 1966) Further in vivo studies are needed to determine whether chronic exposure to a low level

Fig 5 Levels of constitutive phosphorylation and/or

expres-sion of FAK and MMP14 in BT-HaCaT and C-HaCaT

kerati-nocytes Constitutive tyrosine 397 (pY397) phosphorylation

level in FAK (pY397-FAK) and protein expression levels of

FAK, MMP14, and TUBULIN in BT-HaCaT (BT, lane 2) and

C-HaCaT (C, lane 1) keratinocytes, which were cultured in

the presence or absence of 5 mM barium for 4 months, are

shown The levels (mean 6 SD) of pY397/TUBULIN, FAK/

TUBULIN, pY397/FAK, and MMP14/TUBULIN determined

by densitometric analyses of the bands in three

independ-ent experimindepend-ents are presindepend-ented as graphs showing relative

intensities (multiple numbers) for control C-HaCaT

keratino-cytes *, Significantly different (p < 0.05) from C-HaCaT

keratinocytes by the Mann-Whitney U test.

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of barium affects development of skin diseases including

cancer

The authors thank Ms Aoi Sato, Ms Rie Shimizu, and Ms

Yoko Kato for technical assistance.

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