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Trace elements in anadara spp (mollusca bivalva) collected along the coast of vietnam, with emphasis on regional differences and human health risk assessment

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Mollusca: Bivalva collected along the coast of Vietnam, with emphasis on regional differences and human health risk assessment Nguyen Phuc Cam Tu•Nguyen Ngoc Ha•Tetsuro Agusa• Tokutaka I

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O R I G I N A L A R T I C L E Environment

Trace elements in Anadara spp (Mollusca: Bivalva) collected

along the coast of Vietnam, with emphasis on regional differences

and human health risk assessment

Nguyen Phuc Cam Tu•Nguyen Ngoc Ha•Tetsuro Agusa•

Tokutaka Ikemoto•Bui Cach Tuyen• Shinsuke Tanabe•

Ichiro Takeuchi

Received: 23 March 2011 / Accepted: 30 August 2011 / Published online: 4 October 2011

Ó The Japanese Society of Fisheries Science 2011

Abstract This study measured concentrations of 21 trace

elements in whole soft tissue of the blood cockle Anadara

spp., which is a common food for local people, collected

along the coast of Vietnam Results showed that

concen-trations of As, Sr, Mo, Sn, and Pb in cockles collected from

Khanh Hoa Province in the Central Coastal Zone (CCZ)

had higher values than those from the other regions, while

cockles collected from the Mekong River Delta (MRD)

showed the highest concentrations of Hg Regional

differ-ences in trace element concentrations of the cockle may be

due to differences in human activities, i.e., shipyards in the

CCZ and agriculture in the MRD Trace element

concen-trations measured in the soft tissues of blood cockles

investigated here were within safe levels for human

con-sumption following criteria by the European Commission

(EC) and the United States Food and Drug Agency, but

several specimens had Cd levels exceeding the EC

guidelines of 1 lg/g wet weight The estimated target hazard quotients for trace elements via consuming bivalves were \1, indicating that the cumulative noncarcinogenic risk was completely insignificant However, the estimated target cancer risk values by assumed inorganic As con-centrations seem to implicate consumption of these cockles

as posing potential human health concerns

Keywords Blood cockle  Anadara spp  Cadmium  Human health risk  Trace elements  Vietnam

Introduction

At present, nearly a quarter of Vietnam’s population lives

in the coastal provinces, and there is an increasing migra-tion into this region where there are many large cities (e.g., Hochiminh City) in addition to coastal economic and centralized industrial zones These activities have created increased pollution, most likely in hotspots such as the major estuaries and the coastline, which receive different kinds of wastes produced by inland industrial and popu-lation centers [1] The aquaculture industry in Vietnam has encountered serious issues in recent years, including poor water quality, disease outbreaks, and food safety problems

in products for export and local consumption, particularly from contaminated filter feeding bivalve mollusks [2] Besides the lyrate hard clam Meretrix lyrata, the blood cockle Anadara spp (Mollusca: Bivalva: Arcidae) are favored species of edible shellfish in Vietnam Among the blood cockle species, Anadara granosa is one of the most popular cultured species in brackish-water areas, particu-larly in southern Vietnam, whereas A nodifera is found more in the northern and central coast [2] These bivalves are cultured mostly on muddy tidal flats Cockles can also

N P C Tu  T Ikemoto  I Takeuchi (&)

Department of Life Environment Conservation,

Faculty of Agriculture, Ehime University,

Tarumi 3-5-7, Matsuyama, Ehime 790-8566, Japan

e-mail: takeuchi@agr.ehime-u.ac.jp

N N Ha  T Agusa  S Tanabe

Center for Marine Environmental Studies (CMES),

Ehime University, Bunkyo-cho 2-5, Matsuyama,

Ehime 790-8577, Japan

T Agusa

Department of Legal Medicine, Faculty of Medicine,

Shimane University, Enya 89-1, Izumo,

Shimane 693-8501, Japan

B C Tuyen

Research Institute for Biotechnology and Environment (RIBE),

Nong Lam University, Thu Duc District,

Hochiminh City, Vietnam

Fish Sci (2011) 77:1033–1043

DOI 10.1007/s12562-011-0410-3

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be cultured in nutrient-rich ponds and have a high capacity

for removing nutrient-derived primary production from

black tiger shrimp ponds between crops [2] Because

Anadara spp are filter feeding organisms, trace element

contaminants in the mudflats or shrimp pond beds tend to

accumulate in their tissues These cockles may act as the

main environmental sink of trace elements and therefore

may be an effective bioindicator of coastal pollution It is

well known that no single species of bivalve is present on

all coasts and, therefore, environmental monitoring

pro-grams often need to utilize multiple species Studies

comparing trace element profiles from several taxa taken at

the same locations permit an assessment of the relative

bioavailabilities of trace elements to different species

[3, 4] Thus, the different species studied in this work

would be proposed as sentinel biomonitors to assess the

contamination status by trace element in the coastal zone

A number of studies on bivalve mollusks associated with

trace element pollution have been performed, but few

studies have been published related to Anadara spp [5 7]

According to our previous study, concentrations of trace

elements in hard clam Meretrix spp from the Vietnam

coast were typically high, particularly in samples collected

from the central coast, and estimation of cancer risk based

on As concentration indicated that hard clams pose a high

potential risk to local residents [8]

The objective of this study was to determine regional

differences in trace element concentrations of Anadara spp

collected along Vietnam’s coastal waters Furthermore, our

previously reported data on the hard clam Meretrix spp [8]

were compared with the present study in order to clearly

understand the contamination status of trace elements in

Vietnamese coastal environment The potential health risks

associated with consuming trace element levels in cockles

were also estimated

Materials and methods

Sample collection and preparation

Anadara spp were collected from extensive bivalve

pro-duction areas or were purchased from small stalls near

culture sites along the coast of Vietnam between 2003 and

2007 Anadara granosa was taken from Hochiminh City

(HCMC), Ba Ria Vung Tau (BRVT), Long An (LA), and

Tien Giang (TG) Provinces in the South Key Economic

Zone (SKEZ), and from Ben Tre (BT), Tra Vinh (TV), Soc

Trang (ST), Bac Lieu (BL), Ca Mau (CM), and Kien Giang

(KG) Provinces in the Mekong River Delta (MRD)

Anadara nodifera was sampled in Khanh Hoa (KH)

Province in the Central Coastal Zone (CCZ) (Fig 1) Both species are likely to be found on intertidal and marginally subtidal muddy substrates in areas where there is an estu-arine influence and feed on a mixture of detritus (or microorganisms attached to detritus) and benthic microal-gae from the sediment [9] Cockles were not purified because we were interested in estimating human health risks Samples were frozen in plastic bags and transported

to Ehime University, Japan, and maintained in a freezer below -20°C until dissection and trace element analysis could take place

Blood cockles from sampling sites (six individuals per site) were cleansed of mud by washing thoroughly with deionized water (Millipore, Milford, MA, USA) Cockles were measured for shell length and whole body weight, after which soft tissue was carefully removed using a clean stainless steel scalpel blade, then dried at 80°C for 12 h, and finally ground to a fine powder using a mortar and pestle in preparation for analysis Biometry and water content of cockles are shown in Table 1 Trace element concentrations

in blood cockle tissue were measured based on dry weight (wt) but were also converted to wet wt by use of the respective conversion factors given in Table1to allow for comparison with values from other studies and guidelines and to estimate potential health risk on a wet wt basis Trace element analyses

We used previously described methods for analyzing trace elements [8,10,11] Briefly, dried soft tissue was digested with concentrated nitric acid in a microwave system (Ethos

D, Milestone, Sorisole, BG, Italy) Mercury was deter-mined using a cold vapor-atomic absorption spectrometer (AAS) (AA680, Shimadzu, Kyoto, Japan; Model HG-3000 cold vapor system, Sanso, Tsukuba, Japan) The concen-trations of 19 trace elements (V, Cr, Mn, Co, Cu, Zn, Rb,

Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Tl, Pb, and Bi) were determined using an inductively coupled plasma-mass spectrometer (HP-4500, Hewlett-Packard, Avondale, PA, USA) with yttrium as an internal standard For As analysis, samples were digested with an acid mixture (HNO3:H

2-SO4:HClO4= 1:1:2) and determined using a hydride generation-AAS (HVG-1 hydride system, Shimadzu, Kyoto, Japan) Accuracies of the methods were assessed using a certified reference material DOLT-3 (National Research Council of Canada) in triplicate, and recovery of the elements ranged from 83 to 100% of the certified val-ues All data are expressed on a dry weight basis (lg/g dry wt) Detection limits for most trace elements were 0.001 lg/g dry wt, except for As, Sb, and Cs (0.01 lg/g dry wt), and Hg (0.05 lg/g dry wt)

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Potential human health risk assessments

Noncarcinogenic effects were evaluated by comparing the

trace element exposure level over a specified time period

with a reference dose (RfD), otherwise known as the target

hazard quotient (THQ) A THQ value of \1 indicates that

exposures are not likely to be associated with adverse noncarcinogenic effects The sum of all THQ values for multiple trace elements for a particular sampling site is represented by the hazard index (HI) [12] Likewise, target cancer risk (TR) was estimated as the incremental proba-bility of an individual developing cancer over a lifetime as

Fig 1 Map of sampling

locations for blood cockles

Anadara spp For abbreviations,

refer to Table 1

Table 1 Biometry of the blood cockle Anadara spp collected from the coast of Vietnam

Species Region Location Latitude Longitude Number Whole

body

wt (g)a

Shell length (mm)a

Water content (%)b

Conversion factor (dry:wet)b

Anadara

granosa

SKEZ HCMC Can Gio,

Hochiminh City

10°23.202 0 N 106°55.446 0 E 6 15.5 ± 3.3 36.6 ± 2.3 85.2 6.84 BRVT Tan Thanh, Ba

Ria Vung Tau

10°27.413 0 N 107°05.446 0 E 6 11.5 ± 0.8 34.0 ± 1.4 88.6 9.05

LA Can Giuoc,

Long An

10°36.216 0 N 106°40.266 0 E 6 9.9 ± 0.5 31.5 ± 0.6 87.6 8.15

TG Go Cong Dong,

Tien Giang

10°17.277 0 N 106°46.461 0 E 6 9.3 ± 0.3 29.8 ± 1.1 89.9 10.0 MRD BT Binh Dai, Ben Tre 10°11.117 0 N 106°41.375 0 E 6 19.3 ± 1.3 37.1 ± 0.6 83.7 6.17

TV Duyen Hai,

Tra Vinh

09°37.585 0 N 106°29.541 0 E 6 11.8 ± 2.5 32.1 ± 1.4 87.8 8.43

ST Vinh Chau,

Soc Trang

09°19.630 0 N 105°58.867 0 E 6 12.8 ± 1.2 32.7 ± 1.2 85.6 6.98

BL Nha Mat, Bac Lieu 09°12.339 0 N 105°44.321 0 E 6 9.0 ± 0.5 30.7 ± 1.5 86.5 7.45

CM Ward 7 Market,

Ca Mau

09°10.376 0 N 105°08.501 0 E 6 12.7 ± 1.5 34.0 ± 0.8 84.5 6.61

KG Rach Soi,

Kien Giang

09°57.158 0 N 105°07.141 0 E 6 14.5 ± 1.5 34.4 ± 0.3 87.9 8.35 Anadara

nodifera

CCZ KH Nha Phu Bay,

Khanh Hoa

12°20.556 0 N 109°12.336 0 E 6 14.1 ± 1.3 35.4 ± 0.5 84.0 6.62

a Mean and standard deviation

b Mean

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a result of exposures to potential carcinogen (i.e., inorganic

As in the present study) This risk was calculated using

average lifetime exposure values that were multiplied by

the oral slope factor for inorganic As [12] Estimation of

THQ and TR at each location followed the United State

Environmental Protection Agency (US EPA) Region 3

Risk-based Concentration (RBC) Table (US EPA Region

III website: http://www.epa.gov/reg3hwmd/risk/human/

pdf/NOVEMBER_2010_FISH.pdf; accessed 09 Dec 2010)

The methodology for estimating THQ and TR is described

in detail by Tu et al [8] RfDs were obtained from the RBC

table, except for Cr, Rb, In, Cs, Hg, Pb, and Bi Total Cr

was not available on the RBC table, the US EPA assumes

that the ratio of Cr(VI) to total Cr was 1:7 in fish tissue, and

offers the RfD for Cr(VI) Thus, we divided our total Cr

data by 7 to estimate the THQ for Cr Because most Hg in

shellfish tissue is present primarily as methyl mercury

(MeHg) [12], the conservative assumption was made that

total Hg is present as MeHg as recommended by the US

EPA [12] Lead was not listed on the RBC table; a

provi-sional tolerable weekly intake of 25 lg/kg body wt/week

(equal to 3.57 lg/kg body wt/day) was used [13] For

calculation of THQ and TR for inorganic As, we assumed

that inorganic As accounted for 10% of total As [14–16]

The bivalve consumption rate of 2.85 g/Vietnamese

person/day (FAO website: http://faostat.fao.org/site/368/

DesktopDefault.aspx?PageID=368#ancor; accessed 04 Jan

2011) was used for these estimations

Statistical analyses

One half of the value of the respective limit of detection

(LOD) was substituted for those values below the LOD and

used in statistical analysis and risk assessment Statistical

analyses were performed using the SPSS version 15 for

Windows (SPSS, Chicago, IL, USA) All data were tested

for goodness-of-fit to a normal distribution with

Kol-mogorov-Smirnov’s one sample test Because most of the

variables were not normally distributed, the data were

logarithmically transformed and subjected to parametric

statistics Pearson correlation analyses were performed for

shell length and trace element concentrations to determine

size effects in blood cockles Regional differences in trace

element concentrations in blood cockles were tested by

analysis of variance (ANOVA) or analysis of covariance

(ANCOVA) with shell length as the covariate wherever

practicable Prior to the use of ANCOVA, assumption of

equality (homogeneity) of regression slopes of dependent

(trace element concentration)-covariate (shell length)

relationships was tested by fitting a model containing

covariate-by-factor interaction If the homogeneity of

regression assumption was not rejected, ANCOVA was

applied to test differences between regions To compare

regional differences of trace element concentrations between blood cockles and hard clams, a two-independent-samples t test was used A p value of \0.05 indicated statistical significance

Results Trace element concentrations Means and standard deviations of trace element concen-trations of Anadara spp samples are shown in Table2 Concentration of Zn was the highest among the trace ele-ments analyzed, followed by Mn, Sr, As, Cu, Cd, and Rb The mean concentrations of Zn and Mn in Anadara spp ranged from 51.3 to 113 lg/g and from 11.3 to 63.9 lg/g (Table2), respectively Moreover, the mean concentrations

of Cd and As were present at relatively high levels in the tissues of blood cockles, ranging from 2.15 to 9.61 lg/g, and from 3.5 to 26 lg/g, respectively (Table2) Similar mean concentrations of Cu (ranged from 5.37 to 9.89 lg/g),

Rb (ranged from 2.57 to 4.52 lg/g), and Sr (ranged from 21.0 to 40.7 lg/g) were observed in blood cockles from the sampling locations (Table 2) The lowest concentra-tion in cockle tissues was In (ranged from 0.001 to 0.005 lg/g)

For all the blood cockles analyzed, concentrations of Cr (Pearson correlation, r = -0.28, p \ 0.05), Mn (r = -0.53,

p \0.001), Co (r = -0.47, p \ 0.001), Cu (r = -0.30,

p \0.05), Sr (r = -0.31, p \ 0.05), Cd (r = -0.27, p \ 0.05), Sb (r = -0.41, p \ 0.001), Ba (r = -0.52,

p \0.001), and Hg (r = -0.34, p \ 0.01) were negatively correlated with shell length, whereas no correlations were found between concentrations of the others and shell length (p [ 0.05)

Regional differences in trace element concentrations For regional comparisons, the cockle sampling sites were pooled into three regions: SKEZ, MRD, and CCZ Because

of the significant correlations between shell length and tissue concentration of Cr, Mn, Co, Cu, Sr, Cd, Sb, Ba, and

Hg, a comparison among regions was conducted using ANCOVA with shell length as the covariate In contrast, ANOVA was used for assessment of variations between regions for trace elements that had no significant relation-ship with shell length

Results of regional differences in trace element con-centrations with statistical significance are shown in Fig.2 Among analyzed trace elements, concentrations of As, Sr,

Mo, Sn, and Pb in cockles from the CCZ and Hg con-centrations in cockles collected from the MRD were sig-nificantly higher than those from the other regions

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Table 2 Trace element concentrations (mean ± standard deviation; lg/g dry wt) in the blood cockle Anadara spp collected from the coast of Vietnam

SKEZ HCMC 0.19 ± 0.02 0.86 ± 0.40 15.9 ± 7.3 0.81 ± 0.14 6.83 ± 1.08 82.5 ± 10.3 5.6 ± 0.6 3.32 ± 0.21 24.3 ± 1.9 0.664 ± 0.094 0.73 ± 0.44

BRVT 0.52 ± 0.09 1.5 ± 0.9 21.4 ± 6.3 1.3 ± 0.2 7.26 ± 0.80 51.7 ± 2.8 12 ± 1 3.61 ± 0.61 38.3 ± 12.0 0.591 ± 0.077 0.051 ± 0.013

LA 0.81 ± 0.22 1.1 ± 0.3 63.9 ± 31.9 2.1 ± 0.3 5.37 ± 0.34 73.3 ± 7.3 5.4 ± 1.0 4.39 ± 0.36 31.8 ± 2.6 0.512 ± 0.079 0.087 ± 0.107

TG 0.48 ± 0.32 2.1 ± 1.1 36.8 ± 11.6 1.7 ± 0.2 9.55 ± 1.57 113 ± 10 8.2 ± 0.2 4.43 ± 0.66 35.2 ± 14.7 0.725 ± 0.050 1.4 ± 1.1 MRD BT 0.44 ± 0.05 0.58 ± 0.10 29.1 ± 6.6 1.2 ± 0.1 6.87 ± 1.49 90.1 ± 16.4 3.5 ± 0.4 3.78 ± 0.36 21.0 ± 4.0 0.534 ± 0.052 0.19 ± 0.11

TV 0.43 ± 0.08 0.51 ± 0.03 30.3 ± 3.9 2.6 ± 0.8 8.96 ± 1.06 86.1 ± 14.3 4.9 ± 0.5 2.57 ± 0.28 29.1 ± 4.2 0.541 ± 0.054 0.11 ± 0.08

ST 1.0 ± 1.6 1.3 ± 1.4 26.3 ± 13.0 1.1 ± 0.3 7.90 ± 0.30 81.7 ± 9.5 4.8 ± 0.5 3.65 ± 2.23 35.9 ± 5.4 0.621 ± 0.052 0.084 ± 0.034

BL 0.41 ± 0.16 0.84 ± 0.26 56.5 ± 27.2 1.4 ± 0.3 9.89 ± 2.52 107 ± 10 7.0 ± 0.4 4.00 ± 0.34 30.7 ± 2.9 0.701 ± 0.087 0.99 ± 0.47

CM 0.73 ± 0.30 0.78 ± 0.33 33.1 ± 6.4 1.6 ± 0.5 5.97 ± 0.42 92.8 ± 20.2 3.7 ± 0.8 4.52 ± 0.63 21.8 ± 3.9 0.465 ± 0.053 0.085 ± 0.139

KG 0.43 ± 0.27 1.1 ± 0.3 27.5 ± 11.9 1.4 ± 0.4 8.73 ± 2.54 111 ± 11 7.0 ± 1.6 4.31 ± 0.48 26.0 ± 3.6 0.623 ± 0.044 0.64 ± 0.36 CCZ KH 0.62 ± 0.21 0.85 ± 0.31 11.3 ± 3.8 0.77 ± 0.16 6.90 ± 1.34 96.6 ± 5.5 26 ± 5 3.93 ± 0.45 40.7 ± 6.7 1.59 ± 0.64 0.24 ± 0.32

SKEZ HCMC 3.83 ± 0.26 0.003 ± 0.001 0.067 ± 0.010 0.02 ± 0.00 0.01 ± 0.00 0.72 ± 0.29 \ 0.05 0.004 ± 0.001 0.153 ± 0.019 0.011 ± 0.001

BRVT 2.68 ± 0.70 0.005 ± 0.002 0.068 ± 0.014 0.02 ± 0.00 0.03 ± 0.01 0.76 ± 0.31 \ 0.05 0.007 ± 0.002 0.208 ± 0.050 0.018 ± 0.003

LA 5.57 ± 1.15 0.005 ± 0.006 0.064 ± 0.025 0.02 ± 0.01 0.09 ± 0.03 3.0 ± 1.0 0.13 ± 0.04 0.012 ± 0.008 0.625 ± 0.139 0.118 ± 0.028

TG 8.19 ± 1.23 0.002 ± 0.000 0.028 ± 0.008 0.04 ± 0.01 0.05 ± 0.04 2.8 ± 1.6 0.13 ± 0.05 0.006 ± 0.003 0.509 ± 0.144 0.026 ± 0.002 MRD BT 8.97 ± 0.78 0.001 ± 0.000 0.029 ± 0.013 0.02 ± 0.00 0.02 ± 0.00 1.4 ± 0.3 0.12 ± 0.04 0.006 ± 0.002 0.227 ± 0.034 0.024 ± 0.005

TV 9.06 ± 1.00 0.002 ± 0.000 0.047 ± 0.020 0.03 ± 0.00 0.01 ± 0.01 1.9 ± 0.6 0.11 ± 0.02 0.003 ± 0.001 0.401 ± 0.077 0.047 ± 0.005

ST 9.61 ± 1.63 0.003 ± 0.004 0.073 ± 0.050 0.04 ± 0.02 0.10 ± 0.19 4.4 ± 5.2 0.09 ± 0.01 0.009 ± 0.015 0.763 ± 0.501 0.021 ± 0.010

BL 7.12 ± 0.85 0.002 ± 0.001 0.033 ± 0.006 0.03 ± 0.01 0.03 ± 0.02 2.3 ± 0.6 0.11 ± 0.02 0.006 ± 0.002 0.422 ± 0.103 0.023 ± 0.002

CM 2.15 ± 0.60 0.003 ± 0.001 0.033 ± 0.009 0.02 ± 0.01 0.06 ± 0.04 1.4 ± 0.8 0.08 ± 0.04 0.005 ± 0.002 0.530 ± 0.230 0.064 ± 0.046

KG 7.67 ± 1.52 0.001 ± 0.000 0.219 ± 0.535 0.02 ± 0.01 0.04 ± 0.03 2.0 ± 1.1 0.11 ± 0.05 0.004 ± 0.002 0.500 ± 0.166 0.029 ± 0.011 CCZ KH 5.26 ± 1.91 0.004 ± 0.002 0.568 ± 0.471 0.02 ± 0.01 0.02 ± 0.01 0.80 ± 0.50 \ 0.05 0.005 ± 0.002 2.71 ± 0.73 0.055 ± 0.012

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(ANOVA or ANCOVA, p \ 0.05) Concentrations of Mn

and Co in the CCZ cockles, Zn in the SKEZ cockles, and In

in the MRD cockles were the lowest among regions

(p \ 0.05) Chromium levels in the SKEZ blood cockles

were greater than those in the MRD animals (p \ 0.001),

though neither zone was significantly different from the

CCZ measurement (p [ 0.05) Cadmium concentrations in

the SKEZ cockles were lower than those from the MRD

animals (p \ 0.01), but there were no significant

differ-ences between Cd values in cockles from the SKEZ and

CCZ, or between those values from the MRD and CCZ

(p [ 0.05) Barium concentration in the MRD cockles was

higher than those from the CCZ (p \ 0.05), but there were

no significant differences in Ba concentration between the

SKEZ and the other two regions (p [ 0.05) The

concen-tration of V, Cu, Rb, Ag, Sb, Cs, Tl, and Bi did not differ

significantly among regions (p [ 0.05)

In comparison with our previous results for trace

ele-ments in hard clam Meretrix spp [8], concentrations of Cr,

Mn, Cu, Mo, Ag, Cd, Sb, Hg, Pb, and Bi in the SKEZ

cockles, Mn, Zn, Mo, Ag, Cd, Sb, Hg, Pb, and Bi in the

MRD cockles, and As, Cd, Pb, and Bi in the CCZ cockles

were higher (two-independent-samples t test, p \ 0.05;

Fig.3) In contrast, concentrations of Co, Sr, and Cs in the

SKEZ clams, Co, As, Sr, In, Cs, Ba, and Tl in the MRD

clams, and V, Co, Cu, Rb, Sr, Mo, Cs, Ba, and Tl in the

CCZ clams were elevated (p \ 0.05; Fig.3)

Estimation of potential human health risk

As shown in Fig.4 and represented by the THQ and HIs,

the noncarcinogenic risks associated with the consumption

of blood cockle were \1 Considering the composition of

the relative contribution to THQ by trace elements, the

highest risk contribution of trace elements for consumers is

from Cd (range of 20–55%), followed by Co (range of

14–49%) and inorganic As (range of 7–46%) The

contri-bution of Cd to the HIs showed a high value for consumers

from the MRD, particularly in ST (55%), while Co con-stituted the majority of the risk and contributed to nearly half of the total HIs for CM consumers The THQ for

Fig 2 Regional differences in trace element concentrations in blood

cockle Anadara spp All trace elements with significantly different

(p \ 0.05) concentrations between regions are represented in this

figure Data represent the mean and standard deviation of the trace element concentrations (log transformed) *p \ 0.05, **p \ 0.01, and

***p \ 0.001 For abbreviations, refer to Table 1

Fig 3 Species-specific differences in trace element concentrations between blood cockle Anadara spp and hard clam Meretrix spp [ 8 ] Selected trace elements with significantly different (p \ 0.05) con-centrations between two species in all three regions are represented in this figure Data represent the mean and standard deviation of the trace element concentrations (log transformed) *p \ 0.05,

**p \ 0.01, and ***p \ 0.001 For abbreviations, refer to Table 1

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inorganic As had a larger percentage contribution 46% of

HIs from KH in the CCZ

Conversely, the target cancer risk estimates for

inor-ganic As through consuming blood cockles from different

locations along the coast of Vietnam were higher than 10-6

(range of 4.8 9 10-6to 3.3 9 10-5) (Fig.5) The highest

risk for inorganic As was 3.3 9 10-5for consumption of

cockles by KH residents in the CCZ

Discussion

Trace element concentrations in blood cockle

Bivalves are often used as a measure of contamination in

estuarine waters because they usually accumulate high

concentrations of trace elements [17] Among trace

ele-ments, Zn is an essential element that is present in all

organisms, and concentrations of Zn in tissues of several

bivalve species including scallops, clams, oysters, and

mussels are on the order of 100–1,000 lg/g, with little

variation among species [17] Zinc is not limiting to normal

molluscan life processes in the marine environment and

filter-feeding mollusks accumulated the highest

concen-trations of Zn in soft tissues [17] In the present study, the

mean concentrations of Zn in blood cockle differed slightly

among the sampling sites These results showed that blood

cockle could regulate its soft tissue levels of Zn Phillips

and Rainbow [4] reported that several bivalve species are

known to possess this ability

In several studies, trends of decreasing trace element

concentrations with increasing shell length have been

reported and were attributed primarily to increased meta-bolic rates in smaller organisms, which corresponded to a so-called growth dilution effect [8, 18–21] Boyden [18] reported similar size-concentration relationships for Cu,

Zn, and Pb in the limpet Patella vulgate collected from Portishead, Severn Estuary Joiris and Azokwu [20] observed the same results with Cd and Pb in the West African bloody cockle Anadara (Senilia) selinis collected from Bonny River estuary in the Niger Delta area of Nigeria In a previous study of hard clams from Vietnam [8], we also found an inverse relationship of decreasing

Fig 4 Mean hazard indices

(HIs) of individual trace

elements from consuming blood

cockle Anadara spp collected

from different sites For

abbreviations, refer to Table 1

Fig 5 Mean estimated target cancer risks for assumed inorganic As through consuming blood cockle Anadara spp collected from different sites For abbreviations, refer to Table 1

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concentrations of Zn, As, Mo, Sn, and Bi with increasing

shell size

Regional differences in trace element concentrations

The estimated human population density of Khanh Hoa

Province (CCZ) is 220/km2, in contrast with 510/km2and

428/km2 for the SKEZ and MRD, respectively (General

Statistics Office of Vietnam website:http://www.gso.gov

vn/default.aspx?tabid=387&idmid=3&ItemID=9865;

acce-ssed 21 Dec 2010), indicating that human activities in the

CCZ are lower than in the others However, the blood

cockles in the CCZ showed the highest mean

concentra-tions of As (26 lg/g), Sr (40.7 lg/g), Mo (1.59 lg/g), Sn

(0.568 lg/g), and Pb (2.71 lg/g) We observed similar

results in a previous study in which concentrations of As,

Mo, Sn, and Pb were highest in hard clam Meretrix spp

collected from the CCZ [8] These results suggest that

some point sources of trace element contamination are

present in the CCZ, in spite of the relatively lower human

activity Contaminants likely originated from industrial

waste from large shipyards near the sampling site As

compared to a more distant site, elevated levels of Cr, Cu,

Zn, Cd, and Pb were reported in water, sediment, and the

oyster Saccostrea cucullata collected from the vicinity of a

shipyard in Khanh Hoa Province [22] The shipyard used

copper slag as a blasting abrasive for the removal of rust,

paint chips, and marine deposits on the surfaces of ship

hulls The slag contained high levels of Cr (336 lg/g), Cu

(8,549 lg/g), Zn (7,275 lg/g), and Pb (113 lg/g) [22] In

fact, the CCZ was reported as one of the hot spots for trace

element contamination in Vietnam [1]

In contrast, concentrations of Hg were found to be the

highest in the MRD cockles Moreover, accumulated Cd

concentrations were greater in blood cockles from this

region, particularly sampling sites close to the mouth of the

Mekong River such as TV (9.06 lg/g) and ST (9.61 lg/g),

when compared with those in cockles collected from the

other sites Our previous studies also reported relatively

high levels of Cd and Hg in the giant river prawn

Mac-robrachium rosenbergii and black tiger shrimp Penaeus

monodon, and Cd in the hard clam Meretrix lyrata

col-lected from the MRD [8,10,11], suggesting that sources of

Hg and Cd contamination in the MRD may be agricultural

use of mineral fertilizers As stated by the Agency for

Toxic Substances and Disease Registry (ATSDR), Hg is

released to cultivated soils through the direct application of

inorganic and organic fertilizers (e.g., sewage sludge and

compost), lime, and fungicides containing Hg (ATSDR

toxicological profile for mercury website: http://www

atsdr.cdc.gov/ToxProfiles/tp46.pdf; accessed 25 May

2011) Furthermore, because of intensive crop cultivation

on alluvial soils, some soils in the MRD receive large

amounts of fertilizer, particularly phosphates containing Cd levels ranging from 0.02 to 2.76 mg/kg [23] In addition, the high accumulation of Cd in the MRD cockles may be due to Cd bioavailability in the low salinity environment

As mentioned above, salinity is a natural factor influencing metal uptake, and it is well known that there is an increased net uptake of Cd by bivalves at low salinities [19,24–26] According to Debenay and Luan [27], HCMC and its surroundings were the most affected by marine waters, whereas TV and its vicinity were exposed to the strongest freshwater influence

The species-specific variations between blood cockle and hard clam could be due to differences in their habitats and feeding habits Blood cockles live on the muddy bot-tom in the intertidal zone and can be affected by fresh-water, whereas hard clams occur in sand and/or muddy sand flats in large estuarine areas with greater marine influence [2, 28] Several studies have been conducted to evaluate the influence of salinity or sediment type on trace element uptake in bivalve species Sarkar et al [29] reported that a high organic carbon value together with high clay concentration in sediment enhances elevated concentration of Cd, Zn, and Hg by cockle Anadara granosa from Jharkhali (India) Moreover, most studies suggest an increased net uptake of Hg, Pb, and in particular

Cd by bivalves at lower salinities [19, 24, 25] Further-more, the assimilation efficiencies of Ag and Cd in bivalves were higher from organic-rich sediments than those from organic-poor sediments [30]

Comparison with published data and the guidelines Our data were compared with measurements made else-where in Asia (Table 3) Chromium concentrations in cockles from Vietnam were found to be similar to or higher than those reported from Juru and Jejawi, Malaysia [5] This study shows that the average concentrations of Cu, Zn, and

Cd in Anadara spp collected from Vietnam were compa-rable to or higher than those in this species from Perak and Sabah, Malaysia, and from Zhejiang, China, but exceeded the mean Cu, Zn, and Cd in cockles from Juru and Jejawi, Malaysia [3,5,7] Arsenic concentrations in Anadara spp found in the SKEZ and MRD were similar to those in cockles from Juru and Jejawi, Malaysia [5] However, As levels in this species obtained from the CCZ were higher than those in cockles from Juru and Jejawi, Malaysia [5] Comparing the mean Pb concentrations in cockles found in this work from the SKEZ and MRD with those from other countries shows that the levels from Vietnam were com-parable to those in cockles from Juru and Jejawi, Malaysia, and from Zhejiang, China, yet lower than those in cockles from Perak and Sabah, Malaysia [3,5,7,31] However, Pb levels in this species obtained from the CCZ were higher

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than those in cockles from Juru and Jejawi, Malaysia, and

from Zhejiang, China, which were comparable to those of

cockles from Perak and Sabah, Malaysia [3,5,7,31] The

concentrations of Hg reported in this work were lower than

those in blood cockles studied previously [3,5]

The concentrations of most trace elements in Anadara

spp were below the reference values for human

con-sumption set by the European Commission (EC), the US

Food and Drug Agency (US FDA), and the Vietnamese

Ministry of Agriculture and Rural Development (MARD)

[32–34] However, over 30% (21/66) of cockle samples

had Cd levels exceeding the EC guideline of 1 lg/g wet wt

(Fig.6) In particular, most specimens from BT, TV, and

ST were above the EC limit (Fig.6) Recently, the

sanitation monitoring program for the bivalve mollusk

production area in 2010 conducted by the National

Agro-Forestry-Fisheries Quality Assurance Department, MARD

also found Cd concentrations in BT cockle ranging from

1.7 to 2.1 lg/g wet wt [35], exceeding the current

Viet-namese safety guideline of 2 lg/g wet wt for bivalve

mollusks as set by the MARD [32] Therefore, to wholly

meet the European Union (EU) requirements for an

EU-approved better management production area, the authority

recommends that these aquaculture areas open for

har-vesting under the condition that the bivalves go through

purification (relaying) before consumption and proposes a

sampling frequency of once per week when harvesting is

being done [35]

Estimation of human health risks

In the present study, there were no estimated THQs and HIs

for all trace elements [1, suggesting that non-cancer health

effects from consuming blood cockles were insignificant

Concerning the relative contribution of each trace element

to THQs, the potential health risks of Cd were highest in comparison to other trace elements investigated Because

Cd is a cumulative toxin and has a very long half-life (from several months up to several years) in the body, exposure

of children to even low amounts may have long-term adverse consequences The exposure to Cd is associated with renal dysfunction, increased calciuria, osteoporosis, and a risk of fractures (ATSDR toxicological profile for

Table 3 Comparison of mean concentrations of trace elements (lg/g dry wt) in the blood cockle Anadara spp with those from other Asian countries and human consumption guidelines

SKEZ, Vietnam Anadara granosa 1.4 7.25 80.2 7.7 5.07 0.08 0.374 This study

Zhejiang, China Tegillarca granosaa 1.61 5.56 2.42 \ 0.05 0.060 [ 3 ] Juru, Malaysia A granosab 0.17 0.19 0.22 2.67 0.89 1.33 0.11 [ 5 ]

nd Not detected For region abbreviations, see Table 1

a Synonym of A granosa

b Based on wet wt

Fig 6 Comparison of Cd concentrations (lg/g wet wt) in blood cockle Anadara spp with European Commission (EC) guidelines for human consumption [ 33 ] For abbreviations, refer to Table 1

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cadmium website: http://www.atsdr.cdc.gov/ToxProfiles/

tp5.pdf; accessed 25 May 2011) Using the US EPA RfD

of 1 lg/kg/day for estimating noncarcinogenic risk

asso-ciated with Cd, our results indicate that the consumption of

cockles at the current rate was not harmful to consumers

Yet, Satarug and Moore [36] reported that Cd-linked bone

and kidney toxicities have been observed in people whose

dietary Cd intakes were well within 1 lg/kg/day limits

Satarug et al [37] believed that the recommended Cd

intake of 1 lg/kg/day was shown to be too high to ensure

that renal dysfunction does not occur as a result of dietary

Cd intake As stated by Widmeyer and Bendell-Young

[38], there is little to no safety margin between Cd

expo-sure in the normal diet and expoexpo-sure that could produce

deleterious effects, particularly in persons consuming

bivalves on a regular basis Cadmium toxicity via

con-suming bivalves should be considered, particularly for high

risk groups, including women with low iron stores, people

with renal impairment, smokers, children, and indigenous

people as suggested by Cheng and Gobas [39]

On the other hand, the TR values of inorganic As due to

consumption of this cockle indicated that human health risk

might be of concern However, caution must be taken

because this estimation of risk was based on the assumptions

of the ratio of inorganic As to total As due to the lack of

information on the contamination status of As compounds in

Vietnamese bivalves The assumption of 10% inorganic As

from the total As concentration has often been used to

esti-mate health risk [14–16] However, use of this ratio may have

overestimated the true risk levels for As exposure For

example, in two studies from the same location for

con-sumption of oyster Crassostrea gigas in Taiwan, Liu et al

[40] measured the inorganic As fraction in oysters at 1.64%

of total As, and estimated TR nearly 10 times less than Han

et al [14] who assumed 10% as inorganic As in this oyster

[41] Clearly, more studies are needed regarding the

con-centration and speciation of As in bivalves and the

biogeo-chemical cycling of As in aquatic environments of Vietnam

Based on the results of this study, it may be concluded

that the significant differences in trace element

concen-trations in blood cockles Anadara spp among regions may

be explained by differences in human activities, i.e.,

ship-yards in the CCZ and agriculture in the MRD It can also be

concluded that levels of Cd and As in blood cockles in

Vietnam may be a public health concern Further research

on understanding the distribution and accumulation profiles

of potential toxic trace elements in different marine

organisms from these regions is clearly warranted Also, it

is essential that ongoing environmental monitoring

pro-grams should be developed and implemented to ensure that

bivalves are grown from areas with acceptable levels of

chemical pollution

Acknowledgments We express our sincere thanks to Dr Todd Miller, Center for Marine Environmental Studies (CMES), Ehime University, for critical review of the manuscript This study was partially supported by a grant from the Research Revolution 2002 (RR2002) of the Project for Sustainable Coexistence of Humans, Nature, and the Earth (FY2002) from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) of Japan, and Global COE Program from MEXT The Grants-in-Aid for Scientific Research for Postdoctoral Fellows by the Japan Society for the Pro-motion of Science (No 2109237 to NPCT, and No 207871 to TA) are also acknowledged.

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