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Sukanya Boonchalermkit*, Janewit Wongsanoon* ,Munehiro Fukuda**

*»Ÿπ¬å«‘®—¬·≈–Ωñ°Õ∫√¡¥â“π ‘Ëß·«¥≈âÕ¡ °√¡ àß‡ √‘¡§ÿ≥¿“æ ‘Ëß·«¥≈âÕ¡ ‡∑§‚π∏“π’ µ.§≈ÕßÀâ“ Õ.§≈ÕßÀ≈«ß ®.ª∑ÿ¡∏“π’ 12120 ‚∑√. 0-2577-1136 ‚∑√ “√. 0-2577-1138Environmental Research and Training Center, Department of Environmental Quality Promotion. Technopolis. Klong 5 Klong Luang, Pathumthani 12120 e-mail: [email protected]**ºŸâ‡™’Ë¬«™“≠Õß§å°√§«“¡√à«¡¡◊Õ√–À«à“ßª√–‡∑»≠’ËªÿÉπ (JICA Expert)

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ABSTRACTThis paper presents a study of

Arsenic (As) contamination at Nakorn Sri

Thammaraj province, which is known as the

tin-mining area especially in Ronpibool District

where several tin mines are still operational.

Arsenic from this area has been out flowing

through Pak Pa-Nang river into Pak Pa-Nang

bay in the southern part of Thailand which is

the important area for aquatic organism

culture. The study focuses on the marine

environment of Pak Pa-Nang bay with regard

to possible influence of long term arsenic

input from the upstream of Pak Pa-Nang river.

The various biosample including mussel, fish,

shrimp are collected and analyzed for total

arsenic by acid digestion and AAS analysis.

Based on the relative arsenic concentration

level , mussel was selected for fur ther

study. Mussel samples from the bay and

from open sea representing background

were systematically collected and analyzed

for arsenic. The difference between two groups

(inside and outside of the bay) were examined

in order to understand the inf luence

of arsenic in the bay. Arsenic species-distri-

bution of mussel samples were also studied

by MeOH/water-ultrasonic extraction followed

by HPLC-ICP-MS analysis. The data indicated

arsenic composition of the mussel in the bay

have no unique character compared with

those reported in previous study.

1. IntroductionNatural arsenic commonly enriches

in gold and base metal mineralization.

Mining and mineral processing is often

became a source of arsenic contamination

to environment. The granites of the southern

par t of Peninsula Thailand occurred as

isolated plutons associated with numerous

tin and tungsten deposits. Hence the region

is called çtin belté (1). Extensive mining of

tin and associated minerals have been done

throughout the region. Ron-Phibun district,

Nakorn Sri-Tammaraj Province, which lies in

the main range of the tin belt, approximately

800 km. south of Bangkok (Figure 1,2) is one

of such mining area and mining has been

active for almost 100 years. The occurrence

of keratosis and hyperpig-mentation was

known for long time in the region. The skin mani-

festation of chronic arsenic poisoning was first

highlighted in 1987 in Ron Phibun district. (2)

Clinical survey during 1987-1988 showed

that more than 1000 people between age

from 4 months to 85 years were affected.

In some school, over 80% of students showed

high arsenic level in their hair and nails. (3).

According to the most recent survey (1992)

of school children in this district, a 22%

incidence of skin lesions and hyperkeratosis

was recorded. (2) The cause of sickness was

related to the consumption of contaminated

surface and ground water that probably

sourced from tin mining site. (4) Example of

chronic arsenic poisoning associated with

regionally contaminated water have been

documented from numerous countr ies

including Taiwan. (5,6), India (7), and USA (8).

Arsenic accumulation in soil, plankton, aquatic

»Ÿπ¬å«‘®—¬·≈–Ωñ°Õ∫√¡¥â“π ‘Ëß·«¥≈âÕ¡ °√¡ àß‡ √‘¡§ÿ≥¿“æ ‘Ëß·«¥≈âÕ¡ °-13

animals, agricultural products etc. also havebeen reported in many literature (4, 9, 10, 11,12, 13).

Local extent of ground watercontamination by arsenic in Ron-Phibundistrict was evaluated by several studies (2,13).However there was no study investigatingthe influence of long-term arsenic run of todown stream environment. Surface waterfrom Ron-Phibun district are flowing, throughnumerous canals and Pak Pa-Nang river, intoPak Pa-Nang bay which is the importantarea for aqua culture. High level of arsenicrelease to the bay could have been occurredduring geological age, monitoring of currentsurface water alone may not be sufficient tostudy the influence of arsenic. The study ofthis paper intends the assessment of possibleinfluence of long term arsenic inputs from theupstream of Ron Phibun district to the PakPa-Nang bay using marine organisms.

Arsenic and its compounds in marineorganisms has been studied to identifythe chemical species and its toxicologicalimplication in recent research. Arsenicspecies study is very important because itstoxicity and possible carcinogenicity depend

on the chemical form. (14) For example, marineorganisms often contain arsenic in the rangeof 10 to 100mg/kg (15). This is considerablehigh compared with drinking water standardof arsenic at 0.01mg/l (16) In spite of suchhigh arsenic content, marine organism are nottoxic food to human because major arsenic isin the form of organic compounds which arelow in toxicity. Organic arsenic compoundsfound in marine organisms includemonomethylarsenic acid (MMA) anddimethylarsenic acid (DMA), arsenobetaine,arsenocholine and arsenosugar (17). Sean.et al. Reported that arsenosugars wereidentified as the major arsenic compoundspresent in marine algae and arsenobetainewas the dominant arsenic species in craband shrimp. His study also revealed thepresence of arsenosugars in addition toarsenobetaine in the bivalves. (18) Shibataet al. Concluded his researches that somebivalves contained not only arsenobetainebut also the arsenosugar derivatives (19).Arsenobetaine and arsenocholine, whenpresent in seawater , are ef f ic ient lyaccumulated by blue mussels and presentin the t issue as arsenobetaine. (20)

°-14 »Ÿπ¬å«‘®—¬·≈–Ωñ°Õ∫√¡¥â“π ‘Ëß·«¥≈âÕ¡ °√¡ àß‡ √‘¡§ÿ≥¿“æ ‘Ëß·«¥≈âÕ¡

However, the origin such organic arsenic

compounds is still a matter of debate. On

the other hand, as found in the data of

mussel watch program, arsenic concentration

is high in some of the sampling sites than

other sites. It is implying some, but not direct,

relation between arsenic level in mussels and

environmental condition, not necessarily

arsenic level but also other biological/chemical

factors, specific to some sites. Therefore

interpretation of arsenic content in marine

organisms needs careful consideration. In

this study, total arsenic level of mussels in

and out of the Pak Pa-Nang bay would be

statistically compared for objective judgment

of arsenic influence. Then their spatial

distribution in the bay would be investigated.

Further consideration would be given by

the result of arsenic species study by HPLC-

ICP-MS analysis.

2. Methods and Materials2.1 Sampling98 biological sample such as

shrimp (Penaeus merguiensis, P. monodon),

crab (Scylla serrata), fish, (Liza vaigiensis,

Arius truncatus, Plotosus anguillaris, Sillagomaculate , Cynoglossus macrolepidotus),mussel (Perna viridis) were collected fromPak Pa-Nang bay during 1994-1995 forscreening purpose. Shrimp, crab and fishare collected from fishermen who caughtthem in the bay.

After screening, Green musselsamples (Perna viridis) were collected at 48sampling station in and out of Pak Pa-Nangbay (39 in the bay and 9 out of the bay asshown in Figure 2) in November 1995.Each station, about 1 kilogram of musselsthat struck with the bamboo stick werecollected (40-80 mussels) and cleaned bywater at sampling site for 2-3 times to washmud and removed bornacles. Then sampleswere washed by distilled water for 2-3 timesand packed freshly in the plastic bags. Sampleswere then stored at temperature about 4 ÌCbefore analysis.

2.2 Sample preparationShrimp : Only meat of shrimps was

used for analysis. Shell, head, tail and stomachwere removed. Meat from 25-30 shrimps werecombined by using stainless steel cutter andground in glass blender.

Figure 2 Mussel sampling point in Pak Pa-Nang Bay Nakornsritamaraj, Thailand

Out Bay

WESTERN CENTRAL EASTERN


Fish : Only meat of fish was used.

Procedure is similar to that of shrimps. 5-10

fishes of same species were homogenized to

prepare a sample.

Crab: Only meat of crab was used.

Procedure is similar to that of shrimps. 10-20

crabs were used to prepare a sample.

Mussel : In the laboratory, 25-30

mussels of the same size (6-9 cm. In length,

4-5.5 cm. In width) were selected from each

sample. Whole and undeparated soft parts of

the mussels were separated carefully from

the shell to avoid contamination. Then

samples at each station were grounded in

a glass blender equipped with a stainless

steel cutter. The samples were used for total

arsenic determination by acid digestion

fol lowed by hydride generat ion/atomic

adsorption spectrometry.

Another set of samples were prepared

for qualitative arsenic species study of water

soluble arsenic compounds. A mussel each

from 5 sampling stations were used for

preparation. After shells were removed,

samples were weighed and homogenized

into the centrifuge tube 20 ml of methanol/

water (1:1, v/v) was added to the tube and

the tube was sonicated for 10 minutes.

After centrifugation (2000 rpm x 10 minutes),

the extract was removed. Extraction process

was repeated five times and the extracts

were combined. The extract were heated to

40 ÌC in evaporator to dryness. Then sample

dissolved in water were analyzed by

HPLC-ICP-MS.

2.3 AnalysisTotal arsenic determination : Approx.

2 gm of grounded sample (wet weight)

were gently digested by HNO3 at room

temperature for over night and then at

130 ÌC. Then H2SO

4 and HClO

4 were added

and heated up to 290 ÌC until white fume

was observed. Attention was paid to avoid

overheating and boiling during digestion

process. After digestion, HCl (1+1) was

added and heated at 90 ÌC. After filtration

by using filter paper (No.5B), Kl solution (200

g/l) was added. Continuous flow hydride

generator using HCl and NaBH4 solution were

connected to SHIMADZU AA-630 atomic

adsorption spectrometer for analysis (21)

NIES No.6 mussel standard reference

material (SRM) was used for quality control

of analytical procedure. Recovery of the

arsenic from NIES No.6 SRM by the method

was over 90%.

Arsenic species study : Qualitative

arsenic species analysis was done by

HPLC-ICP-MS (Perkin Elmer 410 Bio LC

system combined with a Yokogawa Electric

PMS100 ICP mass spectrometer) . The

analytical condition was as follows; column:

Asahipak GS-220HQ 7.6x300 mm, buffer

solution : 25 mM tetramethylanmonium-

hydroxide, 25 mM maronic acid (pH = 6.8),

flow rate 0.6 ml/minute. Arsenic compounds

used as standards are that of Shibata et.al

(19) and are shown in figure 3.

Figure 3 Arsenic Compounds inMarine environment


3. Result and Discussion3.1 Preliminary investigation:Table above summarized arsenic

concentration (mg/kg dry weight) level of

various biological samples which were

collected as preliminary investigation.

The average total arsenic concen-

tration in surface fish samples (Liza vaigiensis)

and deep fish sample (Sillago maculate, Plotosus

anguillaris, Cynoglossus macrolepidotus, Arius

truncatus) (categorized by their living habitat)

were low and did not show much difference

in arsenic level due to this different habit.

The arsenic level in crab and mussel were

higher than the others. Their average

concentration were 6.40 and 5.92 mg/kg

(dry wt) respectively. Of all 6 collected crab

samples, one sample was found arsenic

concentration at level of 32.3 mg/kg. Which

is big differently level than other crab samples.

If we removed this sample from the data,

the average arsenic concentration in crab

was only 1.1 mg/kg (dry wt). The sample

matrix which has outlier is dif ficult for

statistical treatment. For this reason, crab

may not be the good sample matrix. The

average level of arsenic in green mussel were

5.92 mg./kg (dry wt). Green mussels were

selected for further investigation based on

the reasons that the average arsenic

concentration in green mussel sample was

higher than the other kinds of sample. They

stay stationary in this area while fish, shrimp

and crab can easily move from one area to

the other place. In addition data of mussel watch

program from other location is available

for comparison.

3.2 Comparison of arseniclevel in Mussels

Histograms showing arsenic level

distribution by mg/kg (dry wt.) for the samples

in the bay and out of the bay are shown in

Figure 4. For the samples in the bay, the

distribution of arsenic level seems to follow

normal distribution curve. The histogram for

the samples out of the bay seems somewhat

different from normal distribution. This may

be due to the small number of samples (n=9)

for out of the bay group. For the statistical

method discussed below, we assume out of

the bay group also follow normal distribution.

Based on the statistical discussion, we

could not find any evidence that indicate

the significant difference in the two group, i.e.,

in the bay samples and out of the bay samples.

This implies that mussel in Pak Pa-Nang bay

is not significantly influenced by arsenic.

Absolute arsenic concentration level

of mussels in this study was compared with

the data on mussel watch program in

the United States. The data was obtained from

NOAA (national Oceanic and Atmospheric

Administration) progress report (1986-1988) of

mussel watch project. Table 2 summarize

the descriptive statistics for the arsenic con-

centration of this study and NOAA report.(23)

Table 1 Total arsenic concentration of biological samples

Sample type Average Minimum Maximum Number of

(mg/kg dry wt.) (mg/kg dry wt.) (mg/kg dry wt.) samples

Fish (surface) 0.97 ND 5.25 14

Fish (deep) 0.45 ND 11.0 27

Crab 6.40 (1.10) 0.38 32.3 6

Shrimp 2.23 0.11 12.8 9

Mussel 5.92 0.32 25.2 20

ND < 0.002 ppm


When two independent sample groups are to be compared, statistical method

commonly applied is F-test and t-test. As first step, we compare the variance of two group by

F-test. F value for this study is as follows.

F = S12/ S22 = 4.63 / 3.54

= 1.31

S12 (Variance of in the bay group) = 2.152

S22 (Variance of out of the bay group) = 1.882

Critical value of F at 5% level of significance for the given degree of freedom (for numerator

= α denominator =8 ) is 3.08 (22). F value of 1.31 which is smaller than critical value of 3.08

means the null hypothesis station two groups have equal variance can not be rejected.

Small F value suggests two groups have same variance.

For the comparison of mean value of two groups when variance of each groups is

equal, t-value can be obtained by following.

t = X1 - X

2 / Sp √ (1 /n1)+(1/n2)

X1(mean of out of the bay group) = 4.96

X2(mean of in the bay group) = 4.22

n1 (number of out of the bay group) = 9

n2 (number of in the bay group) = 39

where Sp is the pooled estimate of the population standard deviation based on both groups

and can be given by,

Sp2 = (n1-1) S12 + (n2-1) S22 / (n1+n2-2)

= 4.44

Sp = 2.11

Here we obtain t value = 0.98. Critical value of t value for 40 degree of freedom at

5% level of significance is 1.68. As computed t value of 0.98 is far lower than the

critical value, again we can not reject the null hypothesis stating two groups means

are equal.

Table 2 Arsenic concentration in Mussels

Average Standard Minimum Maximum Number ofDeviation samples

In the bay sample 4.22 2.15 0.74 9.20 39Out of the bay samples 4.96 1.88 2.37 7.56 9United states (23) 11.1 6.36 2.6 41.0 177

Unit in the table : mg/kg (dry wt.)

NOAA report (23) represent statistics

around whole countries of the United States

of America while the data of this study

represents relatively small area. Therefore data

from NOAA report naturally has more variance

in the data set than the data of this study.

However, average value of this study, both

in and out of the bay samples, are less than

half of the NOAA report data. This fact also

supports the previous statistical discussion

that the mussel in the bay is not different

from background level or that of open ocean.


Figure 4 Comparison of Arsenic Level in Mussel Samples

3.3 Spatial distribution ofarsenic level

Figure 5 depict the spatial distribution

of arsenic level in mussel samples. Black

point and its size represents sampling location

as well as arsenic level. When carefully

examined we could see the samples in

eastern side of the bay generally has lower

arsenic level than others.

For fur ther discussion, we f i rst

categorized sampling site inside the bay

into 3 zones by their different geography.

The central zone of the bay is the deepest

area where the Pak Pa-Nang river from

upstream flow directly through this area.

The eastern zone is quite shallow, (The depth

at low tide is around 1 m.) and quite static.

It is dominantly mangrove forest. The western

zone locates on the western bank of the bay.

It is also shallower compared to the central

zone and close to the city of Pak Pak-Nang

district.

The concentration of total arsenic in

ten (10) mussel samples from the eastern zone

were average 2.8 mg/kg (dry wt.) which is

lower than the other zones including outside

bay (11 samples in western : 4.0 mg/kg, 18

samples in central : 5.1 mg/kg). Such large

difference can not be considered as mere

random distribution. Figure 6 is the polynomial

regression surface applied to the data. Left

map is second order polynomial and right

Figure 5 Spatial distribution of arsenic levelin mussel samples

map is third order polynomial trend surface.

Polynomial trend surface map is, in some

cases, very useful in recognizing distribution

pattern from large scale perspective. Left

map shows that arsenic level is decreasing

if the point is more eastern side. Right map

shows that arsenic level is high in central

zone where Pak Pa-Nang river water directly

flows. There are two alternate hypothesis at

this moment.

1) Bio-activities may be different

in eastern side where water is shallow and

mangrove forest is well developed. Unknown

factor may reduce the plankton activities

and populat ion which supply arsenic

compounds to mussels.


2) Central zone is influenced by

the arsenic contaminated water from

upstream because it directly receives water

flowing from Ron Phibun district. Western zone

can be af fected by some act iv i t ies

from city which is quite close to the bay.

Second hypothesis may not be reasonable as

we could not f ind any evidence that

mussels in the bay has higher arsenic level

than that of out of the bay. In addition,

the concentrat ion of arsenic in these

mussel samples also did not show any

correlation with the distance from the mouth

of river as shown in figure 7. Therefore

second hypothesis is unlikely, but we can not

totally exclude the possibility at this moment.

However it is more reasonable to assume

that the mussels in eastern side is low in

arsenic while the mussel in central and

western side is high, in view of comparison

with background (out of bay samples at

average 4.96 mg/kg dry wt.) The issue

remains as future focus of the research.

3.4 Arsenic species studyFigure 8 are HPLC-ICP/MS chroma-

togram of the five mussel samples in the bay.

As seen in the figure, two major peaks are

common to all samples. A peak of retention

time around 610 sec was identified as

arsenosugar (XI). Another peak around 763

sec was identified as arsenobetaine (VIII)

(refer to figure 3 for chemical form of each

compound). Smaller peak before arsenobe-

taine (VIII) around 744 sec was tentatively

assigned as arsenosugar (X). Other minor

peaks could not be positively identified at

this moments. The fact that major arsenic

composition of mussels in this study are

arsenobetaine and arsenosugar as commonly

abserved in other studies suggests no

influence to the mussel in Pak Pa-Nang Bay

by the upstream arsenic contamination.

Figure 6 Polynominal Trend Surface Map

Figure 7 Correlation of Arsenic concentrationvs. distance from the river mouth


One interesting point is that ratio

of arsenosugar (XI) and arsenobetaine (VIII)

are similar to four samples, but ratio is

reversed for sample No.3. For study of

plankton which is considered as major

food source of mussels, Shibata et al. found

that phytoplankton contain arsenosugar as

major arsenic compounds while some of

zooplankton contain high arsenobetaine (24).

Therefore biological condition at sampling

site No.3, specially character of plankton

population might be different from other

sites and it affected ratio of two arsenic

compounds. As we discussed previously

the possible variation of such biological

condition in the bay is interesting topics

for future study. Currently survey of plankton

species distribution in the bay in under

planning.

4. ConclusionIn conclusion, the present study

revealed that the arsenic level in biological

samples in Pak Pa-Nang bay is not consi-

dered as seriously affected by upstream

contamination at Ron Phibun. The conclusion

was reached from three independent

approach as follows.

4.1 Mussels in the bay and out of the

bay does not have any significant difference

in arsenic level and can be considered as

same population.

4.2 Arsenic level of the mussels in the

study is, in average, at (4.359 mg/kg dry wt).

Less than half of mussel watch program

conducted by NOAA.

4.3 Arsenic species in the green

mussels is similar to previous research.

Main arsenic composition is arsenobetain

and arsenosugars.

However, the arsenic level in mussel

samples collected from eastern zone of the bay

(dominant as mangrove forest) were lower

than other zones and outside bay (represented

for natural background). The relat ive

abundance rat io of arsenosugar and

arsenobetaine found in mussel samples are

not similar in all samples. One mussel sample

showed the reversed ratio. These finding

suggests that fur ther study focused on

variation of biological activities, particularly of

planktion, inside the bay is important for

understanding arsenic distribution.

5. AcknowledgementsThe authors wish to express thank

to Dr. Y. Shibata for providing ICP-MS

analysis, Mr. Suthaib Srilachai and Miss

Lamyai Chaiyo for helping in sample prepara-

tion and technical assistance. We also

acknowledge Dr. Monthip Sriratana

Tabucanon, director of Environmental

Research and Training Center (ERTC) and

all Japanese experts in (ERTC) and all

Japanese experts in ERTC for their thoughtful

comments.

Figure 8 HPLC-ICP/MS Chromatograms(m/z=75) of Mussel Extracts


6. Reference1. Ishihara Shunso, Sawata Hideho et.al.,(1980).

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