toxic1

∫∑§—¥¬àÕ°“√»÷°…“°“√·æ√à°√–®“¬¢Õß “√‚æ≈’-

‰´§≈‘°Õ–‚√¡“µ‘°‰Œ‚¥√§“√å∫Õπ (Polycyclic

Aromatic Hydrocarbons, PAHs) 3 ™π‘¥ ‰¥â·°à

Benzo (a) pyrene (BaP) Benzo (k) fluoranthene

(BkF) ·≈– Benzo (g,h,i) perlyrene (BghiP) „π

·À≈àßπÈ”¢Õß°√ÿß‡∑æœ ·≈–ª√‘¡≥±≈ 3 ®—ßÀ«—¥ §◊Õ

®—ßÀ«—¥ππ∑∫ÿ√’ ª∑ÿ¡∏“π’ ·≈– ¡ÿ∑√ª√“°“√ ‚¥¬

∑”°“√‡°Á∫µ—«Õ¬à“ßπÈ”·≈–¥‘πµ–°Õπ√–À«à“ß‡¥◊Õπ

°ÿ¡¿“æ—π∏å - ¡’π“§¡ 2538 ®“°§≈Õßµà“ßÊ ·≈–

·¡àπÈ”‡®â“æ√–¬“ ®”π«π 29 5 4 ·≈– 6 ®ÿ¥‡°Á∫

µ—«Õ¬à“ßµ“¡≈”¥—∫ º≈°“√«‘‡§√“–Àå™π‘¥·≈–ª√‘¡“≥

“√‚æ≈’‰´§≈‘°Õ–‚√¡“µ‘°‰Œ‚¥√§“√å∫Õπ ∑—Èß 3 ™π‘¥

™’È „Àâ‡ÀÁπ«à“°“√ªπ‡ªóôÕπ¢Õß “√‡À≈à“π’È „π·À≈àßπÈ”

°“√»÷°…“°“√·æ√à°√–®“¬¢Õß “√æ‘…™π‘¥‚æ≈’‰´§≈‘° Õ–‚√¡“µ‘°‰Œ‚¥√§“√å∫Õπ (Polycyclic Aromatic Hydrocarbons, PAHs)„π·À≈àßπÈ”¢Õß‡¢µ‡¡◊Õß¢Õßª√–‡∑»‰∑¬Study on the Distribution of Polycyclic Aromatic Hydrocarbons(PAHs) in Water Resources of Urban Areas of Thailand.

Vanvimol Patarasiriwong*,Chuanpit Boonyoy*

*»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]

High Performance Liquid Chromatography (HPLC)

Water sample filtration

¬—ß‰¡àÕ¬Ÿà„π√–¥—∫«‘°ƒµ‘ ‚¥¬æ∫«à“„πµ—«Õ¬à“ßπÈ”π—Èπ

æ∫ “√ BkF ‡æ’¬ß™π‘¥‡¥’¬« „π√–¥—∫§«“¡‡¢â¡¢âπ

µ—Èß·µà πâÕ¬°«à“ 2 - 4.9 π“‚π°√—¡/≈‘µ√ à«π„π

µ—«Õ¬à“ß¥‘πµ–°Õπ “¡“√∂µ√«®æ∫ “√‚æ≈’‰´§≈‘°

Õ–‚√¡“µ‘°‰Œ‚¥√§“√å∫Õπ ∑—Èß 3 ™π‘¥ §◊Õ æ∫ BaP „π

√–¥—∫µ—Èß·µà πâÕ¬°«à“ 20 - 89.6 ‰¡‚§√°√—¡

/≈‘µ√ æ∫ “√ BkF µ—Èß·µàπâÕ¬°«à“ 15 - 66.1 ‰¡‚§√°√—¡

/≈‘µ√ ·≈–æ∫ “√ BghiP µ—Èß·µà πâÕ¬°«à“ 100 - 282.5

‰¡‚§√°√—¡/≈‘µ√ º≈°“√µ√«®«‘‡§√“–Àå™’È „Àâ‡ÀÁπ«à“

“‡Àµÿ°“√ªπ‡ªóôÕπ¢Õß “√‚æ≈’ ‰´§≈‘°Õ–‚√¡“µ‘°

‰Œ‚¥√§“√å∫Õπ „π·À≈àßπÈ”¢Õß°√ÿß‡∑æœ ·≈–®—ßÀ«—¥

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µ√«®æ∫π’È¬—ß‰¡àÕ¬Ÿà„π√–¥—∫«‘°ƒµ‘°Áµ“¡ ·µà‡π◊ËÕß®“°

ª√–‡∑»‰∑¬¬—ß‰¡à¡’°“√°”Àπ¥§à“¡“µ√∞“π ”À√—∫

“√‡À≈à“π’È ®÷ß§«√®–‰¥â¡’°“√µ‘¥µ“¡µ√«® Õ∫‡ªìπ

√–¬–‡æ◊ËÕ„Àâ∑√“∫∂÷ß·π«‚πâ¡¢Õß√–¥—∫°“√ªπ‡ªóôÕπ

¢Õß “√ æ√âÕ¡°—ππ’È§«√®–‰¥â¡’°“√»÷°…“°“√®—¥°“√

°“√ªπ‡ªóôÕπÕ—π‡π◊ËÕß¡“®“°®“° “√¥—ß°≈à“«‡æ◊ËÕ¡‘„Àâ

¡’√–¥—∫°“√ªπ‡ªóôÕπ®π∂÷ß¢—Èπ«‘°ƒµ‘‰¥â

ABSTRACTDetermination of 3 PAHs, Benzo (a)

pyrene (BaP), Benzo (k) fluoranthene (BkF)

and Benzo (g,h,i) perlyrene, (BghiP), in water

resources of Bangkok and perimeters was

conducted. 29, 5, 4 and 6 sampling sites were

selected in Bangkok, Nonthaburi, Pathumthani

and Samutprakan provinces, respectively. The

sampling sites selected on the canals and

major river of Thailand, the Chaopraya River,

were situated along the road sides. The sample

was collected in February-March 1995. The

results showed non-critical level of PAHs

contamination in water resources. Only BkF

was found in water sample in the range of <2

to 4.9 ng/l. All the 3 PAHs were detected in

the sediment sample in the range of <20

to 89.6, < 15 to 66.1 and <100 to 282.5

mg/kg for BaP, BkF and BghiP, respectively.

The results can imply that water resources

of Bangkok and perimeters were contributed

mainly from traffic source. Although the

research results showed quite low level of

PAH detected, however, PAHs monitoring

in water resources is necessary since the

standard regulations for PAH in sur face

water of Thailand has not been established

yet. Evaluation on trend of PAHs pollution

and management strategy should be

provided.

1. IntroductionPolycyclic Aromatic Hydrocarbons

(PAHs) is one of major classes of organic

pol lutants that are released into the

environment and dued mostly to human

activities. PAHs in the environment are

formed mainly during incomplete combustion

of organic matter at high temperature by both

domestic and industrial activities. Exhausted

emission from vehicles is also one of the

major sources of PAHs in urbanized areas.

Major routes of entry of PAHs into aquatic

environment are spillage and seepage of

fossil fuels, discharge of domestic and

industrial wastes, fallout or rainout from air,

and runoff from land. Most of the PAH

enter ing the aquat ic environment are

localized in water resources and are more

persistent in water than in air. PAH can

accumulated by aquatic biota, reaching

levels higher than those in the ambient

medium (Neff, 1985). PAHs in water resources

may vary upon the environmental conditions

of the areas. Water and sediment from heavily

industrialized areas usually contain much more

PAHs concentrations level than those in area

remote from human activities (Bjorseth et al,

1979, Griest, 1980; Neff, 1979 and 1985).

The importance of PAHs in the environment

is discussed because of its carcinogenicity,

mutagenicity and/or teratogenicity to human

(IARC, 1973 and NAS, 1972). PAH can also

cause adverse effect to aquatic animals, for

instant, growth inhibiting or abnormal meiosis

that causing cancer. Fishes in the high-polluted

areas were also found the tumorsis (Neff, 1985).

°-2 »Ÿπ¬å«‘®—¬·≈–Ωñ°Õ∫√¡¥â“π ‘Ëß·«¥≈âÕ¡ °√¡ àß‡ √‘¡§ÿ≥¿“æ ‘Ëß·«¥≈âÕ¡

The objectives of the present study

are to determine PAH concentration levels and

define their possible sources in aquatic

environment of capital city and the perimeters

of Thailand, which have potential of being

polluted by most toxic substances as their

urbanization.

2. Methods and Materials2.1 Sampling sitesWater and sediment samples from

the water resources of the capital city of

Thailand, Bangkok, and the perimeters, i.e.

Pathumthani, Nonthaburi and Samutprakan

provinces, were collected. Bangkok is known

as the center of all business and civilization

of the country. It is much interesting so that

the great number of people has migrated from

upcountry. Consequently, the urbanization

and industrialization have expanded to the

adjacent areas, especially the 3 provinces,

Pathumthani, Nonthaburi and Samutprakan.

Thus, heavy traffic condition cannot be

avoided. Therefore, the cities have high

potential to be polluted by many toxic

substances produced from various activities.

Water resources, including rivers and canals,

have become receiving water body for

domestic discharges, industrial effluent and

even fall out and runoff from the road. The

sampling sites were selected on the Chao-

praya river, one of the most important rivers

of Thailand, and the canals (or klongs) which

are affected by anthropogenic inputs directly

and posing high risk of pollution. Table 1 and

figure 1-4 show details of the selected

sampling sites.

2.2 Sampling procedureSample collection was done during

February - March, 1995. Three liters of water

sample were collected from each sampling

site using water sampler and stored in

narrow-mouth amber glass bottles. Grab

sampler was used for sediment sampling.

One kilogram of sediment sample was stored

in wide-mouth amber glass bottle. All samples

were kept cool until laboratory procedures

were done.

2.3 Sample extractionsPAHs were isolated from the water

samples by solid phase extraction (SPE) on

a C18 column. Each of 1 liter of water

samples was filtered with glass fiber filter

before extraction to separate suspended

solids. The C18 column was rinse with

methanol and acetonitrile consequently.

Then the filtered water was taken over

the column with under pressure applied.

Sucking air through the column for 10 min

was obtained for drying the column. PAHs

in the column was eluted using 3 ml of

dichloromethane twice. The combined

extract was then gently nitrogen-dried

and exactly 1 ml of acetronitrile was added

and analyzed for the PAHs by High

Performance Liquid Chromatography (HPLC).

Ultrasonication method was applied both for

the suspended solid and sediment extraction.

Suspended solid precipitated on glass fiber

filter was air-dried and weighted.

Al l par t iculate samples of each

sampling site were ultrasonicated with

2% dichloromethane in hexane 50 ml for 15

min twice. Ten ml of combined extraction

was pipetted to silica column for cleaning

up, and was eluted with 5 ml of 50%

dichloromethane in hexane and 5 ml of

acetronitrile, respectively. Nitrogen dried

then was done and 1 ml of acetronitrile

was added.

The sediment samples were air-dried

and crashed then sieved using a 150-mesh

screen. A 5-g subsample was transferred

to a flask and mixed with 5 g of anhydrous

sodium sulfate. Fifty ml of 2% dichlorome-

thane in hexane was used as solvent for

ultrasonicat ion for 30 min. After the

precipitation, the dichloromethane/ hexane

»Ÿπ¬å«‘®—¬·≈–Ωñ°Õ∫√¡¥â“π ‘Ëß·«¥≈âÕ¡ °√¡ àß‡ √‘¡§ÿ≥¿“æ ‘Ëß·«¥≈âÕ¡ °-3

Table 1 Details of the selected sampling sites.

Sampling Describtions Sampling Describtionssite site

Bangkok

BKK 1 Chaopraya river, Rama 6 Bridge BKK 16 Klong Prapa , Rama 5 Road

BKK 2 Chaopraya river, Krung Thon Buri Bridge BKK 17 Klong Pra Kha Nong, Sukhumvit Road

BKK 3 Chaopraya river, Pra Pin Klao Bridge BKK 18 Chaopraya river, Khlong Toey Seaport

BKK 4 Klong Bangkok Noi, Arun Amarin Road BKK 19 Pond near the Tobacco plant

BKK 5 Chaopraya river, Pra Putta Yot Fa Bridge BKK 20 Pond in the Lumpini Park

BKK 6 Klong Bangkok Yai, Sang Kha Chai Temple BKK 21 Klong Prem Prachakorn, Rama 6 Road

BKK 7 Klong Bang Sai Kai, Somdej Chaopraya Road BKK 22 Klong Bang Sue, Pracha Rat No. 1 Road

BKK 8 Chaopraya river, Rama 9 Bridge BKK 23 Klong Sam-sen, Samsen Road

BKK 9 Klong Bang Pa Kaew, Suksawad 13 Road BKK 24 Klong Padung, Krung Kasem Road

BKK 10 Chaopraya river, Krung Thep Bridge BKK 25 Klong Rob Krung, Pra Su Meru Road

BKK 11 Chaopraya river, Taksin Bridge BKK 26 Klong Ku Muang Derm, Rajchadamnern Road

BKK 12 Klong Sathon, Sathon Road BKK 27 Klong Padung, Krung Kasem Road

BKK 13 Klong Padung, Charoen Nakhon Road BKK 28 Klong Sam-sen, Paholyothin Road

BKK 14 Klong Padung, Krung Kasem Road BKK 29 Makkasan reservoir

BKK 15 Klong San-sab, Rama 6 Road

Pathumthani province

PTT 1 Klong Prapa, Road no. 3100 PTT 3 Chaopraya river, Pathumthani Bridge

PTT 2 Klong Bang Po Tai, Road no. 307 PTT 4 Klong Rangsit Prayoonsak, Road no. 305

Samutprakan province

SPK 1 Klong Samrong SPK 4 Chaopraya river, fresh market of the Paknam district

SPK 2 Klong Bang Nang Kreng, Poo Chao Saming Prai SPK 5 The mouth of the Chaopraya river, next to

Road (in front of the water gate) the Gulf of Thailand

SPK 3 Klong Bang Nang Kreng, Poo Chao Saming Prai SPK 6 Klong Sappasamit

Road (behind the water gate)

Nonthaburi province

NTB 1 Chaopraya river, Nonthaburi Bridge NTB 4 Chaopraya river, Nonthaburi Port

NTB 2 Chaopraya river, Pak Kred Port NTB 5 Klong Bang-kruai

NTB 3 Chaopraya river, Pra nung Klao Bridge

extract was transferred to another flask.

Another 50 ml of 2% dichloromethane in

hexane was added to the sediment and

ultrasonicated for more 30 min. The second

dichloromethane/hexane extract was

transferred to combine with the first extract.

One milliliter of the combined extract was

pipetted to the silica column for cleaning up

and was eluted with 5 ml of 50%

dichloromethane in hexane and 5 ml of

acetronitrile, respectively. The final extract

was dried with pure nitrogen gas then exactly

1 ml of acetronitrile was added and analyzed

for PAH concentrations with HPLC. Three

replicates of each combined extract were

done for every single sediment sample.

2.4 Analysis of PAHsThree compounds of PAHs selected

for analysis were benzo (a) pyrene, BaP;

benzo (k) fluoranthene, BkF; and benzo (g,h,i)


Figure 1 Sampling sites in Bangkok (BKK).


Figure 2 Sampling sites in Pathumthani (PTT).

Figure 3 Sampling sites in Samutprakan (SPK).


Figure 4 Sampling sites in Nonthaburi (NTB).

perylene, BghiP. BaP was proven as

carcinogens (IARC, 1973 and NAS, 1972).

BkF and BghiP were reported as carcinogenic

initiator and strengthener of BaPûs carcino-

genicity, respectively (Environment Agency of

Japan, 1991). The analysis of PAHs by HPLC

has followed the method by Matsushita

et al (1992). The recovery rate for standard

spiked water and marine sediment (Standard

referent material 1941a, NIST) from five

replicates are presented in table 2.

3. Results and discussionThe 3-PAH concentrations in water

and sediment samples of Bangkok, Nonthaburi,

Pathumthani and Samutprakan provinces are

shown in Table 3. The result of water samples,

include total PAHs in water and suspended

Table 2 The recovery rate for water and sediment samples.

Water Sediment

Compounds Abbreviation N Recovery,mean(%)

DetectionLimit (ng/l)

Recovery,mean(%)

DetectionLimit

(µg/kg)

Benzo (k) fluoranthene BkF 5 98.9 2 98.8 15

Benzo (a) pyrene BaP 5 88.4 3 97.6 20

Benzo (g,h,i) perylene BghiP 5 89.5 10 100 100


solids, showed that carcinogenic PAH, BaP,

and BghiP were not detected. Among 3 PAHs,

only BkF is found in water sample and are

detected in the samples of Bangkok, Pathum-

thani and Samutprakan provinces, but not

detected in the samples of Nonthaburi

province. PAHs in sediment are detected

in the samples of Bangkok, Nontaburi and

Samutprakan provinces, but not detected

in the samples of Pathumthani province.

PAHs concentrations varied from sampling

site to anothers, even in the same water

resources.

From the samples of Bangkok, it was

found that PAHs detected in water and

sediment were markedly different. In water

samples, BaP and BghiP were not detected

(less than 3 and 10 ng/l, respectively). This is

signif icant in that the compounds are

concerning with carcinogenic risk (NAS, 1972).

Only BkF was found non-specifically. Sorrell

et al (1980) reported that PAH concentrations

in surface waters are dependent on the

organic loading of the aqueous system and on

the amount of suspended particulate matters.

And it was believed that PAH concentrations

in water varied by the function of industrial

contamination. BkF concentration detected

in this study is in the range of less than 2 to

4.9 ng/l which is in the same magnitude of

level as those reported for typical unpolluted

water (Arashidani et al, 1985, Hanada et al,

1989, Mori and Naito, 1985, and Sorrell et al,

1980), may reflect non-serious contamination

of PAHs in water resources of Bangkok.

The standard values of maximum

concentration of BaP in drinking water of

U.S., Canada and WHO is 0.00001-0.002 mg/l

(or 10-200 ng/l), but in this study BaP was not

detected. Obana et al (1983) reported that

aquatic organisms could accumulate PAHs

from water rather than from sediment, thus,

the results can ensure that aquatic PAHs will

not lead adverse effects to the organisms

living in these areas. Most of PAHs detected

in sediment samples of Bangkok is specific to

the heavy traffic areas and concentration of

BghiP is ten times higher than BaP and BkF.

The results seem subject to the previous

report (Nielsen, 1996). The author revealed

that main source of PAHs in large cities was

the traffic and BghiP is one of the major PAHs

emitted in relatively high amount from city

traffic exhaust. It was approved that the most

likely sources of PAH in sediment was PAH-

associated airborne dust (Hase and Hites, 1976

and Shinohara et al, 1980). Roads in Bangkok

were constructed parallel with the canals

and high buildings located along the roads,

this may has ceased the distribution of the

atmospheric PAHs, and promoted falling and

raining out into the canals next to the road. This

is in agreement with the analysis by

mathematical model of PCD (1994) which

ascribed the large source of hydrocarbons

in Bangkok Metropolitan Region to traffic.

In the present study, PAHs detected in

other provinces, i.e. Pathumthani, Nonthaburi

and Samutprakan, cannot represent all over

the cities since small numbers of sampling

sites were conducted. However, from the same

magnitude of concentration level as in

Bangkok, it may reflect same major concerning

of PAHs in aquatic environment of the

cities, that is exhausted emission from the

traffic.

4. ConclusionsDetermination of water resources

of Bangkok and perimeters indicated non-

critical level of PAHs contamination in surface

water. PAHs detected in the sediment samples


Table 4 PAHs found in water and sediment samples of Bangkok, Nonthaburi,Pathumthani and Samutprakan provinces, collected in February- March, 1995.

Sampling Suspended SolidsPAHs concentrations in water PAHs concentrations in sediment

Sites (mg/l)samples (ng/l) sample (µg/kg)

BaP BkF BghiP BaP BkF BghiPBKK1 83.1 nd nd nd nd nd ndBKK2 8.5 nd 2.7 nd nd nd ndBKK3 54.5 nd 2.0 nd nd nd ndBKK4 16.9 nd nd nd nd nd ndBKK5 12.4 nd nd nd 28.4 47.4 ndBKK6 22.8 nd nd nd 51.3 35.4 101.6BKK7 32.0 nd nd nd 70.7 46.4 131.1BKK8 18.0 nd 2.7 nd 89.6 66.1 156.1BKK9 14.8 nd 2.6 nd nd nd ndBKK10 15.0 nd nd nd nd nd ndBKK11 39.7 nd nd nd 22.9 19.1 ndBKK12 39.8 nd 3.7 nd 24.8 nd 106.8BKK13 16.5 nd 2.0 nd 25.7 17.2 ndBKK14 22.4 nd nd nd nd 16.5 ndBKK15 21.7 nd nd nd nd nd ndBKK16 23.2 nd nd nd nd nd ndBKK17 26.8 nd 4.6 nd nd nd ndBKK18 31.8 nd 2.0 nd nd nd ndBKK19 29.8 nd 3.4 nd nd nd ndBKK20 77.8 nd nd nd nd nd ndBKK21 75.2 nd nd nd nd nd ndBKK22 16.6 nd 2.5 nd nd nd ndBKK23 196.4 nd nd nd 30.6 43.4 111.6BKK24 20.7 nd nd nd nd nd ndBKK25 17.6 nd nd nd nd 20.1 186.1BKK26 18.2 nd nd nd nd 16.1 281.4BKK27 19.8 nd nd nd nd 41.7 126.4BKK28 54.2 nd 4.2 nd 43.7 55.5 282.5BKK29 13.1 nd 4.9 nd 33.3 18.4 274.9NTB1 31.5 nd nd nd 43.9 36 102.7NTB2 71.6 nd nd nd nd 15 ndNTB3 20.6 nd nd nd 24.3 22 ndNTB4 18.1 nd nd nd nd nd ndNTB5 23.2 nd nd nd nd nd ndPTT1 55.2 nd nd nd nd nd ndPTT2 51.0 nd 4.2 nd nd nd ndPTT3 50.0 nd 2.1 nd nd nd ndPTT4 20.1 nd nd nd nd nd ndSPK1 30.0 nd 2.9 nd 27.3 17.1 ndSPK2 45.6 nd nd nd 68.9 45.3 169.2SPK3 87.6 nd 8.9 nd 42.3 24.7 275.2SPK4 80.6 nd nd nd nd nd ndSPK5 321.5 nd 3.8 nd nd nd ndSPK6 48.5 nd nd nd 21.1 15 ndMDL - 3.0 2.0 10 20 15 100


might reflect that water resources of Bangkok

and perimeters were contributed mainly from

traffic source. The standard regulations for PAH

in surface water of Thailand has not been

established yet and the research results

showed quite low level of PAH detected.

However, it should be noted that population

number in Bangkok and perimeters has

increased continually, meanwhile urbanization

has not expanded or slowly expanded to

upcountry. Thus, there is potential that Bangkok

and perimeters will be affected by many

kinds of pollutants, including PAHs. Then

PAHs should be adopted as one of the

substances in the monitoring survey, as

suggestion by Obana et al (1983), to evaluate

trend of pollution and management strategy

should be studied, simultaneously.

5. AcknowledgementsThe authors like to thank Dr. Takashi

Amagai, Mr. Hiroshi Hoshino, Mr. Yoshifumi

Hanada and Prof. Dr. Hidetsuru Matsushita

for their kind and generous help and advises

in conducting this research. Thanks to the

Kitakyushu Municipal Institute of Environ-

mental health Sciences for giving the chance

of training on PAHs analysis. Thanks to all staffs

in the ERTC for supporting this research work.

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