Distribution of Fecal Sterols and Nonylphenolic Compounds in Sediments from Busan Suyeong Estuary, Impacted by Wastewater Treatment Plant Effluents

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Kor J Fish Aquat Sci 47(6),1006-1013,2014

한수지 47(6), 1006-1013, 2014

Original Article

1006

Copyright © 2014 The Korean Society of Fisheries and Aquatic Science pISSN:0374-8111, eISSN:2287-8815

서 론

부산수영강은온천천

,

^동래천

,

^석대천의^지류를^가지고^있으 며

,

총연장

28 km,

폭

50-90 m

이고전체면적은

200 km ²

에달 하며

,

^{동해바다로}^직접^연결된다

.

^수영강^하구역

(estuary)

^주변 은주거지역

,

^상업지역

,

^{공업지역이}^혼재된^지역으로

,

^주변에^대 형주거단지가건설됨에따라도시화되면서오염화가가중된대 표적인지역이다

(Kwon et al., 2008).

^수영강^{하구역에는}^중대 형인수영

(SY)

과동부

(DB)

하수처리장이위치하고있고

,

방류 수는수영강을통해연안으로배출된다

(ME, 2012). SY

^하수처 리장은

1985

^년에^{건설되었으며}

,

^하루에

452,000

^톤의^하수를 처리하는부산에서

가장큰하수처리장중하나이며

,

표준활성 슬러지법

(activated sludge treatment process)

^으로^처리^후^방

류수를배출하고있다

. DB

하수처리장은

2007

년에건설되었

으며

,

^하루에

135,000

^톤의^하수를^처리하고^있으며

,

^최종처리

방법은생물막여과법

(biofilm filteration process)

^을 ^이용하고 있다

.

또한

,

수영강하구역은동래구

,

수영구

,

해운대구가위치 하고있으며

,

^이들의^하수관거^보급율은

46-51%

^으로^전국^평 균

73%

에크게낮고

,

우수관거보급률은

2.4-18.9%

로전국평 균

59%

^에^크게^낮은^수준으로^도시하수

(municipal effluents)

로인한오염이우려된다

(ME, 2012). Kim et al. (2009)

^은^수영 강수계퇴적물조사결과에서수영강중류지역은중금속과총 인이미국환경청의퇴적물기준을초과하는수준의오염도를보 고한바있다

. Jeon et al. (2010)

의저서성대형무척추동물과어 류를이용해수영강중류수생태건강성을평가한연구결과에 따르면

,

^약간나쁨

(B

^등급

)-

^아주나쁨

(D

^등급

)

^수준으로^평가되었 지만

,

수영강하구역에서환경오염도에대한연구는현재매우 미비한실정이다

.

^따라서^{하수처리장}^방류수^뿐만^아니라^다양 한하수가유입하는수영강하구역에서도시하수로인한오염 도를평가하는것은매우중요하다

.

하수처리장 방류수역에서 분변계스테롤과 노닐페놀류의 분포 특성

백승홍·윤세라·이인석·황동운·최민규*

국립수산과학원 기반연구부 어장환경과

Distribution of Fecal Sterols and Nonylphenolic Compounds in Sediments from Busan Suyeong Estuary, Impacted by Wastewater

Treatment Plant Effluents

Seung-Hong Baek, Sera Yoon, In-Seok Lee, Dong-Woon Hwang and Minkyu Choi*

Marine Environment Research Division, National Fisheries Research and Development Institute, Busan 619-705, Korea Wastewater organic compounds, that is, nonylphenolic compounds (NPs) and fecal sterols, were measured in surface sediments from Busan Suyeong Estuary, where two wastewater treatment plants (WWTPs) are located, to assess contamination from municipal effluents. The NPs analyzed were nonylphenol, and nonylphenol mono- and di-ethox- ylates, all synthetic endocrine disruptors. The fecal sterols analyzed were coprostanol (COP), cholestanol, and epico- prostanol. Concentrations of NPs in the sediments ranged from 146 to 3,723 ng/g, and those of COP ranged from 366 to 13,018 ng/g. Their detection in all of the sediments analyzed indicates widespread pollution by municipal effluents.

The highest concentrations of NPs and COP were detected at stations close to outfalls of WWTPs. Their levels in sediments are categorized in the higher range of those previously reported in Korean coastal areas. Moreover, in comparison with screening values of NPs in the Netherlands, Norway, and Canada, more than 50% of the sampling stations exceeded the guidelines. This indicates that the estuary may be adversely influenced by municipal effluents.

Key words: Sewage, Nonylphenol, Coprostanol, Wastewater treatment plant, Ecotoxicology

This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial Licens (http://creativecommons.org/licenses/by-nc/3.0/)which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

http://dx.doi.org/10.5657/KFAS.2014.1006 Kor J Fish Aquat Sci 47(6) 1006-1013, December 2014

Received 12 September 2014; Revised 3 November 2014; Accepted 6 November 2014

*Corresponding author: Tel: +82. 51. 720. 2531 Fax: +82. 51. 720. 2515

E-mail address: [email protected]

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도시하수로 인한 오염을모니터링하기 위해

,

^{분변계스테롤}

(fecal sterols)

과노닐페놀류

(nonylphenolic compounds; NPs)

를많이이용하고있다

(Li et al., 2008; Froehner et al., 2009;

Choi et al., 2009, 2011a; Kim et al., 2010; Lee et al., 2012; Choi et al., 2014).

^{분변계스테롤중}

coprostanol (COP)

^은^포유류의 장에서

cholesterol (CHOE)

^로부터^생성되는^주요한^분변계스 테롤로서

,

인간이배설하는분변계스테롤중

50-80%

를차지하 고있어서수생태계중분변오염의지시자로널리활용되고있 다

(Leeming et al., 1996; Chan et al., 1998).

분변계스테롤은독 특한분포특성을가지고있어서

COP

^및

cholestanol (CHOA)

와같은분변계스테롤과의분포특성을비교하면하수기인오염 에대한유용한정보를제공하며

, COP/(COP+CHOA)

비율이

0.3

^이하이면^비오염

, 0.6

^이상이면^{도시하수로}^인한^오염을^의

미한다

(Grimalt et al., 1990). NPs

는비이온계면활성제

(non- ionic surfactants)

^의 ^분해물질

(biodegradation products)

^이다

. NPs

^는

1940

^년^이후로^가정용

/

^{상업용세제}^및^{산업공정에}^널리 사용되다가유해성이보고되면서선진국을중심으로사용규 제되었다

.

^{국내에서도}

2007

^년부터^{가정용으로}^전면^사용금지 되었지만

,

현재도하수처리장방류수

,

하천수

,

해수

,

퇴적물등 에서널리검출되고있다

(Choi et al., 2011a; Lee et al., 2012;

Choi et al., 2014).

본연구에서는수영강하구역에위치한하수처리장배출구로 부터동백섬인근까지일정간격별퇴적물을채취한후

,

^하수기 인오염지시자

(

분변계스테롤과

NPs)

를분석하여수영강의도 시하수로인한오염수준을파악하였다

.

재료 및 방법

시료채취

부산수영강하구역퇴적물은

2010

^년

6

^월에^{하수처리장}^방류 구인근부터해운대동백섬인근까지

10

^개^정점

(SY01-SY10)

에서채취하였다

(Fig. 1).

^퇴적물^시료는

van Veen grab sampler

를이용하여표층

(<4 cm)

^을^{채취하였으며}

,

^채취된^퇴적물은^조 사선에서냉동하여실험실로운반하였다

.

퇴적물시료는동결 건조하고균질화하여

2 mm

^체로^걸러^갈색병

(amber bottle)

^에 보관하였다

.

분석방법

NPs

^의 ^분석은

Choi et al. (2009, 2011a,

2014)

의분석방법과동일하게수행하였다

.

분변계스테롤의분

석대상성분은

COP, CHOA, CHOE, epicoprostanol (ECOP)

이며

,

^{분변계스테롤의}^전처리^과정은^다음과^같은^순서로^진행 하였다

.

^우선^{동결건조된}^퇴적물^약

5 g

^을^테프론^{원심분리관에} 넣고

,

^{내부표준물질}

1-nonadecanol (Dr. Theodor Schuchardt

& Co.)

주입후

,

추출용매

1:1 methylene chloride-chloroform (J.T. Baker,

^{잔류농약급}

)

^으로

60

^분간

2

^회^진탕하여 ^추출하였 다

.

^{추출시료는}^{질소농축하여}

Florisil

^컬럼

(60-100 mesh, Sig- ma-Aldrich, 10 g)

^으로^{방해물질을} ^{제거하였다}

.

^정제된^시료 액은다시질소농축후

, 99:1 bis (trimethylsilyl) trifluoroacet- amide-trimethylchlorosilane (Sigma-Aldrich)

으로유도체화하

Fig. 1. Sampling locations of sediments from Suyeong Estuary of Busan, Korea.

0.0 0 2 4

COP/ECOP ratio

COP/(COP+CHOA) ratio _Biogenic

Source

Sewage Pollution

6 12 14

0.2 0.4 0.6 0.8 1.0

0.0 1 10 100

COP (ng/g)

COP/(COP+CHOA) ratio _Biogenic

Source

Sewage Pollution

1000 10000 0.2

0.4 0.6 0.8 1.0

0.0 1 10 100

COP (ng/g)

COP/ECOP ratio

Biogenic Source

Sewage Pollution

1000 10000 2.0

4.5 6.0 12.0 14.0

a b

Concentration (ng/g)

Rank (%)

(a) NP

10 100 1000 10000

0 20 40 60 80 100

Rank (%)

10000 a

Concentration (ng/g) (b) NP 1+2 EO

10 100 1000

0 20 40 60 80 100

Rank (%)

(c) NP-TEQs

10 100 1000 10000

0 20 40 60 80 100

Concentration (ng-TEQ/g, TOC1%) c

126°00' 128°00' 130°00'

129°09' 129°11' 129°13' 129°15'E

0 50 100 km 34 °00' 35 °15' 35 °17' 35 °19'N

36 °00' 38 °00'N

KOREA

N

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백승홍

ㆍ

윤세라

ㆍ

이인석

ㆍ

황동운

ㆍ

최민규

1008

여정량용시료액으로사용하였다

.

NPs

의 분석대상성분은

nonylphenol (NP), nonylphenol mono- & di-ethoxylates (NP ₁₊₂ EO)

^이며

, NPs

^의^전처리^과정 은다음과같은순서로진행하였다

.

테프론원심분리관에동결 건조된퇴적물약

5 g

^을^넣고

,

^{내부표준물질}

nonylphenol- ¹³ C ₆ (Cambridge Isotope Laboratories)

^을^주입^후

, methylene chlo- ride (J.T. Baker,

잔류농약급

)

로

60

분간

2

회진탕추출하였다

.

추출시료는

1 mL

^까지^{질소농축하여}^활성된^구리

(Sigma-Al-

drich)

로황화합물을제거하였다

.

황화합물이제거된추출시료

는

99:1 bis (trimethylsilyl) trifluoroacetamide-trimethylchlo- rosilane

^를^이용하여^{유도체화한}^후

, Florisil

^컬럼

(1 g)

^으로^방 해물질을제거하였다

.

정제된시료액은질소농축하여정량용 시료액으로사용하였으며

, gas chromatograph-mass selective detector (Agilent 6890/5973N)

로정량하였다

.

NPs

^의 ^농도는

ng/g

^의 ^단위

(

^건중량

; dry weight)

^로^{나타내었다}

.

^{분석대상성분의}^검출한계

(limit of de- tection)

는

signal-to-noise ratio

의

3

배로계산하였고

,

분변계스 테롤의검출한계는

4-14 ng/g

^이었고

, NPs

^는

1-4 ng/g

^이었다

.

회수율

(recovery)

은

5

개의

sea sand (washed sea sand, Fisher Scientific)

^에^{분변계스테롤과}

NPs

^{표준용액을}

spike

^하여^동일 한전처리방법을거친후계산하였다

.

^{분변계스테롤의}^회수율 은

77±14%

이었고

, NPs

는

104±15%

이었다

.

현장퇴적물시 료에서내부표준물질

nonylphenol- ¹³ C ₆

^및

1-nonadecanol

^의^회 수율은각각

81±11%, 78±9.5%

로양호한수준이었다

. 총유기탄소 분석

퇴적물내총유기탄소

(Total organic carbon; TOC)

^는

1 N HCl (Merck, Suprapur 30%)

로

calcium carbonate

를제거한후

,

원 소분석기

(Perkin Emler, Model 2400)

^로^{정량하였다}

(Choi et al., 2011a).

결과 및 고찰

분변계스테롤

퇴적물내

COP

의농도는

366-13,018 ng/g (

평균

6,136 ng/g)

의 범위를 보였다

(Table 1). COP

^의 ^가장 ^높은 ^농도

(13,018 ng/g)

^는

SY

^와

DB

^{하수처리장}^방류구^인근

SY01

^정점에서^조 사되었고

,

가장낮은농도는외측

SY10

에서조사되었다

(Fig.

2a).

^수영강^{하구역에서}

COP

^의^농도는^{하수처리장}^방류구^인

근에서외측으로갈수록뚜렷한감소패턴을보였다

.

한편

,

하

수처리장방류구의 하류에서

COP

^농도가^조사정점

SY03

^과

SY05

^보다

SY04, SY06, SY07, SY09

^에서^다소^증가된^농도 를보였다

.

이것은수영강으로유입되는합류식하수관거월류 수

(combined sewer overflows: CSO)

^로^인한^영향일^수^있다

.

조사정점

SY04

와

SY06

주변에

CSO

유입구가있었고

,

이것은 우천시미처리된도시하수가수영강으로직접유입될수있음

을의미한다

.

^퇴적물^내

COP

^농도에^따라^{하수영향수준}^평가가 가능하며

, COP 10 ng/g

이하의농도이면하수오염영향이없는 해역

(Hatcher and McCillivary, 1979), 100 ng/g

^이상의^농도는 하수유입영향과상관성이있는해역

(Writer et al., 1995),

그리

고

500 ng/g

^이상의^농도는^{하수처리장}^{방류수역으로}^하수유

입에의한상당한분변및하수영향해역

(Nichols et al., 1993;

Gonzalez-Oreja and Saiz-Salinas, 1998)

으로보고된다

.

본연 구에서모든정점이

100 ng/g

^{이상이었으며}

, SY10

^정점을^제외 한

9

개정점이

500 ng/g

이상으로수영강하구역은분변및하 수영향해역으로확연히구분되었다

.

수영강하구역중하수처리장방류구인근퇴적물

(SY01)

^에서 조사된

COP

의농도를국내다른연안의하수처리장방류구인 근퇴적물에서보고된자료와비교하였다

(Fig. 3a).

^보고된^결 과들은본조사결과와같이국가해양환경측정망조사지침에따 라동일한시료채취및분석방법으로생산된자료로써

,

^오염수 준비교에좋은정보를제공할수있다

.

^{하수처리장}^방류구^인 근

COP

농도는군산연안

(30 ng/g; Lee et al., 2012),

안산시화 반월공단

(1,300 ng/g; Choi et al., 2011a),

^마산만

(1,380 ng/g;

Moon et al., 2008),

목포연안

(7,900 ng/g; Choi et al., 2007),

울산만

(8,260 ng/g; Choi et al., 2011b)

^으로 ^수영강 ^하구역

(13,018 ng/g)

^이^국내에서^가장^높은^수준의^오염도를^보였다

.

국외의하수처리장방류수역결과와비교시

,

본연구결과는캐 나다

(150-38,000 ng/g; Mayer et al., 2007)

^와^미국

(70-45,000 ng/g; Venkatesan et al., 2010)

보다낮은수준이였으며

,

베트남

(5-4,800 ng/g; Isobe et al., 2002)

^보다^높은^수준으로^나타났다

.

Fig. 2. Spatial distribution of coprostanol (COP) and nonylphenolic compounds (the sum of nonylphenol and nonylphenolic mono-

& di-ethoxylates; ΣNP) in sediments from Suyeong Estuary of Busan. Dotted line indicates 500 ng/g.

SY01

Concentration (ng/g) Concentration (ng/g)

SY02 SY03 SY04 SY05 SY06 SY07 SY08 SY09 SY10 4,000

0 8,000 12,000 16,000

(a) COP

2,000 1,000 0 3,000 4,000 5,000

SY01 SY02 SY03 SY04 SY05 SY06 SY07 SY08 SY09 SY10 (b) ^∑ NP

0 2,000 4000

Gunsan Ansan Masan Mokpo Ulsan Suyeong

6,,000 8,000 10,000 12,000 14,000

(a) COP

Concentration (ng/g)

0 1,000 2,000

Mokpo Ansan Masan Gunsan Suyeong Ulsan

3,000 4,000 5,000 6,000 7,000

(b) NP

Concentration (ng/g)

(4)

도시하수 유입으로 인한 오염도 평가

1009

분변계스테롤은 배출원에 따라 특이한 분포패턴

(profile)

^을 보인다

.

인간과다른 동물들

(

가축

,

조류및해양포유류

)

의배 설물내분포분포는매우상이하고

,

^{해양플랑크톤과}^식물들은

COP

을전혀생성하지않는다

.

따라서분변계스테롤의분포및

COP

^과^다른^스테롤^간의^비율^등은^배출원을^{구분하는데}^유용 하다

. COP

^과

ECOP

^는^인간의^배설물과^직접^관련성이^있어서 하수로오염된퇴적물에서검출된다

(Grimalt et al., 1990).

반 면

,

^고래^등^{해양포유류의}^{배설물에도}^포함되기^때문에^이들의 영향은생물기원배출

(biogenic sources)

으로구분이필요하다

(Venkatesan and Santiago, 1989; Martins et al., 2002).

^많은^연 구자들은생물기원배출의영향을최소화하여하수오염도및

유기물의기원을평가하기위해

COP

농도와함께여러종류의

비율을동시에사용한다

(Fig. 4). COP/ECOP

^비율이

2.5

^이하시 생물기원배출의영향이크므로

,

비율

2.5

이상과

COP

농도

100 ng/g

^이상은^{도시하수유입에}^따른^오염과^관련성이^있다

(Ven-

katesan and Santiago, 1989).

^수영강^하구역의^{퇴적물에서}^조 사된

COP/ECOP

비율은

5.04±3.00

이었으며

, SY10

정점을 제외한모든정점에서모두초과하여생물기원보다도시하수 유입으로인한오염이주요원인이었다

. COP/(COP+CHOA)

비율은하수오염평가에가장널리사용되고있으며

,

^비율

0.5

이상과함께

COP 100 ng/g

^이상인^정점도^{도시하수유입으로}

인한오염으로구분된다

(Grmialt et al., 1990; Leeming et al., 1998).

^본^연구에서

COP/(COP+CHOA)

^비율은

0.71±0.08

^이 었으며

,

모든정점에서초과하였다

. SY10

정점을제외한모든 정점이

COP/(COP+CHOA)

^비율

0.5

^이상

, COP/ECOP 2.5

^이 상이었다

.

^따라서^{분변계스테롤의}^비율과

COP

^농도^결과에서 보듯이

,

수영강하구역에서

COP

등분변계스테롤의농도는생 물보다대부분도시하수에서기원하였다

.

노닐페놀류 화합물

수영강하구역의 퇴적물내

NP

^와

NP ₁₊₂ EO

^의 ^농도는^각각

SY01

Concentration (ng/g) Concentration (ng/g)

SY02 SY03 SY04 SY05 SY06 SY07 SY08 SY09 SY10 4,000

0 8,000

2,000 1,000 0 3,000 4,000 5,000

SY01 SY02 SY03 SY04 SY05 SY06 SY07 SY08 SY09 SY10 (b) ^∑ NP

0 2,000 4000

Gunsan Ansan Masan Mokpo Ulsan Suyeong

6,,000 8,000 10,000 12,000 14,000

(a) COP

Concentration (ng/g)

0 1,000 2,000

Mokpo Ansan Masan Gunsan Suyeong Ulsan

3,000 4,000 5,000 6,000 7,000

(b) NP

Concentration (ng/g)

Fig. 3. Comparison of (a) coprostanol (COP) and (b) nonylphenol (NP) in sediment samples collected around outfalls of wastewater treatment plants in Korea coastal waters, Gunsan (Lee et al. 2012), Ansan (Choi et al. 2011a), Masan (Moon et al. 2008), Mokpo (Choi et al. 2007), and Ulsan (Choi et al. 2011b).

Fig. 4. Scatterplots of (a) coprostanol/epicoprostanol, (b) coprostanol/(coprostanol+cholestanol) vs. coprostanol concentrations and (c) coprostanol/(coprostanol+cholestanol) vs. coprostanol/epicoprostanol in sediments from Suyeong Estuary of Busan.

0.0 0 2 4

COP/ECOP ratio

COP/(COP+CHOA) ratio _Biogenic

Source

Sewage Pollution

6 12 14

0.2 0.4 0.6 0.8 1.0

0.0 1 10 100

COP (ng/g)

COP/(COP+CHOA) ratio _Biogenic

Source

Sewage Pollution

1000 10000 0.2

0.4 0.6 0.8 1.0

0.0 1 10 100

COP (ng/g)

COP/ECOP ratio

Biogenic Source

Sewage Pollution

1000 10000 2.0

4.5 6.0 12.0 14.0

a b

Concentration (ng/g)

Rank (%)

(a) NP

10 100 1000 10000

0 20 40 60 80 100

Rank (%)

10000 a

Concentration (ng/g) (b) NP 1+2 EO

10 100 1000

0 20 40 60 80 100

Rank (%)

(c) NP-TEQs

10 100 1000 10000

0 20 40 60 80 100

Concentration (ng-TEQ/g, TOC1%) c

126°00' 128°00' 130°00'

129°09' 129°11' 129°13' 129°15'E

0 50 100 km 34 °00' 35 °15' 35 °17' 35 °19'N

36 °00' 38 °00'N

KOREA

N

(5)

백승홍

ㆍ

윤세라

ㆍ

이인석

ㆍ

황동운

ㆍ

최민규

1010

80.0-1,583 ng/g (

^평균

553 ng/g), 66.0-2,384 ng/g (

^평균

1,072 ng/g)

를보였고

, ΣNP (NP

와

NP ₁₊₂ EO

의 합

)

의농도는

146- 3,723 ng/g (

^평균

1,625 ng/g)

^의^범위를^보였다

(Table 1).

ΣNP

의가장높은농도

(3,723 ng/g)

는하수처리장방류구인 근정점

SY01

^에서^{조사되었고}

,

^가장^낮은^농도는^외측

SY10

^에 서조사되었다

(Fig. 2b). ΣNP

^의^농도는^내측에서^외측으로^갈 수록감소하였다

. ΣNP

의공간적분포는

COP

의분포와잘일 치하였다

(r=0.837, P<0.01).

이것은

NPs

^와^{분변계스테롤이}^수 영강하구역에서유사한배출원과거동을가지는것을제안한 다

(Choi et al., 2007, 2011b; Li et al., 2008; Moon et al., 2008).

또한

, ΣNP

^과

COP

^는^퇴적물내

(r=00.758-0.764, P <0.01).

퇴적물중

1.22- 47.8 mg/g

^로

ΣNP

^과

COP

^의^기여율은^평균

0.02- 0.09%

이었다

.

따라서퇴적물내

ΣNP

과

COP

의 기여율은낮지만

,

^수영강^하구역의^퇴적물^내

(Choi et al., 2007; Moon et al., 2008; Kim et al., 2010).

수영강하구역중하수처리장방류구인근퇴적물

(SY01)

^에서 조사된

NP

의농도를국내다른연안의하수처리장방류구인 근퇴적물에서보고된자료와비교하였다

(Fig. 3b).

^{하수처리장} 방류수역에서보고된

NP

^농도는^목포연안

(170 ng/g; Choi et al., 2007),

안산시화반월공단

(270 ng/g; Choi et al., 2011a),

마 산만

(270 ng/g; Moon et al., 2008),

^군산연안

(1,120 ng/g: Lee et al., 2012),

울산만

(5,770 ng/g; Choi et al., 2011b)

으로수영 강하구역

(1,583 ng/g)

^에서

NP

^오염도는^울산만^다음으로^높 았다

.

^국외의^{하수처리장}^방류수역^결과와^비교^시

,

^본^연구결

과는캐나다

(40-293 ng/g; Sabik et al., 2003),

^스페인

(8-1,050 ng/g; Petrovic et al., 2002)

에비해비교적높은수준으로나타 났고

,

^일본

(500-13,000 ng/g; Isobe et al., 2001)

^과^중국

(3,500- 32,400 ng/g; Wu et al., 2007)

보다는낮은수준이었다

.

퇴적물내

ΣNP

^중

NP

^가^차지하는^기여율은

40±19%

^로

NP

보다

NP ₁₊₂ EO

^가^높은^기여율을^보였다

.

^{하수처리장에서}

NPs

의생물학적분해는

ethoxylate (EO) chain

의분해로시작되기 때문에

, NP ₁₊₂ EO

^와

NP

^와^같은^짧은^사슬^대사체

(short-chain metabolic intermediates)

로 분해되고

, NPs

중

NP

의 기여율 은증가된다

(Ying, 2006; González et al., 2010). Clara et al.

(2007)

^는^{하수처리장}^유입수에^비해^{배출수에서}

NP

^의^기여율

의증가

(

유입수

28%,

배출수

65%)

를보고한바있다

.

본연구 에서

NP

^의 ^기여율

(40±19%)

^은 ^마산만

(36±13%, Moon et al., 2008),

울산만

(41±17%; Choi et al., 2011b)

와유사한수 준이었지만

,

^안산^{시화반월공단}

(52±7.9%; Choi et al., 2011a)

및목포연안

(68±37%; Choi et al., 2007)

^보다^낮은^수준이었 다

.

따라서수영강하구역은처리되지않은하수의유입이높거 나하수처리장에서

NPs

^{제거효율이}^낮은^것으로^판단된다

.

^실 제로

, Choi et al. (2007)

이부산시내

8

개하수처리장유입수와 방류수내비이온계면활성제를분석한연구결과에따르면

,

^비 이온계면활성제의제거율은

7

^개^{하수처리장}

70-100%

^인^반면

SY

하수처리장은

42-45%

로가장낮았고

,

방류수내비이온계 면활성제의농도도가장높았다고보고하였다

.

노닐페놀류의 오염에 따른 위해도 평가

NP

^와

NP ₁₊₂ EO

^와^같은

NPs

^는^{수생물종의}^단백질과^상호반

Table 1. Concentrations (ng/g) of nonylphenolic compounds and fecal sterols in sediments from Busan Suyeong Estuary of Korea

(mg/g)TOC COP ECOP CHOE CHOA NP NP1+2EO ΣNP COP/

(COP+CHOA) COP/

ECOP

SY01 47.8 13,018 1,008 12,848 8,954 1,583 2,141 3,723 0.59 12.9

SY02 21.0 10,519 2,844 6,957 4,464 717 2,384 3,101 0.70 3.70

SY03 1.54 6,262 1,072 5,212 1,725 174 254 427 0.78 5.84

SY04 6.39 8,368 1,518 5,961 2,179 208 1,876 2,083 0.79 5.51

SY05 9.70 4,206 871 7,222 1,123 224 1,647 1,871 0.79 4.83

SY06 22.8 7,145 1,609 6,548 2,383 516 398 914 0.75 4.44

SY07 17.3 6,144 1,350 9,102 1,897 1,153 1,444 2,597 0.76 4.55

SY08 1.22 1,062 286 2,716 539 172 134 307 0.66 3.71

SY09 12.5 4,274 1,438 2,682 2,569 700 381 1,081 0.62 2.97

SY10 6.21 366 191 1,468 250 80.0 66.0 146 0.59 1.92

Min 1.22 366 191 1,468 250 80.0 66.0 146 0.59 1.92

Max 47.8 13,018 2,844 12,848 8,954 1,583 2,384 3,723 0.79 12.9

Mean 14.6 6,136 1,219 6,072 2,608 553 1,072 1,625 0.71 5.04

SD 13.9 3,927 750 3,369 2,523 495 911 1,245 0.08 3.00

Total organic carbon (TOC), coprostanol (COP), epicoprostanol (ECOP), cholesterol (CHOE), cholestanol (CHOA), nonylphenol (NP), nonylphenol mono- & di-ethoxylates (NP

₁₊₂

EO), the sum of NP and NP

₁₊₂

EO (ΣNP), standard deviation (SD).

(6)

도시하수 유입으로 인한 오염도 평가

1011

응하여만성독성과내분비계교란등수생태계에악영향을미 치는 것으로보고된다

(Scott-Fordsmand and Krough, 2004;

Soares et al., 2008).

^수생물종 ^중^먹이사슬^{하부위치의} ^생물 인

Daphnia magna

에

NPs

는급

·

만성독성과번식이상을일 으키며

(Comber et al., 1993; Baldwin et al., 1998),

^어류의^경 우성장및효소의활성변화그리고체내다량축적으로인한 치사율에영향을미치는것으로알려져있다

(Jeon et al., 2004;

Jin et al., 2008). NPs

^는^{내분비계장애추정물질}

(endocrine dis- rupting chemicals)

로분류되었고

, NP

는유럽연합수질기본지 침

(European Union Water Framework Directive)

^의^우선관리 대상성분

(priority substance)

^에 ^{포함되었다}

(European Com- mission, 2001).

더욱이네덜란드

,

노르웨이

,

캐나다는

NPs

로 부터수생물종을보호하기위해퇴적물가이드라인을제안하 였다

(Environment Canada, 2002; Jonkers et al., 2005; Bakke et al., 2010).

^본^{연구에서는}^네덜란드

(NP 105 ng/g, NP ₁₊₂ EO 150 ng/g),

^노르웨이

(NP 220 ng/g),

^캐나다

(NPs 1,000 ng NP-

TEQ/g, TOC 1%)

가이드라인과비교하여수영강하구역퇴적

물내

NPs

^의^잔류로^인한^위해도를^{평가하였다}

(Fig. 5).

^네덜란 드의가이드라인과비교할때

, NP

가이드라인을초과한정점 은조사정점중

90%

^나^되었고

, NP ₁₊₂ EO

^{가이드라인을}^초과한 정점은

80%

^나^{조사되었다}

.

^노르웨이

NP

^{가이드라인을}^초과한 정점은

60%

조사되었다

.

캐나다의가이드라인과비교에앞서

,

본연구의

NP

^와

NP ₁₊₂ EO

^농도는^{독성등가계수}

(toxic equiva- lency factor; NP 1.0, NP ₁₊₂ EO 0.5)

를곱하여합한후

TOC 1%

로표준화하였다

(ng NP-TEQ/g, TOC 1%).

^그^결과

,

^조사정점 중

50%

^가^캐나다의^{가이드라인을}^{초과하였다}

.

^따라서

,

^부산^수 영강하구역퇴적물에서

NPs

의농도는수생태계에서식하는 민감한수생물종에게잠재적인악영향을줄수있을것으로판 단된다

.

사 사

본 연구는국립수산과학원

(RP-2014-ME-45)

^의 ^{연구지원에} 의해수행되었습니다

.

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Choi M, Moon HB and Choi HG. 2011b. Tracing wastewater

Fig. 5. Concentrations of nonylphenolic compounds in Busan coastal area with comparison of screening values reported elsewhere.

^a

maxi- mum permission concentration (MPC) for NP

₁₊₂

EO and NP in the Netherlands (Jonkers et al. 2005);

^b

sediment quality guideline (SQG) for NP in Norway (Bakke et al. 2010);

^c

SQG for NPs in Canada (Environment Canada, 2002)

0.0 0 2 4

COP/ECOP ratio

COP/(COP+CHOA) ratio _Biogenic

Source

Sewage Pollution

6 12 14

0.2 0.4 0.6 0.8 1.0

0.0 1 10 100

COP (ng/g)

COP/(COP+CHOA) ratio _Biogenic

Source

Sewage Pollution

1000 10000 0.2

0.4 0.6 0.8 1.0

0.0 1 10 100

COP (ng/g)

COP/ECOP ratio

Biogenic Source

Sewage Pollution

1000 10000 2.0

4.5 6.0 12.0 14.0

a b

Concentration (ng/g)

Rank (%)

(a) NP

10 100 1000 10000

0 20 40 60 80 100

Rank (%)

10000 a

Concentration (ng/g) (b) NP 1+2 EO

10 100 1000

0 20 40 60 80 100

Rank (%)

(c) NP-TEQs

10 100 1000 10000

0 20 40 60 80 100

Concentration (ng-TEQ/g, TOC1%) c

126°00' 128°00' 130°00'

129°09' 129°11' 129°13' 129°15'E

0 50 100 km 34 °00' 35 °15' 35 °17'

36 °00'

KOREA

(7)

백승홍

ㆍ

윤세라

ㆍ

이인석

ㆍ

황동운

ㆍ

최민규

1012

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Distribution of Fecal Sterols and Nonylphenolic Compounds in Sediments from Busan Suyeong Estuary, Impacted by Wastewater Treatment Plant Effluents

Kor J Fish Aquat Sci 47(6),1006-1013,2014

Original Article

1006

Copyright © 2014 The Korean Society of Fisheries and Aquatic Science pISSN:0374-8111, eISSN:2287-8815

,

,

,

28 km,

50-90 m

200 km 2

,

.

(estuary)

,

,

,

(Kwon et al., 2008).

(SY)

(DB)

,

(ME, 2012). SY

1985

,

452,000

,

(activated sludge treatment process)

. DB

2007

,

135,000

,

(biofilm filteration process)

.

,

,

,

,

46-51%

73%

,

2.4-18.9%

59%

(municipal effluents)

(ME, 2012). Kim et al. (2009)

. Jeon et al. (2010)

,

(B

)-

(D

)

,

.

.

백승홍·윤세라·이인석·황동운·최민규*

Distribution of Fecal Sterols and Nonylphenolic Compounds in Sediments from Busan Suyeong Estuary, Impacted by Wastewater

Treatment Plant Effluents

Key words: Sewage, Nonylphenol, Coprostanol, Wastewater treatment plant, Ecotoxicology

http://dx.doi.org/10.5657/KFAS.2014.1006 Kor J Fish Aquat Sci 47(6) 1006-1013, December 2014

Received 12 September 2014; Revised 3 November 2014; Accepted 6 November 2014

*Corresponding author: Tel: +82. 51. 720. 2531 Fax: +82. 51. 720. 2515

E-mail address: [email protected]

,

(fecal sterols)

(nonylphenolic compounds; NPs)

(Li et al., 2008; Froehner et al., 2009;

Choi et al., 2009, 2011a; Kim et al., 2010; Lee et al., 2012; Choi et al., 2014).

coprostanol (COP)

cholesterol (CHOE)

,

50-80%

(Leeming et al., 1996; Chan et al., 1998).

COP

cholestanol (CHOA)

, COP/(COP+CHOA)

0.3

, 0.6

(Grimalt et al., 1990). NPs

(non- ionic surfactants)

(biodegradation products)

200 km ²

COP/(COP+CHOA) ratio _Biogenic

COP/(COP+CHOA) ratio _Biogenic