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(1)

한수지 49(1), 007-012, 2016

Korean J Fish Aquat Sci 49(1),007-012,2016

Original Article

서 론

수은은지각에자연적으로존재하는금속으로써지각 기활동뿐만아니고인간의산업활동등을통해수중에방출된

.

이렇게방출된무기형태의수은은장기간수중생태계에

·

축적되며수중생물의영양단계를통해유기형태인메틸수 은으로전환된다

.

메틸수은은육식성어류의먹이활동과 상위영양단계를통해생물학적으로농축된다

.

또한인간은 이들어류의섭취를통해메틸수은에노출된다

(UNEP, 2002).

이와같이

,

어류섭취를통한수은노출의위험성으로인해미국

1990

년대부터어류의수은함량을모니터링해오고있으며

sible level, MPL)

설정하였으며

,

캐나다

(Health Canada, 2007)

일본

(JETRO, 2011)

역시가이드라인을제시하였다

.

어류와수산물에대한주기적인섭취는메틸수은의식이노출

(dietary exposure)

밀접한관계가있으며이로인해

, EFSA (European food safety authority)

주간허용섭취량

(tolerable weekly intake)

설정하여소비자에게권고하고있다

(EFSA,

2012).

최근

EFSA

메틸수은에대한주간허용섭취량을기존

1.6 μg/kg body weight

에서

19%

감소된

1.3 μg/kg body weight

,

기존총수은에대한주간허용섭취량

(5 μg/kg body

weight)

철회하고무기수은에대한주간허용섭취량을

4 μg/

kg body weight

강화하여제안하였다

(EFSA, 2012).

양식산 어류의 부위별 총수은 함량 및 위해도 평가

최우석·윤민철·조미라

·권지영·손광태·김지회

1

·이태식

국립수산과학원 식품위생가공과, 1국립수산과학원 연구기획과

Total Mercury Content and Risk Assessment of Farmed Fish Tissues

WooSeok Choi, Minchul Yoon, MiRa Jo*, Ji Young Kwon, KwangTae Son, Ji Hoe Kim1 and Tae Seek Lee

Food Safety and Processing Research Division, National Institute of Fisheries Science, Busan 46083, Korea

1

Research and Development Planning Department, National Institute of Fisheries Science, Busan 46083, Korea

Total mercury (TM) is a hazardous element that is of particular concern to human health. Due to the diversity of di- etary habits among fishes, tissue-specific analysis of hazardous elements is necessary. In this study, the tissue-specific TM in cultured fish was analyzed to conduct risk assessment. The highest concentrations of TM were found in the farmed marine fish Pagrus major (0.111 mg/kg) and in the farmed freshwater fish Channa argus (0.162 mg/kg). TM concentration was significantly correlated with total fish length ( P <0.01). Significant differences in TM were found between three types of fish tissue, with the concentration in fish muscle being significantly higher than those of gill or liver ( P <0.01). Moreover, the tissue-specific TM concentrations of farmed freshwater fish were significantly higher than those of farmed marine fish ( P <0.01). According to the risk assessment, the TM body exposure rate of muscle and liver in cultured fishes ranged from 0.001 to 0.389% of the Provisional Tolerable Weekly Intake. Therefore, these results showing the tissue-specific TM contents of cultured fish could be useful to assess the health risks of Korean dietary habits.

Key words: Farmed fishes, Total mercury, Tissue-specific analysis, Risk assessment

(2)

함께상대적으로높은국가로나타났다

(NOAA, 2014).

2012

국민영양통계에따르면

,

어패류섭취비율은전체식

품의

3.4%,

동물성식품의

16.8%

나타났다

(MW, 2014).

라서우리나라는수산물섭취를통한유해물질의인체노출 가와위해평가가중요하다

.

특히어류의경우

,

식습관

(Dietary-

habits)

다양성으로인해어류부위별유해물질분석과

과를바탕으로식이노출에의한위해평가가필요하다

.

이에연구에서는우리나라양식산어류의부위별총수은 함량을분석하였으며우리나라뿐만아니라외국의허용기준과 비교하여오염도를평가하였다

.

또한양식해수종과담수종에 대한부위별총수은농도분포의유의성을검증하였으며이상 결과를토대로양식산어류의섭취를통한총수은의주간추 정섭취량을산출하여안전성평가를수행하였다

.

재료 및 방법

시료

시료는

2014

7

월부터

8

월에걸쳐전국

23

·

, 57

식장으로부터

212

시료를채취하여분석에사용했다

(Fig.

1).

이물질등의제거를위해물로

3

세척체장과무게를

측정하였다

.

시료들은해부용가위와해부용칼을이용하여 근육

,

아가미

,

간을분리한이차오염을막기위해표면에 어있는혈액을제거하였으며균질기

(Plytron, PT-MR 3100D, Kinematica, Switzerland)

이용하여균질화하였다

.

분석 과의재현성을위해균질화시킨시료들은분석전까지

-20

o

C

보관하였다

.

시료준비에사용된물은

18 MΩcm

수준의초순수 사용하였으며기구용기는모두

1% (v/v) HNO

3세척 하여사용하였다

.

총수은 함량 분석

0.1 g

균질화된시료는골드아말감법을이용한직접수은

분석기

(DMA-80, Milestone, Milano, Italy)

사용하여

3

석하였다

.

공시료

(blank),

검량표준물질

(calibration standards),

그리고인증표준물질

(CRM; certified reference materials)

함께분석하였다

. DORT-4 (n=30) (Dogfish Liver; NRC- CNRC, Ottawa, Ontario, Canada)

DORM-4 (n=28) (Fish protein; NRC-CNRC, Ottawa, Ontario, Canada)

총수은 석의정확성재현성확인을위하여사용하였다

.

어류의 위별총수은함량은

mg/kg,

생체중량으로나타냈다

.

총수은 석을위한기기조건은건조를

650

o

C

에서

90

,

분해는

650

o

C

에서

180

,

그리고 아말감화

(Amagamation)

850

o

C

에서

12

초로설정하였다

.

모든결과는

Easy-DOC3

프로그램

(Easy- DOC3 for DMA, Ver. 3.30, Milestone, USA)

이용하여 출하였다

.

위해도 평가

위해도평가를위한양식산어류의총수은에대한주간추정섭 취량

(Estimated Weekly Intake)

조사된총수은함량과국민 건강영양조사

5

3

차년도영양조사부문에근거한

2012

국민영양통계로부터산출하였다

(MW, 2013; MW, 2014).

근거로다음과같은수식을통해산출하였다

.

Estimated Weekly Intake=

(mean content of total mercury×daily food intake×7days) /63.5 kg (adult mean body weight)

산출된주간추정섭취량으로부터

FAO/WHO

합동식품 가물전문가위원회

(JECFA)

에서설정한무기수은 잠정주간섭 취허용량

(PTWI, 4 μg/kg body weight)

대한주간추정섭취 량의

%

비율

(% of PTWI)

산출하여위해도를평가하였다

. 통계분석

모든결과는평균

(Mean)

표준편차

(SD)

나타냈으며그룹 간의유의적인차이를확인하기위해일원배치분산분석

(One- way ANOVA),

독립표본

T-

검정

(T-test)

수행하였다

(SAS version 9.2, SAS Institute, Cary, NC, USA) (P<0.01).

총수은

함량의부위별유의한차이를확인하기위해

Duncan

검정법

(Duncan’s multiple-range test)

으로사후검정

(Post-Hoc Test)

하였다

.

마지막으로유의성을확인하기위해피어슨상관계수

(Pearson correlation coefficient)

이용한상관분석을수행하 였다

.

Fig. 1. Distribution of sampling site on farmed marine and fresh- water fishes in Korea.

0.00 0.03 0.06 0.09 0.12 0.15 0.18

Muscle Gill Liver

Mercury concentration (mg/kg)

a

b

c

0.00 0.03 0.06 0.09 0.12 0.15 0.18

Muscle Gill Liver

Mercury concentration (mg/kg)

FARMED MARINE FISH FARMED FRESHWATER FISH

* Significant difference (P < 0.05)

*

*

0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 10 20 30 40 50 60 70

Mercury concentration (mg/kg)

Length (cm) Muscle Gill Liver

0 : 2,100,000

N S

0 80km

(3)

어류 부위별 총수은 함량 및 위해도

9

결과 및 고찰

양식장 어류의 부위별 총수은 농도

총수은 분석의정확성 재현성 확인을위하여

, 2

개의 증표준물질을사용하여회수율을확인하였다

(Table 1).

, DOLT-4

DORM-4

회수율은각각

100.9%, 99.0%

나타났다

.

어류 유래 인증표준물질

(DOLT-4; Dogfish liver, DORM-4; Fish protein)

회수율은

100%

나타났으며 수치는

AOAC guideline

부합하는 것으로나타났다

(AOAC International, 2002).

따라서연구의분석대상인양식산 류에대한총수은분석결과는높은신뢰성을가질것으로사료 된다

.

전국

23

·

, 57

양식장으로부터채취된

212

시료에대한부위별총수은분석결과는

Table 2

나타냈다

.

부위별평균총수은함량분포는해수종에서근육

0.036-0.111 mg/kg (wet weight),

아가미

0.008-0.017 mg/kg,

0.010- 0.060 mg/kg

으로 나타났으며 담수종에서 근육

0.026-0.162

Table 1. Recovery of certified reference materials (CRM) CRM Certified value

(mg/kg) Measured

value(mg/kg)1 Recovery (%)2 DOLT-4 2.580±0.220 2.603±0.094 100.9

DORM-4 0.410±0.055 0.406±0.015 99.0

1Recovery of Hg was calculated by a direct mercury analyzer. 2Re- covery was calculated with mean measured values based on the replicate determination.

Table 2. Tissue-specific total mercury concentrations, length, weight for farmed marine and freshwater fishes in Korea Common name Scientific name Number of Length

(cm) Weight

(g)

Mercury concentration (mg/kg, wet weight)

Muscle Gill Liver

Sample Site Farmed Marine Fish

Olive flounder Paralichthys olivaceus 49 16 34.8±7.5 553.5±300.0 0.048±0.002a 0.013±0.007a 0.023±0.013ab Starry flounder Platichthys stellatus 23 5 24.5±5.5 272.8±148.3 0.036±0.014a 0.008±0.003a 0.010±0.004a Korean rockfish Sebastes schlegelii 18 4 20.8±0.7 170.4±14.3 0.056±0.028a 0.010±0.007a 0.027±0.020abc Red sea bream Pagrus major 11 4 25.6±8.7 507.4±451.6 0.111±0.057b 0.017±0.001ab 0.060±0.038bcd

mg/kg,

아가미

0.004-0.039 mg/kg,

0.011-0.121 mg/kg

으로 나타났다

.

총수은함량은해수종

red sea bream (Pagrus major)

근육에서

0.111 mg/kg,

담수종

snakehead (Channa argus)

근육에서

0.162 mg/kg

으로가장높게나타났다

(P<0.05).

이상 결과는

Kim et al. (2012)

연구

(

양식해수종의총수은

; 0.024-0.0774 mg/kg,

양식담수종의총수은함량

; 0.0118- 0.084 mg/kg)

비교해보았을

,

해수종은

0.7

,

담수종

2

높은수치이지만우리나라

EU

총수은기준치에 비해낮은수치였다

.

어류중금속축적은중금속과어류의 기관과친화도가다르기때문에기관별로축척도가다르게 타난다

(Rao and Padmaja, 2000; Bervoetset al., 2001).

본질적 으로

,

어류는물속에녹아있는미립자의섭취

,

먹이섭취

,

물속에 녹아있는중금속의이온교환등을통해표면과기관에 금속을흡수한다

.

기관간의중금속분포는먹이섭취나수계 노출

(Aqueous exposure)

같은노출경로에의존적이며중금 오염의지표로사용할있다

(Alam et al., 2002).

따라서 부위별유해물질분석과결과를바탕으로유해물질의 식이노출평가가필요하다

.

특히우리나라의경우

,

어류에대한 높은섭취율과다양한식습관

(dietary habits)

으로인해어류 위별오염지표연구가중요한실정이다

.

연구결과에서

,

수은의부위별함량을비교해본결과

,

근육

0.067±0.056 mg/

kg,

아가미

0.017±0.015 mg/kg,

0.045±0.049 mg/kg

으로 나타났다

(Fig. 2).

어류근육총수은함량은다른부위에비해 유의적으로높게나타났으며아가미에서가장낮은함량을 였다

(P<0.01).

또한담수종과해수종간의부위별총수은함량

(4)

최우석

윤민철

조미라

권지영

손광태

김지회

이태식

10

차이는유사한경향을보였으며담수종에서상대적으로높은 함량을나타냈다

(P<0.01) (Fig. 3).

기존연구에서

,

어류근육과 간의다른부위에비해높은수은축적에관한연구는이미보고 된바있다

(Voigt, 2000; Navarro et al., 2009).

이와같은어류 부위별수은축적의차이는어류의생리학적차이에의해기인 하며특히간의경우

,

효소반응

,

단백질생합성뿐만아니고해독

작용과수은과같은외인성

(Exogenous)

독성물질의제거등의

역할을수행하기때문에수계노출먹이섭취를통해흡수된 수은의해독을위해간에축적되는것으로사료된다

(Liu et al., 2013).

또한근육내높은수은축적의경우

,

수은과단백질시스 테인잔기의

SH

그룹과의높은친화도에의한어류근육단백질 과의쉬운결합에기인한것으로사료된다

(Farkas et al., 2003).

따라서양식생물의폐쇄적서식환경

(

사료

,

수질

,

온도

,

염도

)

고려해보았을

,

이와같은생리학적차이가어류부위별 은함량차이로나타나는것으로사료된다

.

일반적으로어류의 길이

,

무게그리고나이는총수은함량과유의한관련성을보인

.

연구결과역시

,

어류의길이와근육

(PCC; 0.486**),

가미

(PCC; 0.528**),

그리고

(PCC; 0.548**)

총수은 량과유의한연관성을보였다

(P<0.01) (Fig. 4).

어류성장은 수은의생물학적축적을야기한다고있다

.

하지만사실

,

수은의생물학적축적은먹이사슬의길이에의존한다

.

다시 상위영양단계를가진육식성어류들이많은수은을축적 하는것이다

(Łuczyńska andBrucka-Jastrzębska, 2006).

구에서육식성어류인

snakehead (Channa argus)

가장높은 평균총수은함량을나타냈지만작은실험그룹

(n=1)

양식이 라는제한된서식조건으로인해이는의미있는결과로보기 들다

.

따라서향후

,

우리나라어류에대하여총수은함량분석 통한지속적인생물학적축적연구가수행되어야것으로 사료된다

.

위해도 평가

비록양식산어류의총수은함량이우리나라

EU

총수

기준치

(0.5 mg/kg)

비해낮은수치를나타냈지만잠재적

위해도평가를위해수은주간추정섭취량을식품첨가물전 문가위원회

(JECFA)

에서설정한무기수은 잠정주간섭취허용

(PTWI)

비교하였다

.

위해도평가를위한양식산어류의

(

근육

)

총수은함량에대한주간추정섭취량

(estimated weekly

intake)

국민건강영양조사

5

3

차년도 영양조사부문에

근거한

2012

국민영양통계자료를통해산출하였다

.

위해도

평가결과

,

총수은에대한주간추정섭취량은

trout (Oncorhyn- chus masou)

0.00003 μg/kg b.w./week

가장낮은수치를 보였고

eel (Anguilla japonica)

0.01555 μg/kg b.w./week

가장높은수치를보였으며이는무기수은잠정주간섭취허용량

0.001-0.389%

나타났다

(Table 3).

따라서연구에서 행한

57

개의양식장어류의총수은노출량을통해평가한위해 도는높지않은것으로판단된다

.

이상의결과를요약하면

,

총수은함량은해수종

red sea bream

Fig. 2. Tissue-specific total mercury concentration in farmed fish-

es. Different letters in bar mean significantly difference at P<0.01 by Duncan’s multiple range test.

0.00 0.03 0.06 0.09 0.12 0.15 0.18

Muscle Gill Liver

Mercury concentration (mg/kg)

a

b

c

0.00 0.03 0.06 0.09 0.12 0.15 0.18

Muscle Gill Liver

Mercury concentration (mg/kg)

FARMED MARINE FISH FARMED FRESHWATER FISH

* Significant difference (P < 0.05)

*

*

0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 10 20 30 40 50 60 70

Mercury concentration (mg/kg)

Length (cm) Muscle Gill Liver

0 : 2,100,000

N S

0 80km

Fig. 3. Tissue-specific total mercury concentration in farmed ma- rine and freshwater fishes.

0.00 0.03 0.06 0.09 0.12 0.15 0.18

Muscle Gill Liver

Mercury concentration (mg/kg)

a

b

c

0.00 0.03 0.06 0.09 0.12 0.15 0.18

Muscle Gill Liver

Mercury concentration (mg/kg)

FARMED MARINE FISH FARMED FRESHWATER FISH

* Significant difference (P < 0.05)

*

*

0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 10 20 30 40 50 60 70

Mercury concentration (mg/kg)

Length (cm) Muscle Gill Liver

0 : 2,100,000

N S

0 80km

Fig. 4. Positive correlations between tissue-specific total mercury concentration and total fish length. The total fish length was signif- icantly correlated with total mercury concentration of fish muscle (PCC; 0.486**), gill (PCC; 0.528**), and liver (PCC; 0.548**) (P<0.01).

0.00 0.03 0.06 0.09 0.12 0.15 0.18

Muscle Gill Liver

Mercury concentration (mg/kg)

a

b

c

0.00 0.03 0.06 0.09 0.12 0.15 0.18

Muscle Gill Liver

Mercury concentration (mg/kg)

FARMED MARINE FISH FARMED FRESHWATER FISH

* Significant difference (P < 0.05)

*

*

0.00 0.05 0.10 0.15 0.20 0.25 0.30

0 10 20 30 40 50 60 70

Mercury concentration (mg/kg)

Length (cm) Muscle Gill Liver

0 80km

(5)

어류 부위별 총수은 함량 및 위해도

11

(Pagrus major)

근육에서

0.111 mg/kg,

담수종

snakehead (Canna argus)

근육에서

0.162 mg/kg

으로가장높게나타났

.

또한어류의총수은함량은부위별로유의하게다른분포를 보였다

(

근육

>

>

아가미

) (P<0.01).

이와같은결과는중금속과 어류의기관간의생리학적친화도차이에의해야기된것으 사료된다

.

마지막으로위해도평가결과

,

양식어류근육의 총수은에대한주간추정섭취량은

JECFA

에서설정한무기수

PTWI

0.001-0.389%

수준으로안전한것으로나타났다

.

따라서연구는어류부위별유해물질분석과결과를바탕 으로유해물질의식이노출평가를위한중요한정보를제공 있으며

,

어류부위별유해물질오염에대한지표연구로 활용가능할것이다

.

사 사

논문은

2015

년도 국립수산과학원 수산과학연구사업

(R2015062)

Bervoets L,Blust R and Verheyen R. 2001. Accumulation of metals in the tissues of three spinedstickelback (Gasteroste-

us aculeatus) from natural freshwaters. Ecotoxicol Environ

Safe 48, 117-127. http://dx.doi.org/10.1006/eesa.2000.2010.

EC (European Comission). 2008. Regulation (EC) no 629//2008 of 2 July 2008 amending regulation (EC) No 1881/2006 set- ting maximum levels for certain contaminantsin foodstuffs.

EFSA (European Food Safety Authority). 2012. Scientific Opin- ion on the risk for public health related to the presence of mercury and methylmercury in food. EFSA J10, 2985.

Farkas A, Salänki J and Specziár A. 2003. Age- and size- specificpatterns of heavy metals in the organs of freshwater fish Abramisbrama L. populating a low-contaminated site.

Water Res 37, 959-964.

FSANZ (Food Standards Australia and New Zealand). 2004.

Mercury in fish (Australia only).

Health Canada. 2007. Health Canada’s revised assessment of mercury in fish enhances protection while reflecting advice Table 3. The estimated weekly intake of farmed marine and freshwater fishes compared with the PTWI set by JECFA

Common name Scientific name Mercury concentration (mg/kg, wet weight)

Daily food intake1 (g/man/day)

Estimated weekly in take

(μg/kg b.w./week) % of PTWI2 Farmed Marine Fish

Olive flounder Paralichthys oliva-

ceus 0.048 0.75 0.00400 0.100

Starry flounder Platichthys stellatus 0.036 0.15 0.00060 0.015

Korean rockfish Sebastes schlegelii 0.056 0.52 0.00322 0.081

Red sea bream Pagrus major 0.111 0.24 0.00294 0.074

Farmed Freshwater Fish

Eel Anguilla Japonica 0.141 1.00 0.01555 0.389

Far eastern catfish Silurus asotus 0.039 0.18 0.00077 0.019

Trout Oncorhynchus

masou 0.031 0.01 0.00003 0.001

Islaeli carp Cyprinus carpio 0.049 0.05 0.00027 0.007

The weekly intake, Mean content of total mercury×daily food intake×7 days/63.5 kg (b.w.). 1National Food & Nutrition Statistics: based on 2012 Korea National Health and Nutrition Examination Survey. 2The percentage of the PTWI (Inorganic mercury; 4 µg/kg b.w./week) set by JECFA.

(6)

Łuczyńska J and Brucka-Jastrzębska E. 2006. Determination of heavy metals in themuscles of some fish species from lakes in North-Eastern Poland. Pol J Food Nutr Sci 15, 141-146.

MW (Ministry of Health and Welfare). 2013. Korea Health Sta- tistics 2012: Korea National Health and Nutrition Examina- tion Survey (KNHANES V-3)

MW (Ministry of Health and Welfare). 2014. National Food &

Nutrition Statistics: based on 2012 Korea National Health and Nutrition Examination Survey.

Navarro A, Quiros L, Casado M, Faria M, Carrasco L, Benejam L, Benito J, Diez S, Raldua D, Barata C, Bayona JM and- Pina B. 2009. Physiological responses to mercury in feral carp populations inhabiting the low Ebro River (NE Spain), a historically contaminated site. Aquat Toxicol 93, 150-157.

http://dx.doi.org/10.1016/j.aquatox.2009.04.009.

NOAA (National Oceanic and Atmospheric Administration).

2014. Fisheries of the United States 2014. (Current Fisher- ies statics No. 2014; <http://st.nmfs.noaa.gov/Assets/com- mercial/fus/fus14/documents/FUS%2014%FINAL.pdf>).

Rao LM and Padmaja G. 2000. Bioaccumulation of heavy met- als in M. cyprinoids from the harbor waters of Visakhapat- nam. Bullet Pure Appl Sci 19, 77-85.

UNEP (United Nations Environment Programme). 2002. Glob- al Mercury Assessment. UNEP Chemicals, Geneva, Swit- zerland.

US FDA (United States Food and Drug Administration).2010.

Mercury levels in commercial fish and shellfish.

Voigt HR. 2000. Heavy metal and organochlorine levels in coastal fishes from the VäikeVäin Strait, western Estonia, in high summers of 1993–94.Proc Estonian Acad Sci Biol Ecol 49, 335-343.

York R and Gossard MH. 2004. Cross-national meat and fish consumption: exploringthe effects of modernization and ecological context. Ecol Econ 48, 293-302. http://dx.doi.

org/10.1016/j.ecolecon.2003.10.009.

수치

Fig. 1. Distribution of sampling site on farmed marine and fresh- fresh-water fishes in Korea.
Table 2. Tissue-specific total mercury concentrations, length, weight for farmed marine and freshwater fishes in Korea Common name Scientific name Number of Length
Fig. 3. Tissue-specific total mercury concentration in farmed ma- ma-rine and freshwater fishes.

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