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Application of nonylphenol and coprostanol to identification of industrial and fecal pollution in Korea

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Application of nonylphenol and coprostanol to identification of industrial and fecal pollution in Korea
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  Application of nonylphenol and coprostanol to identificationof industrial and fecal pollution in Korea Donghao Li  a,b , Won Joon Shim  b,* , Meihua Dong  a , Sang Hee Hong Oh  b a Analysis and Inspection Center, Yanbian University, Park Road 977, Yanji City, Jilin Province 133002, China b South Sea Institute, Korea Ocean Research and Development Institute, Jangmok-myon 391, Geoje-shi, Gyungsangnamdo 656-834, Republic of Korea In order to assess environmental quality and identifypollution sources, many kinds of molecular makers havebeen developed. For example, linear alkylbenzenes havebeen used as molecular tracers of domestic wastes (Chalauxet al., 1995; Ishiwatari et al., 1983); stanol and stenol forfecal pollution (Gagosian et al., 1979; Leeming et al.,1996); and polycyclic aromatic hydrocarbons (PAHs) foroil finger printing (Kennicutt et al., 1994; Yunker et al.,1996).Li et al. (2004a) reported that industrial wastewater is amajor source of nonylphenol in Korea, and concentrationsof nonylphenol determined in industrial areas are severalhundred times higher than those obtained in municipalareas. Nonylphenol is a degradation product of nonylphe-nol polyethoxylates (NPEOs), which is a surfactant used inindustry and household (Giger et al., 1984; Isobe et al.,2001). Due to toxicity and endocrine disruption resultingfrom the degradation products of NPEOs (Hemmeret al., 2002), these substances are no longer used in domes-tic applications in many developed countries. For example,the production and usage of NPEOs has been banned orrestricted in some countries, including the USA and EU(Renner, 1997). However, NPEOs are still in use as indus-trial detergents in the metal, paper and textile industries insome countries, including Korea, because they are inexpen-sive and have excellent cleaning properties. Hence nonyl-phenol and nonylphenol monoethoxylate were used asmolecular tracers of industrial pollution in this study.Coprostanol and related sterols are generally used asmolecular markers for tracing domestic pollution, such ashuman fecal pollution. Coprostanol is produced from thehydrogenation of cholesterol by bacteria in the humandigestive system (Martin et al., 1973; Rosenfeld and Galla-gher, 1964). High levels of coprostanol have been deter-mined in human and mammalian fecal material anddomestic waste waters (Leeming et al., 1996; Jeng et al.,1996). To study pollution sources in the environment, acritical analysis of the sterol group is required becausethe sterols are produced by various organisms and theircompositions vary accordingly (Leeming et al., 1996).Based on sterol composition, the relative contributionsfrom multiple sources of various organic matters (marine,terrestrial, natural and anthropogenetic inputs) can bedetermined (Hudson et al., 2001). In this study, we onlyanalyzed coprostanol, because our main intention was toinvestigate human fecal pollution sources. The study area(Kyeonggi Bay) is in a coastal zone surrounded by indus-trial and housing complexes, both of which are substantialcontributors to local pollution. Eleven phenolic com-pounds and coprostanol were analyzed from sediment sam-ples; nonylphenol and coprostanol were used as industrialand fecal pollution tracers, respectively.Surface sediment samples were collected from 33 sites inMay 2003, as shown in Fig. 1. Stations K1 to K6 werelocated in the Han River estuary area, which is the biggestriver in South Korea; stations K8 and K9 were located inIncheon North Harbor (INH); stations K7 and K10 werelocated in the mouth of INH; and stations K11 to K20were located along the waterway of INH, except for K18,located in Incheon South Harbor (ISH). Drain-outletpumping out industrial waste water produced from the Shi-hwa industrial complex is located nearby to station K30,and stations K28 to K32 were thus exposed to this. Theremaining stations (K21 to K27 and K33) are located farfrom suspected pollution sources. Global positioning sys-tem (GPS) was used to locate the sample positions. Thesediment samples were sampled with a van-Veen grab,and surface sediments (  2 cm) were collected in glass bot-tles with a Teflon lined cap. Immediately after collection,samples were frozen on dry ice to protect them from microbiodegradation, then transferred to the laboratory andstored at   20   C until analysis.For alkylphenols (APs), chlorophenols and bisphenol A(BPA), sediment samples were analyzed according to themethods of Li et al. (2001, 2003). Briefly approximately3 g wet sediment was placed in a 50 mL Teflon centrifugetubewitha Teflon cap.After theaddition ofsurrogate stan-dards (heptylphenol and bisphenol A- d  14 ) and 5 mL of 0.1 M HCl solution, the sediment samples were extractedwith dichloromethane. The extracts were then concentratedto about 1 mL under a gentle dry nitrogen flow. In order toremove water and sulfur from the extract, anhydroussodium sulfate and copper were added sequentially to theextract. The solution was again concentrated to 0.2 mLunder a gentle flow of dry nitrogen, and then 1 mL of ace-tone was added, and the extract further concentrated to0.5 mL. It was submitted to on column derivatization andFlorisil clean up, using 6 mL of hexane as the eluent. The * Corresponding author. Tel.: +82 55 639 8671; fax: +82 55 639 8689. E-mail address:  wjshim@kordi.re.kr (W.J. Shim). Baseline / Marine Pollution Bulletin 54 (2007) 97–116   101  concentrated eluents were analyzed by gas chromatography(Shimadzu GC 2010)-mass spectrometry (Shimadzu MS2010) with selected ion monitoring mode after addition of 200 ng of internal standard. Conditions for GC/MS analy-sis are described in previous reports (Li et al., 2001).In order to determine the concentrations of coprostanol,the wet sediment samples were air dried. Then 1 g samplewas extracted using the accelerated solvent extraction(ASE 200 A) technique with dichloromethane. Beforeextraction, 5 a -androstan-3 b -ol was added for monitoringrecovery of coprostanol in the experimental procedures.Briefly, sediment samples were ground and placed in a33 cm stainless steel cell. Before loading the sample, cellu-lose filter and anhydride sodium sulfate were packed inthe cell. The extraction was carried out at 120   C and1500 psi. Static and extraction times were 5 and 15 min,respectively. Compressed nitrogen gas was used to purgethe extract and solvent into the corresponding vial. Dichlo-romethane was used as extracting solvent. The processesincluding concentration, silyl derivatization and clean-upsteps were similar to phenolic compounds analysis. Thecoprostanol was analyzed on the same GC/MS system usedin the phenolic analytes except for the final temperatureand fragment ions. The oven temperature was held at80   C for 2 min, then programmed at 20   C/min to100   C, 10   C/min to 200   C, 20   C/min to 280   C and heldfor 20 min. The total running time of the GC/MS was37 min. Fragment ions for coprostanol are 370 (quantifica-tion ion), 355 and 215 and for 5 a -androstan-3 b -ol are 333(quantification ion), 258 and 386. Reproducibility andrecovery of coprostanol was examined through six replicateanalyses on spiked sediment samples. The RSD was 8.6%and recoveries ranged from 89% to 103%, with an averageof 92%. For 1 g dry sediment samples, the limit of quanti-fication was about 2 ng/g dw.Concentrations of analytes determined at each site areshown in Table 1. Total concentrations of phenolic com-pounds ranged from 5.47 to 2330 ng/g dw with an average Fig. 1. Sampling locations in Kyeonggi Bay, Korea.102  Baseline / Marine Pollution Bulletin 54 (2007) 97–116   of 108 ng/g dw. Target phenolic analytes selected in thisstudy were  n ( t )-butylphenol (BP),  n -pentylphenol (PP),  n -hexylphenol (HP),  n ( t )-octylphenol (OP), nonylphenol(NP),nonylphenolmonoethoxylate(NPEO1),2,4-dichloro-phenol (DCP), pentachlorophenol (PCP) and bisphenol A(BPA). Among them,  t -butylphenol,  t -octylphenol, nonyl-phenol,nonylphenolmonoethoxylate,andbisphenolAweredetected in Kyeonggi Bay sediments with 100% frequency,and concentrations ranged from 0.06 to 3.1 ng/g dw withaverage of 0.22 ng/g dw, from 0.07 to 15 ng/g dw with aver-age of 0.81 ng/g dw, from 3.2 to 1070 ng/g dw with averageof 50 ng/g dw, from 1.5 to 1200 ng/g dw with averageof 55 ng/g dw and from 0.17 to 16 ng/g dw with average of 1.3 ng/g dw, respectively. Nonylphenol and nonylphenolmonoethoxylate amounted to approximately 95% of totalphenolic analytes, and they showed similar concentrationsand percentage profiles at each site (Table 1). As shown inFig. 2, percentages of relatively water insoluble analytes( t -octylphenol, nonylphenol and nonylphenol monoethoxy-late) decreased in relation to distance from the suspectedpollution source. Percentages of water soluble analytes ( t -butylphenol and bisphenol A), on the other hand, increasedgradually with distance.Coprostanol concentrations ranged from 3.4 to 3800 ng/g dw with an average of 220 ng/g dw (Table 1). Significantlyhigh levels of coprostanol were found in INH. In general,the levels of coprostanol were two times higher than levelsof total phenolic analytes. Based on these results, nonylphe-nol, nonylphenol monoethoxylate and coprostanol were thedominant pollutants in Kyeonggi Bay.Several studies on nonylphenol have been carried outin Ulsan Bay, Masan Bay and Shihwa Lake (Table 2).The areas are known to be highly polluted with industrialwaste. Nonylphenol concentrations ranged from 1.0 to 19.9ng/g dw with an average of 3.0 ng/g dw and from 102 to1900 ng/g dw with an average of 410 ng/g dw in UlsanBay (Khim et al., 2001) and Masan Bay (Khim et al.,1999) sediments, respectively. Li et al. (2004b) reported highlevels of nonylphenol in the manmade Shihwa Lake, theconcentrations ranging from 10.4 to 5100 ng/g dw with an Table 1Concentrations (ng/g dw) of phenolic compounds and coprostanol in surface sediments from Kyeonggi Bay, KoreaStation  t -BP  t -OP NP NPEO1 BPA Coprostanol Total (PCs)Concen-tration% a Concen-tration% Concen-tration% Concen-tration% Concen-tration% Concen-trationConcen-tration1 0.21 0.23 0.70 0.75 62.47 67.17 27.76 29.84 1.87 2.01 941.4 93.012 0.06 0.23 0.22 0.80 16.43 60.85 9.73 36.05 0.56 2.07 76.27 26.993 0.07 0.21 0.24 0.75 17.63 55.39 13.15 41.30 0.75 2.35 117.1 31.834 0.12 0.25 0.53 1.07 34.30 69.48 13.24 26.83 1.17 2.38 72.69 49.375 0.07 0.79 0.07 0.79 4.74 55.34 3.52 41.11 0.17 1.98 16.38 8.566 0.06 0.21 0.26 0.86 18.58 61.88 10.74 35.76 0.39 1.28 213.5 30.027 0.19 0.73 0.26 1.02 15.58 61.40 8.72 34.36 0.63 2.49 92.54 25.378 3.14 0.13 15.37 0.66 1070 45.84 1220 52.68 15.93 0.68 3800 23309 0.44 0.11 2.30 0.59 110.6 28.49 270.6 69.72 4.24 1.09 408.5 388.110 0.26 0.34 0.53 0.68 38.60 49.64 36.41 46.81 1.97 2.53 427.4 77.7711 0.16 0.27 0.51 0.87 29.16 49.90 27.28 46.68 1.33 2.28 309.0 58.4412 0.06 0.62 0.19 1.85 6.68 63.58 3.11 29.63 0.45 4.32 23.37 10.5013 0.06 0.52 0.12 1.03 5.47 47.16 5.68 48.97 0.27 2.32 37.65 11.6014 0.07 0.88 0.10 1.32 4.40 58.77 2.59 34.65 0.33 4.39 16.52 7.4915 0.07 0.26 0.46 1.70 16.79 62.39 8.92 33.16 0.67 2.49 57.24 26.9116 0.06 0.71 0.09 1.06 5.13 60.99 2.59 30.85 0.54 6.38 35.23 8.4117 0.09 0.34 0.33 1.24 15.04 56.18 10.50 39.21 0.81 3.03 90.77 26.7818 0.09 0.48 0.26 1.43 14.48 80.57 2.69 14.97 0.46 2.55 8.44 17.9719 0.06 0.75 0.08 1.13 4.55 61.65 2.53 34.21 0.17 2.26 9.83 7.3820 0.39 1.60 0.26 1.06 12.87 52.53 10.26 41.89 0.72 2.93 87.66 24.5021 0.18 0.86 0.21 1.03 10.31 50.00 9.25 44.85 0.67 3.26 53.40 20.6222 0.06 1.10 0.12 2.21 3.50 64.09 1.54 28.18 0.24 4.42 3.38 5.4723 0.10 1.16 0.10 1.16 4.99 59.07 2.97 35.14 0.29 3.47 29.90 8.4524 0.10 1.89 0.24 4.40 3.16 57.23 1.81 32.70 0.21 3.77 15.57 5.5325 0.14 1.03 0.24 1.79 7.57 55.90 5.14 37.95 0.45 3.33 14.27 13.5426 0.10 0.86 0.27 2.31 6.83 57.35 4.22 35.45 0.48 4.03 24.90 11.9027 0.08 0.81 0.12 1.21 5.56 54.03 4.02 39.11 0.50 4.84 45.26 10.2928 0.08 0.59 0.17 1.18 7.52 53.45 5.80 41.22 0.50 3.55 37.12 14.0829 0.12 1.02 0.17 1.52 6.91 60.66 3.61 31.73 0.58 5.08 45.89 11.3830 0.21 0.22 1.35 1.45 43.88 47.05 45.80 49.12 2.01 2.15 104.6 93.2531 0.22 0.31 0.52 0.75 45.07 64.97 21.99 31.70 1.57 2.26 140.5 69.3732 0.08 0.47 0.31 1.87 9.43 56.91 5.94 35.83 0.81 4.92 35.35 16.5733 0.10 1.05 0.17 1.74 5.91 62.37 2.94 31.01 0.36 3.83 14.90 9.48Average 0.22 0.64 0.81 1.31 50.43 57.34 54.09 37.66 1.28 3.05 223.2 108.0 a The data indicates relative percentage for total phenolic analytes. Baseline / Marine Pollution Bulletin 54 (2007) 97–116   103  average of 810 ng/g dw. As listed in Table 2, levels of nonylphenol found in this study were lower than those inMasan Bay and Shihwa Lake, but higher than those inUlsan Bay.There are several reports on nonylphenol contaminationaround the world (Table 2). Although Kyeonggi Bay is asemi-enclosed system with many factories and a large citylocated in the vicinity, concentrations of nonylphenol wereconsiderably lower than those in the Great Lakes (170– 72,000) and in Hamilton Harbor Canada (1300–6700 ng/g dw), and those found in Jamaica Bay of USA (7.0– 14,000 ng/g dw). The Korean levels are similar to the aver-age observed in Waddensea, Germany (58 ng/g dw).Coprostanol has been studied intensively around theworld (Table 2), but reports from Korea are sparse. Theconcentration range and average values of coprostanolmeasured in Kyeonggi Bay are similar to those reportedby Isobe et al. (2002) in river sediment from the MekongDelta, Vietnam and those reported by Chalaux et al.(1995) in sediment from Tokyo Bay, Japan. In the caseof the Venice Lagoon in Italy, the maximum concentrationwas similar to Kyeonggi Bay levels, but average concentra-tion (1100 ng/g dw) was five times higher.Although there were three suspected pollution sourcesfor Kyeonggi Bay, we found significantly high levels of tar-get pollutants were found in Incheon North Harbor (INH).As shown in Table 1, concentrations of total phenolic ana-lytes found at station KB (located in INH) were 20 timeshigher than those found in other areas, such as stationK1 (located in the Han River estuary) and station K30(located in the Shihwa industrial waste drain outlet area).The levels of coprostanol found at station KB were 4 and30 times higher than those found in station K1 and stationK30, respectively. Concentrations of nonylphenol andcoprostanol showed a clear gradient from the suspectedpollution source to remote sites with similar variation in 89909192939495969798991001 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 Sampling sites 0.01.02.03.04.05.06.07.08.0 SourcePointSourcePointSourcePoint 1 1 2    P  e  r  c  e  n   t  a  g  e   (   %   )  o   f  w  a   t  e  r   i  n  s  o   l  u   b   l  e  a  n  a   l  y   t  e  s   P  e  r  c  e  n   t  a  g  e   (   %   )  o   f  w  a   t  e  r  s  o   l  u   b   l  e  a  n  a   l  y   t  e  s water solublewater insoluble Fig. 2. Composition profiles of relatively water soluble ( t -butylphenol and bisphenol A) and water insoluble (nonylphenol and nonylphenolmonoethoxylate) chemicals from sediments in Kyeonggi Bay, Korea.Table 2Comparison of nonylphenol and coprostanol levels in surface sediments from various regions (ng/g dw)Location (country) Concentration (ng/g dw) Sample No. ReferenceRange MeanNonylphenol Kyeonggi Bay (Korea) 4.7–1100 51 33 This studyUlsan Bay (Korea) 1.0–19.9 3.0 Khim et al. (2001)Masan Bay (Korea) 102–1900 410 28 Khim et al. (1999)Shihwa Lake (Korea) 10.4–5100 810 20 Li et al. (2004b)Waddensea (German) 10–153 58 14 Bester et al. (2001)Great Lake (Canada) 170–72,000 10,600 9 Bennie et al. (1997)Hamilton Harbor (Canada) 1300–6700 Lee and Peart (1995)Jamaica Bay (USA) 7.0–14,000 2107 10 Ferguson et al. (2001)Coprostanol Kyeonggi Bay (Korea) 3.4–3800 220 33 This studyVenice Lagoon (Italy) 150–4400 1100 5 Fattore et al. (1996)Tokyo Bay (Japan) 20–243 120 11 Chalaux et al. (1995)Rivers (Malaysia) 37–15,500 380   15 Isobe et al. (2002)Rivers (Vietnam) 5–4500 170   44 Isobe et al. (2002)104  Baseline / Marine Pollution Bulletin 54 (2007) 97–116   patterns. Typical variation profiles are shown in Fig. 3. Thelevels of nonylphenol and coprostanol were decreasedabruptly from inside to outside of INH, and this impliesthat industrial waste water and fecal pollutants were dis-charged to INH from the surrounding industrial complexand municipal area. As a result, INH becomes a secondarypollution source of industrial and domestic pollutants toKyeonggi Bay. Furthermore, although the srcin of indus-trial and fecal pollution is different, their source is samein the Kyeonggi Bay environment. This conclusion isstrongly supported by the correlation between nonylphenoland nonylphenol monoethoxylate, BPA and coprostanol(Fig. 4), and the correlation coefficients ( R 2 ) are 0.92,0.89, 0.76, respectively. It is well known that nonylphenolis a biodegradation product of nonylphenol monoethoxy-late under anaerobic environmental conditions, and bothof them are produced by the biodegradation of nonyl-phenol polyethoxylates (Ahel et al., 1996). The strongcorrelation between nonylphenol and nonylphenol mono-ethoxylate concentrations indicates that fresh nonylphenolpolyethoxylates surfactants are discharged into INH, andthey are degraded into nonylphenol and nonylphenolmonoethoxylate in the local environment. BPA, on theother hand, has been used as an intermediate in polycar-bonate and epoxy resins, flame retardants, and otherspecialty products, and industrial waste water is a majorsource of BPA. Thus, the strong correlation betweennonylphenol and BPA concentrations may result fromthe same pollution source. Although the srcins of nonyl-phenol and coprostanol are different, they demonstratedsimilar spatial distribution profiles and a reasonable corre-lation ( R 2 = 0.76). This implies that the discharge points of both pollutants were adjacent to each other.Because INH is a semi-enclosed system, pollution is con-tained with in a localized area due to the lack of physicalmixing with open sea waters. Because nonylphenol andcoprostanol are hydrophobic chemicals, most of the pollu-tants are absorbed in sediment and settle locally. Fig. 3. Distribution profiles of nonylphenol (A) and coprostanol (B) with distance from suspected pollution sources. Baseline / Marine Pollution Bulletin 54 (2007) 97–116   105
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