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Octylphenol and Nonylphenol in SurfaceWater of Ráckevei-Soroksári DanubeBranch, HungaryPETER NAGY a , JENO FEKETE a & VIRENDER K. SHARMA ba Institute of General and Analytical Chemistry, Budapest Universityof Technology and Economics, Budapest, Hungaryb Chemistry Department, Florida Institute of Technology, Melbourne,Florida, USAVersion of record first published: 06 Feb 2007.

To cite this article: PETER NAGY , JENO FEKETE & VIRENDER K. SHARMA (2005): Octylphenoland Nonylphenol in Surface Water of Ráckevei-Soroksári Danube Branch, Hungary, Journal ofEnvironmental Science and Health, Part A: Toxic/Hazardous Substances and EnvironmentalEngineering, 40:9, 1679-1688

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Journal of Environmental Science and Health, 40:1679–1688, 2005Copyright C© Taylor & Francis Inc.ISSN: 1093-4529 (Print); 1532-4117 (Online)DOI: 10.1081/-ESE-200067983

Octylphenol and Nonylphenolin Surface Water ofRackevei-Soroksari DanubeBranch, Hungary

Peter Nagy,1 Jeno Fekete,1 and Virender K. Sharma2

1Institute of General and Analytical Chemistry, Budapest University of Technology andEconomics, Budapest, Hungary2Chemistry Department, Florida Institute of Technology, Melbourne, Florida, USA

Concentrations of 4-octylphenol (OP) and 4-nonylphenol (NP) in surface water sam-ples were determined at 10 sites during eight samplings (October 2002 to April 2004) atRackevei-Soroksari Danube (RSD) branch, Hungary. OP levels in surface waters rangedfrom <0.0016 to 0.0907 µg L−1, whereas NP concentrations varied from <0.008 to 0.428µg L−1. The highest concentrations were found at a specific site, which receives inputfrom an industry. A seasonal trend with higher concentrations of OP and NP was ob-served in waters during the warmer months. Concentrations of OP and NP in surfacewater were compared with other reported concentrations around the world. The con-centrations of NP in RSD were found to be below the reported toxic concentrations formarine and freshwater species.

Key Words: Octylphenol; Nonylphenol; River Danube; Endocrine disruptors; Water.

INTRODUCTION

Alkylphenol polyethoxylates (APEs) are an important group of non-ionic sur-factants, which are commonly used as household and industrial detergents.In 1995, about 500,000 tons of APEs were produced worldwide.[1] Nonylphe-nol ethoxylates and octylphenol ethoxylates are the most important APEs. Themicrobial breakdown of nonylphenol ethoxylate is 4-nonylphenol (NP) and ofoctylphenol ethoxylate, 4-octylphenol (OP).[2] NP is also used as an adjuvantin pesticides.[3] There are great concerns that NP and OP can mimic natural

Received November 16, 2004.Address correspondence to Virender K. Sharma, Chemistry Department, Florida Insti-tute of Technology, 150 West University Boulevard, Melbourne, FL 32901, USA; E-mail:vsharma@fit.edu

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hormones, and their presence in the environment may disrupt endocrine func-tion in wildlife and humans. Reports state that NP has three times higher es-trogenic activity than that of dichlrodiphenyltrichloroethane (DDT) and causesdeformities and reproductive problems in wildlife.[4−6] This compound may alsobe involved in breast cancer increases and sperm count declines in humans.[7]

APEs can enter into the aquatic environment through landfill leachatesand sewage effluents from treatment plants.[8] Once in the environment, theycan accumulate in the fatty tissue of marine organisms, such as shrimp andcommon mussel, as well as freshwater fish and ducks.[3,9,10] The degradationproducts of APEs have shown chronic toxicity to shrimp, salmon, and mussels.For example, the 96-h LC50 of NP is 0.3 mg L−1 for shrimp and 0.16 mg L−1 forsalmon. The determination of concentrations of OP and NP is thus importantfor the regulation of endocrine disruptors in the environment.[3]

In the present work, concentrations of OP and NP in the surface watersof the Rackevei-Soroksari Danube (RSD) branch in Hungary were determined.The RSD is the second longest branch of the Danube River in Hungary, andsurface waters of the Danube are used as a source of drinking water.[11] Itis therefore important to assess the levels of pollution from OP and NP inwaters of the RSD. Moreover, the Danube is the second longest river in Europe,with a length of about 2.857 km. It flows through nine countries (Germany,Austria, Slovakia, Hungary, Croatia, Serbia, Bulgaria, Ukraine, and Romania).Assessing the water quality of the Danube and its branches in Hungary istherefore ecologically important.

MATERIALS AND METHODS

Study Area and SamplingThe study area of the RSD branch is about 57.3 km in length. The flow

rate of the RSD is 0.2 km/h in winter and 0.4 km/h in summer. The ends of thebranch are closed with floodgates, which allows adjustment of the water levelof the branch irrespective of the water level of the Danube. The 180-km-longbank of the RSD is used for holiday and sport resorts. The first 11-km reach ofthe RSD in Budapest is narrow (40 m) and shallow (2.7 m), so the silt the fromthe Danube is mostly deposed in this reach.

Surface (0.3 m) water samples were taken in 0.5-L glass bottles from 10 sam-pling sites located on branch. Samples were collected eight times from October2002 to April 2004. Three samples were taken from each sampling site. Addedto each sample (500 mL) were 50 ML methanol and 3 ML orthophosphoric acid(pH< 3) at sampling sites to avoid bacterial growth. Samples were later trans-ferred to the laboratory within 3 h and were stored at 4◦C to perform solid-phaseextraction (SPE, normally within 48 h).

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Octylphenol and Nonylphenol in Surface Water 1681

Sample HandlingThe samples were filtered through a Schleicher & Schull 100 filter to remove

the solid particles greater than 10 µm. Waters Sep-Pak©R Plus C18 cartridgeswere used for SPE of alkylphenols in the water samples. The SPE cartridgeswere first washed with 10 mL of dichloromethane and then conditioned with10 mL of acetonitrile, followed by 10 mL de-ionized water. Samples were passedthrough the cartridges at a flow rate of 5 mL min−1 under vacuum. Columnswere then dried with vacuum for 15 min. The alkylphenols were finally elutedwith 4 mL of acetonitrile and 5 mL of dichloromethane. The samples wereconcentrated to 0.5 mL under nitrogen stream at room temperature.

Instrumental AnalysisAlkylphenols in samples were determined by high performance liquid chro-

matography (HPLC) with programmable fluorescence detection. The mobilephase was 70/30% (v/v) acetonitrile/water at a flow rate of 1 mL min−1. Theexcitation and the emission wavelength of the fluorescence detection were 275nm and 300 nm, respectively. The calibration standards of OP and NP wereobtained from Supelco Inc., Bellefonte. The limits of detection were calculatedfrom the calibration curve using 3*noise/sensitivity. Detection limits were foundto be 0.0016 and 0.008 µg L−1 for OP and NP, respectively. Quality controls ofthe measurements were established by spiking standards of OP and NP inacetonitrile into the water samples. The level of spiking was 1 µg L−1. Theconcentrations of alkylphenol in samples (Cs) were determined by using thefollowing relationship:

Cs = (Cm/( f × r)) × 100 (1)

where concentration factor ( f ) = (Vs/macn) × dacn, Cm is the measured concen-tration (mg L−1) determined from the calibration curve, r is the recovery ofalkylphenol (%), Vs is the volume of sample passed through cartridge (mL), dacn

is the density of acetonitrile (0.7822 g mL−1 at 20◦C), and macn is the mass ofthe concentrated sample (g).

RESULTS AND DISCUSSION

Typical chromatograms of OP and NP obtained for standards, spiked sample,and water samples collected from different sites are shown in Figure 1. Peak ar-eas were used to determine concentrations. In spiked sample, recoveries were60.1% ± 4.4% and 52.8% ± 4.4% for OP and NP, respectively. All results re-ported in the study were corrected for recoveries. Table 1 shows concentrationsof OP and NP in surface waters of the RSD. Concentrations of OP and NP didnot change significantly at different sites at each sampling event. The log Kow

(octanol water partition coefficient) of OP is 4.65 ± 0.42, whereas that of NP

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Figure 1: HPLC chromatograms of (a) 1.08 mg L−1 OP and 0.96 mg L−1 NP, (b) spikedwater sample, (c) water sample collected from site 3 on April 2004, and (d) water samplecollected from site 5 on April 2004.

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Table 1: 4-octyphenol (OP), and 4-nonylphenol (NP) concentrations (µg L−1) insurface waters in Rackevei-Soroksari Danube branch.

Site Oct, 02 Apr, 03 May, 03 Jul, 03 Nov, 03 Feb, 04 March, 04 Apr, 04

4-Octylphenol (OP)1 0.016 <0.0016 <0.0016 0.0288 0.0084 0.0148 0.0117 0.01762 <0.0016 0.021 0.049 0.0275 0.0058 0.0249 0.0054 0.01253 <0.0016 <0.0016 0.0069 0.0289 0.0044 0.0137 0.0039 0.01644 <0.0016 <0.0016 <0.0016 0.027 0.0042 0.0173 0.0152 0.01575 <0.0016 <0.0016 <0.0016 0.0277 0.005 0.0131 0.0064 0.01676 <0.0016 0.0067 <0.0016 0.0175 0.0041 0.0109 0.0075 0.00167 <0.0016 <0.0016 <0.0016 0.0211 0.0091 0.0061 0.0028 0.00028 <0.0016 <0.0016 <0.0016 0.012 <0.0016 0.009 0.0014 0.00169 <0.0016 0.049 <0.0016 0.0868 0.0311 0.0907 0.0352 0.0178

10 <0.0016 0.0037 <0.0016 0.027 0.0101 0.0053 0.0021 0.00114-Nonylphenol (NP)

1 0.08 <0.008 0.122 0.279 0.033 0.067 0.019 0.1362 0.08 0.224 0.135 0.221 0.018 0.104 <0.008 0.13 0.18 0.212 0.065 0.273 0.027 0.021 0.125 0.1194 0.156 0.114 0.117 0.211 0.034 0.027 0.103 0.1075 0.11 0.206 <0.008 0.229 0.041 0.018 0.037 0.1196 0.115 0.024 <0.008 0.204 0.014 0.188 0.081 0.0497 0.14 0.068 <0.008 0.254 <0.008 0.121 0.027 0.0598 0.14 0.091 <0.008 0.17 <0.008 0.113 0.01 0.0489 0.08 0.179 <0.008 0.42 0.08 0.291 0.114 0.428

10 0.143 0.155 <0.008 0.361 <0.008 0.054 <0.008 0.044

is 5.22 ± 0.38.[12] This suggests low levels of OP and NP in water samples dueto strong adsorption of alkylphenols to aquatic particles of RSD. OP levels inwater ranged from <0.0016 to 0.0907 µg L−1 (Table 1). Generally, the concen-trations of NP were found to be an order of magnitude higher than the OPconcentrations in the RSD. Higher NP concentrations than those of OP havealso been found in other rivers of Europe.[13−18] The NP concentrations in watervaried from <0.008 to 0.428 µg L−1. The water quality of the studied region ishighly influenced by the urban region of Budapest. However, the highest con-centrations of OP and NP were at sampling site 9. This site is close to industry,which may have caused the observed values.

Seasonal trends of OP and NP concentrations in water samples of RSD areshown in Figure 2. Concentrations were highest in the summer month of Julythan the other months of sampling events. This could be due to either higherinput of alkylphenols or less efficient removal of these compounds during asummer month. Higher concentrations of OP and NP in the warmer seasonthan in the colder season were also observed in rivers of Japan.[12,19]

The concentrations of alkylphenols in surface water were compared withwaters of other countries (Table 2). The concentrations of NP in our study weresimilar to levels in surface waters from various sites in Europe.[13−18,20−22] Theconcentration of NP in our study was much lower than a concentration found insurvey of NP in rivers and estuaries in the United Kingdom.[13,14] The levels of

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Figure 2: Concentrations of octylphenol (A) and nonylphenol (B) in surface water. Theboxes closest and farthest to zero indicate the 25th and 75th percentiles, respectively, anda line within the box marks the median. Whiskers above and below the box indicate, the90th and 10th percentiles, respectively.

NP in the RSD surface water were similar to the results in the 30 rivers studiedin the United State and an environmental monitoring study conducted in theGreat Lakes basin and upper St. Lawrence River.[23,24] The concentration of NPin the RSD was lower than in Japanese rivers.[12] This is possibly related to thefact that nonylphenol ethoxylates are mainly used as industrial surfactants inEurope, whereas the are rarely used in Japan for household applications.

Figure 3 represents aquatic toxicity data for marine and freshwater speciesrelative to the concentrations found for NP in our study. The aquatic toxicitydata were taken from Jobling et al.[25] Concentrations of NP in the RSD surfacewater are 2–3 orders of magnitude lower than the observed toxic concentrationsfor shrimp, salmon, and Daphnia. The threshold for vitellogenin, a yolk proteinnormally found in female fish, inductions has been determined as 10 µg L−1

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Table 2: 4-octyphenol (OP), and 4-nonylphenol (NP) concentrations in surfacewaters from various locations in World.

Location Alkylphenol Concentration µg L−1 Reference

Danube branch, OP <0.0016–0.178 This studyBudapest, Hungary NP <0.008–0.428

Elbe River & its OP <0.005–0.005 [18]

Tributaries, Germany NP 0.013–0.087Danube River. OP <0.020–0.163 [14]

Southwest Germany NP 0.056–0.233Korsch River, OP 0.019–0.189 [14]

South-west, Germany NP <lod–0.164Krahenbach River, OP <lod–0.155 [14]

South-west Germany NP <lod–0.485Weiße Elster River, OP 0.0015–0.006 [17]

Germany NP 0.078–0.220Danube River, NP 0.006–0.135 [20]

Southern GermanyRivers & lakes, Italy NP <0.1–1.4 [22]

Frenc River, France NP 0.006–0.550 [21]

Glatt River, Switzerland NP <0.001–0.48 [16]

Rivers & Estuariess, UK NP <lod–30 [13]

Great Lakes, Canada NP 0.01–0.92 [22]

30 U.S. Rivers NP <0.11–0.64 [24]

Samidagawa River OP 0.01–0.18 [12]

Japan NP 0.08–1.08Tamagawa River OP 0.01–0.07 [12]

Japan NP 0.05–0.17

Figure 3: Reported toxicity (LC50, 96 h) for shrimp and salmon and (LC50, 48 h) for Daphniaand environmental concentrations of nonylphenol in RSD branch.

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and 3 µg L−1 for NP and OP, respectively.[25] These values are much higherthan the values obtained from the RSD samples to be concerned. However,stickleback and Atlantic salmon have bioconcentration factors of 1300 and 280,respectively.[26] Observed environmental concentrations in the RSD are thuspotentially within the limits to have effect on vitellogenin production in femalefish.

CONCLUSION

A survey of concentrations of OP and NP in surface water of the RSD wastaken to establish environmental concentrations of endocrine disruptors. Thehighest concentrations were found at a site close to industry. The warmer seasonshowed relatively higher concentrations of alkylphenols than the colder season.Concentrations of OP and NP were found to the similar to concentrations inmost of the rivers around the world and are well below those observed to be ofconcern.

ACKNOWLEDGMENT

This study was sponsored partly by Hungarian Environmental ministry projectnumber K-36-02-00318A and German-Hungarian Scientific and TechnologicalCooperation project number D36/02. V.K. Sharma acknowledges the supportfrom the Environmental Partnership Science Program of the U.S. State De-partment. This article was improved from the useful comments of reviewersand editors.

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