Estimation of physicochemical properties of 2-ethylhexyl-4-methoxycinnamate (EHMC) degradation products and their toxicological evaluation

Estimation of physicochemical properties of 2-ethylhexyl-4-methoxycinnamate (EHMC) degradation... The organic UV filters, commonly used in personal protection products, are of concern because of their potential risk to aquatic ecosystems and living organisms. One of UV filters is ethylhexyl-4-methoxycinnamate (EHMC) acid. Studies have shown that, in the presence of oxidizing and chlorinating factors, EHMC forms a series of products with different properties than the substrate. In this study, the toxicities of EHMC and its transformation/degradation products formed under the influence of NaOCl/UV and H O /UV systems in the water medium were tested using Microtox® bioassay and by observation of mortality 2 2 of juvenile crustaceans Daphnia magna and Artemia Salina. We have observed that oxidation and chlorination products of EHMC show significantly higher toxicity than EHMC alone. The toxicity of chemicals is related to their physicochemical characteristic such as lipophilicity and substituent groups. With the increase in lipophilicity of products, expressed as log K , the toxicity (EC ) increases. On the basis of physicochemical properties such as vapour pressure (VP), solubility (S), OW 50 octanol-water partition coefficient (K ), bioconcentration factor (BCF) and half-lives, the overall persistence (P ) and long- OW OV range transport potential (LRTP) of all the products and EHMC were calculated. It was shown that the most persistent and traveling on the long distances in environment are methoxyphenol chloroderivatives, then methoxybenzene chloroderivatives, EHMC chloroderivatives, methoxybenzaldehyde chloroderivatives and methoxycinnamate acid chloroderivatives. These com- pounds are also characterised by high toxicity. . . . . . Keywords EHMC transformation products Physicochemical properties EPI suite P LRTP Toxicity OV Introduction Highlights � Toxicity of EHMC transformation products was studied � Analysis of EHMC transformation products in terms of their persistence Chemical UV filters are used in personal protection products in environment and ability to propagate in air and water to protect our skin from harmful UVradiation. They are one of � Application of the EPI Suite program to determine values of the selected the components of sunscreens, lotions, shampoos, body physicochemical parameters of EHMC and its conversion products washes, hair sprays and protective lipsticks (Ji et al. 2013; Responsible editor: Ester Heath MacManus-Spencer et al. 2011). They are also added to paints Electronic supplementary material The online version of this article and varnishes because they can prevent polymer degradation (https://doi.org/10.1007/s11356-018-1796-6) contains supplementary or pigmentation (Christiansson et al. 2009; Ferrari et al. 2013). material, which is available to authorized users. One of the commonly used UV filter is 2-ethylhexyl-4- methoxycinnamate ester (EHMC) (Kikuchi et al. 2011). * Alicja Gackowska alicja.gackowska@utp.edu.pl EHMC shows a high absorbing capacity in the UVB range. The maximum permissible concentration of EHMC in cos- 1 metic products in the European Union cannot exceed 10% Faculty of Chemical Technology and Engineering, UTP University (Gilbert et al. 2013). Slightly smaller concentration, i.e. of Science and Technology, Seminaryjna 3, 85-326 Bydgoszcz, Poland 7.5%, is valid in the USA (Janjua et al. 2008). The dynamic development of cosmetic industry has resulted Institute of Water and Wastewater Engineering, Silesian University of Technology, Konarskiego 18, 44-100 Gliwice, Poland in a higher consumption of chemical UV filters. Unfortunately, 16038 Environ Sci Pollut Res (2018) 25:16037–16049 it has been observed that the chemical UV filters contribute to products and possible risks associated with their long-range pollution of environment. EHMC has been detected in surface transport in the environment. waters (Straub 2002; Poiger et al. 2004; Tarazona et al. 2010), From the toxicological point of view, the toxicity of EHMC swimming pool waters (Cuderman and Heath 2007; Santos degradation products is mostly unknown. There is no data on et al. 2012), drinking water (Loraine and Pettigrove 2006; the environmental risk assessment of EHMC transformation Diaz-Cruz et al. 2012), wastewater (Damiani et al. 2006;Li products. In some cases, the toxicity of photolytic mixtures et al. 2007; Rodil et al. 2012), sewage sludge (De la Cruz was tested e.g. Vibrio fischeri microtox assay for 4- et al. 2012; Zuloaga et al. 2012; Barón et al. 2013)and even methoxybenzaldehyde that showed higher toxicity than in human breast milk and human urine (León et al. 2010). In EHMC (Vione et al. 2015). It should be noted that EHMC treated wastewater, EHMC was identified at a level of 120– transformation products are formed at low concentrations in 849 ng/L (Ekpeghere et al. 2016). Continuous and uncontrolled complex matrices. Their separation and isolation is laborious emission of the chemical UV filters into environment, even at and difficult to perform. Hence, the toxicity assessment of a low concentrations, is unfavourable as they accumulate in living single product is difficult. The solution is to carry out a biotest organisms. EHMC accumulates in aquatic biota of different for a mixture of compounds. Commonly applied test is trophic levels with concentrations of up to 340 ng/g lipids in Microtox® biotest, which uses natural luminescence of cormorants (Fent et al. 2010). EHMC is known as endocrine Vibrio fisheri exhibiting sensitivity to a wide spectrum of toxic disrupting compound that cause adverse effects on human and organic and inorganic substances. (Hsieh et al. 2004; wildlife. On this basis, the Commission of the European Union Bohdziewicz et al. 2016;Kudlek et al. 2016). (EU 2015/495) placed EHMC on the list of 17 substances sub- Other tests were carried out using the freshwater crustacean jected to monitoring (Directive 2008/105/EC of the European Daphnia magna (Rozas et al. 2016) and the saltwater crusta- Parliament and of the Council). EHMC has estrogenic proper- cean Artemia salina (Vasquez and Fatta-Kassinos 2013). tiesbothin vitro andin vivo(Schlumpf et al. 2001). The aims of the studies were to estimate physicochemical Recent studies have shown that EHMC under sun and UV parameters and to model P and LRTP for EHMC and its OV irradiation forms transformation products (TPs) (MacManus- transformation products formed in oxidation, chlorination and Spencer et al. 2011; Rodil et al. 2009; Santiago-Morales et al. photodegradation processes, simultaneously, to perform vari- 2013; Vione et al. 2015). Under the influence of UV radiation ous ecotoxicological bioassays so as to be able to correlate if and hydrogen peroxide, EHMC is degraded to compounds possible the findings between the physicochemical and bio- which, in the presence of reactive forms of oxygen or chlorine, logical assessments. can produce new products, sometimes even more toxic than the substrates themselves (Sakkas et al. 2003; Gackowska et al. 2014; Gackowska et al. 2016). In turn, in the presence Experimental of sodium hypochlorite used to disinfect pool waters, chloroorganic derivatives of EHMC are formed (Nakajima Materials and methods et al. 2009; Santos et al. 2012;Gackowskaetal. 2016). Understanding the mechanism of EHMC transformations in Materials the environment and the environmental fate of products of these transformations requires knowledge of their physico- Analytical standard of 2-ethylhexyl 4-methoxycinnamate (E- chemical properties such as water solubility (S), octanol- EHMC) (98%) was obtained from ACROS Organics (USA) water partition coefficient (K ), vapour pressure (VP) and and was kept in lightproof container at 4 °C. Sodium hypo- OW bioconcentration factors as well as half-life in air, water and chlorite NaOCl with a nominal free chlorine content of −1 soil. Determination of the properties of all products is time- 100gL and H O (30%) was obtained from POCh 2 2 consuming and sometimes difficult to perform. A useful tool (Poland). The toxicity tests: Microtox®, Daphtoxkit F® and for the determination of physicochemical parameters is EPI Artoxkit M® were purchased from MicroBioTest Inc. Suite. It allows estimating the physicochemical properties of (Belgium). all EHMC transformation products identified so far. Based on the calculated parameters and half-lives, the overall persis- Oxidation processes tence (P ) and long-range transport potential (LRTP) of all OV EHMC transformation products were calculated with the The experimental oxidation processes were performed in a Organization for Economic Cooperation and Development laboratory glass batch reactor with a capacity of 0.7 L of (OECD) P and LRTP Screening Tool (http://www.oecd. Heraeus (Hanau, Germany). The reactor was equipped with OV org/document/24/0,3746,en_2649_34379_45373336_1_1_ an immersion medium pressure UV lamp of 150 W located in 1_1,00.htm; Wegmann et al. 2009). The data obtained provide a cooling jacket made of Duran 50 glass. The cooling process information on potential persistence of the transformation was performed with water from the mains. The cooling Environ Sci Pollut Res (2018) 25:16037–16049 16039 Table 1 The reaction conditions and substrate proportions used in this process enabled a constant temperature of 20 ± 1 °C to be study maintained. The lamp emitted radiation of λ equal to 313, exc 365, 405, 436, 546 and 578 nm. Additionally, the reactor was Reagents EHMC [M] H O [M] NaOCl [M] UV [W] 2 2 situated on a magnetic stirrer to guarantee the even mixing of −4 EHMC 3.4·10 00 – contents during the execution process. The reaction conditions −4 EHMC/UV 3.4·10 0 0 150 are presented in Table 1. −4 −5 EHMC/NaOCl/UV 3.4·10 01.7·10 150 The research subjects were model solutions containing −4 EHMC/H O /UV 3.4·10 0.05 0 150 2 2 deionised water and E-EHMC model. In order to test toxicity −5 NaOCl/UV 0 0 1.7·10 150 of the E-EHMC oxidation and chlorination products, E- −4 H O /UV 0 0.05 0 150 EHMC solution at concentration of 3.4·10 M was prepared 2 2 and subjected to the action of UVonly, H O /UVand NaOCl/ 2 2 UV. The concentration of sodium hypochlorite and hydrogen bacteria to toxic substances, the metabolic changes occur or peroxide were respectively 1.7·10–5 M and 0.05 M. After 30, population of bacteria is reduced, what in turn results in 60, 90 and 180 min, mixtures of the products obtained were change in the intensity of light emitted by microorganisms. sampled from reaction systems and subjected to toxicity tests. The test was conducted according to MicrotoxOmni The effectiveness of E-EHMC elimination was assessed by Screening Test procedure in the Microtox Model 500 analyser monitoring for changes in concentrations of compound in wa- from Tigret Sp. z o.o. (Poland), which operated both as an ter before and after the oxidation process, respectively. incubator and as a photometer. Percentage of bioluminescence inhibition relative to control sample (bacteria not exposed to Method for the determination of EHMC transformation toxicant) was measured after 5 and 15 min of exposure time products (volume of samples 1 mL). The EC value was determined on the basis of the Basic Dilution Test. A GC-MS 5890 HEWLETT PACKARD instrument equipped with column ZB-5MS (0.25 mm × 30 m × 0.25 μm) was used Daphtoxkit F® The test procedure is based on observation of for the identification of the transformation products applying the mortality of juvenile Daphnia magna crustaceans subject- the following chromatographic conditions: injector tempera- ed to the action of toxicant. The results were checked after 24 ture 250 °C, oven temperature program from 80 to 260 °C at and 28 h of exposure of animals to the tested solutions. All 10 °C/min, from 260 to 300 °C (held for 2 min) at a rate of organisms that did not demonstrate a motion reaction to swirl 5 °C min. Helium was used as a carrier gas. The volume of the induced by stirring the solution were considered dead. sample was 1 μL. Reaction products were identified by com- Experiment was carried out in accordance with the OECD paring recorded MS spectra with standard spectra from Guideline 202 and ISO 6341 standards. NIST/EPA/NIH Mass Spectral Library. The detailed descrip- tion of the methodology for identification of EHMC transfor- Artoxkit M® Toxicity of solutions was also tested on Artemia mation products was presented in previous papers Salina crustaceans. Survival of indicatory organisms was (Gackowska et al. 2014; Gackowska et al. 2016). assessed after 24 h of exposure to water solutions. The indi- viduals showing no signs of life were recognised as dead. Test Toxicity tests was conducted according to the ASTM E1440-91 standard. The effect of the toxicity (%) was determined according to All samples from the reactor were diluted 1:100 before the equation: performing toxicity tests. Additionally, control tests were car- ried out. In order to eliminate the effects of the reagents, tests 100∙ðÞ E −E K T E ¼ ; ½ % ð1Þ for E-EHMC-free systems were performed. Moreover, the toxicity tests were performed without EHMC. Changes in the toxicity of samples were assessed on the basis of the results where from three biotests: Microtox®, Daphtoxkit F® and Artoxkit E the effect observed in a blank sample and M®. On the basis of the difference in results obtained for E the effect observed in a test sample. EHMC systems with and without EHMC, the toxicity of the mixture of transformation products was determined. All sam- ples for toxicity tests were performer in four replicates. Depending on the given test, the effect was measured by Microtox® In Microtox® test, bioluminescent bacteria the decrease in bioluminescence (i.e. the enzymatic Aliivibrio fischeri, which are highly sensitive to a wide spec- Microtox® test) or organism viability (i.e. the Daphnia magna trum of toxic substances, were used. During exposure of test and Artemia Salina test). 16040 Environ Sci Pollut Res (2018) 25:16037–16049 The evaluation of results programs jointly developed by the US EPA and Syracuse Research Corp. (SRC). The US EPA develops and uses The results are the arithmetic average of the four replicates of models based on (quantitative) structure-activity relationships each experiment. For all the cases, assigned error (estimated ([Q]SARs) to estimate critical parameters. Structure-activity based on the standard deviation) did not exceed 5%, so the relationship (SAR) and quantitative structure-activity relation- results are presented in the form of error bars. ship (QSAR) models are theoretical models that can be used to quantitatively or qualitatively predict the physicochemical, biological (e.g. an (eco) toxicological endpoint) and environ- Results and discussion mental fate properties of a chemical substance from the knowledge of its chemical structure. The results were presented in Table 3. Analysis of param- Based on the analysis of previous studies, the identified prod- ucts of EHMC transformation have been gathered. These eters has shown that EHMC transformation products are characterised by different properties than the substrate. products have been presented in Supplementary (S Figs. 1– 8) and the listofproductsstudied waspresented in Table 2. In order to make a preliminary assessment of EHMC trans- Boiling point and vapour pressure formation products for potential threats to the environment, their characteristic physicochemical parameters were deter- Boiling point (BP) and vapour pressure (VP) are the parameters mined using EPI Suite program. The EPI (Estimation that provide information on whether the compounds, after en- Programs Interface) Suite™ is a suite of physical/chemical tering the environment, will evaporate into the atmosphere rel- properties, aquatic toxicity and environmental fate estimation atively quickly. Studies have shown that EHMC transformation Table 2 List of chemicals Abbreviation Chemical name No. 1E-EHMC trans 2-Ethylhexyl-4-methoxycinnamate 2 EHA 2-Ethylhexyl alcohol 3 4MCA 4-Methoxycinnamic acid 4 4MBA 4-Methoxybenzaldehyde 5 4MP 4-Methoxyphenol 6 1Cl4MB 1-Chloro-4-methoxybenzene 7 1.3DCl2MB 1.3-Dichloro-2-methoxybenzene 8 2-EHCA 2-Ethylhexyl chloroacetate 9 3Cl4MBA 3-Chloro-4-methoxybenzaldehyde 10 Z-EHMC cis 2-Ethylhexyl-4-methoxycinnamate 11 EHMCCl Chloro-2-Ethylhexyl-4-methoxycinnamate 12 EHMCCl Dichloro-2-Ethylhexyl-4-methoxycinnamate 13 2.4DClP 2.4-Dichlorophenol 14 2.6DCl1.4BQ 2.6-Dichloro-1.4-benzoquinone 15 1.2.4TCl3MB 1.2.4-Trichloro-3-methoxybenzene 16 2.4.6TClP 2.4.6-Trichlorophenol 17 3.5DCl2HAcP 3.5-Dichloro-2-hydroxyacetophenone 18 3Cl4MCA 3-Chloro-4-methoxycinnamic acid 19 3.5DCl4MCA 3.5-Dichloro-4-methoxycinnamic acid 20 3.5DCl4MBA 3.5-Dichloro-4-methoxybenzaldehyde 21 3Cl4MP 3-Chloro-4-methoxyphenol 22 2.5DCl4MP 2.5-Dichloro-4-methoxyphenol 23 TP Transformation product 24 TP Transformation product 307e 25 TP Transformation product 307f 26 TP Transformation product 305a 27 TP Transformation product 305b 28 TP Transformation product 305c 29 TP Transformation product 305d 30 TP Transformation product 305e 31 TP Transformation product 305f 32 TP Transformation product 469a 33 TP Transformation product 469b 34 DIAMC 2.4-bis-((2Z.4E)-4-Methoxyhepta-2.4.6-trienyl)- cyclobutane-1.3-dicarboxylic acid bis- (3-methyl-butyl) ester 35 TP Transformation product 581b Environ Sci Pollut Res (2018) 25:16037–16049 16041 Table 3 Physical–chemical properties of EHMC and its transformation products Compound Molecular Mol wt MP BP S VP Log Log Log Log Henry’sLC Half-life Half-life Half-life P LRTP OV −1 −1 −3 −1 No. References formula [g mol ] [°C] [°C] [mg L ] [mmHg] BCF K = K K K [mol dm atm ] air [h] water [h] soil [h] [days] [km] OW OA OC AW log P −5 1E-EHMC – C H O 290.41 99.87 360.54 0.1548 1.38·10 667.6 5.80 9.938 4.089 − 4.138 29.4 4.17 360 720 43.26 90.80 18 26 3 2EHA 1,2 C H O 130.23 − 70 184.6 880 0.185 25.33 2.73 5.69 1.415 − 2.965 44.9 19.4 208 416 23.02 385.20 8 18 1 −4 34MCA 1,3 C H O 178.19 96 317 712 1.6·10 3.162 2.68 10.19 1.536 − 7.505 19,300 5.02 360 720 41.41 37.37 10 10 3 44MBA 1,2 C H O 136.15 0 248 4290 0.0303 4.521 1.76 6.25 1.367 − 4.489 54,600 10.4 360 720 33.49 204.03 8 8 2 54MP 1 C H O 124.14 57 243 40,000 0.0083 3.285 1.58 7.447 2.28 − 5.867 12,200 8.62 360 720 34.36 150.24 7 8 2 61Cl4MB 4 C H CIO 142.59 ≤ 18 197.5 237 0.409 27.58 2.78 4.796 2.280 − 2.016 4.46 36.1 900 1.8e + 003 40.73 740.0 7 7 71.3DCl2MB 4 C H Cl O 177.03 < 25 215.67 140 0.164 52.22 3.14 5.825 2.508 − 2.145 3.1 96.4 900 1.8e + 003 67.67 1912.83 7 6 2 82-EHCA 4 C H ClO 192.69 − 8.26 207 48.86 0.168 236.2 3.50 3.655 2.632 − 1.736 2.03 24.9 360 720 33.86 514.10 10 19 2 9 3Cl4MBA 1 C H ClO 170.60 42.61 250.91 508.2 0.0176 14.98 2.44 7.058 1.518 − 4.618 130.0 13 900 1.8e + 003 87.91 250.74 8 7 2 −5 10 Z-EHMC 1, 5 C H O 290.41 99.87 360.54 0.1548 1.38·10 667.6 5.80 9.938 4.089 − 4.138 29.4 4.17 360 720 43.26 90.80 18 26 3 −6 11 EHMCCl 6, 7 C H ClO 324.85 128.01 386.23 0.01943 1.68·10 661.4 6.45 10.777 4.344 − 4.268 33.0 4.63 900 1.8e + 003 108.13 133.19 18 25 3 −7 12 EHMCCl 4, 6, 7 C H Cl O 359.30 149.44 404.93 0.00437 3.42·10 1215 7.16 11.559 4.562 − 4.399 25.6 5.65 900 1.8e + 003 108.15 410.66 2 18 24 2 3 13 2.4 DClP 4 C H Cl O 163.0 45.0 210.0 4500 0.09 18.04 3.06 7.108 2.856 − 3.756 43.7 242 900 1.8e + 003 99.62 2473.19 6 4 2 14 2.6DCl1.4BQ 4 C H Cl O 176.99 123 268.4 5056 0.00189 1.771 1.23 8.818 1.0 − 7.588 11,500 52 900 1.8e + 003 70.56 93.35 6 2 2 2 15 1.2.4TCl3MB 4 C H Cl O 211.45 45 227 29.73 0.056 126.7 3.64 5.569 2.726 − 1.929 1.89 121 1.44e + 003 2.88e + 003 113.33 2433.26 7 5 3 16 2.4.6TClP 4 C H Cl O 197.45 69 246 800 0.008 55.12 3.69 7.663 3.074 − 3.973 385 423 1.44e + 003 2.88e + 003 166.36 2977.4 6 3 3 −4 17 3.5DCl2HAcP 4 C H Cl O 205.04 90.66 299.08 258 1.6·10 3.713 3.26 7.8 2.31 − 4.540 5940 492 900 1.8e + 003 103.71 2663.03 8 6 2 2 −5 18 3Cl4MCA 1 C H ClO 212.63 109.81 337.48 382.6 3.75·10 3.162 2.80 10.435 1.75 − 7.635 36,500 6.98 360 720 41.81 37.37 10 9 3 −6 19 3.5DCl4MCA 1 C H Cl O 247.08 128.70 356.76 70.28 8.38·10 3.162 3.44 11.205 1.973 − 7.765 25,800 8.1 900 1.8e + 003 105.91 93.34 10 8 2 3 20 3.5DCl4MBA 1 C H Cl O 205.04 63.98 277.85 96.55 0.00271 46.95 3.08 7.829 1.803 − 4.749 132 14.2 900 1.8e + 003 101.28 270.76 8 6 2 2 21 3Cl4MP 1 C H ClO 158.59 51.00 241.49 3238 0.0103 10.55 2.24 8.238 2.499 − 5.998 151 12.1 900 1.8e + 003 87.81 187.43 7 7 2 22 2.5DCl4MP 1 C H Cl O 193.03 67.83 269.20 623.1 0.00379 13.17 2.88 9.008 2.717 − 6.128 1640 37.2 900 1.8e + 003 100.89 330.32 7 6 2 2 −7 8 23 TP 3C H O 198.18 152.73 371.83 9287 1.35·10 3.162 0.80 18.901 3.458 − 18.105 2.64·10 1.04 360 720 31.72 37.37 199 9 10 5 −7 24 TP 3C H O 306.41 141.55 395.38 1.221 1.54·10 2500 5.32 13.441 4.308 − 8.121 19,700 1.06 360 720 43.27 846.70 307e 18 26 4 −7 25 TP 3C H O 306.41 141.55 395.38 0.5314 1.54·10 1588 5.07 13.191 4.308 − 8.121 8560 3.75 360 720 43.26 634.76 307f 18 26 4 −6 26 TP 3C H O 304.39 124.33 383.31 7.226 2.17·10 154.6 3.75 11.306 3.031 − 7.556 8310 4.09 900 1.8e + 003 107.01 93.33 305a 18 26 4 −6 27 TP 3C H O 304.39 129.46 389.96 2.402 1.31·10 417.5 4.31 11.609 3.155 − 7.299 4580 2.86 900 1.8e + 003 100.75 93.35 305b 18 26 4 −5 28 TP 3C H O 304.39 90.85 348.94 2.186 3.24·10 454.6 4.36 9.312 3.217 − 4.952 168 4.51 900 1.8e + 003 107.71 92.91 305c 18 26 4 −6 29 TP 3C H O 304.39 129.46 389.96 2.402 1.31·10 417.5 4.31 11.609 3.155 − 7.299 4580 3.02 900 1.8e + 003 107.82 101.10 305d 18 26 4 −6 30 TP 3C H O 304.39 124.33 383.11 7.226 2.17·10 154.6 3.75 11.306 3.05 − 7.556 8310 3.82 900 1.8e + 003 107.01 93.34 305e 18 26 4 −6 31 TP 3C H O 304.39 124.33 383.31 7.226 2.17·10 154.6 3.75 11.306 3.06 − 8.121 8310 3.75 360 720 43.09 44.32 305f 18 26 4 −12 10 32 TP 3C H O 468.60 246.19 571.92 0.012 1.58·10 56.23 6.27 19.064 3.817 − 12.794 4.23·10 2.93 900 1.8e + 003 108.14 2373.53 469a 28 36 6 −12 10 33 TP 3C H O 468.60 246.19 571.92 0.012 1.58·10 56.23 6.27 19.064 3.817 − 12.794 4.23·10 2.93 900 1.8e + 003 108.14 2373.53 469b 28 36 6 −12 5 34 DIAMC 8 C H O 496.65 243.43 566.01 0.009 2.42·10 5410 5.76 17.679 3.644 − 11.919 5.76·10 2.68 900 1.8e + 003 108.123 1718.79 30 40 6 −5 −14 5 35 TP 2, 3, 8 C H O 580.81 269.42 621.64 1.057·10 4.12·10 15.03 8.56 19.742 5.167 − 11.182 3.36·10 2.18 1.44e + 003 2.88e + 003 173.03 2857.92 581b 36 52 6 1 Gackowska et al. (2014), 2 MacManus-Spencer et al. (2011), 3 Jentzsch et al. (2016), 4 Gackowska et al. (2016), 5 Serpone et al. (2002), 6 Nakajima et al. (2009), 7 Santos et al. (2013), 8 Rodil et al. (2009) 16042 Environ Sci Pollut Res (2018) 25:16037–16049 products can be classified as medium- or low-volatility com- toxicity to aquatic organisms (USEPA 1991;EC 2001;Xing pounds (BP > 184 °C). Medium-volatility compounds are: et al. 2012;) and potentially carcinogenic properties, the inter- EHA; 1Cl4MB; 1,3DC2MB and 2EHCA (BP 184–216 °C). national environmental organisations (WHO, UNEP, USEPA, The above-mentioned products are also characterised by the EC) included chlorophenols into a group of pollutants with a highest vapour pressure value, which ranges from 0.164 to special risk to the environment (WHO 1989; WHO 2003; 0.409 mmHg. Other products TP ,TP , DIAMC and UNEP 2001;USEPA 1991,USEPA 2014;EC 2001). These 469a 469b TP belong to the group of low-volatility compounds. On compounds were identified in surface water and groundwater 581b the basis of the BP and VP, these transformation products have (He et al. 2000;Czaplicka 2004; Gao et al. 2008; Sim et al. no predisposition to evaporate and be in gas phase (Table 3). 2009). An example of drinking water pollution with chlorophenol (including 2,4,6TClP) in Finland shows how many effects can be caused by EHMC transformation products, Water solubility where an increased incidence of gastrointestinal infections, asthma and depression morbidity was observed (Lampi 1992). High solubility in water suggests that pollutants can migrate with water over long distances. Hydrophilic compounds also have the ability to be readily absorbed by plants. These pol- Octanol/water partition coefficient lutants can be phytotoxic by damaging shoots and roots, re- ducing plant growth and disturbing transpiration (Yu-Hong Logarithmic value of octanol/water partition coefficient (log and Yong-Guan, 2006). In turn, pollutants with low solubility K ) allows determining quantitatively lipophilic character of OW can accumulate in sediments. the compound. Octanol is considered as a representative of Analysis of the results indicates that the products (besides organic matter. Analysis of the results obtained showed that Z-EHMC, EHMCCl, TP ,TP , DIAMC and TP )are log K EHMC was higher than 5 (Fig. 2). The value obtain- 469a 469b 581b OW characterised by significantly better water solubility than the ed is consistent with the data presented by Ramos et al. (2015). substrate (Fig. 1). Water solubility of EHMC at temperature of EHMC has lipophilic properties and can accumulate in −1 25 °C is lower than 0.1548 mg L . Considerably higher sol- sediments. Kupper et al. (2006) and Liu et al. (2012)showed 3 2 ubility (1.0 × 10 ≥ S ≤ 1.0 × 10 ) has the following oxidation that EHMC concentration in raw sludge is within the range products: EHA and 4MCA, and chlorination products: from 13 to 14.45 ng/g dw; however, Langford et al. (2015) 1Cl4MB; 1,3DCl2MB; 3Cl4MBA; 2,4,6TCP; reported that it was up to 4689 ng/g dw in treated sludge. The 3,5DCl2HAcP; 3Cl4MCA and 2,5DCl4MP. Metabolites very differences in concentration among authors is due to the var- 4 −1 well soluble in water (S ≤ 1.0 × 10 mg L ) are 4MBA; 4MP; iable composition of the sludge used, and more likely results 2,4DClP; 2,6DC1,4BQ; 3Cl4MP and TP .It should be not- from the variable organic matter content they had. ed that compounds with an OH and Cl group have high S A similar lipophilic character has most of the analysed values. This pattern indicates that the partitioning potential products for which the calculated coefficient log K >3. OW from water to air of such chemicals is quite low. Among EHMCCl, EHMCCl2, TP ,TP and TP for which 469a 469b 581b EHMC transformation products, 2,4-dichlorophenol log K > 6 deserve a special attention. A different character OW (2,4DClP), 2,4,6-trichlorophenol (2,4,6TClP) and benzene have the products of EHMC oxidation: EHA; 4 MCA; 4MP; chloroderivatives deserve special attention. Due to their high 3Cl4MBA; 2,6DCl1,4BQ; 1Cl4MB; 3Cl4MCA; 3Cl4MP; Fig. 1 Water solubility of EHMC transformation products Environ Sci Pollut Res (2018) 25:16037–16049 16043 Fig. 2 Octanol/water coefficient (log K ) of EHMC transformation products OW 2,5DCl4MP and TP (Fig. 2). Soluble compounds (log 2015). BCF of analysed products with hydrophylic character K < 3) will not accumulate in organisms, soil or sediments is in the range of 1.7 < BCF < 56. These include OW but instead will be contaminating all water sources and thus chloroderivatives of phenols, methoxybenzene or spreading around larger areas. Cinnamic acid derivatives with methoxycinnamic acid. For this group of compounds, no dis- high log K values show high phytotoxic potential tinct relationship between log K and BCF was observed. OW OW (Jitareanu et al. 2011). According to Legierse et al. (1998), The bioconcentration ability of EHMC was confirmed by the rate of absorption of chloroderivatives by snails is directly Fent et al. (2010). EHMC was identified in fish, cormorants proportional to log K . and shellfish on a level of nanograms per gram and OW chlorophenols were present in urine, umbilical cord blood Bioconcentration factor and mother’s milk (Sandau et al. 2002; Bradman et al. 2003; Hong et al. 2005; Philippat et al. 2013; Kim et al. 2014; Forde et al. 2015). These compounds can cause unfavourable histo- The ability of pollutants to bioconcentrate in living organisms is one of parameters taken into account in assessing a threat pathological, genotoxic, mutagenic and carcinogenic effects in humans and animals (Igbinosa et al. 2013). Other metabo- posed by the new environmental pollutants. For many com- pounds, there is a linear relationship between log K and lites that accumulate in the food chains and are ultimately OW identified in human adipose tissue, breast milk and blood are bioconcentration factor (BCF), but this is not a rule, and each example should be considered separately (Axelman et al. chlorobenzenes (Ivanciuc et al. 2005;Tor 2006;Kozani etal. 2007). Because EHMC transformations result in formation of 1995). Analysis of products showed that EHMC chloroderivatives (EHMCCl and EHMCCl )were many chloroorganic compounds at low concentrations, it should be checked how BCF of the mixture of products will characterised by high bioconcentration factor (BCF > 600) (Fig. 3). These are compounds with hydrophobic properties change. According to Kondo et al. (2005), BCF of the mixture of chloroorganic compounds can be significantly higher than (log K > 5). It is accepted that adipose tissue of living or- OW that of a single substance. ganisms is the place where the hydrophobic organic com- pounds are accumulated. Hydrophobicity is the principal de- termining factor of bioconcentration and plays a very impor- Overall persistence and long-range transport tant role in the bioconcentration of hydrophobic organic com- potential pounds (Wang et al. 2014). Hydrophilic compounds appear instead in soluble phases inside the organisms, such as blood As the environmental overall persistence (P ) and long- OV serum and mother’s milk (Armitage et al. 2013). They appear range transport potential (LRTP) of all transformation prod- also in eggs (Lopez-Antia et al. 2017). They affect not only ucts cannot be determined in laboratory experiment, they have animals but also plants, where they appear in all plant tissues, to be calculated utilising physical–chemical parameters such including sap and nectar, and thus constitute a major problem as n-octanol/water (log K ), n-octanol/air (log K ) and air/ OW OA in environmental contamination nowadays (Bonmatin et al. water (log K ) partition coefficients, as well as half-lives in AW 16044 Environ Sci Pollut Res (2018) 25:16037–16049 Fig. 3 Bioconcentration factor (BCF) of EHMC transformation products with the highest BCF value air, water, and soil and molar masses of compounds calculated with the increase of chlorine atoms in molecule. The impact of by EPI Suite (Mackay and Webster 2006;Mostrągetal. 2010; the compound structure, molar mass and type of atom in the Kuramochi et al. 2014). P and LRTP of all the products and individual molecules was described by Mostrągetal. (2010). In OV EHMC were calculated by P and LRTP Screening Tool their opinion, there is a relationship between the long-range OV created by OECD. The tool requires estimated degradation transport potential of pollutants and presence of halogens (Cl, half-lives in soil, water and air, and partition coefficients be- F, Br) in the molecule. However, each group of compounds tween air and water and between octanol and water as chem- should be analysed individually. Other products that can be ical specific input parameters. From these inputs, the tool cal- transported over considerable distances in the environment are culates metrics of P and LRTP from a multimedia chemical photodegradation products formed by the path of dimerization OV fate model and provides a graphical presentation of the results. (TP ,TP ,TP , dIAMC) (Vione et al. 2015). These 469a 469b 581b Studies on the environmental mobility of products showed compounds can travel up to 3000 km in the environment that the highest long-range transport potential expressed by (Table 3). EHMC oxidation products (4MBA, 4MP, TP ) 305a–f characteristic travel distance (CTD) was observed for can be transported over much shorter distances. Similar rela- methoxyphenol chloroderivatives, then methoxybenzene tionships are observed in the case of the overall persistence. The chloroderivatives, EHMC chloroderivatives, methoxybenzal most durable are chloroorganic products. P of these com- OV dehyde chloroderivatives and methoxycinnamate acid pounds is in the range of 100–170 days. Similarly, EHMC chloroderivatives (S Fig. 9). It was observed that CTD increases oxidation products (TP ) are also stable (S Fig. 10). On 305a–f Fig. 4 P and LRTP of the OV selected EHMC transformation products calculated by the OECD P and LRTP Screening Tool OV using property date from EPI Suite Environ Sci Pollut Res (2018) 25:16037–16049 16045 Fig. 5 Toxic effect of the systems studied, determined by Microtox® test after 90 min of reaction the basis of LRTP and P values obtained, it can be deter- 90 min of reaction. The toxicity classification of the mixture OV mined to which class of persistent organic pollutants (POPs) the of products was performed based on the magnitude of effects tested products are classified. Klasmeier et al. (2006) deter- observed in the indicator organisms. The toxicity classification mined the critical values of LRTP and P and divided pollut- system is presented in Table 4. Such a system is used by many OV ants into four classes: I class—persistent organic pollutants researchers (Põllumaa et al. 2004; Ricco et al. 2004; Werle and (POP-like) (pollutants of the Bhighest priority^), both parame- Dudziak 2013). EHMC is characterised by low toxicity; toxic ters are higher than the critical value; II and III classes—mole- effect is lower than 30% (S Figs. 13 and 14). The acute toxicity cules which have POP-like characteristic for one of the refer- shows the products formed as a result of EHMC reaction with ence parameters, (pollutants of Bintermediate priority^)and IV NaOCl and UV. After 1.5-h-lasting reaction, toxic effect is class—pollutants with LRTP and P lower than critical value higher than 90%. In the system with hydrogen peroxide and OV (compounds of the Blowest priority^). LRTP and P values of UV, the toxic products are formed. The effect is on the level OV the products studied are lower than the critical value (P — of 75%. Low toxicity was observed in the system in which OV 195 days, LRTP—5096.73 km); therefore, they can be classi- EHMC was exposed to UV. Toxic effect was about 30%. fied into IV class (Fig. 4). Similar results were obtained using tests with Daphnia manga and Artemia Salina (S Figs. 15–17). Studies have shown that Toxicity testing the presence of oxidizing and chlorinating agents affects the increase of toxicity of EHMC photodegradation products. A Toxicity of products was estimated by monitoring changes in similar effect of additional factors was observed by Vione the natural emission of the luminescent bacteria Aliivibrio et al. (2015). They have found that in the presence of TiO fisheri and by observation of mortality of juvenile crustaceans and UV, toxicity of photoproducts increased by 40–50% with Daphnia magna and Artemia Salina treated with solutions respect to EHMC. containing EHMC transformation products. The reaction mix- A distinct increase in toxicological response of products, in tures EHMC/UV, EHMC/H O /UV and EHMC/NaOCl/UV the case of hydrogen peroxide and sodium hypochlorite, can 2 2 were tested after different times of reaction (S Figs. 11–17). be explained by formation of cinnamic acid derivatives, In order to eliminate the effects of reagents, tests for reaction among others (esters, aldehydes and alcohols). These systems with/without EHMC were performed. Based on the difference in results obtained, the toxicity of the mixture of Table 4 Sample toxicity transformation products was determined. Toxicity [%] Classification classification system Analysis of solutions from systems containing only oxidiz- (Ricco et al. 2004; ing agents (NaOCl/UV, H O /UV) showed a slight toxic effect 2 2 <25 Not toxic Põllumaa et al. 2014) (S Figs. 11 and 12). After an hour of reaction, the toxic effect is 25–50 Low toxicity close to zero. Figure 5 presents percentage of toxic effect of the 50.1–75 Toxicity systems studied (EHMC, EHMC/UV, EHMC/H O /UV, 2 2 75.1–100 High toxicity EHMC/NaOCl/UV), determined by Microtox®testafter 16046 Environ Sci Pollut Res (2018) 25:16037–16049 Fig. 6 EC concentration of the systems studied (determined by Microtox® after 180 min of reaction) compounds have strong toxic action for some bacterial and 60 days in water or 180 days in soil, respectively, are used to fungal species (Narasimhan et al. 2004;Guzman 2014). The identify chemicals with high potential to be persistent in the highest toxicity in the EHMC/NaOCl/UV system can be at- environment, and a half-life of longer than 2 days in air is the tributed to formation of chloroorganic products. On the exam- screening criterion for atmospheric LRTP (Klasmeier et al. ple of chlorophenols and chlorobenzene, it was found that the 2006). Products such as chlorobenzene and chlorophenol de- toxicity increases with the increase in the number of chlorine rivatives have tair1/2 values longer than 2 days and tsoil1/2 atoms in molecule (Pepelko et al. 2005; Zhang et al. 2016). values longer than 6 months. In addition, they are the com- The difference in results between the Microtox® (bacteria) pounds with proven mutagenic and carcinogenic effect in and the other two kits is due to the higher sensitivity of water humans and animals (Igbinosa et al. 2013). Comprehensive risk crustaceans (both Daphnia and Artemia) (S Figs. 13–17). assessment also included studies on toxicity of the products Moreover, toxicological potential of the tested systems formed. We observed that oxidation and chlorination products expressedbyEC , calculated in milligrams per liter, was eval- of EHMC show significantly higher toxicity than EHMC alone. −1 uated (Fig. 6). EC value was 0.15 mg L for EHMC/H O / It was found that chloroorganic products are a greater environ- 50 2 2 −1 UV and 0.094 mg L for EHMC/NaOCl/UV, respectively. mental hazard. They are characterised by higher toxicity in the These values are significantly lower than EC obtained for environment than oxidation products. −1 EHMC (0.4 mg L ) using bacteria Aliivibrio fisheri. The results obtained can be a valuable information in the context of assessing the quality of water resources, especial- ly in countries where water shortages are replenished by treated sewage. Incomplete removal of EHMC in conven- Conclusions tional wastewater treatment plants (Ekpeghere et al. 2016) indicates that this compound is recalcitrant and contami- As a result of the EHMC transformations, a number of products nates the environment. Analysis of the risk of environmen- with different properties other than the substrate are produced. tal pollution by new pollutants and their transformation Two main classes of EHMC degradation products have been products can be useful in assessing water quality in order identified. The first includes oxidation products, which due to to ensure maximum safety for water resources. their hydrophilic character disperse in water, and some of them can evaporate into the air. Whereas, the second class includes Open Access This article is distributed under the terms of the Creative chloroorganic products that probably disperse in air and water Commons Attribution 4.0 International License (http:// andcanaccumulateinanadiposetissueoflivingorganisms. creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give Both of them can reach anywhere on the planet, so both are a appropriate credit to the original author(s) and the source, provide a link cause of concern. However, it is only their persistence and to the Creative Commons license, and indicate if changes were made. toxicity that can make them problematic. Oxidation products are characterised by a relatively low durability and small range References of dispersal in the environment. Much more harmful to the environment are EHMC chlorination products. Based on the Armitage JM, Arnot JA, Wania F, Mackay D (2013) Development and guidelines established in Convention Stockholm (2001), the evaluation of a mechanistic bioconcentration model for ionogenic identified chloroorganic products show the properties of persis- organic chemicals in fish. Environ Toxicol Chem 32:115–128. tent organic pollutants. Degradation half-lives of more than https://doi.org/10.1002/etc.2020 Environ Sci Pollut Res (2018) 25:16037–16049 16047 Axelman J, Broman D, Näf C, Pettersen H (1995) Compound depen- the list of priority substances in the field of water policy and amending Directive 2000/60/EC (L 331 of 15-12-2001) dence of the relationship log K(ow) and log BCF L : a comparison between chlorobenzenes (CBs) for rainbow trout and polycyclic Fent K, Zenker A, Rapp M (2010) Widespread occurrence of estrogenic aromatic hydrocarbons (PAHs) for Daphnia. Environ Sci Pollut UV-filters in aquatic ecosystems in Switzerland. Environ Pollut 158: Res Int 2:33–36. https://doi.org/10.1007/BF02987509 1817–1824. https://doi.org/10.1016/j.envpol.2009.11.005 Barón E, Gago-Ferrero P, Gorga M, Rudolph I, Mendoza G, Zapate AM, Ferrari H, Chen R, Lavezza C, Santinelli I, Longo E, Bramanti (2013) Díaz-Cruz S, Barra R, Ocampo-Duque W, Páez M, Dabra RM, Photodegradation of rhodamine B using the microwave/UV/H O : 2 2 Eljarrat E, Barceló D (2013) Occurrence of hydrophobic organic effect of temperature. Int J Photoenergy 2013:1–12. https://doi.org/ pollutants (BFRs and UV-filters) in sediments from South 10.1155/2013/854857 America. Chemosphere 92:309–316. https://doi.org/10.1016/j. Forde MS, Robertson L, Laouan Sidi EA, Côté S, Gaudreau E, Drescher chemosphere.2013.03.032 O, Ayotte P (2015) Evaluation of exposure to organophosphate, Bohdziewicz J, Dudziak M, Kamińska G, Kudlek E (2016) carbamate, phenoxy acid, and chlorophenol pesticides in pregnant Chromatographic determination and toxicological potential evalua- women from 10 Caribbean countries. Environ Sci Process Impacts tion of selected micropollutants in aquatic environment—analytical 17:1661–1671. https://doi.org/10.1039/c5em00247h problems. Desalin Water Treat 57:1361–1369. https://doi.org/10. Gackowska A, Przybyłek M, Studziński W, Gaca J (2014) Experimental 1080/19443994.2015.1017325 and theoretical studies on the photodegradation of 2-ethylhexyl 4- Bonmatin J-M, Giorio C, Girolami V, Goulson D, Kreutzweiser DP, methoxycinnamate in the presence of reactive oxygen and chlorine Krupke C, Liess M, Long E, Marzaro M, Mitchell EAD, Noome species. Cent Eur J Chem 12:612–623. https://doi.org/10.2478/ DA, Simon-Delso N, Tapparo A (2015) Environmental fate and s11532-014-0522-6 exposure; neonicotinoids and fipronil. Environ Sci Pollut Res 22: Gackowska A, Przybyłek M, Studziński W, Gaca J (2016) Formation of 35–67. https://doi.org/10.1007/s11356-014-3332-7 chlorinated breakdown products during degradation of sunscreen Bradman A, Barr DB, Claus Henn BG, Drumheller T, Curry C, Eskenazi agent, 2-ethylhexyl-4 methoxycinnamate in the presence of sodium B (2003) Measurement of pesticides and other toxicants in amniotic hypochlorite. Environ Sci Pollut Res 23:1886–1897. https://doi.org/ fluid as a potential biomarker of prenatal exposure: a validation 10.1007/s11356-015-5444-0 study. Environ Health Perspec 111:1179–1782. https://doi.org/10. Gao J, Liu L, Liu X, Zhou H, Huang S, Wang Z (2008) Levels and spatial 1289/ehp.6259 distribution of chlorophenols-2,4-dichlorophenol, 2,4,6- Christiansson A, Eriksson J, Teclechiel D, Bergman Å (2009) trichlorophenol, and pentachlorophenol in surface water of China. Identification and quantification of products formed via photolysis Chemosphere 71:1181–1187. https://doi.org/10.1016/j. of decabromodiphenyl ether. Environ Sci Pollut Re 16:312–321. chemosphere.2007.10.018 https://doi.org/10.1007/s11356-009-0150-4 Gilbert E, Pirot F, Bertholle V, Falson F, Padois K (2013) Commonly used Cuderman P, Heath E (2007) Determination of UV filters and antimicro- UV filter toxicity on biological functions: review of last decade bial agents in environmental water samples. Anal Bioanal Chem studies. Int J Cosmetic Sci 35:208–219. https://doi.org/10.1111/ics. 387:1343–1350. https://doi.org/10.1007/s00216-006-0927-y 12030 Czaplicka M (2004) Sources and transformations of chlorophenols in the Guzman JD (2014) Natural cinnamic acids, synthetic derivatives and natural environment. Sci Total Environ 322:21–39. https://doi.org/ hybrids with antimicrobial activity. Molecules 19:19292–19349. 10.1016/j.scitotenv.2003.09.015 https://doi.org/10.3390/molecules191219292 Damiani E, Rosati L, Castagna R, Carloni P, Greci L (2006) Changes in He Y, Wang Y, Lee HK (2000) Trace analysis of ten chlorinated benzenes ultraviolet absorbance and hence in protective efficacy against lipid in water by headspace solid-phase microextraction. J Chromatogr A peroxidation of organic sunscreens after UVA irradiation. J 874:149–154. https://doi.org/10.1016/S0021-9673(00)00067-4 Photochem Photobiol B 82:204–213. https://doi.org/10.1016/j. Hong H, Zhou H, Luan T, Lan C (2005) Residue of pentachlorophenol in jphotobiol.2005.03.011 freshwater sediments and human breast milk collected from the De la Cruz N, Giménez J, Esplugas S, Grandjean D, de Alencastro LF Pearl River Delta, China. Environ Int 31:643–649. https://doi.org/ (2012) Degradation of 32 emergent contaminants by UVand neutral 10.1016/j.envint.2004.11.002 photo-Fenton in domestic wastewater effluent previously treated by Hsieh C-Y, Tsai M-H, Ryan DK, Pancorbo OC (2004) Toxicity of the 13 activated sludge. Water Res 46:1947–1957. https://doi.org/10.1016/ priority pollutant metals to Vibrio fisheri in the Microtox® chronic j.watres.2012.01.014 toxicity test. Sci Total Environ 320:37–50. https://doi.org/10.1016/ Diaz-Cruz MS, Gago-Ferrero P, Liorca M, Barcelo D (2012) Analysis of S0048-9697(03)00451-0 UV filters in tap water and other clean waters in Spain. Anal Bioanal Igbinosa EO, Odjadjare EE Chigor VN, Igbinosa IH, Emoghene AO, Chem 402:2325–2333. https://doi.org/10.1007/s00216-011-5560-8 Ekhaise FO, Igiehon NO, Idemudia OG (2013) Toxicological pro- DIRECTIVE 2008/105/EC OF THE EUROPEAN PARLIAMENTAND file of chlorophenols and their derivatives in the environment: the OF THE COUNCIL of 16 December 2008 on environmental quality public health perspective. Sci World J 2013:1–11. https://doi.org/10. standards in the field of water policy, amending and subsequently 1155/2013/460215 repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/ Ivanciuc T, Ivanciuc O, Klein DJ (2005) Posetic quantitative EEC, 84/491/EEC, 86/280/EEC and amending Directive 2000/60/ superstructure/activity relationships (QSSARs) for chlorobenzenes. EC of the European Parliament and of the Council J Chem Inf Model 45:870–879. https://doi.org/10.1021/ci0501342 Ekpeghere KI, Kim U-J, S-H O, Kim H-Y Oh J-E (2016) Distribution and Janjua NR, Kongshoj B, Andersson AM, Wulf HC (2008) Sunscreens in seasonal occurrence of UV filters in rivers and wastewater treatment human plasma and urine after repeated whole-body topical applica- plants in Korea. Sci Total Environ 542:121–128. https://doi.org/10. tion. J Eur Acad Dermatol Venereol 22:456–461. https://doi.org/10. 1016/j.scitotenv.2015.10.033 1111/j.1468-3083.2007.02492.x EU 2015/495- COMMISSION IMPLEMENTING DECISION (EU) Ji Y, Zhou L, Zhang Y, Ferronato C, Brigante M, Mailhot G, Yang X, 2015/495 of 20 March 2015 establishing a watch list of substances Chovelon J-M (2013) Photochemical degradation of sunscreen for Union-wide monitoring in the field of water policy pursuant to agent 2- phenylbenzimidazole-5-sulfonic acid in different water ma- Directive 2008/105/EC of the European Parliament and of the trices. Water Res 47:5865–5875. https://doi.org/10.1016/j.watres. Council 2013.07.009 European Commission (EC) Decision 2455/2001/EC of the European Ji tăreanu A, Tataringa G, Zbancioc AM, Stănescu U (2011) Toxicity of Parliament and of the Council of November 20, 2001 establishing some cinnamic acid derivatives to common bean (Phaseolus 16048 Environ Sci Pollut Res (2018) 25:16037–16049 vulgaris). Not Bot Horti Agrobo 39:130–134 https://doi.org/10. Loraine GA, Pettigrove ME (2006) Seasonal variations in concentrations 15835/nbha3927183 of pharmaceuticals and personal care products in drinking water and Kikuchi A, Saito H, Mori M, Yagi M (2011) Photoexcited triplet states of reclaimed wastewater in southern. California. Environ Sci Technol 40:687−695–687−695. https://doi.org/10.1021/es051380x new UV absorbers, cinnamic acid 2-methylphenyl esters. Photochem Photobiol Sci 10:1902–1909. https://doi.org/10.1039/ Mackay D, Webster E (2006) Environmental persistence of chemicals. C1PP05168G Environ Sci Pollut Res 13:43–49. https://doi.org/10.1065/espr2006. 01.008 Kim K, Park H, Lee JH (2014) Urinary concentrations of trichlorophenols in the Korean adult population: results of the national human bio- MacManus-Spencer LA, Tse ML, Klein JL, Kracunas AE (2011) Aqueous photolysis of the organic ultraviolet filter chemical octyl monitoring survey 2009. Environ Sci Pollut Res Int 21:2479–2485. https://doi.org/10.1007/s11356-013-2180-1 methoxycinnamate. Environ Sci Technol 45:3931–3937. https://doi. org/10.1021/es103682a Klasmeier J, Matthies M, Macleod M, Scheringer M, Stroebe M, Fenner K, Le Gall AC, Mckone T, Van De Meent D, Wania F (2006) Mostrąg A, Puzyn T, Haranczyk M (2010) Modeling the overall persis- Application of multimedia models for screening assessment of tence and environmental mobility of sulfur-containing long-range transport potential and overall persistence. Environ Sci polychlorinated organic compounds. Environ Sci Res 17:470–477. Technol 40:53–60. https://doi.org/10.1021/es0512024 https://doi.org/10.1007/s11356-009-0257-7 Nakajima M, Kawakami T, Niino T, Takahashi Y, Onodera S (2009) Kondo T, Yamamoto H, Tatarazako N, Kawabe K, Koshio M, Hirai N, Morita M (2005) Bioconcentration factor of relatively low concen- Aquatic fate of sunscreen agents octyl-4-methoxycinnamate and trations of chlorophenols in Japanese medaka. Chemosphere 61: octyl-4-dimethylaminobenzoate in model swimming pools and the 1299–1304. https://doi.org/10.1016/j.chemosphere.2005.03.058 mutagenic assays of their chlorination byproducts. J Health Sci 55: Kozani RR, Assadi Y, Shemirani F, Hosseini MRM, Jamali MR (2007) 363–372. https://doi.org/10.1248/jhs.55.363 Part-per-trillion determination of chlorobenzenes in water using dis- Narasimhan B, Belsare D, Pharande D, Mourya V, Dhake A (2004) persive liquid–liquid microextraction combined gas Esters, amides and substituted derivatives of cinnamic acid: synthe- chromatography-electron capture detection. Talanta 72:387–393. sis, antimicrobial activity and QSAR investigations. Eur J Med https://doi.org/10.1016/j.talanta.2006.10.039 Chem 39:827–834. https://doi.org/10.1016/j.ejmech.2004.06.013 Kudlek E, Dudziak M, Bohdziewicz J (2016) Influence of inorganic ions Pepelko WE, Gaylor DW, Mukeriee D (2005) Comparative toxic potency and organic substances on the degradation of pharmaceutical com- ranking of chlorophenols. Toxicol Ind Health 21:93–111. https://doi. pound in water matrix. Water 8:532–550. https://doi.org/10.3390/ org/10.1191/0748233705th204oa w8110532 Philippat C, Wolff MS, Calafat AM, Ye X, Bausell R, Meadows M, Stone Kupper T, Plagellat C, Brändli RC, de Alencastro LF, Grandjean D, J, Slama R, Engel SM (2013) Prenatal exposure to environmental Tarradellas J (2006) Fate and removal of polycyclic musks, UV phenols: concentrations in amniotic fluid and variability in urinary filters and biocides during wastewater treatment. Water Res 40: concentrations during pregnancy. Environ Health Perspect 121: 2603–2612. https://doi.org/10.1016/j.watres.2006.04.012 1225–1231. https://doi.org/10.1289/ehp.1206335 Kuramochi H, Takigami H, Scheringer M, Sakai S (2014) Estimation of Poiger T, Buser H-R, Balmer ME, Bergqvist P-A, Müller MD (2004) physicochemical properties of 52 non-PBDE brominated flame re- Occurrence of UV filter compounds from sunscreens in surface tardants and evaluation of their overall persistence and long-range waters: regional mass balance in two Swiss lakes. Chemosphere transport potential. Sci Total Environ 491-492:108–117. https://doi. 55:951–963. https://doi.org/10.1016/j.chemosphere.2004.01.012 org/10.1016/j.scitotenv.2014.04.004 Põllumaa L, Kahru A, Manusadzianas L (2014) Biotest- and chemistry- Lampi P (1992) Cancer incidence following chlorophenol exposure in a based hazard assessment of soils, sediments and solid wastes. J Soil community in Southen Finland. Arch Environ Health 47:167–175. Sci 4:267–275. https://doi.org/10.1007/BF02991123 https://doi.org/10.1080/00039896.1992.9938346 Ramos S, Homem V, Alves A, Santos L (2015) Advances in analytical Langford KH, Reid MJ, Fjeld E, Øxnevad S, Thomas KV (2015) methods and occurrence of organic UV-filters in the environment— Environmental occurrence and risk of organic UV filters and stabi- a review. Sci Total Environ 526:278–311. https://doi.org/10.1016/j. lizers in multiple matrices in Norway. Environ Int 80:1–7. https:// scitotenv.2015.04.055 doi.org/10.1016/j.envint.2015.03.012 Ricco G, Tomei MC, Ramadori R, Laera G (2004) Toxicity assessment of Legierse KCHM, Sijm DTHM, van Leeuwen CJ, Seinen W, Hermens common xenobiotic compounds on municipal activated sludge: JLM (1998) Bioconcentration kinetics of chlorobenzenes and the comparison between respirometry and Microtox®. Water Res 38: organophosphorus pesticide chlorthion in the pond snail Lymnaea 2103–2110. https://doi.org/10.1016/j.watres.2004.01.020 stagnalis—a comparison with the guppy Poecilia reticulate.Aquat Rodil R, Moeder M, Altenburgr R, Schmitt-Jansen M (2009) Toxicol 41:301–323. https://doi.org/10.1016/S0166-445X(97) Photostability and phytotoxicity of sunscreen agents and their deg- 00092-1 radation mixtures in water. Anal Bioanal Chem 395:1513–1524. León Z, Vlieger J, Chisvert A, Salvador A, Lingeman H, Irth H, Giera M https://doi.org/10.1007/s00216-009-3113-1 (2010) Identification of the biotransformation products of 2- Rodil R, Quintana JB, Concha-Graña E, López-Mahía P (2012) ethylhexyl 4-(N,N-dimethylamino) benzoate. Chromatographia 71: Emerging pollutants in sewage, surface and drinking water in 55–63. https://doi.org/10.1365/s10337-009-1386-3 Galicia (NW Spain). Chemosphere 86:1040–1049. https://doi.org/ Li W, Ma Y, Guo C, Hu W, Liu K, Wang Y, Zhu T (2007) Occurrence and 10.1016/j.chemosphere.2011.11.053 behavior of four of the most used sunscreen UV filters in wastewater Rozas O, Vidal C, Baeza C, Jardim WF, Rossner A, Mansilla HD (2016) reclamation plant. Water Res 41:3506–3512. https://doi.org/10. Or ganic micropollutants (OMPs) in natural waters: oxidation by 1016/j.watres.2007.05.039 UV/H O treatment and toxicity assessment. Water Res 98:109– 2 2 Liu YS, Ying G-G, Shareef A, Kookana RS (2012) Occurrence and 118. https://doi.org/10.1016/j.watres.2016.03.069 removal of benzotriazoles and ultraviolet filters in a municipal Sakkas VA, Giokas DL, Lambropoulou DA, Albanis TA (2003) Aqueous wastewater treatment plant. Environ Pollut 165:225–232. https:// photolysis of the sunscreen agent octyl-dimethyl-p-aminobenzoic doi.org/10.1016/j.envpol.2011.10.009 acid Formation of disinfection byproducts in chlorinated swimming Lo pez-Antia A, Dauwe T, Meyer J, Maes K, Bervoets L, Eens M (2017) poolwater. J Chromatogr A 1016:211–222. https://doi.org/10.1016/ S0021-9673(03)01331-1 High levels of PFOS in eggs of three bird species in the neighbourhood of a fluoro-chemical plant. Ecotoxicol Environ Saf Sandau CD, Ayotte P, Dewailly E, Duffe J, Norstrom RJ (2002) Pentachlorophenol and hydroxylated polychlorinated biphenyl 139:165–171. https://doi.org/10.1016/j.ecoenv.2017.01.040 Environ Sci Pollut Res (2018) 25:16037–16049 16049 metabolites in umbilical cord plasma of neonates from coastal pop- swguidance/standards/criteria/current/upload/Draft-Updateof- Human-Health-Ambient-Water-Quality-Criteria-2-Chlorophenol- ulations in Quebec. Environ Health Perspect 110:411–417. https:// doi.org/10.1289/ehp.02110411 95-57-8.pdf Santiago-Morales J, Gómez MJ, Herrera-López S, Fernández-Alba AR, Vasquez MI, Fatta-Kassinos D (2013) Is the evaluation of Btraditional^ García-Calvo E, Rosal R (2013) Energy efficiency for the removal physicochemical parameters sufficient to explain the potential tox- of non-polar pollutants during ultraviolet irradiation, visible light icity of the treated wastewater at sewage treatment plants? Environ photocatalysis and ozonation of a wastewater effluent. Water Res Sci Pollut Res 20:3516–3528. https://doi.org/10.1007/s11356-013- 47:5546–5556. https://doi.org/10.1016/j.watres.2013.06.030 1637-6 Santos AJM, Miranda MS, Esteves da Silva JCG (2012) The degradation Vione D, Calza P, Galli F, Fabbri D, Medana C (2015) The role of direct products of UV filters in aqueous and chlorinated aqueous solutions. photolysis and indirect photochemistry in the environmental fate of Water Res 46:3167–3176. https://doi.org/10.1016/j.watres.2012.03. ethylhexyl methoxy cinnamate (EHMC) in surface water. Sci Total 057 Environ 15:58–68. https://doi.org/10.1016/j.scitotenv.2015.08.002 Schlumpf M, Cotton B, Conscience M, Haller V, Steinmann B, Wang Y, Wen Y, Li JJ, He J, Qin WC, Su LM, Zhao YH (2014) Lichtensteiger W (2001) In vitro and in vivo estrogenicity of UV Investigation on the relationship between bioconcentration factor screens. Environ Health Perspect 109:239–244. https://doi.org/10. and distribution coefficient based on class-based compounds: the 1289/ehp.01109239 factors that affect bioconcentration. Environ Toxicol Pharmacol Sim W, Lee S, Lee I, Choi S, Oh J (2009) Distribution and formation of 38:388–396. https://doi.org/10.1016/j.etap.2014.07.003 chlorophenols and bromophenols in marine and riverine environ- Wegmann F, Cavin L, MacLeod M, Scheringer M, Hungerbuhler K ments. Chemosphere 77:552–558. https://doi.org/10.1016/j. (2009) The OECD software tool for screening chemicals for persis- chemosphere.2009.07.006 tence and long-range transport potential. Environ Model Softw 24: Straub JO (2002) Concentrations of the UV filter ethylhexyl 228–237 methoxycinnamate in the aquatic compartment: a comparison of Werle S, Dudziak M (2013) Evaluation of toxicity of sewage sludge and modelled concentrations for Swiss surface waters with empirical gasification waste-products. Przem Chem 92:1350–1353 (in Polish) monitoring data. Toxicol Lett 131:29–37. https://doi.org/10.1016/ WHO, 1989. Chlorophenols other than pentachlorophenol, environmen- S0378-4274(02)00042-5 tal health criteria 93. International Programme on Chemical Safety Tarazona I, Chisvert A, León Z, Salvador A (2010) Determination of WHO, 2003. Chlorophenols in drinking-water. Background document hydroxylated benzophenone UV filters in sea water samples by for preparation of WHO guidelines for drinking-water quality. dispersive liquid-liquid microextraction followed by gas World Health Organization, Geneva (WHO/SDE/WSH/03.04/47) chromatography-mass spectrometry. J Chromatogr A 1217:4771– Xing L, Sun J, Liu H, Yu H (2012) Combined toxicity of three 4778. https://doi.org/10.1016/j.chroma.2010.05.047 chlorophenols 2,4-dichlorophenol, 2,4,6-trichlorophenol and penta- Tor A (2006) Determination of chlorobenzenes in water by drop-based chlorophenol to Daphnia magna. J Environ Monit 14:1677–1683. liquid-phase microextraction and gas chromatography-electron cap- https://doi.org/10.1039/c2em30185g ture detection. J Chromatogr A 1125:129–132. https://doi.org/10. Yu-Hong S, Yong-Guan Z (2006) Bioconcentration of atrazine and 1016/j.chroma.2006.06.081 chlorophenols into roots and shoots of rice seedlings. Environ UNEP. Stockholm Convention on persistent organic pollutants; United Pollut 139:32–39. https://doi.org/10.1016/j.envpol.2005.04.035 Nations Enviroment Programme: Geneva, Switzerland; 2001. http:// Zhang S, Lin D, Wu F (2016) The effect of natural organic matter on www.pops.int bioaccumulation and toxicity of chlorobenzenes to green algae. J USEPA (United States Environmental Protection Agency), 1991. Water Hazar Mater 5:186–193. https://doi.org/10.1016/j.jhazmat.2016.03. quality criteria summary. Ecological risk assessment branch (WH- 017 585) and human risk assessment branch (WH-550D). Health and Zuloaga O, Navarro P, Bizkarguena E, Iparraguirre A, Vallejo A, Olivares ecological criteria division, USEPA, Washington, DC, USA M, Prieto A (2012) Overview of extraction, clean-up and detection USEPA (United States Environmental Protection Agency), 2014. Update techniques for the determination of organic pollutants in sewage of human health ambient water quality criteria: 2-chlorophenol 95- sludge: a review. Anal Chem Acta 29:7–29. https://doi.org/10. 57-8 draft. Available on line at: http://water.epa.gov/scitech/ 1016/j.aca.2012.05.016 http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Environmental Science and Pollution Research Springer Journals

Estimation of physicochemical properties of 2-ethylhexyl-4-methoxycinnamate (EHMC) degradation products and their toxicological evaluation

Free
13 pages
Loading next page...
 
/lp/springer_journal/estimation-of-physicochemical-properties-of-2-ethylhexyl-4-0TD1YmZKpS
Publisher
Springer Berlin Heidelberg
Copyright
Copyright © 2018 by The Author(s)
Subject
Environment; Environment, general; Environmental Chemistry; Ecotoxicology; Environmental Health; Atmospheric Protection/Air Quality Control/Air Pollution; Waste Water Technology / Water Pollution Control / Water Management / Aquatic Pollution
ISSN
0944-1344
eISSN
1614-7499
D.O.I.
10.1007/s11356-018-1796-6
Publisher site
See Article on Publisher Site

Abstract

The organic UV filters, commonly used in personal protection products, are of concern because of their potential risk to aquatic ecosystems and living organisms. One of UV filters is ethylhexyl-4-methoxycinnamate (EHMC) acid. Studies have shown that, in the presence of oxidizing and chlorinating factors, EHMC forms a series of products with different properties than the substrate. In this study, the toxicities of EHMC and its transformation/degradation products formed under the influence of NaOCl/UV and H O /UV systems in the water medium were tested using Microtox® bioassay and by observation of mortality 2 2 of juvenile crustaceans Daphnia magna and Artemia Salina. We have observed that oxidation and chlorination products of EHMC show significantly higher toxicity than EHMC alone. The toxicity of chemicals is related to their physicochemical characteristic such as lipophilicity and substituent groups. With the increase in lipophilicity of products, expressed as log K , the toxicity (EC ) increases. On the basis of physicochemical properties such as vapour pressure (VP), solubility (S), OW 50 octanol-water partition coefficient (K ), bioconcentration factor (BCF) and half-lives, the overall persistence (P ) and long- OW OV range transport potential (LRTP) of all the products and EHMC were calculated. It was shown that the most persistent and traveling on the long distances in environment are methoxyphenol chloroderivatives, then methoxybenzene chloroderivatives, EHMC chloroderivatives, methoxybenzaldehyde chloroderivatives and methoxycinnamate acid chloroderivatives. These com- pounds are also characterised by high toxicity. . . . . . Keywords EHMC transformation products Physicochemical properties EPI suite P LRTP Toxicity OV Introduction Highlights � Toxicity of EHMC transformation products was studied � Analysis of EHMC transformation products in terms of their persistence Chemical UV filters are used in personal protection products in environment and ability to propagate in air and water to protect our skin from harmful UVradiation. They are one of � Application of the EPI Suite program to determine values of the selected the components of sunscreens, lotions, shampoos, body physicochemical parameters of EHMC and its conversion products washes, hair sprays and protective lipsticks (Ji et al. 2013; Responsible editor: Ester Heath MacManus-Spencer et al. 2011). They are also added to paints Electronic supplementary material The online version of this article and varnishes because they can prevent polymer degradation (https://doi.org/10.1007/s11356-018-1796-6) contains supplementary or pigmentation (Christiansson et al. 2009; Ferrari et al. 2013). material, which is available to authorized users. One of the commonly used UV filter is 2-ethylhexyl-4- methoxycinnamate ester (EHMC) (Kikuchi et al. 2011). * Alicja Gackowska alicja.gackowska@utp.edu.pl EHMC shows a high absorbing capacity in the UVB range. The maximum permissible concentration of EHMC in cos- 1 metic products in the European Union cannot exceed 10% Faculty of Chemical Technology and Engineering, UTP University (Gilbert et al. 2013). Slightly smaller concentration, i.e. of Science and Technology, Seminaryjna 3, 85-326 Bydgoszcz, Poland 7.5%, is valid in the USA (Janjua et al. 2008). The dynamic development of cosmetic industry has resulted Institute of Water and Wastewater Engineering, Silesian University of Technology, Konarskiego 18, 44-100 Gliwice, Poland in a higher consumption of chemical UV filters. Unfortunately, 16038 Environ Sci Pollut Res (2018) 25:16037–16049 it has been observed that the chemical UV filters contribute to products and possible risks associated with their long-range pollution of environment. EHMC has been detected in surface transport in the environment. waters (Straub 2002; Poiger et al. 2004; Tarazona et al. 2010), From the toxicological point of view, the toxicity of EHMC swimming pool waters (Cuderman and Heath 2007; Santos degradation products is mostly unknown. There is no data on et al. 2012), drinking water (Loraine and Pettigrove 2006; the environmental risk assessment of EHMC transformation Diaz-Cruz et al. 2012), wastewater (Damiani et al. 2006;Li products. In some cases, the toxicity of photolytic mixtures et al. 2007; Rodil et al. 2012), sewage sludge (De la Cruz was tested e.g. Vibrio fischeri microtox assay for 4- et al. 2012; Zuloaga et al. 2012; Barón et al. 2013)and even methoxybenzaldehyde that showed higher toxicity than in human breast milk and human urine (León et al. 2010). In EHMC (Vione et al. 2015). It should be noted that EHMC treated wastewater, EHMC was identified at a level of 120– transformation products are formed at low concentrations in 849 ng/L (Ekpeghere et al. 2016). Continuous and uncontrolled complex matrices. Their separation and isolation is laborious emission of the chemical UV filters into environment, even at and difficult to perform. Hence, the toxicity assessment of a low concentrations, is unfavourable as they accumulate in living single product is difficult. The solution is to carry out a biotest organisms. EHMC accumulates in aquatic biota of different for a mixture of compounds. Commonly applied test is trophic levels with concentrations of up to 340 ng/g lipids in Microtox® biotest, which uses natural luminescence of cormorants (Fent et al. 2010). EHMC is known as endocrine Vibrio fisheri exhibiting sensitivity to a wide spectrum of toxic disrupting compound that cause adverse effects on human and organic and inorganic substances. (Hsieh et al. 2004; wildlife. On this basis, the Commission of the European Union Bohdziewicz et al. 2016;Kudlek et al. 2016). (EU 2015/495) placed EHMC on the list of 17 substances sub- Other tests were carried out using the freshwater crustacean jected to monitoring (Directive 2008/105/EC of the European Daphnia magna (Rozas et al. 2016) and the saltwater crusta- Parliament and of the Council). EHMC has estrogenic proper- cean Artemia salina (Vasquez and Fatta-Kassinos 2013). tiesbothin vitro andin vivo(Schlumpf et al. 2001). The aims of the studies were to estimate physicochemical Recent studies have shown that EHMC under sun and UV parameters and to model P and LRTP for EHMC and its OV irradiation forms transformation products (TPs) (MacManus- transformation products formed in oxidation, chlorination and Spencer et al. 2011; Rodil et al. 2009; Santiago-Morales et al. photodegradation processes, simultaneously, to perform vari- 2013; Vione et al. 2015). Under the influence of UV radiation ous ecotoxicological bioassays so as to be able to correlate if and hydrogen peroxide, EHMC is degraded to compounds possible the findings between the physicochemical and bio- which, in the presence of reactive forms of oxygen or chlorine, logical assessments. can produce new products, sometimes even more toxic than the substrates themselves (Sakkas et al. 2003; Gackowska et al. 2014; Gackowska et al. 2016). In turn, in the presence Experimental of sodium hypochlorite used to disinfect pool waters, chloroorganic derivatives of EHMC are formed (Nakajima Materials and methods et al. 2009; Santos et al. 2012;Gackowskaetal. 2016). Understanding the mechanism of EHMC transformations in Materials the environment and the environmental fate of products of these transformations requires knowledge of their physico- Analytical standard of 2-ethylhexyl 4-methoxycinnamate (E- chemical properties such as water solubility (S), octanol- EHMC) (98%) was obtained from ACROS Organics (USA) water partition coefficient (K ), vapour pressure (VP) and and was kept in lightproof container at 4 °C. Sodium hypo- OW bioconcentration factors as well as half-life in air, water and chlorite NaOCl with a nominal free chlorine content of −1 soil. Determination of the properties of all products is time- 100gL and H O (30%) was obtained from POCh 2 2 consuming and sometimes difficult to perform. A useful tool (Poland). The toxicity tests: Microtox®, Daphtoxkit F® and for the determination of physicochemical parameters is EPI Artoxkit M® were purchased from MicroBioTest Inc. Suite. It allows estimating the physicochemical properties of (Belgium). all EHMC transformation products identified so far. Based on the calculated parameters and half-lives, the overall persis- Oxidation processes tence (P ) and long-range transport potential (LRTP) of all OV EHMC transformation products were calculated with the The experimental oxidation processes were performed in a Organization for Economic Cooperation and Development laboratory glass batch reactor with a capacity of 0.7 L of (OECD) P and LRTP Screening Tool (http://www.oecd. Heraeus (Hanau, Germany). The reactor was equipped with OV org/document/24/0,3746,en_2649_34379_45373336_1_1_ an immersion medium pressure UV lamp of 150 W located in 1_1,00.htm; Wegmann et al. 2009). The data obtained provide a cooling jacket made of Duran 50 glass. The cooling process information on potential persistence of the transformation was performed with water from the mains. The cooling Environ Sci Pollut Res (2018) 25:16037–16049 16039 Table 1 The reaction conditions and substrate proportions used in this process enabled a constant temperature of 20 ± 1 °C to be study maintained. The lamp emitted radiation of λ equal to 313, exc 365, 405, 436, 546 and 578 nm. Additionally, the reactor was Reagents EHMC [M] H O [M] NaOCl [M] UV [W] 2 2 situated on a magnetic stirrer to guarantee the even mixing of −4 EHMC 3.4·10 00 – contents during the execution process. The reaction conditions −4 EHMC/UV 3.4·10 0 0 150 are presented in Table 1. −4 −5 EHMC/NaOCl/UV 3.4·10 01.7·10 150 The research subjects were model solutions containing −4 EHMC/H O /UV 3.4·10 0.05 0 150 2 2 deionised water and E-EHMC model. In order to test toxicity −5 NaOCl/UV 0 0 1.7·10 150 of the E-EHMC oxidation and chlorination products, E- −4 H O /UV 0 0.05 0 150 EHMC solution at concentration of 3.4·10 M was prepared 2 2 and subjected to the action of UVonly, H O /UVand NaOCl/ 2 2 UV. The concentration of sodium hypochlorite and hydrogen bacteria to toxic substances, the metabolic changes occur or peroxide were respectively 1.7·10–5 M and 0.05 M. After 30, population of bacteria is reduced, what in turn results in 60, 90 and 180 min, mixtures of the products obtained were change in the intensity of light emitted by microorganisms. sampled from reaction systems and subjected to toxicity tests. The test was conducted according to MicrotoxOmni The effectiveness of E-EHMC elimination was assessed by Screening Test procedure in the Microtox Model 500 analyser monitoring for changes in concentrations of compound in wa- from Tigret Sp. z o.o. (Poland), which operated both as an ter before and after the oxidation process, respectively. incubator and as a photometer. Percentage of bioluminescence inhibition relative to control sample (bacteria not exposed to Method for the determination of EHMC transformation toxicant) was measured after 5 and 15 min of exposure time products (volume of samples 1 mL). The EC value was determined on the basis of the Basic Dilution Test. A GC-MS 5890 HEWLETT PACKARD instrument equipped with column ZB-5MS (0.25 mm × 30 m × 0.25 μm) was used Daphtoxkit F® The test procedure is based on observation of for the identification of the transformation products applying the mortality of juvenile Daphnia magna crustaceans subject- the following chromatographic conditions: injector tempera- ed to the action of toxicant. The results were checked after 24 ture 250 °C, oven temperature program from 80 to 260 °C at and 28 h of exposure of animals to the tested solutions. All 10 °C/min, from 260 to 300 °C (held for 2 min) at a rate of organisms that did not demonstrate a motion reaction to swirl 5 °C min. Helium was used as a carrier gas. The volume of the induced by stirring the solution were considered dead. sample was 1 μL. Reaction products were identified by com- Experiment was carried out in accordance with the OECD paring recorded MS spectra with standard spectra from Guideline 202 and ISO 6341 standards. NIST/EPA/NIH Mass Spectral Library. The detailed descrip- tion of the methodology for identification of EHMC transfor- Artoxkit M® Toxicity of solutions was also tested on Artemia mation products was presented in previous papers Salina crustaceans. Survival of indicatory organisms was (Gackowska et al. 2014; Gackowska et al. 2016). assessed after 24 h of exposure to water solutions. The indi- viduals showing no signs of life were recognised as dead. Test Toxicity tests was conducted according to the ASTM E1440-91 standard. The effect of the toxicity (%) was determined according to All samples from the reactor were diluted 1:100 before the equation: performing toxicity tests. Additionally, control tests were car- ried out. In order to eliminate the effects of the reagents, tests 100∙ðÞ E −E K T E ¼ ; ½ % ð1Þ for E-EHMC-free systems were performed. Moreover, the toxicity tests were performed without EHMC. Changes in the toxicity of samples were assessed on the basis of the results where from three biotests: Microtox®, Daphtoxkit F® and Artoxkit E the effect observed in a blank sample and M®. On the basis of the difference in results obtained for E the effect observed in a test sample. EHMC systems with and without EHMC, the toxicity of the mixture of transformation products was determined. All sam- ples for toxicity tests were performer in four replicates. Depending on the given test, the effect was measured by Microtox® In Microtox® test, bioluminescent bacteria the decrease in bioluminescence (i.e. the enzymatic Aliivibrio fischeri, which are highly sensitive to a wide spec- Microtox® test) or organism viability (i.e. the Daphnia magna trum of toxic substances, were used. During exposure of test and Artemia Salina test). 16040 Environ Sci Pollut Res (2018) 25:16037–16049 The evaluation of results programs jointly developed by the US EPA and Syracuse Research Corp. (SRC). The US EPA develops and uses The results are the arithmetic average of the four replicates of models based on (quantitative) structure-activity relationships each experiment. For all the cases, assigned error (estimated ([Q]SARs) to estimate critical parameters. Structure-activity based on the standard deviation) did not exceed 5%, so the relationship (SAR) and quantitative structure-activity relation- results are presented in the form of error bars. ship (QSAR) models are theoretical models that can be used to quantitatively or qualitatively predict the physicochemical, biological (e.g. an (eco) toxicological endpoint) and environ- Results and discussion mental fate properties of a chemical substance from the knowledge of its chemical structure. The results were presented in Table 3. Analysis of param- Based on the analysis of previous studies, the identified prod- ucts of EHMC transformation have been gathered. These eters has shown that EHMC transformation products are characterised by different properties than the substrate. products have been presented in Supplementary (S Figs. 1– 8) and the listofproductsstudied waspresented in Table 2. In order to make a preliminary assessment of EHMC trans- Boiling point and vapour pressure formation products for potential threats to the environment, their characteristic physicochemical parameters were deter- Boiling point (BP) and vapour pressure (VP) are the parameters mined using EPI Suite program. The EPI (Estimation that provide information on whether the compounds, after en- Programs Interface) Suite™ is a suite of physical/chemical tering the environment, will evaporate into the atmosphere rel- properties, aquatic toxicity and environmental fate estimation atively quickly. Studies have shown that EHMC transformation Table 2 List of chemicals Abbreviation Chemical name No. 1E-EHMC trans 2-Ethylhexyl-4-methoxycinnamate 2 EHA 2-Ethylhexyl alcohol 3 4MCA 4-Methoxycinnamic acid 4 4MBA 4-Methoxybenzaldehyde 5 4MP 4-Methoxyphenol 6 1Cl4MB 1-Chloro-4-methoxybenzene 7 1.3DCl2MB 1.3-Dichloro-2-methoxybenzene 8 2-EHCA 2-Ethylhexyl chloroacetate 9 3Cl4MBA 3-Chloro-4-methoxybenzaldehyde 10 Z-EHMC cis 2-Ethylhexyl-4-methoxycinnamate 11 EHMCCl Chloro-2-Ethylhexyl-4-methoxycinnamate 12 EHMCCl Dichloro-2-Ethylhexyl-4-methoxycinnamate 13 2.4DClP 2.4-Dichlorophenol 14 2.6DCl1.4BQ 2.6-Dichloro-1.4-benzoquinone 15 1.2.4TCl3MB 1.2.4-Trichloro-3-methoxybenzene 16 2.4.6TClP 2.4.6-Trichlorophenol 17 3.5DCl2HAcP 3.5-Dichloro-2-hydroxyacetophenone 18 3Cl4MCA 3-Chloro-4-methoxycinnamic acid 19 3.5DCl4MCA 3.5-Dichloro-4-methoxycinnamic acid 20 3.5DCl4MBA 3.5-Dichloro-4-methoxybenzaldehyde 21 3Cl4MP 3-Chloro-4-methoxyphenol 22 2.5DCl4MP 2.5-Dichloro-4-methoxyphenol 23 TP Transformation product 24 TP Transformation product 307e 25 TP Transformation product 307f 26 TP Transformation product 305a 27 TP Transformation product 305b 28 TP Transformation product 305c 29 TP Transformation product 305d 30 TP Transformation product 305e 31 TP Transformation product 305f 32 TP Transformation product 469a 33 TP Transformation product 469b 34 DIAMC 2.4-bis-((2Z.4E)-4-Methoxyhepta-2.4.6-trienyl)- cyclobutane-1.3-dicarboxylic acid bis- (3-methyl-butyl) ester 35 TP Transformation product 581b Environ Sci Pollut Res (2018) 25:16037–16049 16041 Table 3 Physical–chemical properties of EHMC and its transformation products Compound Molecular Mol wt MP BP S VP Log Log Log Log Henry’sLC Half-life Half-life Half-life P LRTP OV −1 −1 −3 −1 No. References formula [g mol ] [°C] [°C] [mg L ] [mmHg] BCF K = K K K [mol dm atm ] air [h] water [h] soil [h] [days] [km] OW OA OC AW log P −5 1E-EHMC – C H O 290.41 99.87 360.54 0.1548 1.38·10 667.6 5.80 9.938 4.089 − 4.138 29.4 4.17 360 720 43.26 90.80 18 26 3 2EHA 1,2 C H O 130.23 − 70 184.6 880 0.185 25.33 2.73 5.69 1.415 − 2.965 44.9 19.4 208 416 23.02 385.20 8 18 1 −4 34MCA 1,3 C H O 178.19 96 317 712 1.6·10 3.162 2.68 10.19 1.536 − 7.505 19,300 5.02 360 720 41.41 37.37 10 10 3 44MBA 1,2 C H O 136.15 0 248 4290 0.0303 4.521 1.76 6.25 1.367 − 4.489 54,600 10.4 360 720 33.49 204.03 8 8 2 54MP 1 C H O 124.14 57 243 40,000 0.0083 3.285 1.58 7.447 2.28 − 5.867 12,200 8.62 360 720 34.36 150.24 7 8 2 61Cl4MB 4 C H CIO 142.59 ≤ 18 197.5 237 0.409 27.58 2.78 4.796 2.280 − 2.016 4.46 36.1 900 1.8e + 003 40.73 740.0 7 7 71.3DCl2MB 4 C H Cl O 177.03 < 25 215.67 140 0.164 52.22 3.14 5.825 2.508 − 2.145 3.1 96.4 900 1.8e + 003 67.67 1912.83 7 6 2 82-EHCA 4 C H ClO 192.69 − 8.26 207 48.86 0.168 236.2 3.50 3.655 2.632 − 1.736 2.03 24.9 360 720 33.86 514.10 10 19 2 9 3Cl4MBA 1 C H ClO 170.60 42.61 250.91 508.2 0.0176 14.98 2.44 7.058 1.518 − 4.618 130.0 13 900 1.8e + 003 87.91 250.74 8 7 2 −5 10 Z-EHMC 1, 5 C H O 290.41 99.87 360.54 0.1548 1.38·10 667.6 5.80 9.938 4.089 − 4.138 29.4 4.17 360 720 43.26 90.80 18 26 3 −6 11 EHMCCl 6, 7 C H ClO 324.85 128.01 386.23 0.01943 1.68·10 661.4 6.45 10.777 4.344 − 4.268 33.0 4.63 900 1.8e + 003 108.13 133.19 18 25 3 −7 12 EHMCCl 4, 6, 7 C H Cl O 359.30 149.44 404.93 0.00437 3.42·10 1215 7.16 11.559 4.562 − 4.399 25.6 5.65 900 1.8e + 003 108.15 410.66 2 18 24 2 3 13 2.4 DClP 4 C H Cl O 163.0 45.0 210.0 4500 0.09 18.04 3.06 7.108 2.856 − 3.756 43.7 242 900 1.8e + 003 99.62 2473.19 6 4 2 14 2.6DCl1.4BQ 4 C H Cl O 176.99 123 268.4 5056 0.00189 1.771 1.23 8.818 1.0 − 7.588 11,500 52 900 1.8e + 003 70.56 93.35 6 2 2 2 15 1.2.4TCl3MB 4 C H Cl O 211.45 45 227 29.73 0.056 126.7 3.64 5.569 2.726 − 1.929 1.89 121 1.44e + 003 2.88e + 003 113.33 2433.26 7 5 3 16 2.4.6TClP 4 C H Cl O 197.45 69 246 800 0.008 55.12 3.69 7.663 3.074 − 3.973 385 423 1.44e + 003 2.88e + 003 166.36 2977.4 6 3 3 −4 17 3.5DCl2HAcP 4 C H Cl O 205.04 90.66 299.08 258 1.6·10 3.713 3.26 7.8 2.31 − 4.540 5940 492 900 1.8e + 003 103.71 2663.03 8 6 2 2 −5 18 3Cl4MCA 1 C H ClO 212.63 109.81 337.48 382.6 3.75·10 3.162 2.80 10.435 1.75 − 7.635 36,500 6.98 360 720 41.81 37.37 10 9 3 −6 19 3.5DCl4MCA 1 C H Cl O 247.08 128.70 356.76 70.28 8.38·10 3.162 3.44 11.205 1.973 − 7.765 25,800 8.1 900 1.8e + 003 105.91 93.34 10 8 2 3 20 3.5DCl4MBA 1 C H Cl O 205.04 63.98 277.85 96.55 0.00271 46.95 3.08 7.829 1.803 − 4.749 132 14.2 900 1.8e + 003 101.28 270.76 8 6 2 2 21 3Cl4MP 1 C H ClO 158.59 51.00 241.49 3238 0.0103 10.55 2.24 8.238 2.499 − 5.998 151 12.1 900 1.8e + 003 87.81 187.43 7 7 2 22 2.5DCl4MP 1 C H Cl O 193.03 67.83 269.20 623.1 0.00379 13.17 2.88 9.008 2.717 − 6.128 1640 37.2 900 1.8e + 003 100.89 330.32 7 6 2 2 −7 8 23 TP 3C H O 198.18 152.73 371.83 9287 1.35·10 3.162 0.80 18.901 3.458 − 18.105 2.64·10 1.04 360 720 31.72 37.37 199 9 10 5 −7 24 TP 3C H O 306.41 141.55 395.38 1.221 1.54·10 2500 5.32 13.441 4.308 − 8.121 19,700 1.06 360 720 43.27 846.70 307e 18 26 4 −7 25 TP 3C H O 306.41 141.55 395.38 0.5314 1.54·10 1588 5.07 13.191 4.308 − 8.121 8560 3.75 360 720 43.26 634.76 307f 18 26 4 −6 26 TP 3C H O 304.39 124.33 383.31 7.226 2.17·10 154.6 3.75 11.306 3.031 − 7.556 8310 4.09 900 1.8e + 003 107.01 93.33 305a 18 26 4 −6 27 TP 3C H O 304.39 129.46 389.96 2.402 1.31·10 417.5 4.31 11.609 3.155 − 7.299 4580 2.86 900 1.8e + 003 100.75 93.35 305b 18 26 4 −5 28 TP 3C H O 304.39 90.85 348.94 2.186 3.24·10 454.6 4.36 9.312 3.217 − 4.952 168 4.51 900 1.8e + 003 107.71 92.91 305c 18 26 4 −6 29 TP 3C H O 304.39 129.46 389.96 2.402 1.31·10 417.5 4.31 11.609 3.155 − 7.299 4580 3.02 900 1.8e + 003 107.82 101.10 305d 18 26 4 −6 30 TP 3C H O 304.39 124.33 383.11 7.226 2.17·10 154.6 3.75 11.306 3.05 − 7.556 8310 3.82 900 1.8e + 003 107.01 93.34 305e 18 26 4 −6 31 TP 3C H O 304.39 124.33 383.31 7.226 2.17·10 154.6 3.75 11.306 3.06 − 8.121 8310 3.75 360 720 43.09 44.32 305f 18 26 4 −12 10 32 TP 3C H O 468.60 246.19 571.92 0.012 1.58·10 56.23 6.27 19.064 3.817 − 12.794 4.23·10 2.93 900 1.8e + 003 108.14 2373.53 469a 28 36 6 −12 10 33 TP 3C H O 468.60 246.19 571.92 0.012 1.58·10 56.23 6.27 19.064 3.817 − 12.794 4.23·10 2.93 900 1.8e + 003 108.14 2373.53 469b 28 36 6 −12 5 34 DIAMC 8 C H O 496.65 243.43 566.01 0.009 2.42·10 5410 5.76 17.679 3.644 − 11.919 5.76·10 2.68 900 1.8e + 003 108.123 1718.79 30 40 6 −5 −14 5 35 TP 2, 3, 8 C H O 580.81 269.42 621.64 1.057·10 4.12·10 15.03 8.56 19.742 5.167 − 11.182 3.36·10 2.18 1.44e + 003 2.88e + 003 173.03 2857.92 581b 36 52 6 1 Gackowska et al. (2014), 2 MacManus-Spencer et al. (2011), 3 Jentzsch et al. (2016), 4 Gackowska et al. (2016), 5 Serpone et al. (2002), 6 Nakajima et al. (2009), 7 Santos et al. (2013), 8 Rodil et al. (2009) 16042 Environ Sci Pollut Res (2018) 25:16037–16049 products can be classified as medium- or low-volatility com- toxicity to aquatic organisms (USEPA 1991;EC 2001;Xing pounds (BP > 184 °C). Medium-volatility compounds are: et al. 2012;) and potentially carcinogenic properties, the inter- EHA; 1Cl4MB; 1,3DC2MB and 2EHCA (BP 184–216 °C). national environmental organisations (WHO, UNEP, USEPA, The above-mentioned products are also characterised by the EC) included chlorophenols into a group of pollutants with a highest vapour pressure value, which ranges from 0.164 to special risk to the environment (WHO 1989; WHO 2003; 0.409 mmHg. Other products TP ,TP , DIAMC and UNEP 2001;USEPA 1991,USEPA 2014;EC 2001). These 469a 469b TP belong to the group of low-volatility compounds. On compounds were identified in surface water and groundwater 581b the basis of the BP and VP, these transformation products have (He et al. 2000;Czaplicka 2004; Gao et al. 2008; Sim et al. no predisposition to evaporate and be in gas phase (Table 3). 2009). An example of drinking water pollution with chlorophenol (including 2,4,6TClP) in Finland shows how many effects can be caused by EHMC transformation products, Water solubility where an increased incidence of gastrointestinal infections, asthma and depression morbidity was observed (Lampi 1992). High solubility in water suggests that pollutants can migrate with water over long distances. Hydrophilic compounds also have the ability to be readily absorbed by plants. These pol- Octanol/water partition coefficient lutants can be phytotoxic by damaging shoots and roots, re- ducing plant growth and disturbing transpiration (Yu-Hong Logarithmic value of octanol/water partition coefficient (log and Yong-Guan, 2006). In turn, pollutants with low solubility K ) allows determining quantitatively lipophilic character of OW can accumulate in sediments. the compound. Octanol is considered as a representative of Analysis of the results indicates that the products (besides organic matter. Analysis of the results obtained showed that Z-EHMC, EHMCCl, TP ,TP , DIAMC and TP )are log K EHMC was higher than 5 (Fig. 2). The value obtain- 469a 469b 581b OW characterised by significantly better water solubility than the ed is consistent with the data presented by Ramos et al. (2015). substrate (Fig. 1). Water solubility of EHMC at temperature of EHMC has lipophilic properties and can accumulate in −1 25 °C is lower than 0.1548 mg L . Considerably higher sol- sediments. Kupper et al. (2006) and Liu et al. (2012)showed 3 2 ubility (1.0 × 10 ≥ S ≤ 1.0 × 10 ) has the following oxidation that EHMC concentration in raw sludge is within the range products: EHA and 4MCA, and chlorination products: from 13 to 14.45 ng/g dw; however, Langford et al. (2015) 1Cl4MB; 1,3DCl2MB; 3Cl4MBA; 2,4,6TCP; reported that it was up to 4689 ng/g dw in treated sludge. The 3,5DCl2HAcP; 3Cl4MCA and 2,5DCl4MP. Metabolites very differences in concentration among authors is due to the var- 4 −1 well soluble in water (S ≤ 1.0 × 10 mg L ) are 4MBA; 4MP; iable composition of the sludge used, and more likely results 2,4DClP; 2,6DC1,4BQ; 3Cl4MP and TP .It should be not- from the variable organic matter content they had. ed that compounds with an OH and Cl group have high S A similar lipophilic character has most of the analysed values. This pattern indicates that the partitioning potential products for which the calculated coefficient log K >3. OW from water to air of such chemicals is quite low. Among EHMCCl, EHMCCl2, TP ,TP and TP for which 469a 469b 581b EHMC transformation products, 2,4-dichlorophenol log K > 6 deserve a special attention. A different character OW (2,4DClP), 2,4,6-trichlorophenol (2,4,6TClP) and benzene have the products of EHMC oxidation: EHA; 4 MCA; 4MP; chloroderivatives deserve special attention. Due to their high 3Cl4MBA; 2,6DCl1,4BQ; 1Cl4MB; 3Cl4MCA; 3Cl4MP; Fig. 1 Water solubility of EHMC transformation products Environ Sci Pollut Res (2018) 25:16037–16049 16043 Fig. 2 Octanol/water coefficient (log K ) of EHMC transformation products OW 2,5DCl4MP and TP (Fig. 2). Soluble compounds (log 2015). BCF of analysed products with hydrophylic character K < 3) will not accumulate in organisms, soil or sediments is in the range of 1.7 < BCF < 56. These include OW but instead will be contaminating all water sources and thus chloroderivatives of phenols, methoxybenzene or spreading around larger areas. Cinnamic acid derivatives with methoxycinnamic acid. For this group of compounds, no dis- high log K values show high phytotoxic potential tinct relationship between log K and BCF was observed. OW OW (Jitareanu et al. 2011). According to Legierse et al. (1998), The bioconcentration ability of EHMC was confirmed by the rate of absorption of chloroderivatives by snails is directly Fent et al. (2010). EHMC was identified in fish, cormorants proportional to log K . and shellfish on a level of nanograms per gram and OW chlorophenols were present in urine, umbilical cord blood Bioconcentration factor and mother’s milk (Sandau et al. 2002; Bradman et al. 2003; Hong et al. 2005; Philippat et al. 2013; Kim et al. 2014; Forde et al. 2015). These compounds can cause unfavourable histo- The ability of pollutants to bioconcentrate in living organisms is one of parameters taken into account in assessing a threat pathological, genotoxic, mutagenic and carcinogenic effects in humans and animals (Igbinosa et al. 2013). Other metabo- posed by the new environmental pollutants. For many com- pounds, there is a linear relationship between log K and lites that accumulate in the food chains and are ultimately OW identified in human adipose tissue, breast milk and blood are bioconcentration factor (BCF), but this is not a rule, and each example should be considered separately (Axelman et al. chlorobenzenes (Ivanciuc et al. 2005;Tor 2006;Kozani etal. 2007). Because EHMC transformations result in formation of 1995). Analysis of products showed that EHMC chloroderivatives (EHMCCl and EHMCCl )were many chloroorganic compounds at low concentrations, it should be checked how BCF of the mixture of products will characterised by high bioconcentration factor (BCF > 600) (Fig. 3). These are compounds with hydrophobic properties change. According to Kondo et al. (2005), BCF of the mixture of chloroorganic compounds can be significantly higher than (log K > 5). It is accepted that adipose tissue of living or- OW that of a single substance. ganisms is the place where the hydrophobic organic com- pounds are accumulated. Hydrophobicity is the principal de- termining factor of bioconcentration and plays a very impor- Overall persistence and long-range transport tant role in the bioconcentration of hydrophobic organic com- potential pounds (Wang et al. 2014). Hydrophilic compounds appear instead in soluble phases inside the organisms, such as blood As the environmental overall persistence (P ) and long- OV serum and mother’s milk (Armitage et al. 2013). They appear range transport potential (LRTP) of all transformation prod- also in eggs (Lopez-Antia et al. 2017). They affect not only ucts cannot be determined in laboratory experiment, they have animals but also plants, where they appear in all plant tissues, to be calculated utilising physical–chemical parameters such including sap and nectar, and thus constitute a major problem as n-octanol/water (log K ), n-octanol/air (log K ) and air/ OW OA in environmental contamination nowadays (Bonmatin et al. water (log K ) partition coefficients, as well as half-lives in AW 16044 Environ Sci Pollut Res (2018) 25:16037–16049 Fig. 3 Bioconcentration factor (BCF) of EHMC transformation products with the highest BCF value air, water, and soil and molar masses of compounds calculated with the increase of chlorine atoms in molecule. The impact of by EPI Suite (Mackay and Webster 2006;Mostrągetal. 2010; the compound structure, molar mass and type of atom in the Kuramochi et al. 2014). P and LRTP of all the products and individual molecules was described by Mostrągetal. (2010). In OV EHMC were calculated by P and LRTP Screening Tool their opinion, there is a relationship between the long-range OV created by OECD. The tool requires estimated degradation transport potential of pollutants and presence of halogens (Cl, half-lives in soil, water and air, and partition coefficients be- F, Br) in the molecule. However, each group of compounds tween air and water and between octanol and water as chem- should be analysed individually. Other products that can be ical specific input parameters. From these inputs, the tool cal- transported over considerable distances in the environment are culates metrics of P and LRTP from a multimedia chemical photodegradation products formed by the path of dimerization OV fate model and provides a graphical presentation of the results. (TP ,TP ,TP , dIAMC) (Vione et al. 2015). These 469a 469b 581b Studies on the environmental mobility of products showed compounds can travel up to 3000 km in the environment that the highest long-range transport potential expressed by (Table 3). EHMC oxidation products (4MBA, 4MP, TP ) 305a–f characteristic travel distance (CTD) was observed for can be transported over much shorter distances. Similar rela- methoxyphenol chloroderivatives, then methoxybenzene tionships are observed in the case of the overall persistence. The chloroderivatives, EHMC chloroderivatives, methoxybenzal most durable are chloroorganic products. P of these com- OV dehyde chloroderivatives and methoxycinnamate acid pounds is in the range of 100–170 days. Similarly, EHMC chloroderivatives (S Fig. 9). It was observed that CTD increases oxidation products (TP ) are also stable (S Fig. 10). On 305a–f Fig. 4 P and LRTP of the OV selected EHMC transformation products calculated by the OECD P and LRTP Screening Tool OV using property date from EPI Suite Environ Sci Pollut Res (2018) 25:16037–16049 16045 Fig. 5 Toxic effect of the systems studied, determined by Microtox® test after 90 min of reaction the basis of LRTP and P values obtained, it can be deter- 90 min of reaction. The toxicity classification of the mixture OV mined to which class of persistent organic pollutants (POPs) the of products was performed based on the magnitude of effects tested products are classified. Klasmeier et al. (2006) deter- observed in the indicator organisms. The toxicity classification mined the critical values of LRTP and P and divided pollut- system is presented in Table 4. Such a system is used by many OV ants into four classes: I class—persistent organic pollutants researchers (Põllumaa et al. 2004; Ricco et al. 2004; Werle and (POP-like) (pollutants of the Bhighest priority^), both parame- Dudziak 2013). EHMC is characterised by low toxicity; toxic ters are higher than the critical value; II and III classes—mole- effect is lower than 30% (S Figs. 13 and 14). The acute toxicity cules which have POP-like characteristic for one of the refer- shows the products formed as a result of EHMC reaction with ence parameters, (pollutants of Bintermediate priority^)and IV NaOCl and UV. After 1.5-h-lasting reaction, toxic effect is class—pollutants with LRTP and P lower than critical value higher than 90%. In the system with hydrogen peroxide and OV (compounds of the Blowest priority^). LRTP and P values of UV, the toxic products are formed. The effect is on the level OV the products studied are lower than the critical value (P — of 75%. Low toxicity was observed in the system in which OV 195 days, LRTP—5096.73 km); therefore, they can be classi- EHMC was exposed to UV. Toxic effect was about 30%. fied into IV class (Fig. 4). Similar results were obtained using tests with Daphnia manga and Artemia Salina (S Figs. 15–17). Studies have shown that Toxicity testing the presence of oxidizing and chlorinating agents affects the increase of toxicity of EHMC photodegradation products. A Toxicity of products was estimated by monitoring changes in similar effect of additional factors was observed by Vione the natural emission of the luminescent bacteria Aliivibrio et al. (2015). They have found that in the presence of TiO fisheri and by observation of mortality of juvenile crustaceans and UV, toxicity of photoproducts increased by 40–50% with Daphnia magna and Artemia Salina treated with solutions respect to EHMC. containing EHMC transformation products. The reaction mix- A distinct increase in toxicological response of products, in tures EHMC/UV, EHMC/H O /UV and EHMC/NaOCl/UV the case of hydrogen peroxide and sodium hypochlorite, can 2 2 were tested after different times of reaction (S Figs. 11–17). be explained by formation of cinnamic acid derivatives, In order to eliminate the effects of reagents, tests for reaction among others (esters, aldehydes and alcohols). These systems with/without EHMC were performed. Based on the difference in results obtained, the toxicity of the mixture of Table 4 Sample toxicity transformation products was determined. Toxicity [%] Classification classification system Analysis of solutions from systems containing only oxidiz- (Ricco et al. 2004; ing agents (NaOCl/UV, H O /UV) showed a slight toxic effect 2 2 <25 Not toxic Põllumaa et al. 2014) (S Figs. 11 and 12). After an hour of reaction, the toxic effect is 25–50 Low toxicity close to zero. Figure 5 presents percentage of toxic effect of the 50.1–75 Toxicity systems studied (EHMC, EHMC/UV, EHMC/H O /UV, 2 2 75.1–100 High toxicity EHMC/NaOCl/UV), determined by Microtox®testafter 16046 Environ Sci Pollut Res (2018) 25:16037–16049 Fig. 6 EC concentration of the systems studied (determined by Microtox® after 180 min of reaction) compounds have strong toxic action for some bacterial and 60 days in water or 180 days in soil, respectively, are used to fungal species (Narasimhan et al. 2004;Guzman 2014). The identify chemicals with high potential to be persistent in the highest toxicity in the EHMC/NaOCl/UV system can be at- environment, and a half-life of longer than 2 days in air is the tributed to formation of chloroorganic products. On the exam- screening criterion for atmospheric LRTP (Klasmeier et al. ple of chlorophenols and chlorobenzene, it was found that the 2006). Products such as chlorobenzene and chlorophenol de- toxicity increases with the increase in the number of chlorine rivatives have tair1/2 values longer than 2 days and tsoil1/2 atoms in molecule (Pepelko et al. 2005; Zhang et al. 2016). values longer than 6 months. In addition, they are the com- The difference in results between the Microtox® (bacteria) pounds with proven mutagenic and carcinogenic effect in and the other two kits is due to the higher sensitivity of water humans and animals (Igbinosa et al. 2013). Comprehensive risk crustaceans (both Daphnia and Artemia) (S Figs. 13–17). assessment also included studies on toxicity of the products Moreover, toxicological potential of the tested systems formed. We observed that oxidation and chlorination products expressedbyEC , calculated in milligrams per liter, was eval- of EHMC show significantly higher toxicity than EHMC alone. −1 uated (Fig. 6). EC value was 0.15 mg L for EHMC/H O / It was found that chloroorganic products are a greater environ- 50 2 2 −1 UV and 0.094 mg L for EHMC/NaOCl/UV, respectively. mental hazard. They are characterised by higher toxicity in the These values are significantly lower than EC obtained for environment than oxidation products. −1 EHMC (0.4 mg L ) using bacteria Aliivibrio fisheri. The results obtained can be a valuable information in the context of assessing the quality of water resources, especial- ly in countries where water shortages are replenished by treated sewage. Incomplete removal of EHMC in conven- Conclusions tional wastewater treatment plants (Ekpeghere et al. 2016) indicates that this compound is recalcitrant and contami- As a result of the EHMC transformations, a number of products nates the environment. Analysis of the risk of environmen- with different properties other than the substrate are produced. tal pollution by new pollutants and their transformation Two main classes of EHMC degradation products have been products can be useful in assessing water quality in order identified. The first includes oxidation products, which due to to ensure maximum safety for water resources. their hydrophilic character disperse in water, and some of them can evaporate into the air. Whereas, the second class includes Open Access This article is distributed under the terms of the Creative chloroorganic products that probably disperse in air and water Commons Attribution 4.0 International License (http:// andcanaccumulateinanadiposetissueoflivingorganisms. creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give Both of them can reach anywhere on the planet, so both are a appropriate credit to the original author(s) and the source, provide a link cause of concern. However, it is only their persistence and to the Creative Commons license, and indicate if changes were made. toxicity that can make them problematic. Oxidation products are characterised by a relatively low durability and small range References of dispersal in the environment. Much more harmful to the environment are EHMC chlorination products. Based on the Armitage JM, Arnot JA, Wania F, Mackay D (2013) Development and guidelines established in Convention Stockholm (2001), the evaluation of a mechanistic bioconcentration model for ionogenic identified chloroorganic products show the properties of persis- organic chemicals in fish. Environ Toxicol Chem 32:115–128. tent organic pollutants. Degradation half-lives of more than https://doi.org/10.1002/etc.2020 Environ Sci Pollut Res (2018) 25:16037–16049 16047 Axelman J, Broman D, Näf C, Pettersen H (1995) Compound depen- the list of priority substances in the field of water policy and amending Directive 2000/60/EC (L 331 of 15-12-2001) dence of the relationship log K(ow) and log BCF L : a comparison between chlorobenzenes (CBs) for rainbow trout and polycyclic Fent K, Zenker A, Rapp M (2010) Widespread occurrence of estrogenic aromatic hydrocarbons (PAHs) for Daphnia. Environ Sci Pollut UV-filters in aquatic ecosystems in Switzerland. Environ Pollut 158: Res Int 2:33–36. https://doi.org/10.1007/BF02987509 1817–1824. https://doi.org/10.1016/j.envpol.2009.11.005 Barón E, Gago-Ferrero P, Gorga M, Rudolph I, Mendoza G, Zapate AM, Ferrari H, Chen R, Lavezza C, Santinelli I, Longo E, Bramanti (2013) Díaz-Cruz S, Barra R, Ocampo-Duque W, Páez M, Dabra RM, Photodegradation of rhodamine B using the microwave/UV/H O : 2 2 Eljarrat E, Barceló D (2013) Occurrence of hydrophobic organic effect of temperature. Int J Photoenergy 2013:1–12. https://doi.org/ pollutants (BFRs and UV-filters) in sediments from South 10.1155/2013/854857 America. Chemosphere 92:309–316. https://doi.org/10.1016/j. Forde MS, Robertson L, Laouan Sidi EA, Côté S, Gaudreau E, Drescher chemosphere.2013.03.032 O, Ayotte P (2015) Evaluation of exposure to organophosphate, Bohdziewicz J, Dudziak M, Kamińska G, Kudlek E (2016) carbamate, phenoxy acid, and chlorophenol pesticides in pregnant Chromatographic determination and toxicological potential evalua- women from 10 Caribbean countries. Environ Sci Process Impacts tion of selected micropollutants in aquatic environment—analytical 17:1661–1671. https://doi.org/10.1039/c5em00247h problems. Desalin Water Treat 57:1361–1369. https://doi.org/10. Gackowska A, Przybyłek M, Studziński W, Gaca J (2014) Experimental 1080/19443994.2015.1017325 and theoretical studies on the photodegradation of 2-ethylhexyl 4- Bonmatin J-M, Giorio C, Girolami V, Goulson D, Kreutzweiser DP, methoxycinnamate in the presence of reactive oxygen and chlorine Krupke C, Liess M, Long E, Marzaro M, Mitchell EAD, Noome species. Cent Eur J Chem 12:612–623. https://doi.org/10.2478/ DA, Simon-Delso N, Tapparo A (2015) Environmental fate and s11532-014-0522-6 exposure; neonicotinoids and fipronil. Environ Sci Pollut Res 22: Gackowska A, Przybyłek M, Studziński W, Gaca J (2016) Formation of 35–67. https://doi.org/10.1007/s11356-014-3332-7 chlorinated breakdown products during degradation of sunscreen Bradman A, Barr DB, Claus Henn BG, Drumheller T, Curry C, Eskenazi agent, 2-ethylhexyl-4 methoxycinnamate in the presence of sodium B (2003) Measurement of pesticides and other toxicants in amniotic hypochlorite. Environ Sci Pollut Res 23:1886–1897. https://doi.org/ fluid as a potential biomarker of prenatal exposure: a validation 10.1007/s11356-015-5444-0 study. Environ Health Perspec 111:1179–1782. https://doi.org/10. Gao J, Liu L, Liu X, Zhou H, Huang S, Wang Z (2008) Levels and spatial 1289/ehp.6259 distribution of chlorophenols-2,4-dichlorophenol, 2,4,6- Christiansson A, Eriksson J, Teclechiel D, Bergman Å (2009) trichlorophenol, and pentachlorophenol in surface water of China. Identification and quantification of products formed via photolysis Chemosphere 71:1181–1187. https://doi.org/10.1016/j. of decabromodiphenyl ether. Environ Sci Pollut Re 16:312–321. chemosphere.2007.10.018 https://doi.org/10.1007/s11356-009-0150-4 Gilbert E, Pirot F, Bertholle V, Falson F, Padois K (2013) Commonly used Cuderman P, Heath E (2007) Determination of UV filters and antimicro- UV filter toxicity on biological functions: review of last decade bial agents in environmental water samples. Anal Bioanal Chem studies. Int J Cosmetic Sci 35:208–219. https://doi.org/10.1111/ics. 387:1343–1350. https://doi.org/10.1007/s00216-006-0927-y 12030 Czaplicka M (2004) Sources and transformations of chlorophenols in the Guzman JD (2014) Natural cinnamic acids, synthetic derivatives and natural environment. Sci Total Environ 322:21–39. https://doi.org/ hybrids with antimicrobial activity. Molecules 19:19292–19349. 10.1016/j.scitotenv.2003.09.015 https://doi.org/10.3390/molecules191219292 Damiani E, Rosati L, Castagna R, Carloni P, Greci L (2006) Changes in He Y, Wang Y, Lee HK (2000) Trace analysis of ten chlorinated benzenes ultraviolet absorbance and hence in protective efficacy against lipid in water by headspace solid-phase microextraction. J Chromatogr A peroxidation of organic sunscreens after UVA irradiation. J 874:149–154. https://doi.org/10.1016/S0021-9673(00)00067-4 Photochem Photobiol B 82:204–213. https://doi.org/10.1016/j. Hong H, Zhou H, Luan T, Lan C (2005) Residue of pentachlorophenol in jphotobiol.2005.03.011 freshwater sediments and human breast milk collected from the De la Cruz N, Giménez J, Esplugas S, Grandjean D, de Alencastro LF Pearl River Delta, China. Environ Int 31:643–649. https://doi.org/ (2012) Degradation of 32 emergent contaminants by UVand neutral 10.1016/j.envint.2004.11.002 photo-Fenton in domestic wastewater effluent previously treated by Hsieh C-Y, Tsai M-H, Ryan DK, Pancorbo OC (2004) Toxicity of the 13 activated sludge. Water Res 46:1947–1957. https://doi.org/10.1016/ priority pollutant metals to Vibrio fisheri in the Microtox® chronic j.watres.2012.01.014 toxicity test. Sci Total Environ 320:37–50. https://doi.org/10.1016/ Diaz-Cruz MS, Gago-Ferrero P, Liorca M, Barcelo D (2012) Analysis of S0048-9697(03)00451-0 UV filters in tap water and other clean waters in Spain. Anal Bioanal Igbinosa EO, Odjadjare EE Chigor VN, Igbinosa IH, Emoghene AO, Chem 402:2325–2333. https://doi.org/10.1007/s00216-011-5560-8 Ekhaise FO, Igiehon NO, Idemudia OG (2013) Toxicological pro- DIRECTIVE 2008/105/EC OF THE EUROPEAN PARLIAMENTAND file of chlorophenols and their derivatives in the environment: the OF THE COUNCIL of 16 December 2008 on environmental quality public health perspective. Sci World J 2013:1–11. https://doi.org/10. standards in the field of water policy, amending and subsequently 1155/2013/460215 repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/ Ivanciuc T, Ivanciuc O, Klein DJ (2005) Posetic quantitative EEC, 84/491/EEC, 86/280/EEC and amending Directive 2000/60/ superstructure/activity relationships (QSSARs) for chlorobenzenes. EC of the European Parliament and of the Council J Chem Inf Model 45:870–879. https://doi.org/10.1021/ci0501342 Ekpeghere KI, Kim U-J, S-H O, Kim H-Y Oh J-E (2016) Distribution and Janjua NR, Kongshoj B, Andersson AM, Wulf HC (2008) Sunscreens in seasonal occurrence of UV filters in rivers and wastewater treatment human plasma and urine after repeated whole-body topical applica- plants in Korea. Sci Total Environ 542:121–128. https://doi.org/10. tion. J Eur Acad Dermatol Venereol 22:456–461. https://doi.org/10. 1016/j.scitotenv.2015.10.033 1111/j.1468-3083.2007.02492.x EU 2015/495- COMMISSION IMPLEMENTING DECISION (EU) Ji Y, Zhou L, Zhang Y, Ferronato C, Brigante M, Mailhot G, Yang X, 2015/495 of 20 March 2015 establishing a watch list of substances Chovelon J-M (2013) Photochemical degradation of sunscreen for Union-wide monitoring in the field of water policy pursuant to agent 2- phenylbenzimidazole-5-sulfonic acid in different water ma- Directive 2008/105/EC of the European Parliament and of the trices. Water Res 47:5865–5875. https://doi.org/10.1016/j.watres. Council 2013.07.009 European Commission (EC) Decision 2455/2001/EC of the European Ji tăreanu A, Tataringa G, Zbancioc AM, Stănescu U (2011) Toxicity of Parliament and of the Council of November 20, 2001 establishing some cinnamic acid derivatives to common bean (Phaseolus 16048 Environ Sci Pollut Res (2018) 25:16037–16049 vulgaris). Not Bot Horti Agrobo 39:130–134 https://doi.org/10. Loraine GA, Pettigrove ME (2006) Seasonal variations in concentrations 15835/nbha3927183 of pharmaceuticals and personal care products in drinking water and Kikuchi A, Saito H, Mori M, Yagi M (2011) Photoexcited triplet states of reclaimed wastewater in southern. California. Environ Sci Technol 40:687−695–687−695. https://doi.org/10.1021/es051380x new UV absorbers, cinnamic acid 2-methylphenyl esters. Photochem Photobiol Sci 10:1902–1909. https://doi.org/10.1039/ Mackay D, Webster E (2006) Environmental persistence of chemicals. C1PP05168G Environ Sci Pollut Res 13:43–49. https://doi.org/10.1065/espr2006. 01.008 Kim K, Park H, Lee JH (2014) Urinary concentrations of trichlorophenols in the Korean adult population: results of the national human bio- MacManus-Spencer LA, Tse ML, Klein JL, Kracunas AE (2011) Aqueous photolysis of the organic ultraviolet filter chemical octyl monitoring survey 2009. Environ Sci Pollut Res Int 21:2479–2485. https://doi.org/10.1007/s11356-013-2180-1 methoxycinnamate. Environ Sci Technol 45:3931–3937. https://doi. org/10.1021/es103682a Klasmeier J, Matthies M, Macleod M, Scheringer M, Stroebe M, Fenner K, Le Gall AC, Mckone T, Van De Meent D, Wania F (2006) Mostrąg A, Puzyn T, Haranczyk M (2010) Modeling the overall persis- Application of multimedia models for screening assessment of tence and environmental mobility of sulfur-containing long-range transport potential and overall persistence. Environ Sci polychlorinated organic compounds. Environ Sci Res 17:470–477. Technol 40:53–60. https://doi.org/10.1021/es0512024 https://doi.org/10.1007/s11356-009-0257-7 Nakajima M, Kawakami T, Niino T, Takahashi Y, Onodera S (2009) Kondo T, Yamamoto H, Tatarazako N, Kawabe K, Koshio M, Hirai N, Morita M (2005) Bioconcentration factor of relatively low concen- Aquatic fate of sunscreen agents octyl-4-methoxycinnamate and trations of chlorophenols in Japanese medaka. Chemosphere 61: octyl-4-dimethylaminobenzoate in model swimming pools and the 1299–1304. https://doi.org/10.1016/j.chemosphere.2005.03.058 mutagenic assays of their chlorination byproducts. J Health Sci 55: Kozani RR, Assadi Y, Shemirani F, Hosseini MRM, Jamali MR (2007) 363–372. https://doi.org/10.1248/jhs.55.363 Part-per-trillion determination of chlorobenzenes in water using dis- Narasimhan B, Belsare D, Pharande D, Mourya V, Dhake A (2004) persive liquid–liquid microextraction combined gas Esters, amides and substituted derivatives of cinnamic acid: synthe- chromatography-electron capture detection. Talanta 72:387–393. sis, antimicrobial activity and QSAR investigations. Eur J Med https://doi.org/10.1016/j.talanta.2006.10.039 Chem 39:827–834. https://doi.org/10.1016/j.ejmech.2004.06.013 Kudlek E, Dudziak M, Bohdziewicz J (2016) Influence of inorganic ions Pepelko WE, Gaylor DW, Mukeriee D (2005) Comparative toxic potency and organic substances on the degradation of pharmaceutical com- ranking of chlorophenols. Toxicol Ind Health 21:93–111. https://doi. pound in water matrix. Water 8:532–550. https://doi.org/10.3390/ org/10.1191/0748233705th204oa w8110532 Philippat C, Wolff MS, Calafat AM, Ye X, Bausell R, Meadows M, Stone Kupper T, Plagellat C, Brändli RC, de Alencastro LF, Grandjean D, J, Slama R, Engel SM (2013) Prenatal exposure to environmental Tarradellas J (2006) Fate and removal of polycyclic musks, UV phenols: concentrations in amniotic fluid and variability in urinary filters and biocides during wastewater treatment. Water Res 40: concentrations during pregnancy. Environ Health Perspect 121: 2603–2612. https://doi.org/10.1016/j.watres.2006.04.012 1225–1231. https://doi.org/10.1289/ehp.1206335 Kuramochi H, Takigami H, Scheringer M, Sakai S (2014) Estimation of Poiger T, Buser H-R, Balmer ME, Bergqvist P-A, Müller MD (2004) physicochemical properties of 52 non-PBDE brominated flame re- Occurrence of UV filter compounds from sunscreens in surface tardants and evaluation of their overall persistence and long-range waters: regional mass balance in two Swiss lakes. Chemosphere transport potential. Sci Total Environ 491-492:108–117. https://doi. 55:951–963. https://doi.org/10.1016/j.chemosphere.2004.01.012 org/10.1016/j.scitotenv.2014.04.004 Põllumaa L, Kahru A, Manusadzianas L (2014) Biotest- and chemistry- Lampi P (1992) Cancer incidence following chlorophenol exposure in a based hazard assessment of soils, sediments and solid wastes. J Soil community in Southen Finland. Arch Environ Health 47:167–175. Sci 4:267–275. https://doi.org/10.1007/BF02991123 https://doi.org/10.1080/00039896.1992.9938346 Ramos S, Homem V, Alves A, Santos L (2015) Advances in analytical Langford KH, Reid MJ, Fjeld E, Øxnevad S, Thomas KV (2015) methods and occurrence of organic UV-filters in the environment— Environmental occurrence and risk of organic UV filters and stabi- a review. Sci Total Environ 526:278–311. https://doi.org/10.1016/j. lizers in multiple matrices in Norway. Environ Int 80:1–7. https:// scitotenv.2015.04.055 doi.org/10.1016/j.envint.2015.03.012 Ricco G, Tomei MC, Ramadori R, Laera G (2004) Toxicity assessment of Legierse KCHM, Sijm DTHM, van Leeuwen CJ, Seinen W, Hermens common xenobiotic compounds on municipal activated sludge: JLM (1998) Bioconcentration kinetics of chlorobenzenes and the comparison between respirometry and Microtox®. Water Res 38: organophosphorus pesticide chlorthion in the pond snail Lymnaea 2103–2110. https://doi.org/10.1016/j.watres.2004.01.020 stagnalis—a comparison with the guppy Poecilia reticulate.Aquat Rodil R, Moeder M, Altenburgr R, Schmitt-Jansen M (2009) Toxicol 41:301–323. https://doi.org/10.1016/S0166-445X(97) Photostability and phytotoxicity of sunscreen agents and their deg- 00092-1 radation mixtures in water. Anal Bioanal Chem 395:1513–1524. León Z, Vlieger J, Chisvert A, Salvador A, Lingeman H, Irth H, Giera M https://doi.org/10.1007/s00216-009-3113-1 (2010) Identification of the biotransformation products of 2- Rodil R, Quintana JB, Concha-Graña E, López-Mahía P (2012) ethylhexyl 4-(N,N-dimethylamino) benzoate. Chromatographia 71: Emerging pollutants in sewage, surface and drinking water in 55–63. https://doi.org/10.1365/s10337-009-1386-3 Galicia (NW Spain). Chemosphere 86:1040–1049. https://doi.org/ Li W, Ma Y, Guo C, Hu W, Liu K, Wang Y, Zhu T (2007) Occurrence and 10.1016/j.chemosphere.2011.11.053 behavior of four of the most used sunscreen UV filters in wastewater Rozas O, Vidal C, Baeza C, Jardim WF, Rossner A, Mansilla HD (2016) reclamation plant. Water Res 41:3506–3512. https://doi.org/10. Or ganic micropollutants (OMPs) in natural waters: oxidation by 1016/j.watres.2007.05.039 UV/H O treatment and toxicity assessment. Water Res 98:109– 2 2 Liu YS, Ying G-G, Shareef A, Kookana RS (2012) Occurrence and 118. https://doi.org/10.1016/j.watres.2016.03.069 removal of benzotriazoles and ultraviolet filters in a municipal Sakkas VA, Giokas DL, Lambropoulou DA, Albanis TA (2003) Aqueous wastewater treatment plant. Environ Pollut 165:225–232. https:// photolysis of the sunscreen agent octyl-dimethyl-p-aminobenzoic doi.org/10.1016/j.envpol.2011.10.009 acid Formation of disinfection byproducts in chlorinated swimming Lo pez-Antia A, Dauwe T, Meyer J, Maes K, Bervoets L, Eens M (2017) poolwater. J Chromatogr A 1016:211–222. https://doi.org/10.1016/ S0021-9673(03)01331-1 High levels of PFOS in eggs of three bird species in the neighbourhood of a fluoro-chemical plant. Ecotoxicol Environ Saf Sandau CD, Ayotte P, Dewailly E, Duffe J, Norstrom RJ (2002) Pentachlorophenol and hydroxylated polychlorinated biphenyl 139:165–171. https://doi.org/10.1016/j.ecoenv.2017.01.040 Environ Sci Pollut Res (2018) 25:16037–16049 16049 metabolites in umbilical cord plasma of neonates from coastal pop- swguidance/standards/criteria/current/upload/Draft-Updateof- Human-Health-Ambient-Water-Quality-Criteria-2-Chlorophenol- ulations in Quebec. Environ Health Perspect 110:411–417. https:// doi.org/10.1289/ehp.02110411 95-57-8.pdf Santiago-Morales J, Gómez MJ, Herrera-López S, Fernández-Alba AR, Vasquez MI, Fatta-Kassinos D (2013) Is the evaluation of Btraditional^ García-Calvo E, Rosal R (2013) Energy efficiency for the removal physicochemical parameters sufficient to explain the potential tox- of non-polar pollutants during ultraviolet irradiation, visible light icity of the treated wastewater at sewage treatment plants? Environ photocatalysis and ozonation of a wastewater effluent. Water Res Sci Pollut Res 20:3516–3528. https://doi.org/10.1007/s11356-013- 47:5546–5556. https://doi.org/10.1016/j.watres.2013.06.030 1637-6 Santos AJM, Miranda MS, Esteves da Silva JCG (2012) The degradation Vione D, Calza P, Galli F, Fabbri D, Medana C (2015) The role of direct products of UV filters in aqueous and chlorinated aqueous solutions. photolysis and indirect photochemistry in the environmental fate of Water Res 46:3167–3176. https://doi.org/10.1016/j.watres.2012.03. ethylhexyl methoxy cinnamate (EHMC) in surface water. Sci Total 057 Environ 15:58–68. https://doi.org/10.1016/j.scitotenv.2015.08.002 Schlumpf M, Cotton B, Conscience M, Haller V, Steinmann B, Wang Y, Wen Y, Li JJ, He J, Qin WC, Su LM, Zhao YH (2014) Lichtensteiger W (2001) In vitro and in vivo estrogenicity of UV Investigation on the relationship between bioconcentration factor screens. Environ Health Perspect 109:239–244. https://doi.org/10. and distribution coefficient based on class-based compounds: the 1289/ehp.01109239 factors that affect bioconcentration. Environ Toxicol Pharmacol Sim W, Lee S, Lee I, Choi S, Oh J (2009) Distribution and formation of 38:388–396. https://doi.org/10.1016/j.etap.2014.07.003 chlorophenols and bromophenols in marine and riverine environ- Wegmann F, Cavin L, MacLeod M, Scheringer M, Hungerbuhler K ments. Chemosphere 77:552–558. https://doi.org/10.1016/j. (2009) The OECD software tool for screening chemicals for persis- chemosphere.2009.07.006 tence and long-range transport potential. Environ Model Softw 24: Straub JO (2002) Concentrations of the UV filter ethylhexyl 228–237 methoxycinnamate in the aquatic compartment: a comparison of Werle S, Dudziak M (2013) Evaluation of toxicity of sewage sludge and modelled concentrations for Swiss surface waters with empirical gasification waste-products. Przem Chem 92:1350–1353 (in Polish) monitoring data. Toxicol Lett 131:29–37. https://doi.org/10.1016/ WHO, 1989. Chlorophenols other than pentachlorophenol, environmen- S0378-4274(02)00042-5 tal health criteria 93. International Programme on Chemical Safety Tarazona I, Chisvert A, León Z, Salvador A (2010) Determination of WHO, 2003. Chlorophenols in drinking-water. Background document hydroxylated benzophenone UV filters in sea water samples by for preparation of WHO guidelines for drinking-water quality. dispersive liquid-liquid microextraction followed by gas World Health Organization, Geneva (WHO/SDE/WSH/03.04/47) chromatography-mass spectrometry. J Chromatogr A 1217:4771– Xing L, Sun J, Liu H, Yu H (2012) Combined toxicity of three 4778. https://doi.org/10.1016/j.chroma.2010.05.047 chlorophenols 2,4-dichlorophenol, 2,4,6-trichlorophenol and penta- Tor A (2006) Determination of chlorobenzenes in water by drop-based chlorophenol to Daphnia magna. J Environ Monit 14:1677–1683. liquid-phase microextraction and gas chromatography-electron cap- https://doi.org/10.1039/c2em30185g ture detection. J Chromatogr A 1125:129–132. https://doi.org/10. Yu-Hong S, Yong-Guan Z (2006) Bioconcentration of atrazine and 1016/j.chroma.2006.06.081 chlorophenols into roots and shoots of rice seedlings. Environ UNEP. Stockholm Convention on persistent organic pollutants; United Pollut 139:32–39. https://doi.org/10.1016/j.envpol.2005.04.035 Nations Enviroment Programme: Geneva, Switzerland; 2001. http:// Zhang S, Lin D, Wu F (2016) The effect of natural organic matter on www.pops.int bioaccumulation and toxicity of chlorobenzenes to green algae. J USEPA (United States Environmental Protection Agency), 1991. Water Hazar Mater 5:186–193. https://doi.org/10.1016/j.jhazmat.2016.03. quality criteria summary. Ecological risk assessment branch (WH- 017 585) and human risk assessment branch (WH-550D). Health and Zuloaga O, Navarro P, Bizkarguena E, Iparraguirre A, Vallejo A, Olivares ecological criteria division, USEPA, Washington, DC, USA M, Prieto A (2012) Overview of extraction, clean-up and detection USEPA (United States Environmental Protection Agency), 2014. Update techniques for the determination of organic pollutants in sewage of human health ambient water quality criteria: 2-chlorophenol 95- sludge: a review. Anal Chem Acta 29:7–29. https://doi.org/10. 57-8 draft. Available on line at: http://water.epa.gov/scitech/ 1016/j.aca.2012.05.016

Journal

Environmental Science and Pollution ResearchSpringer Journals

Published: Mar 28, 2018

References

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off