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 firstname.lastname@example.org 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. 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