Journal Pre-proof

Making waves: Water-soluble polymers in the aquatic environment: An overlooked

class of synthetic polymers?

Sven Huppertsberg, Daniel Zahn, Frances Pauelsen, Thorsten Reemtsma, Thomas

P. Knepper

PII: S0043-1354(20)30468-1
DOI: https://doi.org/10.1016/j.watres.2020.115931
Reference: WR 115931

To appear in: Water Research

Received Date: 3 March 2020

Revised Date: 6 May 2020
Accepted Date: 11 May 2020

Please cite this article as: Huppertsberg, S., Zahn, D., Pauelsen, F., Reemtsma, T., Knepper, T.P.,
Making waves: Water-soluble polymers in the aquatic environment: An overlooked class of synthetic
polymers?, Water Research (2020), doi: https://doi.org/10.1016/j.watres.2020.115931.

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 1 Making Waves: Water-soluble polymers in the aquatic environment: An overlooked class of

2 synthetic polymers?

4 Sven Huppertsberg1*, Daniel Zahn1*, Frances Pauelsen1, Thorsten Reemtsma2,3, Thomas P. Knepper1

5 *The Authors are equally responsible for this paper

1
6 Hochschule Fresenius, University of Applied Sciences, Limburger Straße 2, 65510 Idstein, Germany
2
7 Helmholz Centre for Environmental Research – UFZ, Department of Analytical Chemistry,

8 Permoserstrasse 15, 04318, Leipzig, Germany

9 3 University of Leipzig, Institute of Analytical Chemistry, Linnéstrasse 3, 04103 Leipzig

10 Corresponding author: Thomas P. Knepper knepper@hs-fresenius.de

11

12 Abstract

13 Synthetic polymers have been one of the defining environmental topics of the last decade. Synthetic

14 polymers in the environment are usually classified by their size. They encompass the widely

15 discussed size fractions of macroplastic, microplastic, and nanoplastic. Water-soluble polymers

16 (WSPs), however, are mostly absent in this discussion. In this paper, we argue that WSPs are

17 produced in large quantities and have many applications that facilitate a discharge into the

18 environment, where their fate and impact remain mostly unclear. We argue that there are yet no

19 suitable analytical methods for the quantification of WSPs in environmental matrices and propose an

20 analytical method that utilizes size exclusion chromatography - mass spectrometry to detect and

21 potentially also quantify WSPs through specific fragments generated by in-source fragmentation.

22 With the detection of polyethylene glycol in a wastewater treatment plant effluent and a surface

23 water sample we provide a first prove of principle for the applicability of this novel analytical

24 approach to WSPs. Ultimately, we conclude that WSPs are currently in a similar position as MP were
25 in the advent of their investigation: We know of an environmental contamination but are uncertain

26 of its extent and impact and still lack the tools to investigate them thoroughly.

27 1. Are water-soluble polymers relevant environmental contaminants?

28 Synthetic polymers in the environment are nowadays one of the academically, socio-economically,

29 and politically most controversially discussed topics (Triebskorn et al. (2018), Sharma et al. (2017),

30 ECHA (I)). In this context especially polymer particles with varying sizes are discussed and

31 investigated. One major size fraction of these polymer particles is referred to as microplastics (MP)

32 which has gained significant public and scientific attention, albeit lacking a universally accepted

33 definition (Hartmann et al. (2019). A reasonable approach to define and classify synthetic polymers in

34 the (aquatic) environment was suggested by Hartmann et al. (2019). Besides polymer material and

35 size a critical condition to fulfil the suggested definition for MP is the solid state and insolubility in

36 water. Water-soluble polymers (WSPs) do not fit into this particle size-based framework of polymer

37 classification and thus need to be discussed separately. The last decade of studying MP has

38 demonstrated that the environmental analysis of synthetic polymers and the assessment of their

39 impact on the ecosystem are exceedingly complex (Gregory et al. (2003), Fendall et al. (2009), Betts

40 (2008), Koelmans et al. (2019)). Thus, we believe that the efforts to understand the impacts of WSPs

41 on the ecosystem that are currently still in their infancy should be intensified (Arp et al. (2020),

42 Bertling et al. (2018)).

43 The presence of a chemical in the aquatic environment may strongly depend on three major factors:

44 Its production volume, its applications that may or may not facilitate a release into the environment,

45 and its fate in the environment and during water treatment.

46 WSPs applications are plentiful and often facilitate either a direct or indirect release into the

47 environment (Table 1). Applications of WSPs in washing agents (Koltzenburg et al. (2014), Umoren et

48 al. (2006)), cosmetics (Koltzenburg et al. (2014)), personal care products (Koltzenburg et al. (2014)),

49 pharmaceuticals (Koltzenburg et al. (2014), Kadajji et al. (2011)) and many branches of industry (e.g.
50 textile industry) (Koltzenburg et al. (2014), Umoren et al. (2006)) inevitably lead to the discharge of

51 WSPs into the sewage system. Rain runoff from applications in paints, coatings and building materials

52 (Koltzenburg et al. (2014), Taylor et al. (1998), Knapen et al. (2009)) may also enter the sewage

53 systems or are discharged into surface waters. WSPs in pesticide formulations, fertilizers, and other

54 products used during crop cultivation are applied directly onto fields (Koltzenburg et al. (2014), Krogh

55 et al. (2009), Xiong et al. (2018)). They may either sorb to soil and crops, percolate into groundwater

56 or are washed off during rain events into surface waters. WSPs that are used as flocculants during

57 wastewater and drinking water production (Koltzenburg et al. (2014) , Hoke (1971)) sorb either to

58 particulate matter (e.g. sludge) (Pocurull et al. (2009), Petrović et al. (2000)) or remain in the

59 aqueous phase. In seawater desalination WSPs may be employed to prevent precipitation of salts

60 from brine (Koltzenburg et al. (2014), Taylor et al. (1998)) and are then discharged with this brine.

61 These examples illustrate the high potential of WSPs to enter the environment.

62 Table 1: Examples of the most prominent WSPs, their acronyms, and typical fields of application;

63 Acronyms: polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG),

64 polyethylene imide (PEI), polyvinylpyrrolidone (PVP), polyacrylic acid (PAA), Polyacrylamide (PAM).

Characteristic Applications WSPs References

Koltzenburg et
Paints, coatings, concrete additives, PEO, PPO, PAA, al. (2014),
additives in pesticide formulations, polycarboxylate- Taylor et al.
Dispersing agent
fertilizers, desalination of sea water ether (PEG (1998), Hoke
and paper manufacturing, oil recovery derivatives), PEI (1971), Wang
(2016)
Koltzenburg et
Dye transfer al. (2014),
inhibitors, Umoren et al.
Washing agents PAA, PVP
incrustation (2006),
inhibitors Holderbaum et
al. (2004)
Koltzenburg et
Flocculation PAM (modified),
Wastewater treatment al. (2014), Hoke
agent PAM, PEI
(1971)
 Surface PEG (modified Koltzenburg et
modification/ Textile impregnation, washing agents with glycol and al. (2014), Yilgör
functionalisation terephthalic acid) et al. (1996)
All WSPs suitable
Koltzenburg et
commonly
al. (2014),
Thickener Cosmetics polyelectrolytes
Arraudeau et al.
as poly carboxylic
(1989)
acids
Hygiene products, agricultural Koltzenburg et
Super-absorber products, building materials for PAA al. (2014), Illner
moisture control et al. (2017)
(crosslinked-)
PVP, PEO
modified with
Koltzenburg et
Formulations for Pharmaceuticals: as matrix materials, vinylacetate,
al. (2014),
pharmaceutical coatings, disintegrants, and copolymers of
Kadajji et al.
active ingredients solubilisation agents methacrylic acid
(2011)
and ethylacrylate,
PEG modified
with fatty acids;

Xiong et al.
(2018),
Conditioner Soil conditioner to avoid erosion PAM
Bjorneberg et
al. (2000)

65

66 Unlike most other chemicals in Europe, synthetic polymers are not registered under REACH

67 (regulation, evaluation, authorization, and restriction of chemicals) (ECHA (II)), and thus information

68 about their production volumes is often scarce or not freely available. The educts of polymer

69 synthesis, however, are REACH registered and as long as there are no other major applications

70 besides polymer production their production volume can be utilized to estimate the annual

71 production of WSPs in the European Union.

72 Estimations based on this approach place the total annual production of WSPs in Europe in the

73 millions of tons range (e.g. PEG > 106 t/a (ECHA (III)), PAA 105-106 t/a (ECHA (IV)); for each assuming

74 WSP synthesis as the main application of the monomers), and thus in the same order of magnitude
75 as surfactants, which are known to enter wastewater treatment plants in exceptionally high

76 concentrations (Faria et al. (2019)).

77 This high annual production in combination with many applications that facilitate a discharge of

78 WSPs result in a high potential for the presence of WSPs in the environment. For WSPs released into

79 the sewer system wastewater treatment may help to reduce its discharge into environment.

80 During wastewater treatment WSPs can be removed by two mechanisms, namely sorption and

81 biotransformation. Which of these mechanisms takes a dominating role in WSP removal depends on

82 the WSP type and its molecular weight (MW). Generally, higher MW WSPs have a stronger sorption

83 tendency (Krogh et al. (2003), Pocurull et al. (2009), Eubeler et al. (2010)). The MW where sorption

84 becomes the dominant removal mechanism, however, may vary significantly between different WSP

85 types. Biotransformation of WSPs is also strongly dependent on the polymer type and decreases with

86 increasing MW (Eubeler et al. (2010)). Some WSPs (e.g. PVP) have been shown to be persistent

87 against biotic transformation even at low MW (Eubeler et al. (2010)). Biotransformation of WSPs

88 often results in chain degradation and thus a MW reduction and a reduced sorption tendency

89 (Trimpin et al. (2001)). As long as no complete mineralization is achieved the transformation

90 products (TPs) of lower MW are likely to remain in the aqueous phase. Consequently, sorption to

91 sludge remains likely the main elimination mechanism of high MW, persistent WSPs while all other

92 WSPs and their TPs are, likely, discharged into the environment with the effluent.

93 If sewage sludge is subjected to thermal sludge recycling, WSPs sorbed to it are fully eliminated

94 (Pocurull et al. (2009)). While the use of sludge as fertilizer in Germany is intended to be phased out

95 by 2032 (Wiechman (2013)), it is still practiced widely in many countries, and consequently acts as an

96 environmental entry pathway for sorbed WSPs. Further degradation of sorbed WSPs in the soil may

97 result in reduction of the MW and a remobilization of TPs that may then percolate to groundwater or

98 be transported via runoff to surface waters. Uptake of monomers and low MW TPs by crops may also

99 be possible.
100 Based on the limited data (Eubeler et al. (2010)) that is available so far, the extent of removal of PEG

101 and PVP during wastewater treatment is not known and many other WSPs are not yet investigated,

102 rendering the effective removal of WSPs during wastewater treatment highly uncertain. Possibly

103 incomplete removal in conjunction with high production volumes and applications facilitating a

104 release into the aquatic environment lead to the conclusion that WSPs are very likely present in the

105 environment, partially even in significant concentrations. While this is certainly the case for

106 persistent WSPs (Arp et al. (2020)), we assume that even biodegradable WSPs like PEG enter the

107 environment in significant concentrations with yet unknown effects. Most WSPs themselves are

108 unlikely to cause direct eco-toxicological effects i.e. PEG itself only shows toxicity at very high

109 parenteral doses (Webster et al. (2009)). Albeit, polymers are not part of REACH as they are

110 considered of “low concern” due to their high MW (ECHA (V)) their degradation products may be not.

111 PAM can serve as prominent example for this case as its monomer acrylamide has carcinogenic and

112 toxic characteristics (ECHA (VI)).

113 Generally, WSP monomers and oligomers and their TPs may fall into the chemical domain of

114 persistent and mobile substances (Reemtsma et al. (2016)) and potentially toxic substances, which

115 are under discussion for regulation under REACH (Neumann et al. (2017)). Indirect effects of WSPs

116 may be caused by one of their key functionalities: Facilitating the solubility and thus, bioavailability of

117 non-polar substances as in pharmaceutical and agricultural formulations. If environmental WSP

118 concentrations are sufficient to also facilitate a mobilization or enhanced bioavailability of non-polar

119 chemicals, this may be detrimental to aquatic ecosystems and increases their potential of exposure

120 through the aqueous phase. Certainly, any effect that WSPs might have in the environment is

121 intrinsically tied to the specific polymer class that is present and the concentrations, both of which

122 are largely unknown.

123 Consequently, WSPs are chemicals with a high potential for release into the environment, unknown

124 environmental occurrence and concentrations, and an unclear impact on the ecosystem. Thus, we

125 believe that they should be thoroughly studied alongside MP and nanoplastics (NP).
126 2. Which challenges do we face in the analysis of water-soluble polymers?

127 As outlined above, quantitative and qualitative information on the occurrence of WSPs is very

128 limited, covering only a few polymer types and chain lengths (Petrović et al. (2000)). This may be

129 attributed to a general lack of awareness in the scientific community (Arp et al. (2020)) and some

130 severe analytical challenges.

131 Methods commonly used in the analysis of WSPs are often used for rather pure products or

132 formulations with no or only few other high MW constituents. These methods like size exclusion

133 chromatography (SEC) coupled with a UV-, refraction index, or evaporative light scattering detection

134 are inherently unspecific and therefore may not be able to cope with the complex matrices present

135 in environmental samples, where naturally occurring macromolecules like humic substances are also

136 present. In addition, these methods may also lack the sensitivity to detect WSPs at environmental

137 concentrations, which may be in the µg/L range instead of the g/L range like in many product

138 formulations (Lechner et al. (2010)). For these reasons the established methods for polymer analysis

139 are not expected to be suitable for the determination of WSPs in the environment.

140 Depending on the polymer type and chain lengths, WSP molecules may have sizes up to tens to

141 hundreds of nanometres. Consequently, a ‘polymeric continuum’ may exist from monomers and

142 oligomers that are truly dissolved over high Mw polymeric colloids to particulate polymers like NPs.

143 However, method development for NPs is still in its infancy and no established and reliable methods

144 exist, especially towards the lower end of the nm range (Schwaferts et al. (2019)). Future

145 developments in this field may be transferred to WSP analysis but depending on the underlying

146 analytical principle their applicability to dissolved polymers is not guaranteed.

147 In contrast to the particular MP and NP WSPs are molecular organic pollutants, and thus

148 environmental trace-analytical methods may be applied. These methods usually combine a

149 chromatographic separation of the analytes of interest with a sensitive and selective mass

150 spectrometric detection. These methods can cope with complex matrices and low environmental
151 concentrations (Zwiener et al. (2004)). In the case of WSPs, however, analytical difficulties may arise

152 from the complexity of the analytes itself. Organic trace contaminants are often defined by one or

153 few specific ions (the monoisotopic analyte and its isotopologues). The structural variability and

154 complexity of WSPs results in numerous mass spectrometric signals that may differ only slightly or

155 even overlap between different members of one polymer type. This inherent complexity is further

156 increased upon ionization by the formation of ions of multiple charge states and by adduct

157 formation. While pure polymer standards can be readily characterized with and without a

158 chromatographic separation by high-resolution mass spectrometry (Dimzon et al. (2015)), this is less

159 promising for WSPs in environmental matrices due to the lower concentrations and the co-occurring

160 signals of the environmental matrix. Here, the differentiation between matrix and analyte signals

161 may be complex but may be facilitated by computer-assisted data evaluation tools.

162 Quantification or organic contaminants by mass spectrometric detection relies on specific ions (single

163 ion monitoring, SIM) or, more commonly, the combination of an ion and its product ions (multiple

164 reaction monitoring, MRM) (Gross (2006)). The latter approach is exceptionally sensitive and

165 selective. The selection of these ions, however, is almost impossible for synthetic polymers: due to

166 their polydispersity, multiple charge-states, and various adducts there is no single molecular ion that

167 is representative for all chain lengths of a synthetic polymer. Consequently, polymers like PEG cannot

168 be analysed as one analyte but rather every single PEG chain length would have to be treated as a

169 separate analyte for which there are still several charge states and adducts. Additionally, the total

170 concentration of a polymer type is distributed over multiple ions of different chain lengths, charge

171 states and adducts. Thus, the intensity of single ions is expected to be low, resulting in a poor

172 sensitivity. This is evident from a study by Petrović et al. (2000) in which the sensitivity for PEG was

173 much lower than for other, less polydisperse ionic and non-ionic surfactants.

174 From this, it can be concluded that traditional methods of polymer analysis may suffer from

175 comparatively low environmental concentrations and complex matrices, while methods used in NP

176 analysis are not yet established (and may not even be suitable), and quantitative trace-analytical
177 methods cannot cope with the complexity of the analytes themselves. While mass spectrometry with

178 computer-assisted data treatment may prove valuable for polymer characterization, quantification

179 methods that sensitively and selectively capture polymer types instead of individual chain lengths are

180 not yet present in our method portfolio.

181 3. How can we overcome these challenges? – A proof of principle

182 We propose a modification of mass spectrometry-based trace-analytical methods established for

183 organic micro-pollutants as a promising way forward in WSP analysis from environmental samples.

184 This modification combines high selectivity to cope with complex matrices and high sensitivity to

185 cope with low environmental concentrations. We propose an in-source fragmentation of WSPs to

186 convert polymers of one type but different chain lengths into one or more specific fragment ions: this

187 reduces the analyte complexity and simultaneously increases the signal intensity (Figure 1 A). First

188 experiments we conducted with PEG demonstrate that the nature of the fragment ions (for PEG:

189 C4H9O2+, C6H13O3+, C8H17O4+, and C10H21O5+) is independent from the chain lengths. After in-source

190 fragmentation the WSP fragments are small organic ions and can thus be analysed either by a high-

191 resolution MS in scan mode, which is essentially an orbitrap variant of MSE, or by a triple-quad-

192 instrument in MRM-mode which we hereinafter referred to as MRME (MRM after initial in-source

193 fragmentation).

194
195

196 Figure 1: Analytical methodology for the quantification of WSPs in environmental matrices. A) Depiction of analytical

197 concept: in addition to conventional trace-analytical methods an in-source fragmentation (green) of generated ions is

198 utilized to convert the numerous ions of the polymer into few chain-lengths independent fragments. This step severely

199 reduces the analyte complexity while simultaneously increasing method sensitivity. Information about chain-length

200 distribution is lost during this step but can be retained when the mass spectrometer is interfaced with size exclusion
201 chromatography. B) Proof of principle: size exclusion chromatography interfaced with a triple quadrupole mass

202 spectrometer was utilized to analyse PEG in enriched wastewater treatment plant (WWTP) effluent and surface water. In-

203 source fragmentation of PEG was performed by increasing the declustering potential and subsequent analysis of fragments

204 was performed in MRM-mode. Response factors were determined with standards of different MWs each containing 10

205 µg/mL PEG. Accurate quantification is still hampered by a chain-length specific response factor, but concentrations were

206 roughly estimated in the 10-100 µg/L range.

207 The applicability of this analytical concept to environmental samples is demonstrated by the analysis

208 of PEG in a wastewater treatment plant effluent and a surface water sample (Figure 1 B). The solid

209 phase enriched samples (HLB cartridges, Waters, Darmstadt, Germany, 50fold enrichment,

210 recoveries of spiked samples between 90 and 110%) were injected onto an SEC column (PSS

211 SUPREMA Micro Linear M, 4.6 x 150 mm PSS Polymer Standards Service GmbH, Mainz Germany),

212 isocratic elution with methanol/water 70/30 containing 5 mM ammonium formate) interfaced with

213 an AB Sciex 3200 triple quadrupole MS (AB Sciex, Darmstadt, Germany) in MRM-mode. In-source

214 fragmentation of PEG was provoked by increasing the declustering potential to 100 V. Through the

215 hyphenation of MS to SEC information about the MW distribution is retained despite the conversion

216 of the polymer into low molecular mass fragment ions already during ionization. This first experiment

217 with PEG determination in a wastewater treatment plant effluent and a surface water lead to

218 concentration estimates in the double digit µg/L range; it can be seen as a proof-of-principle. It also

219 suggests that even biodegradable WSPs are present in the aquatic environment.

220 Conceptually, this approach allows the sensitive quantification of WSPs either as sum parameter per

221 polymer type or, in conjunction with the SEC information, MW-specific. However, in its current state

222 the approach still has drawbacks: (I) Some polymer types require fragmentation energies that cannot

223 be provided during in-source fragmentation, especially for high MW polymers. (II) It is yet unclear if

224 the method allows a differentiation between mixed polymer types (e.g. PEG and PEG/PPG

225 copolymer) or polymers and only terminally modified TPs. (III) The ionization and fragmentation

226 efficiencies for one type of polymer are MW-dependent, which complicates quantification. The first

227 issue may be overcome when utilizing a different instrument like a quadrupole time-of-flight mass
228 spectrometer where fragmentation of all ions can be achieved in the collision cell enabling increased

229 collision energies, while the latter would require MW dependent response factors. With the data

230 presented herein it was proven that this methodology does in principle allow the sensitive analysis of

231 WSPs in environmental matrices. With further development and refinement it might become the

232 method of choice for WSP quantification in the environment.

233 4. Conclusions

234 • The current situation of WSPs might be comparable to early stages of microplastics research:

235 We have a vague notion that there are substances present in the environment but are highly

236 uncertain about their distribution, concentrations, and impact and lack suitable analytical

237 methods to investigate them.

238 • Analytical method development, validation, and standardisation should have priority in the

239 investigation of WSPs since the reliable determination of WSP occurrence, distribution, and

240 concentrations in the environment is a prerequisite for assessing their environmental risk.

241 • It is imperative that we consider the lessons learned from a decade of microplastic research

242 to avoid repetition of the same mistakes: We should be critical towards the results published

243 especially as long as no validated methods are available and consider actual environmental

244 concentrations when assessing the impacts of WSPs.

245

246
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362
Highlights:

-WSP are high volume chemicals

-applications of WSP facilitate discharge in the environment

-environmental data for WSP still scarce

-there are no established trace analytical methods for WSP in the environment

-development of a new approach for the detection of WSP as sum parameter is required
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: