Selectivity of solid phase extraction of freshwater dissolved organic matter and its

Transcription

1 Electronic Supplementary Material (ESI) for Environmental Science: Processes & Impacts. This journal is The Royal Society of hemistry 216 Supplementary material Selectivity of solid phase extraction of freshwater dissolved organic matter and its effect on ultrahigh resolution mass spectra Julia Raeke a, Oliver J. Lechtenfeld a, b, Martin Wagner c, Peter Herzsprung d, Thorsten Reemtsma a a Helmholtz entre for Environmental Research - UFZ, epartment of nalytical hemistry, Permoserstrasse 15, 4318 Leipzig, Germany b Helmholtz entre for Environmental Research - UFZ, ProVIS entre for hemical Microscopy, Permoserstrasse 15, 4318 Leipzig, Germany c TZW: VGW Water Technology enter, Wasserwerkstrasse 2, 1326 resden, Germany d Helmholtz entre for Environmental Research UFZ, epartment of Lake Research, rueckstrasse 3a, Magdeburg, Germany orresponding author: Thorsten Reemtsma Helmholtz entre for Environmental Research UFZ, epartment of nalytical hemistry Permoserstrasse 15, 4318 Leipzig, Germany Phone: thorsten.reemtsma@ufz.de 1

2 Table of ontents Page Table S1 Properties of SPE cartridges used for extraction 3 Table S2 SPE extraction method 3 Table S3 dditional properties of the model compounds 3 Table S4 Gradient used for UPL-QTOF-MS of the model compounds 4 Table S5 Table S6 Table S7 Table S8 Table S9 Fig. S1 Fig. S2 Fig. S3 Fig. S4 Fig. S5 Fig. S6 Extraction efficiencies of model compounds for the PPL and the HL cartridge and the response factors (peak area/concentration) O concentrations of SE fractions of the OM of the freshwater sample I and the extracts and permeates of the three SPE cartridges O concentrations of SE fractions of the OM of the freshwater sample II and the extracts and permeates of the three SPE cartridges from sample II O concentrations of SE-O fractions of the extracts for freshwater sample II using additional 4 ml of methanol (MeOH 2) and 4 ml of acetonitrile (N) for elution Nitrogen containing compounds in the original samples I and III and in the extracts SE-O chromatograms of the original freshwater sample I and the extracts and permeates of PPL, HL and 18 SE-O chromatograms of the original freshwater sample II and the extracts and permeates of PPL, HL and 18 SE-O chromatogram of the original sample II and of the extracts of the HL, the PPL and the 18 cartridge containing the methanol peak FT-IR mass spectra of the original sample III and the extracts of the different SPE cartridges Van Krevelen diagrams of molecular formulae (only x H y O z ) in the original sample III, the PPL extract, the HL extract and the 18 extract Frequency distribution of the O/ ratios and the E value of sample I and III, based on the original samples

3 Table S1. Properties of SPE cartridges used for extraction. artridge Manufacturer Material verage particle size (µm) ond Elut PPL gilent modified styrenedivinylbenzene copolymer Oasis HL Waters poly(n-vinylpyrrolidonedivinylbenzene) akerbond Octadecyl 18 verage pore size (Å) ed mass (mg) J. T. aker Volume (ml) Table S2. SPE extraction method. Step Solvent elivery rate Soak time Wash cartridge 4 ml methanol ml min s Wash cartridge 3 ml methanol ml min -1 2 s Wash cartridge 4 ml ultrapure water ml min -1 s Wash cartridge 3 ml.1 M Hl ml min -1 s Wash cartridge 4 ml.1 M Hl ml min -1 s Load 5 ml sample at ml min -1 5 ml min -1 Wash cartridge 3 ml.1 M Hl ml min -1 s Wash cartridge 3 ml.1 M Hl ml min -1 s ry for min with N 2 Elute cartridge 2 ml methanol 5 ml min s Elute cartridge 2 ml methanol 5 ml min s ry cartridge 6 ml air 5 ml min -1 Table S3. dditional properties of the model compounds. Index Name Supplier Purity (%) 1 -Sorbitol Sigma-ldrich Glucoronic acid lfa esar 98 3 ellobiose Merck - 4 Naphthalene-1,5-disulfonic acid Sigma-ldrich 97 5 Gallic acid Merck - 6 Glutaric acid Sigma-ldrich ,2-ihydroxybenzene Sigma-ldrich Hydroxybenzoic acid Merck 98 9 Phthalic acid Merck 99.5 hlorogenic acid Sigma-ldrich Vanillic acid Sigma-ldrich (-)-Epicatechin Fluka > Hydroxy-2-phenylacetic acid Sigma-ldrich Syringic acid Fluka Naphthalene-2-sulfonic acid Sigma-ldrich Ferulic acid Fluka Hydroxydodecanoic acid Sigma-ldrich Sodium dodecyl sulfate Merck 99 3

4 Table S4. Gradient used for UPL-QTOF-MS of the model compounds. Time (min) Eluent (%) Eluent (%) Table S5. Extraction efficiencies of model compounds for the PPL and the HL cartridge and the response factor (peak area/concentration) in negative ESI, * determined in positive ESI. Index Substance Extraction efficiency (%) Response PPL 1 PPL 2 Mean HL 1 HL 2 Mean (L µmol -1 ) 1 -Sorbitol.*.*..2* 1.3* (7855)* 2 -Glucuronic acid.*.*..*.* (538)* 3 ellobiose.*.*..* 3.1* (47523)* 4 Napthalene-1, disulfonic acid 5 Gallic acid Glutaric acid ,2-ihydroxybenzene Hydroxybenzoic acid 9 Phthalic acid hlorogenic acid Vanillic acid (-)-Epicatechin Hydroxy phenylacetic acid 14 Syringic acid Napthalene sulfonic acid 16 Ferulic acid Hydroxy dodecanoic acid 18 Sodium dodecyl sulfate

5 Table S6. O concentrations of SE fractions of the OM of the freshwater sample I and the extracts and permeates of the three SPE cartridges, * % of original sample, LO = µg L -1, LOQ = 4 µg L -1, n.d. = not determined, = arithmetical mean, the mean molecular weight M n was only determined for fraction ( humic substances ) and no fraction was determined in these samples. Sum of to Fraction Fraction Fraction Sample I µg L -1 %* µg L -1 %* M n (g mol -1 ) µg L -1 %* µg L -1 %* original I original II original PPL extract I PPL extract II extracts PPL permeate I < 4 n.d. PPL permeate II < 4 n.d. permeate < 4 n.d. extracts + permeates > 29 > 93 HL extract I HL extract II extracts HL permeate I < n.d. HL permeate II < n.d. permeates < n.d. extracts + permeates extract I extract II extracts permeate I permeate II permeates extracts +permeates

6 Table S7. O concentrations of SE fractions of the OM of the freshwater sample II and the extracts and permeates of the three SPE cartridges from sample II, * % of original sample, LO = µg L -1, LOQ = 4 µg L -1, n.d. = not determined, the mean molecular weight M n was only determined for fraction ( humic substances ). Sum of to Fraction Fraction Fraction Fraction Sample II µg L -1 %* µg L -1 %* µg L -1 %* M n (g mol -1 ) µg L -1 %* µg L -1 %* original PPL extract PPL permeate < n.d. 34 n.d. < 4 n.d > 55 > > 548 > HL extract HL permeate < 4 n.d > 68 > extract permeate

7 Table S8. O concentrations of SE-O fractions of the extracts for freshwater sample II using additional 4 ml of methanol (MeOH 2) and 4 ml of acetonitrile (N) for elution. LO = µg L -1, LOQ = 4 µg L -1. Sample Sum of to Fraction Fraction Fraction Fraction µg L -1 % of original µg L -1 µg L -1 µg L -1 µg L -1 original PPL MeOH < 59 < 4 < 4 PPL N 76 2 < 4 < 4 < 4 < 4 HL MeOH < < 4 HL N < < 4 < 4 < 18 MeOH < < 4 < < 4 18 N 42 1 < < < 4 < Table S9. Nitrogen containing compounds in the original samples I and III and in the extracts. Sum of relative intensities (%) Proportion of the original (%) Number of sum formulae Proportion of the original (%) Sample I Sample III Original PPL HL 18 Original PPL HL

8 relative signal height O a relative signal height O b relative signal height O c original sample extract permeate extract + permeate Fig. S1. SE-O chromatograms of the original freshwater sample I and the extracts and permeates of a: PPL, b: HL and c: 18, : biopolymers, : humic substances, : building blocks, : low molecular weight acids. relative signal height O a relative signa height O b relative signal height O c original sample extract permeate extract + permeate Fig. S2. SE-O chromatograms of the original freshwater sample II and the extracts and permeates of a: PPL, b: HL and c: 18, : biopolymers, : humic substances, : building blocks, : low molecular weight acids. 8

9 relative signal height O original sample extract HL extract PPL extract 18 methanol Fig. S3. SE-O chromatogram of the original sample II and of the extracts of the HL, the PPL and the 18 cartridge containing the methanol peak (t R 7 min). % a e 13/13/ 14/17/9 16/9/8 17/13/7 12/9/11 18/17/6 15/21/8 relative peak magnitude % % b c relative peak magnitude f g % d h m/z m/z Fig. S4. FT-IR mass spectra of the original sample III and the extracts of the different SPE cartridges, full spectrum (left) and nominal mass 329 (right), a, e: original sample, b, f: PPL extract, c, g: HL extract, d, h: 18 extract. Numbers at peak tops denote the numbers of /H/O in the respective molecular anions. 9

10 Fig. S5. Van Krevelen diagrams of molecular formulae (only x H y O z ) in a: the original sample III, b: the PPL extract, c: the HL extract, d: the 18 extract. The RI was calculated relative to the original sample III (see eqn (2) in the main text). sum of relative intensities (%) a < sample I sample III >.8 sum of relative intensities (%) b O/ E sample I sample III Fig. S6. Frequency distribution of the O/ ratios (a) and the E values (b) of sample I and III, based on the original samples.