Supplementary Materials

Table S1. Characteristics of the used media in the column and batch experiments

  Bulk

density

Porosity Organic

matter

Fe Mn As

 Unit g/cm3 --- mg-C/g mg/g mg/g mg/g

IOC

S

1.2±0.1 0.42 10.8±5.4 32.8±1.2 12.1±0.8 0.3±0.1

Table S2. Water quality parameters of the influent water

unit DC NCTW DCWW WEOM

pH --- 7.73±0.61 7.92±0.54 7.67±0.84 8.1±0.58

DOC mg-C/L 11.64±3.51 3.98±0.73 11.73±1.06 18.23±1.6

SUVA L/mg-m 3.52±0.34 1.51±0.18 3.29±0.28 4.85±0.51

NO3-N mg-N/L 1.7±0.3 0.2±0.02 1.9±0.2 1.4±0.3

NH4-N mg-N/L 0.19±0.04 nd 0.28±0.05 0.86±0.1

PO4-P mg-P/L 0.21±0.1 nd 0.25±0.06 0.41±0.12

SO42- mg/L 86±39 42±22 103±29 5.5±0.5

Cl- mg/L 74±24 48±18 87±26 12±3

nd: not detected

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2

Figure S1. Contour plots of the four components identified from the complete measured F-EEMs dataset for the influents and effluents water of column experiment.

PARAFAC is a multi-way statistical technique that uses an alternating least squares

algorithm to decompose the fluorescence dataset into trilinear terms and a residual array as

described by Andersen et al. (2003). Each term represents a group of fluorescent organic

compounds. Models with (3–7) fluorescence components were tested and different validation

tools (i.e., split-half validation and residual error) were used to define the right number of

components. PFFCA-EEM and PARAFAC-EEM models were developed and validated using

the N-Way and drEEM MATLAB toolboxes in MATLAB (version 8.3, R2014a).

It can be observed (Figure S1) that there is no remarkable dissimilarity between the two

protein-like components (FC3 & PC3). Likewise, microbial humic components (FC4 & PC4)

showed similar spectral characteristics. By contrast, PFFCA terrestrial humic component FC1

peak exhibited a blue-shifted emission spectrum compared to the spectral characteristics of

the corresponded PARAFAC component PC1, implying that FC1 encompass organic

compounds with less condensed structure than PC1. The maxima λex/λem wavelengths for

PC1 component was 332/480 nm. On the other hand, the other PFFCA humic component

FC2 covered a wider range of excitation and emission wavelengths than its corresponded

PARAFAC component PC2, referring that it is a mixture of two or more humic fluorophores.

PC2 maxima λex and λem were taken place at 308 and 420 nm, respectively.

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Table S2. The spectral slopes of the identified PARAFAC fluorescence components and their

corresponded components in previous studies from the OpenFluor database (Murphy et al., 2014)

Ex.

Wave.

(nm)

Em.

Wave.

(nm)

Tucker

congruence

coefficient

(TCC)

Previous study

Traditional

classification

(Coble, 1996)

Description

PC1 240,340 480

0.99 (Shutova et al., 2014) PC1

Peak A

Terrestrial humic

(higher molecular

weight)

0.99 (Osburn et al., 2016) PC 1

0.99 (Yamashita et al., 2010) PC 1

0.99 (Murphy et al., 2011) PC 1

PC2 240,308 402

0.99(Gonçalves-Araujo et al.,

2016)PC 2

Peak M +Peak

A

Terrestrial

fulvic /Microbial

humic (lower

molecular

weight )

0.99 (Shutova et al., 2014) PC 2

0.99 (Murphy et al., 2011) PC 2

0.98 (Li et al., 2016) PC 2

PC3 240, 268 308

0.98 (Osburn et al., 2016) PC 4

Peak T+ Peak

B

protein-like

(tyrosine and

tryptophan -like

fluorophores)

0.98 (Wünsch et al., 2017) PC 1

0.98(Gonçalves-Araujo et al.,

2016)PC 3

PC4 240, 296 408

0.99 (Walker et al., 2009), PC3

Peak MMarine/microbial

humic0.99 (Li et al., 2016) PC4

0.98 (Kowalczuk et al., 2013) PC3

4

5

Figure S2. Correlation between the FI of the PFFCA components and the Fe concentration of the effluent water (column study, 30 °C, anaerobic, HRL = 0.5 m/d)

Figure S3. Correlation between the FI of the PFFCA components and the Mn concentration of the effluent water (column study, 30 °C, anaerobic, HRL = 0.5 m/d)

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Figure S4. Correlation between the FI of the PFFCA components and the As concentration of the effluent water (column study, 30 °C, anaerobic, HRL = 0.5 m/d)

Figure S5. F-EEM spectra analysed for humic acid (a), fulvic acid (b) and tyrosine, initial concentration ( 5 mg-C/L)