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SUPPORTING INFORMATION Removal of fluorescent dissolved organic matter in biologically treated textile effluents by NDMP anion exchange process: efficiency and mechanism Wen-Tao Li a , Zi-Xiao Xu a , Chen-Dong Shuang a , Qing Zhou a , Hai-Bo Li a , Ai-Min Li a,* a State Key Laboratory of Pollution Control and Resources Reuse, Collaborative Innovation Center for Advanced Water Pollution Control Technology and Equipment, School of the Environment, Nanjing University, Nanjing, 210023, China CORRESPONDING AUTHOR FOOTNOTE Prof. Ai-Min Li

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SUPPORTING INFORMATION

Removal of fluorescent dissolved organic matter in biologically

treated textile effluents by NDMP anion exchange process: efficiency

and mechanism

Wen-Tao Lia, Zi-Xiao Xua, Chen-Dong Shuanga, Qing Zhoua, Hai-Bo Lia, Ai-Min Lia,*

a State Key Laboratory of Pollution Control and Resources Reuse, Collaborative

Innovation Center for Advanced Water Pollution Control Technology and Equipment,

School of the Environment, Nanjing University, Nanjing, 210023, China

CORRESPONDING AUTHOR FOOTNOTE

Prof. Ai-Min Li

School of the Environment, Nanjing University, Nanjing, 210023, China

Fax: +86 25 86269876; Phone: +86 25 83318402

E-mail: [email protected]

SUPPORTING INFORMATION

Table S1- The gradient elution program of preparative HPLC system

Time (min) Solvent A (%) Solvent B (%) Flow rate (ml/min)

0.00 85.0 15.0 20

3.00 70.0 30.0 20

5.5 30.0 70.0 20

7 20.0 80.0 20

8 10.0 90.0 20

10 10.0 90.0 20

Solvent A: Water; Solvent B: Methanol

SUPPORTING INFORMATION

Table S2- Reproducibility of HPLC fluorescence signal integration

Em 340 Em 460

Ex230 Ex280 Ex250 Ex310 Ex370

QY Sample

3083.3 1191.1 635.8 132.3 96.4

3080.6 1198.1 636.1 132.7 97.5

3080.3 1194.3 635.1 133.0 97.6

AVG a 3081.40 1194.50 635.67 132.67 97.17

SD b 1.65 3.50 0.51 0.35 0.67

RSD c 0.05% 0.29% 0.08% 0.26% 0.69%a Average; b Standard Deviation; c Relative Standard Deviation

The same QY sample was measure by HPLC multi-excitation scan for 6 times: 3

times with parameters of Em340/Ex220~300 nm and 3 times with parameters of

Em460/Ex230~400 nm. Then fluorescence signals at 5 selected pairs were integrated

to assess the reproducibility.

SUPPORTING INFORMATION

Table S3- Linearity of HPLC fluorescence signal integration

Sample DOC

(mg/L)

Em 340 Em 460

Ex230 Ex280 Ex250 Ex310 Ex370

QY_1 8.31 607.1 239.5 129.1 129.1 18.2

QY_2 16.62 1222.8 481.5 257.0 52.1 37.6

QY_3 24.92 1815.9 715.6 383.7 78.1 56.5

QY_4 33.23 2445.2 951.9 508.0 104.8 77.2

QY_5 41.54 3080.3 1194.3 635.7 132.7 97.2

R2 0.9998 1 1 0.9998 0.9997

QY_1~5 are diluted solutions of QY textile effluent. The fluorescence signals at the

selected pairs were integrated and used the linear regression analysis to assess its

accuracy in quantitative analysis. Additionally, the good linear regression suggests

that the inner-filtering effect was avoided.

SUPPORTING INFORMATION

Table S4 Estimation of NDMP operation cost

Treatment capacity 24 (h/d)* 80 (m3/h) = 1920 m3/d

Electricity cost The electricity consumed about 300 (kW·h / d) one day. With

the price of 0.9 (CNY/kW·h), the electricity cost per m3 is

estimated as ~0.14 CNY, calculated as:

300*0.9/1920.

Chemical cost for

regeneration

The NaCl solution for regeneration is assumed as 12 m3, i.e.,

the treatment of about 150 m3 wastewater needs 1 m3 NaCl

solution for regeneration.

The price of NaCl is assumed as 600 CNY/ton.

If the concentration of NaCl solution is ~15%, the

regeneration chemical cost is about 0.56 CNY, calculated as:

12 *0.15*600/1920.

If the concentration of NaCl solution is ~10%, the

regeneration chemical cost is about 0.37 CNY, calculated as:

12 *0.10*600/1920.

Note: the treatment of brine wastewater or the reclamation of NaCl are not considered in this estimation. The NaCl price might also vary across regions.

SUPPORTING INFORMATION

Fig. S1 NDMP pilot-scale engineering cases

For TQ, the NDMP process used the 1st generation reactor, which is a horizontal

flow tank; For QY, FZY and LF, the NDMP process used the 2nd generation reactor,

which is an up-flow cylinder.

SUPPORTING INFORMATION

Fig. S2 The HPLC Excitation-Time Maps (Em340/Ex220~300 nm) of the

bench-scale experiment

The Ex-axis denotes the excitation wavelength and the Time-axis represents the

elution time of DOM species containing aniline-like fluorophores. The color

variation represents the fluorescence intensity in arbitrary units.

The two columns represent the duplicate results of 5 anion exchange and

adsorption material.

SUPPORTING INFORMATION

Fig. S3 The HPLC Excitation-Time Maps (Em460/Ex230~400 nm) of the

bench-scale experiment

The Ex-axis denotes the excitation wavelength and the Time-axis represents the

elution time of humic-like species. The color variation represents the fluorescence

intensity in arbitrary units.

The two columns represent the duplicate results of 5 anion exchange and

adsorption material.

SUPPORTING INFORMATION

Fig. S4 The HPLC Excitation-Time Maps of humic fractions.

The fluorescence parameters were set at: Em460/Ex220~400 nm for HS-Em460-Ex3

fractions from TQ and QY; Em430/Ex220~400 nm for HS-Em430-Ex2 fractions from

TQ and QY.

SUPPORTING INFORMATION

Fig. S5 The acid-base titration curves of humic fractions

The DOC concentration of sample solutions is as follows:

TQ HS-Em460-Ex3: 6.933 mg/L; TQ HS-Em430-Ex2: 10.163 mg/L;

QY HS-Em46-Ex3: 19.837 mg/L; QY HS-Em430-Ex2: 23.489 mg/L.

SUPPORTING INFORMATION

Fig. S6 The performance of the pilot-scale NDMP process in TQ: (a) the COD

concentration before and after NDMP treatment; (b) the UV254 absorbance

before and after NDMP treatment; (c) the EEM spectra before NDMP treatment

(diluted by 25 times); (d) the EEM spectra after NDMP treatment (diluted by 25

times)

SUPPORTING INFORMATION

Fig. S7 The performance of the pilot-scale NDMP process in FZY: (a) the COD

concentration before and after NDMP treatment; (b) the UV254 absorbance

before and after NDMP treatment; (c) the EEM spectra before NDMP

treatment; (d) the EEM spectra after NDMP treatment

SUPPORTING INFORMATION

Fig. S8 The performance of the pilot-scale NDMP process in LF: (a) the COD

concentration before and after NDMP treatment; (b) the Color Degree before

and after NDMP treatment

SUPPORTING INFORMATION

Fig. S9 Photographs of textile effluents: before NDMP treatment VS after NDMP

treatment