Supplementary Information

In situ hydrothermal growth of a zirconium-based porphyrinic metal-organic framework on stainless steel fibers for solid-phase microextraction of nitrated polycyclic aromatic hydrocarbons

Jingkun Li1# • Yaxi Liu1# • Hao Su1 • Y.-L. Elaine Wong2 • Xiangfeng Chen1* • T.-W. Dominic Chan2 • Qingfeng Chen1 1Key Laboratory for Applied Technology of Sophisticated Analytical Instruments, Shandong Analysis and Test Centre, Shandong Academy of Sciences, Shandong, P. R. China 2Department of Chemistry, The Chinese University of Hong Kong, Hong Kong SAR

Address correspondence to: Dr. X.F. Chen, Shandong Academy of Sciences, Jinan, China. E-mail: [email protected]. # equal contribution Contents

1. Sample collection.

2. Real sample preparation.

3. SPME procedure.

4. Definition of enrichment factors.

5. Calculation of recovery. 1. Sample collection.

(i) Particulate matter (PM2.5): Two samplers were set on the roof (25 m above ground level) in Shandong University in Jinan. The other two samples were collected from the top of mountain Tai (1500 m above the ground level). After sampling, the filters were sealed in clean plastic bags, transported to the laboratory, and then stored in a freezer at −80 °C. (ii) Soil: The topsoil and subsurface soil (-20cm) samples were collected from a steel mills. The soil samples were homogenized and kept covered in a refrigerator at −20°C. Before use, the soil samples were freeze drying, grading and sieving. The 80-mesh fraction of real soil sample was taken and maintained at −20°C until analysis. (iii) Water: All the water samples were collected by glass bottles from local lakes and stored in the dark at 4C before analysis.

2. Real sample preparation

2 (i) Particulate matter (PM2.5): 1 cm of quartz filters were cut and put into 20 mL glass vials. Then, the PAHs were ultrasonically extracted by DCM for 60 min. Finally, the collected extract was evaporated to dryness using a gentle stream of nitrogen at 30°C and reconstituted by de-ionized water (10 mL) to form the solution for SPME. (ii) Soil: The homogenized soil sample (1.0 g) was added to a 50 mL polypropylene centrifuge tube and ultrasonically extracted for 40 min with 10 mL of extract phase (acetone and n-hexane: 1:1) in an ultrasonic bath and then centrifuged at 9000×g for 5 min. The supernatant was collected and evaporated to dryness under nitrogen stream at 30°C and diluted to 10 mL with de-ionized water to form the solution for SPME. (iii) Water samples: The water samples were filtered through a 0.45 μm membrane filter (Tianjin Jinteng Experimental Equipment Ltd., Co., Tianjin, China). 10 mL water sample was used for DI-SPME directly.

3. SPME procedure

Sample solution (10 mL) was added into a 20 mL glass vial equipped with a Teflon- coated magnetic stirrer bar and covered with a cap. Magnetic stirring was used to agitate the solution at a constant speed. Based on the semi-volatility nature of the target analytes, DI-SPME was used for all the selected samples. The needle was pulled away from the vial and inserted into the GC inlet after extraction. Thermal desorption was conducted at 280°C for 5 min.

4. Definition of enrichment factors The enrichment factor (EF) was defined as the ratio of the extracted ion chromatographic peak areas of the target analyte obtained with SPME to that with direct injection of 1 μL of standard mixture solution. The sample volume of SPME is 10 mL. The concentration of each individual analyte was 1 μg L-1. 5. Calculation of recovery

Recovery (R) was calculated on the basis of the following equation: where is the measured concentration of the spiked samples, is the concentration of the sample before spiking, and is the spiked concentration. Table S-1 Names and structures of the selected analytes. Compounds Structure

1 1-Nitronaphthalene (1N-NAP)

2 2-Nitronaphthalene (2N-NAP)

3 2-Nitrobiphenyl (2N-BiPh)

4 3-Nitrobiphenyl (3N-BiPh)

5 5-Nitroacenaphthene (5N-ACE)

6 2-Nitrofluorene (2N-FLO)

7 9-Nitroanthracene (9N-ANT)

8 9-Nitrophenanthrene (9N-PHE)

9 3-Nitrophenanthrene (3N-PHE)

10 2-Nitroanthracene (2N-ACE)

11 2-Nitrofluoranthene (2N-FLA)

12 3-Nitrofluoranthene (3N-FLA)

13 1-Nitropyrene (1N-PYR)

14 2-Nitropyrene (2N-PYR)

15 7-Nitrobenz[a]anthracene (7N-BaA)

16 6-Nitrochrysene (6N-CHR)

17 6-Nitrobenz(a)pyrene (6N-BaP) Table S-2. GC-NCI-MS SIM data acquisition method for the selected analytes.

Quantity Qualification Compounds Retention time (min) Mw Monitored ion (m/z) Monitored ion (m/z)

1N-NAP 11.51 173 173 174 2N-NAP 12.19 173 173 174 2N-BiPh 13.03 191 199 200 3N-BiPh 15.37 199 199 200 5N-ACE 18.80 199 199 200 2N-FLO 20.49 211 211 212 9N-ANT 21.06 223 223 224 9N-PHE 22.28 223 223 224 3N-PHE 23.03 223 223 224 2N-ACE 23.78 223 223 224 2N-FLA 27.58 247 247 248 3N-FLA 27.66 247 247 248 1N-PYR 28.50 247 247 248 2N-PYR 28.82 247 247 248 7N-BaA 31.40 273 273 274 6N-CHR 32.61 273 273 274 6N-BaP 36.89 297 297 298 Table S-3 Method comparisons for analysis of NPAHs from water samples.

Materials Method LODs Samples Linearity Precision (%) Reference 0.01-0.06 PDMS PA/HS-SPME-GC/NICI-MS River water 5-5000 pg/mL <12.7 30 pg/mL PDMS/DVB DI-SPME-GC/MS 4-60 ng/L Tap water/well water 0.1-10 µg/L <5.9 28

C18 SPE-µLC/UV 8-54 ng/L Tap water 2-60 mg/L <4 31

C18 SPE-GC/EI-MS 1.35-2.97 ng/L River water - - 32

- SDME-GC/EI-MS 0.26-1.07 µg/L Surface and ground water 1.24-10.3 µg/L <19% 33

- DLLME-SFO 1.7-2.3 ng/mL Lake and drinking water 2.5-500 ng/mL <4.2 34

- HPLC 2.9-44.5 ng/L River water 4.4-1188 ng/L <6.8 35

PCN-222 SPME-GC/NICI-MS 0.1-20 ng/L Water/soil/ PM2.5 0.4-400 ng/L <13.3 This work Table S-4 SPME recoveries of the selected analytes from drink water sample (n=5).

drinking water Analyte Recoverya (%) Recoveryb (%) Recoveryc (%) 1N-NAP 105.0±6.3 93.6±7.2 87.5±13.1 2N-NAP 104.0±8.0 89.5±6.7 90.6±11.5 2N-BiPh 102.0±4.9 90.5±4.7 94.2±11.2 3N-BiPh 113.2±4.8 109.9±5 113.8±5.5 5N-ACE 110.0±5.3 116.3±1.1 104.1±8.8 2N-FLO 110.8±8.4 106.9±2.2 85.4±11.8 9N-ANT 87.6±10.8 85.5±2.8 87.9±8.2 9N-PHE 81.2±6.8 87.1±6.9 89.2±7.1 3N-PHE 88.4±11.3 100.3±4.4 88.3±9.5 2N-ANT 113.2±6.3 90.9±12.8 96.5±9.0 2N-FLA 117.6±2.7 107.8±8.3 99.6±13.1 3N-FLA 102.5±3.9 110.9±3 98.3±11.7 1N-PYR 83.6±8.6 88.6±5.6 97.4±7.7 2N-PYR 100.8±5.2 96.1±8.6 89.3±5.6 7N-BaA 92.0±13.7 107.5±3.2 96.5±10.1 6N-CHR 87.2±9.9 85.9±4.7 93.6±11.2 6N-BaP 114.4±7.1 95.5±3.7 94.8±8.8 a: recovery of spiked 50 ng·L-1 b: recovery of spiked 100 ng·L-1 C: recovery of spiked 200 ng·L-1

Table S-5 Liquid extraction and SPME recoveries of the selected analytes from soil sample (n=3).

Soil (Liquid extraction) Soil (SPME of extract)

Recoverya (%) Recoveryb (%) Recoveryc (%) Recoveryd (%) 1N-NAP 84.1±6.2 79.0±5.8 108.3±6.7 87.3±7.9 2N-NAP 92.6±8.3 104.3±4.6 94.2±12.3 117.1±12.0 2N-BiPh 76.4±6.5 80.3±3.2 99.7±6.2 100.3±10.1 3N-BiPh 67.3±5.3 99.9±4.6 86.4±9.7 100.5±4.1 5N-ACE 84.7±9.6 94.4±9.4 109.3±10.3 117.2±5.7 2N-FLO 79.5±13.0 94.2±10.1 95.0±8.7 79.4±9.0 9N-ANT 73.0±8.4 76.3±12.0 99.0±7.6 76.1±7.1 9N-PHE 85.3±9.3 90.8±7.7 78.0±7.3 97.4±9.6 3N-PHE 95.3±11.0 136.4±6.3 102.5±9.2 94.3±10.2 2N-ACE 83.2±9.0 113.9±8.9 114.6±3.2 81.9±4.1 2N-FLA 88.3±5.6 119.9±2.5 93.6±9.2 110.2±9.4 3N-FLA 79.3±8.4 99.5±13.7 75.4±10.4 98.6±6.6 1N-PYR 67.5±10.4 70.9±10.2 69.6±9.5 102.5±11.2 2N-PYR 97.5±7.9 120.9±5.7 87.4±12.4 99.7±8.4 7N-BaA 92.7±9.2 129.8±10.5 97.3±11.3 92.3±9.3 6N-CHR 89.3±9.7 114.7±9.5 76.3±5.6 79.6±3.4 6N-BaP 76.8±8.9 89.5±6.8 119.2±10.2 81.2±7.2 a,b Recovery obtained by spiking of PAHs on the blank filters (0.2 ng/g and 0.4 ng/g ), c,d Recovery obtained by spiking of PAHs in the extract (c: 50 ng·L-1 and d: 200 ng·L-1) Table S-6 Liquid extraction and SPME recoveries of the selected analytes from quartz filters (PM2.5, n=3). PM 2.5 (Liquid extraction) PM 2.5 (SPME of extract)

Recoverya (%) Recoveryb (%) Recoveryc (%) Recoveryd (%) 1N-NAP 84.1±6.2 79.0±5.8 119.4±2.3 77.7±11.1 2N-NAP 92.6±8.3 104.3±4.6 96.6±6.1 113.9±5.5 2N-BiPh 76.4±6.5 80.3±3.2 100.9±9.8 100.6±3.1 3N-BiPh 67.3±5.3 99.9±4.6 100.1±11.8 104.8±8.2 5N-ACE 84.7±9.6 94.4±9.4 126.1±4.1 115.2±11.3 2N-FLO 79.5±13.0 94.2±10.1 97.3±11.9 112.2±9 9N-ANT 73.0±8.4 76.3±12.0 93.4±8.9 85.7±7.3 9N-PHE 85.3±9.3 90.8±7.7 89.2±9.0 93.2±7.1 3N-PHE 95.3±11.0 136.4±6.3 101±4.5 87.1±8.8 2N-ACE 83.2±9.0 113.9±8.9 115.7±4.9 79±2.9 2N-FLA 88.3±5.6 119.9±2.5 92.5±8.2 86.5±9.1 3N-FLA 79.3±8.4 99.5±13.7 69.2±12.2 94.9±6.5 1N-PYR 67.5±10.4 70.9±10.2 71±7.9 109.4±9.5 2N-PYR 97.5±7.9 120.9±5.7 70.6±15.5 82.2±8.0 7N-BaA 92.7±9.2 129.8±10.5 99±13.5 74.8±6.1 6N-CHR 89.3±9.7 114.7±9.5 62.4±16.7 78.6±2.7 6N-BaP 76.8±8.9 89.5±6.8 102.5±11.8 93.5±6.6 a,b Recovery obtained by spiking of PAHs on the blank filters, cd Recovery obtained by spiking of PAHs in the extract (c: 5 ng·L-1 and d: 50 ng·L-1)

Table S-7 Analytical results for determination of selected analytes in PM2.5 , soil and water samples. Analyte PM2.5 Water Soil Sample 1a Sample 2b Sample 3c Sample 4d Sample 1e Sample 2f Sample 2h Sample1g (ng/g) (pg/m3) (pg/m3) (pg/m3) (pg/m3) (ng/L) (ng/L) (ng/g) 1N-NAP 53.2 76.5 13.0 28.7 15.0 17.4 0.54 0.24 2N-NAP 48.3 70.2 13.6 29.7 10.2 15.2 0.90 N.D. 2N-BiPh 2.5 17.9 11.8 18.5 7.1 N.D. N.D. N.D. 3N-BiPh N.D. N.D. N.D. N.D. 6.0 15.1 1.74 0.20 5N-ACE 23.1 28.7 21.0 13.5 N.D. N.D. 5.24 0.68 2N-FLO N.D. 15.3 N.D. N.D. N.D. N.D. N.D. 0.83 9N-ANT 101.2 617.9 58.4 34.2 17.0 26.3 1.18 0.15 9N-PHE 7.9 6.1 N.D. N.D. N.D. N.D. N.D. N.D. 3N-PHE N.D. 5.8 12.8 N.D. N.D. N.D. N.D. N.D. 2N-ANT N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. (2+3)N-FLA 66.0 212.5 49.9 35.3 21.2 43.2 N.D. N.D. 1N-PYR 20.8 133.0 N.D. N.D. 14.5 N.D. N.D. N.D. 2N-PYR N.D. 163.0 37.9 26.6 N.D. N.D. N.D. N.D. 7N-BaA N.D. 41.6 113.7 24.3 N.D. N.D. N.D. N.D. 6N-CHR N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 6N-BaP 18.2 53.1 N.D. N.D. N.D. N.D. N.D. N.D. aJinan daytime-1; bJinan daytime-2; cTaian daytime; dTaian nighttime; eWaste water; fSnow water; gTop soil; hSubsurface soil Figure S-1 Estimated response surface from the Box-Behnken design for the absolute mean responsive of the analytes obtained by plotting (a) extraction time vs. temperature; (b) ionic strength vs. temperature; and (c) extraction time vs. ionic strength for the optimization of the extraction step. Figure S-2 Comparisons of EFs of PCN-222 with commercial fibers.