Hong Yana, Ian T. Cousinsb, Chaojie Zhanga,*, Qi Zhoua

Supplementary material

Perfluoroalkyl acids in municipal landfill leachates from China: Occurrence, fate during leachate treatment and potential impact on groundwater

Hong Yana, Ian T. Cousinsb, Chaojie Zhanga,*, Qi Zhoua aState Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092, China bDepartment of Applied Environmental Science (ITM), Stockholm University, Svante Arrhenius väg 8, Stockholm, Sweden * Corresponding author. Tel.: +86 21 65982692; fax: +86 21 65983869; E-mail address: [email protected]

1 1 Chemicals and standards. A total of 14 individual PFAAs were selected as target analytes and were purchased either as the pure acid or as salts (purity provided in parenthesis).

Perfluoroundecanoic acid (PFUnA, 95%) was purchased from Sigma-Aldrich (St. Louris, MO).

Pentafluoropropionic acid (PFPrA, 97%), perfluorobutyric acid (PFBA, 99%), perfluoroheptanoic acid (PFHpA, 99%), perfluorodecanoic acid (PFDA, 98%), perfluorododecanoic acid (PFDoA, 95%) and the perfluoro-1-butanesulfonic acid potassium salt

(PFBS, 98%) were obtained from Aldrich Chemical Co. (Milwaukee, WI). Perfluoropentanoic acid (PFPeA, ≥94%), perfluorohexanoic acid (PFHxA, ≥97.0%), perfluorooctanoic acid (PFOA,

≥90%), perfluorononanoic acid (PFNA, ≥95.0%), and the potassium salts of perfluorohexane sulfonic acid (PFHxS, ≥98.0%) and perfluorooctane sulfonic acid (PFOS, 98%) were purchased from Fluka (Buchs, Switzerland). Perfluorotetradecanoic acid (PFTA, 96%) was provided by

Alfa Aesar (Ward Hill, MA). The internal standards, perfluoro-n-[1,2,3,4-13C4]octanoic acid

(MPFOA) and sodium perfluoro-1-[1,2,3,4-13C4]octane sulfonate (MPFOS), were purchased from Wellington Laboratories Inc. (Guelph, ON, Canada).

Oasis® WAX (6cc, 150 mg, 30 μm) solid phase extraction (SPE) cartridges were acquired from Waters (Milford, MA, USA). Bulk ENVI-Carb sorbent (100 m2 g-1, 120/400 mesh) was purchased from Supelco (Bellefonate, PA). HPLC-grade formic acid (96%), glacial acetic acid

(99.7%) and ammonium acetate (97.0%) were purchased from TEDIA (Fairfield, OH).

Ammonium hydroxide solution (25%), HPLC-grade sodium acetate (≥99.0%) and 2-propanol

(≥99.9%) were obtained from Fluka, and HPLC-grade methanol (≥99.9%) was acquired from

Sigma-Aldrich. Milli-Q water was used throughout.

2 Fig. S1. Average mass flows (g d-1) of PFAAs for each landfill site. UF=ultrafiltration, RO=reverse osmosis, NF=nanofiltration, RS=recycled sludge, WS=waste sludge, n.d.= not detected.

Landfill CZ

3 4 5 Landfill GZ

6 7 8 Landfill NJ

9 10 11 Landfill SH

12 13 14 Landfill SZ

15 16 Table S1. Recoveries and method detection limit (MDL) of the target PFAAs (n=7).

Analyt Raw leachate, NF/RO concentrate Bioreactor supernatant UF/NF/RO effluent Sludge e Recoverya MDL (ng L-1) Recover MDL (ng L-1) Recover MDL (ng L-1) Recover MDL (ng g-1) y y y PFPrA 91±9 10.00 82±8 5.00 95±3 1.00 111±4 0.30 PFBA 90±10 2.00 86±9 1.00 94±8 0.20 99±2 0.06 PFPeA 111±6 10.00 104±2 5.00 100±3 1.00 104±6 0.20 PFHxA 102±4 2.00 103±5 1.00 103±7 0.20 91±14 0.04 PFHpA 103±8 2.00 106±3 1.00 105±3 0.20 93±2 0.06 PFOA 100±5 5.90 94±13 2.95 108±6 0.59 110±3 0.13 PFNA 104±3 2.00 104±14 1.00 102±2 0.20 97±3 0.06 PFDA 110±2 2.00 85±7 1.00 87±4 0.20 83±6 0.06 PFUnA 110±8 2.00 82±5 1.00 77±11 0.20 67±7 0.06 PFDoA 108±10 2.00 92±4 1.00 85±3 0.20 66±10 0.06 PFTA 95±8 2.00 96±9 1.00 77±5 0.20 60±18 0.15 PFBS 87±6 1.50 103±11 0.75 109±4 0.15 107±10 0.15 PFHxS 104±8 1.50 101±10 0.75 110±3 0.15 103±7 0.09 PFOS 97±3 11.80 96±3 5.90 99±3 1.18 105±10 0.25 a Recovery % ± RSD%

17 Table S2. Concentrations (ng L-1) of PFAAs in landfill leachate samples from China a.

PFPrA PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA ∑PFCAs PFBS PFHxS PFOS ∑PFSAs ∑PFAAs b CZ Raw leachate 638(2) 1100(1) 609(11) 269(8) 75.4(4) 990(8) n.d.c n.d. 3690 2440(7) n.d. 1150(11) 3600 7280 Bioreactor supernatant 156(8) 1000(10) 478(3) 112(7) 37.4(5) 971(8) 21(4) 8(9) 2790 1520(7) 28.8(7) 238(11) 1780 4570 Sludge (ng g-1) 0.130(2) 1.36(4) 3.35(5) 1.02(7) 0.468(7) 38.2 (7) 1.73(6) 1.55(7) 47.8 12.5(3) 0.862(5) 13.6 (6) 27.1 74.9 UF effluent n.d. 95.1(6) n.d. 155(11) 12.8(11) 808(4) 19.7(7) n.d. 1090 1300(8) n.d. 49(5) 1350 2440 NF effluent n.d. 90.8(5) n.d. n.d. n.d. 151(6) n.d. n.d. 241 617(13) n.d. n.d. 617 859 NF concentrate n.d. 418(6) n.d. 306(9) 154(1) 2400(7) 14.0(7) n.d. 3290 4010(5) n.d. 275(3) 4290 7580 GZ Raw leachate 5880(9) 2720(8) 2130(2) 146(11) 128(7) 281(3) 81.4(6) 18.8(7) 11400 9240(10) n.d. 1450(8) 10700 22100 Bioreactor supernatant 4760(2) 3160(5) 2230(10) 61.5(8) 133(6) 543(8) 15.3(6) 8.42(5) 10900 6350(3) 93.4(7) 324(10) 6760 17700 Sludge (ng g-1) 18.1(9) 6.33(10) 7.60(8) n.d. 2.11(3) 14.9(7) 5.07(4) 1.64(10) 55.8 43.0(7) 0.766(13) 11.5(4) 55.2 111 UF effluent 2250(8) 117(5) 225(6) n.d. n.d. 670(11) 15.8(6) n.d. 3280 2690(7) 45.5(6) 123(5) 2850 6130 RO effluent n.d. n.d. n.d. n.d. n.d. 30.7(8) n.d. n.d. 30.7 83.4(4) n.d. 11.0(8) 94.5 125 RO concentrate 4110(10) 260(5) 1090(7) 52.7(6) n.d. 1900(6) 126(4) n.d. 7530 11300(6) n.d. 279(10) 11600 19100 NJ Raw leachate 3490(8) 1170(10) 1530(12) 233(7) 176(5) 2260(5) 1.56(4) n.d. 8870 1600(6) 34.6(10) 1740(7) 3370 12200 Bioreactor supernatant 60.9(4) 1590(8) 1220(7) 103(13) 127(5) 909(6) 1.88(5) n.d. 4020 1180(10) 2.69(8) 263(10) 1450 5470 Sludge (ng g-1) n.d. n.d. 23.5(6) n.d. 8.14(1) 29.9(3) 3.91(14) 3.55(5) 69.1 2.86(1) n.d. 18.5(3) 21.4 90.4 UF effluent n.d. 181(13) n.d. n.d. n.d. 862(6) n.d. n.d. 1042 872(7) n.d. 218(2) 1090 2130 NF effluent n.d. n.d. n.d. n.d. n.d. 31.9(11) n.d. n.d. 31.9 72.2(8) n.d. 17.8(5) 90.0 122 NF concentrate n.d. 366(5) n.d. n.d. n.d. 1500(7) n.d. n.d. 1862 3430(5) n.d. 318(6) 3750 5610 SH Raw leachate 10000(4) 3330(7) 6530(3) 4430(7) 5830(12) 214000(3) 268(4) 1.51(7) 244000 41600(8) 140(4) 6020(10) 47700 292000 Bioreactor 2850(3) 6260(13) 5290(2) 3710(7) 2560(9) 70900(7) 68.9(4) 50.0(7) 91700 18300(6) 242(6) 494(5) 19000 111000

18 supernatant Sludge (ng g-1) 18.1(7) 40.3 (9) 15.6(6) 34.6(4) 26.7(13) 1300(8) 5.62(6) 7.83(7) 1450 189(4) 1.65(6) 50.4(8) 241 1690 UF effluent 726(4) 1590(9) 1100(8) 3030(8) 2840(1) 48300(3) 91.3(8) n.d. 57700 21000(10) 121(10) 222(12) 21300 79000 RO effluent n.d. 6.74(4) n.d. n.d. n.d. 94.8(6) 1.59(5) n.d. 103 63.2(3) 2.09(6) 21.9(1) 87 190 RO concentrate 983(6) 1690(7) 2000(10) 7780(4) 8240(12) 206000(3) 239(6) n.d. 227000 54600(5) 416(3) 798(8) 55900 282000 SZ Raw leachate 9350(11) 9270(6) 1670(11) 2070(12) 277(7) 28700(11) 381(3) n.d. 51700 21300(9) 479(7) 3220(9) 25000 76800 Bioreactor supernatant 2370(8) 8500(13) 1970(2) 752(5) 172(2) 29600(7) 76.7(10) 24.7(9) 43400 17500(4) 242(8) 717(5) 18500 61900 Sludge (ng g-1) 16.8(4) 61.3(5) 5.81(5) 4.93(5) 5.10(11) 836(6) 5.62(5) 11.1(5) 946 130(4) 1.46(9) 116(7) 247 1190 UF effluent 459(10) 93.4(7) n.d. 521(9) n.d. 24300(7) 49.6(6) n.d. 25400 13100(6) 80.1(10) 374(1) 13600 39000 RO effluent n.d. n.d. n.d. n.d. n.d. 55.0(11) n.d. n.d. 55.0 22.4(11) n.d. 21.0(8) 43.4 98.4 RO concentrate 1570(8) 228(9) n.d. 2960(10) n.d. 93300(7) 267(5) n.d. 98300 55300(10) n.d. 1670(7) 56900 155000 a Values in parentheses are % relative standard deviations (RSDs, n=3). b Total concentration of PFAAs, which is calculated using MDL or one-half of MQL, whichever is greater, when the value is