Occurrence and fate of trace contaminants during aerobic and anaerobic sludge digestion and dewatering

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1 Supplementary Information Occurrence and fate of trace contaminants during aerobic and anaerobic sludge digestion and dewatering Paula Guerra 1, Sonya Kleywegt 2, Michael Payne 3, M. Lewina Svoboda 1, Hing-Biu (Bill) Lee 1, Eric Reiner 4, T. Kolic 4, Chris Metcalfe 5, Shirley Anne Smyth 1* 1. Science and Technology Branch, Environment Canada, 867 Lakeshore Rd, Burlington, ON L7R 4A6, Canada 2. Standards Development Branch, Ontario Ministry of Environment, 40 St. Clair Ave. West, Toronto, ON, M4V 1M2, Canada 3. Black Lake Environmental; 246 Black Lake Road, Route 2, Perth ON, L7H 3C5 4. Laboratory Services Branch, Ontario Ministry of Environment, 125 Resources Rd, Etobicoke, ON M9P 3V6, Canada 5. Water Quality Centre, Trent University, 1600 West Bank Drive, Peterborough, ON K9J 7B8, Canada *Corresponding author address: Table S1. Summary of sludge treatment, sampling points, and temperatures Table S2. Median ratios of Volatile to Total Solids (VS/TS) Table S3. Summary of methods used for extraction, cleanup, and analysis of pharmaceuticals in liquid and solid samples Table S4. Summary of Mann-Whitney test results. Figure S1. Mean concentrations of individual and total musks in aerobically digested and centrifuged dewatered at Plant P (ng/g, n=3) S1

2 Table S1. Summary of sludge treatment, sampling points, and temperatures. WWTP P R S Wastewater Treatment Process type Extended aeration Extended aeration Extended aeration Solids Digestion Process type Aerobic Aerobic Aerobic Season Cold (March 2008) Sampling Point Mean Sample temperatures ( C, n=3 ) Season Sampling Point Mean Sample temperatures ( C, n=3) WAS 11.0 WAS not applicable not applicable Centrate WAS 9.0 Warm (July/ Centrate WAS 21.7 August ) 24.0 WAS 9.7 WAS Supernatant not applicable Supernatant not applicable A G Conventional activated sludge Activated sludge with nitrification Mesophilic Anaerobic Mesophilic Anaerobic (April 2008) (April 2008) Primary sludge Thickened WAS Dewatering centrate liquid Primary sludge Thickened WAS not available not available Dewatering filtrate WAS: waste activated sludge, WWTP: waste water treatment plant. S2

3 Table S2. Median ratios of volatile to total solids (VS/TS). Process, sampling point and temperature Median VS/TS Number of measurements Aerobic raw warm all Aerobic digested warm all Aerobic digested warm P only Aerobic dewatered warm P only Aerobic raw cold Aerobic digested cold Aerobic digested cold P only Aerobic dewatered cold P only Anaerobic primary A Anaerobic WAS A Anaerobic digested A Anaerobic dewatered A Anaerobic primary G Anaerobic WAS G Anaerobic digested G Anaerobic dewatered G WAS: waste activated sludge. S3

4 Table S3. Summary of methods used for extraction, cleanup, and analysis of pharmaceuticals in liquid and solid samples (Topp et al 2008, Edwards et al 2009). Method Cotinine, carbamazepine, caffeine, trimethoprim Atenolol, propranolol, nadolol, sotalol, metoprolol Sulfamethoxazole, sufapyridine Triclosan, triclocarban PLE 90 C/3 50 C/2 25 C/2 60 C/3 (temperature/cycle) PLE extraction Acetone/water (30:70) Methanol/water/Acetic 0.05 M phosphoric Dichloromethane (DCM) solvent acid (49:49:2) acid/methanol (50:50) SPE cleanup Oasis HLB Oasis MCX Oasis HLB Oasis HLB SPE elution solvent 3x3mL methanol 3x3mL 5% ammonium hydroxide in methanol LC-MS/MS analysis 0.1% formic acid solution and acetonitrile mobile phase, QTRAP mass spectrometer with atmospheric pressure chemical ionization (APCI), positive mode. acetonitrile and 20mM aqueous ammonium acetate, Quattro LC triple quadrupole mass spectrometer with electrospray (ESI), positive mode. 2x3mL of methanol;3 ml 2% ammonium hydroxide in methanol 0.1% formic acid solution and acetonitrile mobile phase, QTRAP mass spectrometer with atmospheric pressure chemical ionization (APCI), positive mode Wash step with 2mL of hexane, 2x2mL DCM, 2x3mL water; elute with 3x3mL methanol/acetone (50:50) acetonitrile and 20mM aqueous ammonium acetate, Quattro LC triple quadrupole mass spectrometer with ESI, negative mode S4

5 Details of Analytical Method for PBDEs in sludge and Samples (1-2 g) were weighed into a glass-fritted thimble containing a 2 4 mm layer of silica and were fortified with 13C12 BDE labeled quantification standards that contained at least one BDE congener per homologue group (BDE 28, 47, 99, 153, 154, 183, 209). Samples were Soxhlet extracted overnight in toluene for approximately h. The obtained extracts were cleaned using a 2 stage cleanup. The first cleanup column consisted of layers of AgNO3 silica- NaOH silica H2SO4 silica, which was prewashed with hexane. The sample was added to the column and then eluted with hexane followed by dichloromethane (DCM) hexane. Eluant was collected in a round bottom flask, concentrated, and subjected to alumina cleanup. Alumina column was prewashed with hexane, sample was added and eluted with hexane, which was discarded, followed by CCl4 hexane, which was also discarded. The desired analytes were then eluted into a round bottom flask with methanol (MeOH) DCM. Extracts were analyzed by gas chromatography with high resolution mass spectrometry (GC-HRMS) instrumentation in EI positive using isotope dilution. The chromatographic separation was carried out on a DB-5HT 15 m 0.25 mm 0.10 μm. PBDEs in centrate and filtrate were extracted by C18 solid phase adsorption disk without prior filtration, eluted using toluene/ethanol, cleaned up using single stage silica cleanup, and analyzed by GC-HRMS (Ontario Ministry of the Environment, 2004). S5

6 Table S4. Summary of Mann-Whitney test results. Higher levels (p<0.05) in digested Higher levels (p<0.05) in WAS Higher levels (p<0.05) in cold WAS Higher levels (p<0.05) in PS Higher levels(p<0.05) in anaerobically digested Aerobic digestion WAS vs. digested Caffeine, Sulfapyridine cold vs. warm WAS cold vs. warm digested Anaerobic digestion propanolol, sulfamethoxazole, triclosan, ADBI, AHDI, ATII, HHCB, AHTN, MK, MX propanolol, sulfamethoxazole, triclosan, ADBI, AHDI, ATII, HHCB, AHTN, MK, PS vs. digested caffeine, trimethoprim, sotalol TWAS vs. digested carbamazepine, atenolol, propanolol, nadolol, triclosan, triclocarban digested vs. dewatered sulfamethoxazole Aerobic digestion vs. Anaerobic digestion Aerobic digested (both seasons) vs. anaerobic digested Aerobic digested (cold) vs. anaerobic digested WAS: waste activated sludge, PS: primary sludge, TWAS: thickened waste activated sludge. carbamazepine, metoprolol, triclosan, triclocarban, total musks, total PBDEs atenolol, propanolol, sulfamethoxazole S6

7 DPMI ADBI AHDI ATII HHCB AHTN MX MK 100,000 Median musk concentration (ng/g) 10,000 1, Biosolids Cold Biosolids Warm Biosolids Cold Biosolids Warm Temperature and soilds type, Aerobic Digestion DPMI ADBI AHDI ATII HHCB AHTN MX MK 100,000 10,000 Median musk concentration 1, Biosolids Cold Biosolids Warm Biosolids Cold Biosolids Warm Temperature and soilds type, Aerobic Digestion Figure S1. Mean concentrations of individual musks in aerobically digested and centrifuged dewatered at Plant P (ng/g, n=3). S7