Quality assessment of digested sludge produced by different advanced stabilization processes

Transcription

1 Quality assessment of digested sludge produced by different advanced stabilization processes C.M. Braguglia* 1, A. Coors 2, A. Gallipoli 1, A. Gianico 1, E. Guillon 3, U. Kunkel 4, G. Mascolo 5,E. Richter 2, M.C. Tomei 1, T.A. Ternes 4, G. Mininni 1 1 Istituto di Ricerca sulle Acque-CNR, Area della Ricerca RM1, Monterotondo (Rome), Italy 2 ECT Oekotoxikologie, Flörsheim/Main, Germany 3 GRECI (Groupe de Recherche En Chimie Inorganique), Universite de Reims Champagne-Ardenne, Reims, France 4 Federal Institute of Hydrology (BfG), Koblenz, Germany 5 Istituto di Ricerca sulle Acque-CNR, Bari, Italy *Corresponding author. Tel.: ; fax: address: braguglia@irsa.cnr.it

2 Online Resource 1. List of analysed linearalkylbenzenesulphonates (LAS) by HPLC/MS Compound Target ion (m z -1 ) C10-LAS 297 C11-LAS 311 C12-LAS 325 C13-LAS 339 C14-LAS 353 C8-LAS (intern std) 269 Online Resource 2. List of analysed nonylphenolethoxylates by UPLC/MS-MS. Compound abbreviation CAS # LOQ polarity Precursor Product ion ion (m z -1 ) (m z -1 ) 4-tert-Octylphenol OP1EO (+) monoethoxylate 4-tert-Octylphenol diethoxylate OP2EO (+) onylphenol monoethoxylate NP1EO n.a. 0.8 (+) (technical) Nonylphenol diethoxylate NP2EO n.a. 0.8 (+) (technical) 13 C 6 4-tert-Octylphenol OP2EO-C13 (+) diethoxylate, labeled 4-n-octylphenol 4n-OP (-) t-octylphenol t-op (-) t-nonylphenol (technical) t-np (-) nonylphenol 4n-NP (-) C 6 4-t-octylphenol, labeled t-op-c13 (-) Online Resource 3. List of analysed PAHs by GC/MS. Compound CAS # LOQ molecular ion (m z -1 ) Naphthalene Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Indeno[1,2,3-cd]pyrene Dibenzo[a,h]anthracene Benzo[g,h,i]perylene

3 Online Resource 4: List of analysed PCBs by GC/MS-MS. Compound CAS # LOQ Precursor ion (m z -1 ) Product ions scan range (m z -1 ) PCB PCB PCB PCB PCB PCB PCB C 12 PCB-104, labelled Online Resource 5. List of analysed phthalates by GC/MS. Compound CAS # LOQ molecular ion (m z -1 ) Dimethyl phthalate Diethyl phthalate Di-n-butyl phathalate Butyl benzyl phathalate Bis (2-ethylexyl) phthalate Di-n-octyl phathalate Online Resource 6. List of analyzed quaternary ammonia compounds (QACs) Compound CAS # (*) LOQ polarity Precursor ion Product ions (m z -1 ) (m z -1 ) Benzethonium chloride (+) /72 Benzyldimethyldodecylammonium chloride (+) /212 Benzyldimethylhexadecylammonium chloride (+) /268 Benzyldimethyloctadecylammonium chloride (+) /296 Benzyldimethyltetradecylammonium chloride (+) /240 Benzyltributylammonium chloride (+) /187 Bis(triphenylphos-phoranylidene) (+) /384 Dibenzyldimethylammonium chloride (+) /134 Didecyldimethylammonium chloride (+) /43 Didodecyldimethylammonium chloride (+) /43 Ditetradecyldimethylammonium chloride (+) /57 Dodecyltrimethylammonium chloride (+) /60 Ethylhexadecyldimethylammonium chloride (+) /43 Hexadecyltrimethylammonium chloride (+) /57 Octadecyltrimethylammonium chloride (+) /43 Tetrabutylammonium chloride (+) /100 Tetradecyltrimethylammonium chloride (+) /43 Tetrapropylammonium chloride (+) /144 Tributylmethylammonium chloride (+) /100 Vinylbenzyltrimethylammonium chloride (+) /58 (*) CAS number for the chloride salt, some substances was alternatively purchased as bromide salt

4 Online resource 7. List of analyzed pharmaceuticals, biocides, and fungicides Compound Compound class CAS # LOQ polarity Precursor ion Product ions (m z -1 ) (m/z) Acetylsulfamethoxazole (Ac- (+) /188 Pharmaceutical SMX) 15 Bezafibrate Pharmaceutical (-) /154 Carbamazepine Pharmaceutical (+) /179 Clarithromycin Pharmaceutical (+) /590 Dihydrodihydroxycarbamazepine (+) /180 Pharmaceutical (DHDH-CBZ) 25 Dihydrohydroxycarbamazepine (+) /194 Pharmaceutical (DHH-CBZ) 25 Diclofenac Pharmaceutical (+) /215 Metoprolol Pharmaceutical (+) /74 Primidone Pharmaceutical (+) /162 Sulfamethoxazole (SMX) Pharmaceutical (+) /188 Trimethoprim Pharmaceutical (+) /261 Venlafaxine Pharmaceutical (+) /58 2-Benzyl-4-chlorophenol Biocide (-) /181 Carbendazim Fungicide (+) /132 Climbazole Fungicide (+) /69 Diuron Biocide (+) 233/235 72/72 Fluconazole Fungicide (+) /238 Irgarol (Cybutryn) Biocide (+) /83 Isoproturone Biocide (+) /165 Propiconazole Fungicide (+) 342/ /161 Tebuconazole Fungicide (+) 308/310 70/70 Terbutryn Biocide (+) /91 Mecoprop Biocide (-) /71 Triclocarban (TCC) Biocide (-) 313/ /162 Triclosan (TCS) Biocide (-) 287/289 35/37

5 Online Resource 8. EU limit values for concentration of heavy metals in biosolids for use on land Element Limit Values (mg kg -1 ) Directive 86/279/EEC 3rd Draft (CEC 2000) Cd Cr Cu Hg Ni Pb Zn Online Resource 9. Concentration (mg kg -1 ) of heavy metals in the feed sludges of TT Test 1 Test 2 TT-FU TT-FP TT-FU TT-FP Cd 0.8± ± ±0.04 1±0.03 Cr 28.6± ± ± ±0.2 Cu 205±1 192±1 241± ±1.2 Ni 30±0.5 22±0.2 29± ±0.3 Pb 94.3± ± ±0.4 87±0.4 Zn 662±3 651±3 764±4 616±3 Hg n.d. n.d. n.d. n.d. n.d. not determined Online Resource 10. Concentration (mg kg -1 ) of heavy metals in the feed sludges of UMT UMT-FU UMT-FP Cd 1.2± ±0.03 Cr 19.6± ±0.1 Cu 144±1 137±1 Ni 14± ±0.1 Pb 58±0.3 57±0.2 Zn 442±2 423±2 Hg 0.5± ±0.04 Online Resource 11. Concentration (mg kg -1 ) of heavy metals in the feed sludges of AA AA-FU AA-FU (secondary) (mixed) Cd 1±0.03 1±0.03 Cr 26.1±0.3 26±0.2

6 Cu 234± ±1.5 Ni 38.1±0.2 28±0.1 Pb 94± ±0.4 Zn 720±4 771±4 Hg n.d. n.d. n.d. not determined Online Resource 12. Proposed limit concentrations for organic pollutants in biosolids (CEC 2000) Pollutants Limit Concentration (mg kg -1 ) Halogenated organic compounds 500 Linear alkylbenzene sulphonates 2600 Di(2-ethylhexyl)phthalate 100 Nonylphenol and nonylphenolethoxylates PAHs 6 50 Polychlorinated biphenyls 0.8 Polychlorinated dibenzodioxins/dibenzofurans (total equivalents) Online Resource 13. Concentration of conventional organic micropollutants in the feed sludges of TT Test 1 TT-FU TT-FP EOX µgcl kg ± total non-ionic surfactants µg kg ± ±66 total anionic surfactants mg kg ±10 310±15 total PAHs µg kg ± ±83 total PCBs µg kg ± ±0.4 total Phthalates µg kg ± ±1286 Test 2 TT-FU TT-FP EOX µgcl kg ± ±220 total non-ionic surfactants µg kg ± ±48 total anionic surfactants mg kg ±16 91±9 total PAHs µg kg ± ±103 total PCBs µg kg -1 11±0.6 11±0.6 total Phthalates µg kg ± ±2844

7 Online Resource 14. Concentration of conventional organic micropollutants in the feed sludges of UMT EOX µgcl kg ± ±1100 total non-ionic surfactants µg kg ±9 2264±21 total anionic surfactants mg kg ±54 486±38 total PAHs µg kg ± ±134 total PCBs µg kg ± ±0.1 total Phthalates µg kg ± ±3478 FU FP Online Resource 15. Concentration of conventional organic micropollutants in the feed sludges of AA AA-FU (secondary) AA-FU (mixed) EOX µgcl kg ± ±40 total non-ionic surfactants µg kg ± ±35 total anionic surfactants mg kg -1 n.d. 1550±14 total PAHs µg kg ± ±145 total PCBs µg kg -1 22±0.5 42±1.5 total Phthalates µg kg ± ±3550 Online Resource 16. Concentration of emerging micropollutants in the feed sludges of TT Test 1 TT-FU TT-FP QACs µg kg ± ±1300 Pharmaceuticals µg kg ± ±5.3 Biocides and fungicides µg kg ± ±160 Test 2 TT-FU TT-FP QACs µg kg ± ±900 Pharmaceuticals µg kg ± ±6.5 Biocides and fungicides µg kg ± ±170 Online Resource 17. Concentration of emerging organic micropollutants in the feed sludges of UMT UMT-FU UMT-FP QACs µg kg ± ±3300 Pharmaceuticals µg kg ±31 130±27 Biocides and fungicides µg kg ± ±390

8 Online Resource 18. Concentration of emerging organic micropollutants in the feed sludges of AA AA-FU(secondary) AA-FU(mixed) QACs µg kg ± ±6300 Pharmaceuticals µg kg ± ±10 Biocides and fungicides µg kg ± ±460 Online Resource 19: Results of biotests with sludge samples Sample code and experiment Inhibition of dehydrogenase activity in A. globiformis, EC 50 [g kg -1 ] 1 Avoidance behaviour of earthworms (%) 2 TT-FU_I 40 (35-48) n.d. TT-DU_I 30 (26-36) n.d. TT-FP_I 59 (49-71) n.d. TT-DP_I 217 ( ) n.d. TT-FU_II 25 (14-36) 85 (9) TT-DU_II 31 (19-43) 28 (23) TT-FP_II 15 (4-25) 64 (15) TT-DP_II 36 (25-46) 68 (23) UMT-FU_I 104 (69-194) 36 (26) UMT-MDU_I 405 ( ) -37 (36) UMT-MTDU_I 88 (67-127) -6 (50) UMT-FP_I 38 (23-93) 64 (22) UMT-MDP_I 203 ( ) 8 (47) UMT-MTDP_I 110 (83-152) -32 (39) AA-FU_I 55 (44-70) 68 (27) AA-DAA_I 373 ( ) 52 (23) AA-FU_II 1 (0-3) n.d. AA-DAA_II 19 (15-23) n.d. CAN_I 1544 ( ) 22 (30) CAN_II 889 ( ) -8 (42) 1 Arthrobacter globiformis test (ISO 2012). Shown are estimated sample concentration causing 50% effect compared to quartz sand control (EC50), and their 95% confidence intervalls. Values in italic indicate extrapolated EC50. Measurements based on four biological replicates. 2 Earthworm (Eisenia fetida) avoidance test (ISO 2008). Shown are mean avoidance responses (%) with their standard deviation tested at a concentration of 25 g sludge/kg soil d.w.