Removal of priority and emerging substances by municipal treatment plants

Transcription

1 Session 2: Existing and upcoming pressures Removal of priority and emerging substances by municipal treatment plants Jean-Marc CHOUBERT and Marina COQUERY Institut de Recherche en Ingénierie de l Agriculture et de l Environnement (CEMAGREF) 7th EWA Brussels Conference - 25 th October 2011 Effective Urban Waste Water Treatment

2 Context and challenge Fate through municipal treatment plants Conclusions and perspectives AMPERES project 21 WWTPs 250 samples 127 substances > 3000 analyses 15 analytical methods Station d épuration de Pierre-Bénite ( Le Grand Lyon/J. Léone) 2

3 What are we talking about? Micropollutants= Change of scale in comparison to conventional pollutants (C, N, P) Pollutants harmful at low concentration levels (µg/l, may be ng/l) Difficult to measure and need expertise for data analysis Macropollutants TSS, COD, BOD 5, NH 4, NO 3, PO 4,... Micropollutants organic Polycyclic aromatic hydrocarbures (PAH), Phenols, Plasticizers, Organic chlorinated solvants, Phtalates, Detergents, Pesticides, PCB inorganic Pb, Hg, Cd, Ni, Cu, Zn, As, Cr, Co, Fe, Ag, Ti 3 Pharmaceuticals, Hormones, New substances (emergents)

4 4 41 substances for the good chemical status WFD (EC, 2008) 8 substances DDT (avec DDD et DDE) Aldrine Dieldrine Endrine Isodrine Tétrachlorure de carbone Tétrachloroethylene Trichloroethylene 18 Substances liste I Dir 76/464/CEE Cadmium Hexachlorobenzene Hexachlorobutadiene Hexachlorocyclohexane Mercury 1.2 Dichloroethane Pentachlorophénol Trichlorobenzene Trichloromethane (chloroforme) 139 relevant substances liste II - Dir 76/464/CEE Regulation aspects Brominated diphenylether C10-13-chloroalcanes Nonylphenols Pentachlorobenzene Tributyl(tin Alachlore Octylphenols Chlorfenvinphos Chlorpyrifos Di(2-éthylhexyl)phtalate (DEHP) Diuron Isoproturon PAHs Anthracene, Naphthalene Fluoranthene Benzène, Dichloromethane Atrazine Endosulfan Simazine Trifluraline Lead, Nickel Chlorobenzene Chloroprene 3-chloroprene Dichlorobenzenes 1.1 Dichloroethane Ethylbenzene Monovinyl chloride Toluene, Xylenes Trichloroethanes Metals (Cu, Zn, Cr, ) others pesticides, etc 33 priority substances WFD Hazardous priority substances Priority substances Specific list for industry (RSDE, France) + Emerging pollutants On-going revisions of the list

5 Occurence of priority substances in municipal raw wastewater Occurrence Frequence wastewater of : quantification frequence Metals Priority substances (to be reduced) Nickel Lead Priority substances (WFD) Hazardous priority substances (to be stopped) Cadmium Mercury Additional Other dangeroous emerging substances substances with EQS High (frequence > 70%) Medium (frequence 10% - 70%) Low (frequence < 10%) 15 WWTPs (32 samples) PAH Pesticides Industry Solvents and surfactants Fluoranthene Anthracene Naphtalene Benzo(a)pyrene Benzo(b)fluoranthene Benzo(g,h,i)perylene Benzo(k)fluoranthene Indeno(1,2,3-cd)pyrene Alachlor Hexachlorocyclohexane Aldrin Chlorfenvinphos Endosulfan DDT Chlorpyrifos Tributyltin Dieldrin Diuron Endrin Isoproturon Isodrin Atrazine Trifluraline Simazine Pentachlorophenol Benzene Hexachlorobutadiene Trichlorobenzene C10-13 Chloroalcanes DEHP Pentachlorobenzene Hexachlorobenzene Pentabromodiphenylether Dichloroethane Nonylphenols Carbon tetrachloride Dichloromethane Tetrachloroethylene Chloroform Trichloroéthylène Octylphenols 21 priority substances measured at concentrations > 0.1 µg/l; concentrations > 1 µg/l in raw WW for : DEHP, (di-,tri-)chloromethane, tetra-chlorethylene, PBDE (deca, tri), 5 C10-C13 chloroalcanes, triclosan, alkylphenols, metals

6 Loads received (dry weather, municipal WWTPs) DEHP 2% Pha rmac eutiques 15% Pharmaceuticals 15% DEHP 2% Alkylphenols Alkylphé nols 0.3% VOCs 0.1% COV 0.1% Others 1.2% A utres 1.2% Metals 82% Metaux 82% Median (g /d /PE) Total load Metals Pharmaceuticals DEHP Alkylphenols VOCs Others Main loads in wastewater : metals > pharmaceuticals > DEHP > Alkylphenols > VOCs > other organics 6 WWTP not designed to remove micropollutants reduction of load in conventional WWTP by 80% Some micropollutants still present in natural waters (carbamazepine, AMPA, nonyphenol)

7 Partition (dissolved/particular) in domestic WW organic substances Chloroalcanes Benzo(b,k)fluoranthene Benzoperylene Hexachlorocyclohexane Indenopyrene PBDE (pentabde) Trichlorobenzene Alkylphenols (NP2EO, NP1EO, NP, OP, NP1EC) Chlorpyrifos DEHP Fluoranthene Amitriptyline Bromazepam Doxepine Fluoxetine Hydrophilic pesticides Betablockers Cafeine Carbamazepine Diazepam Hormones Nordiazepam Naphtalene Terbutaline Theophylline Salbutamol Paracetamol Tributylphosphate Benzothiazoles 4-Terbutylphenols Pharmaceuticals Priority substances 7 30% 70% AMPERES project % in dissolved phase C_dissolved C_total

8 Partition (dissolved/particular) in domestic WW inorganic substances Ag Hg Al 100% 80% 60% B Li Rb f_diss moyen C_dissolved C_total Mo Fe 40% As Pb Sn 20% 0% U Ni Cd Co Zn Se 8 Cu Ba Cr Sb Ti AMPERES project

9 Context and challenge Fate through municipal treatment plants Conclusions and perspectives AMPERES project 21 WWTPs 250 samples 127 substances > 3000 analyses 15 analytical methods Station d épuration de Pierre-Bénite ( Le Grand Lyon/J. Léone) 9

10 Transformation pathways Substance Aeration supply Stripping / volatilisation volatile for H > 500 Pa.m 3 /mol Not volatile if H < 10 Pa.m3/mol CO 2 +H 2 O by-products Sorption Adsorbable if log Kow > 5 Poorly adsorbable if log Kow < 3 Biological sludge Biodegradation + hydrolysis Better knowledge required: Biodegradable if T 1/2 < 10 d Non biodegradable if T 1/2 > 500 d 1. Towards reliable predictions for transformation processes? which mechanism is predominant for each micropollutant? elimination rate? available fraction? what happens under anoxic conditions and N-removal? 2. Towards reliable data and interpretation for WWTP? assess treatment efficiency + role of operating conditions (conventional WWTP)? Quantify 10 occurrence and concentrations. Identify promising technical solutions? collaborations needed between chemists and process engineers

11 Evaluation of various treatment processes [primary + secondary treatment (C) / more rigorous treatment (C+N)] Municipal WWTP: 7 rural / 14 urban Supplementary treatment studied: Conventional (chemical settling, polishing pond, sand filtration) and Advanced (reverse osmosis, ozone oxydation, activated carbon filtration) Sludge treatment (drying reed bed, anaerobic digestion, composting) 11 AMPERES project

12 Examples of analytical requirements Raw and treated wastewater; solid matrices (suspended solids, sludge) Family of compounds Semi-volatiles (PAH, pesticides, DEHP, ) Dissolved (ng/l) Sludge (µg/g MS) Volatiles Purge and Trap GC-MS 20 to to 1 Multi-residues ELL-GC- MS Chlorophenols 50 to SPME-GC-MS Antibiotics and pesticides hydrophilic 1 to to 20 SPE extraction HPLC-MS-MS Glyphosate, AMPA LC-ESI(+) MS-MS PBDE, bisphénol A, triclosan 1 to to 0.05 SBSE-TD-GC-MS C10-C13 chloroalcanes SBSE-TD-GC-ECD Metals (22 elements) 10 to to 3 ICP-MS Mercury 0,5 0,01 pre-concentration, AFS Alkylphenols + polyethoxylates 1 to to 0.1 LC-ESI-MS Hormones (free and total, after deconjugation) 0.5 to 5 - Betablockers 1 to 10 - Analgesics, anti-inflammatories, hypolipemiants, bronchodilatants, 0.5 to to 0.01 Analysis method SPE extraction LC-ESI(-) MS-MS SPE extraction LC-ESI(+) MS-MS SPE extraction UPLC-MS-MS ESI(-or+) 12 AMPERES project

13 Influent Effluent intermediate Good sampling strategy required! material (glass containers, teflon pipes) + Specific cleaning Checking procedure (blank fields) Flow proportional composite samples Mixing before conditioning 24 containers (2 4 C Buhler 5010 Isco 4230 Q in (m3/h) JOUR 1 JOUR 2 JOUR mai 22-mai 23-mai 24 -mai 2 5-ma Hourly inflow rate (m 3 /h) Average sample (glass, 20L) 13 D 9h D+1 9h D+1 : 9h 12h D 1 ; D 2

14 Measured concentration 10 LoQ (threshold) LoQ WW 0 High level Low level 14 Quantified (<30% accuracy) Quantified (50-100% accuracy) Not quantified (Detection zone) RET R 2 Water treatment line Sludge treatment line Specific data processing required (R) Always compare to limit of quantification (LoQ)! LS Is the calculation of (R) possible? Allowed Prohibited R 4 TW DS Case 1 (in) (out) (in) AMPERES project Case 2 (a) (out) (b) Max R & 2 R Min 2 [%] (in) (out) 100% 80% 60% 40% 20% % 30-70% <30% Case 3 (in) (out) Case 4 (out) (out) LoQ/2 Ex. case 3 R values of 50% or 75% indifferently calculated considering uncertainties (sampling and analytical) Choubert J.-M., et al. (2011). Mesurer les rendements d élimination des micropolluants. Techniques Sciences et Méthodes 1-2. R 2 (B)=60% R 2 (A)=88% 0% R 2 [%] 0% 20% 40% 60% 80% 100% peu éliminé Uncertainties R 2 Max R 2 R 2 Min R 2 Max (B) R 2 Min (B) (B) R 2 Max (A) R 2 Min (A) (A) < 30% 30-70% % R 2

15 Removal efficiencies: Primary treatment; Secondary treatment (C), More rigorous treatment (C+N) Efficiency < 30% 30% < Efficiency < 70% Efficiency >70% C removal C+N removal Primary settling (PS) Primary settling + reactant (PSR) PS + CAS medium load PSR + Biofilter (1 stage) PSR + MBBR PSR + Biofilter (2 stages) Constructed wetlands CAS low load Number of substances with calculable efficiency MBR AMPERES project 15

16 BDE: Deca Bisphenol A Trichlorobenzene chlorophenols:mono,di Chlorpyrifos, tributyl-sn metals (Ni,Zn, Se, Mo, Cd, Ba, U) benzothiazole betablockers (métop, timol., aténol.) antibiotic (sulfamethoxazol, roxitromycine) Antidepressants (amitriptyline, doxepine, fluoxetine) COV (di-,tri-chlorométhane; tri-, tétrachloroéthylène) BDE : tri-, tétra-, penta- HAP, DEHP metals (Hg, Al, Ti, Cr, Fe, Cu, Pb) butylphenol : tri, 4-tert triclosan, C 10 -C 13 chloroalcane 16 More rigorous treatment (C+N): Activated sludge COVs, HAP BDE (Octa, Hexa) Chlorobenzene (hexa, penta) Chlorophénols (tri, tetra, penta) pesticides (alachlore, endosulfan, aldrine, DDT, dieldrine, endrine, isodrine) R non % 31-70% Not calculable calculable R > 70% R>70% R<30% R <= 30% AKP (NP, OP, NP1EO) hormones (E1, Eb2, E3) betablockers (nadolol, betaxolol, bisoprol., acebut.) analgesics (paracetamol, aspirine, ibuprofene) other pharmaceuticals (cafeine, theophiline) extended aeration (n=6) 127 substances pesticides (glyphosate, atrazine, diuron, isoprot.)+ampa metals (Li, B, Co, As, Rb) O-Sn: mono, di betablockers (oxprenolol, propanolol, sotalol) antidepressant (carbamazepine, diazepam, nordiazepam) bronchodilat. (salbutamol, terbutaline) diclofenac AMPERES project

17 WW RET R 2 Water treatment line Sludge treatment line Only storage in sludge 0 PAH Metals [Hg, Ni, Cd, Pb, Cr, Sn, Ni, Ag, Al, As, U, Cd] Pesticides [aldrine, DDT, dieldrine, endrine, isodrine, trifluraline] C 10 -C 13 chloroalcanes AKP [OP, 4-17 NP1EC] PBDE, Benzothiazoles LS Transfer + partial conversion DEHP, bisphénol A Triclosan AKP [NP] Hormones + Pharmaceuticals R 4 TW DS Concentration (mg/kgms) Transfer to sludge? Metals and hydrophobic organic substances (ex: industrial products, plasticizers, detergents, PAH) often quantified Pesticides, pharmaceuticals and hormones were quantified < 1 mg/kg DM For metals and HAP, concentrations always below standard (MEEDAD, 1998) Hg Mercure Métaux Metals Concentration (mg/kgms) Cd Cadmium 4 Concentration (mg/kgms) HAP 0 PAH Cmoyenne+/-écart-type Creglementation Fluoranthène Benzo(a)pyrène Benzo(b)fluoranthène Chrome Nickel Cuivre Zinc Plomb 1,5 Cmoyenne+/-écart-type Creglementation Metals Cr Ni Cu Zn Pb 2,5 800

18 Frequence of quantification (%) Priority substances in treated WW >70% Mercure Cadmium 4t-NP, 4t-OP Plomb Diuron DEHP Nickel 30-70% <30% Atrazine Simazine Isoproturon Fluoranthene Trichlorobenzene Pentachlorophenol Benzo(b)fluoranthene Chlorpyrifos Isodrine Tributyl-tin Benzo(k)fluoranthene 1,2-dichloroethane Tetrachlorure de carbone Hexachlorobenzene Pentabromodiphenylether Dieldrine Endosulfan Hexachlorocyclohexane Benzene Aldrine Anthracene Naphtalene Dichloromethane Trichloromethane Trichlororethylene Tétrachloroethylene Never quantified : Benzo(g,h,i)perylene Indeno(1,2,3-cd)pyrene Benzo(a)pyrene C Chloroalcanes Hexachlorobutadiene Pentachlorobenzene Alachlore Chlorfenvinphos Trifluraline DDT Endrine Concentration (µg/l)

19 Other pollutants in treated WW Frequence of quantification (%) <30% 30-70% >70% Monobutyltin 4-tert-butylphenol BisphenolA Tributylphosphate Dibutyltin 2,4,6-tribromophenol Trichlorophenol Tetrabromodiphenylether Decabromodiphenylether Tetrachlorophenol Benzothiazole 4-NP1EO 4-NP2EO Dichlorophenol Glyphosate Tribromodiphenylether Triclosan Monochlorophenol Pharmaceuticals : AMPA 4-NP1EC Concentration (µg/l) 0,01 0, analgesics: paracetamol, ibuprofen, ketoprofen, naproxen, diclofenac betablockers: acebutolol, atenolol, sotalol antibiotics: sulfamethox., roxythromycin antidepressants : carbamazepine Organic substances : Nonylphenol ethoxylates and carboxylates Pesticides: glyphosate / byproduct: AMPA benzothiazole, chlorophenols Flame retardants: bromodiphenylethers Concentration (µg/l) Groupe 2 ACE ATE SOT SFMX ROXI CAF Min Médiane Max Moyenne CARBA IBU PARA KETO NAPRO DICLO THEO Probably others new chemicals, pharmaceuticals, by-products, perfluorinated susbtances, illicit drugs, 19 radiative substances, nanoparticules,

20 Specific treatment for chemical substances? Efficiency of existing technical solutions 20 Polishing processes e.g. sand filtration, rapid settling, pond 30 to 70% removal for less than 20% of susbtances released by secondary treatment (susp. solids) Advanced treatments e.g. reverse osmosis, ozonation, activated carbon 90% removal for a 80% of susbtances released by secondary treatment

21 Context and challenge Fate through municipal treatment plants Conclusions and perspectives Station d épuration de Pierre-Bénite ( Le Grand Lyon/J. Léone) 21

22 22 Conclusions Relevant substances About half of priority substances > 0.1 µg/l in WW. variations with time? variations with seasons? Main loads of micropollutants identified in wastewater : metals > pharmaceuticals > DEHP > Alkylphenols > VOCs > other organics. Partitioning : low SS contribution (pesticides, pharmaceuticals, hormones) high SS contribution (some metals, PAH, PBDE) Treated wastewater: Main concern for Cd, DEHP, diuron, alkylphenols, chloroform Emerging substances of particular concern : By-products (AMPA, NP1EC); Chemicals (triclosan, benzothiazole) Pharmaceuticals (ketoprofen, diclofenac, sotalol, sulfamethoxazole, carbamazepine) Lists of relevant substances in constant evolution : need of screening methods, global ecotoxicity assessment, passive samplers Comparison to other emissions: agriculture (manure, pesticides), geochemical background, storm water Transfer from sludge to groundwater and crops?

23 Conclusions Fate in WWTPs About 80% of the load of micro-pollutants already removed by rigorous WWTP (C+N) SUBSTANCES PARTIALLY REMOVED Removal to optimize alkylphenols (NP, OP, NP1EO) hormones (E1, Eb2, E3) betablockers (nadolol, betaxolol, bisoprol., acebutolol) others (cafeine, theophiline) analgesics. (paracetamol, aspirine, ibuprofene) SUBSTANCES POORLY REMOVED Removal to increase or Consumption to reduce pesticides (glyphosate, AMPA) betablockers (oxprenolol, propranolol, sotalol) antidepress. (carbamazepine, diazepam, nordiazepam) bronchodilat. (salbutamol, terbutaline), anti-inflam. (diclofenac) antibiotic (sulfamethoxazol, roxytromycine) ARMISTIQ Project (ONEMA funding) Influence of biological process design on removal efficiency. Best when full nitrification occurs. How to increase biodegradation? About 2/3 of removed substances mainly transferred to sludge. Identification of promising treatment required? Still research required for setting-up supplementary treatment to remove micro-pollutants Improve source reduction! Need of research studies 23 + preventive approach aiming at reducing the use of chemicals + plan d'action national (29-sept 2011)

24 Conclusions Methodological aspects Winning strategy to deal with micropollutants in wastewater What method for studying micropolluants in raw/treated wastewater? Significance of the definition of objectives before sampling/analysing campaigns Crucial role of the discussions between chemists and process engineers Development, validation and dissemination of analytical methods (WW and sludge) still required Continuous improvement of sampling method and analysis required Crucial role of the definitions of calculation rules for removal rates Storage of data DANGER for sampling / analysis when cost is the only driving force of analytical choice Development of new tools dealing with chemical and biological screening On-going investigations set-up a robust and simple sampling strategy for systematic application by stakeholders (AQUAREF, Improvement of sludge monitoring, need of long-term diagnostic, representativness of sampling and more sensitive analysis sampling uncertainties and impact on the results 24

25 Perspectives How to limit the release in environment? 1. Reduction (sources) preventive approach (permit for sell) environmental citizen practices Limit dosage (laundry, pesticids, hand soap), prefer chemicals with vegetal tensio-actifs, use mecanic cleaning accessory, limit dispersion (disposal in wate collection center, recycling) 2. Optimisation WWTP PRETRAITEMENT TRAITEMENT BIOLOGIQUE CLARIFICATION 3. Supplementary treatment FILTRATION (activated carbon, clay, zeolite) Ultra-FILTRATION (membranes) OXYDATION (ozone, H 2 O 2 ) Photo-Phyto-DEGRADATION (UV, plants) 25

26 Perspectives Evolution of superficial water quality after both source reduction of P + DERU application source: French Ministry of the Environment (B. Rakedjian) source : DEB - MEDDTL - autostep 100 Conventional parameters DBO5 DCO NTK NGL Pt Rdt 60 PO Overall removal of french sewer prev année PO4 Micropollutants Pharmaceuticals PAH 26 PCB

27 Perspectives Emissions in the urban water cycle source: Axelera, Rhodanos Atmosphere Rain event / Storm Domestic Domestic WWTP Industries Industrial WWTP Ground water Agriculture (pesticides, fertilizers) Run-off Infiltration Sludge and by-products 27 Emission Transport / Treatment Receiving body

28 !! THANK YOU FOR YOUR KIND ATTENTION!! funding Contacts: collaborations Team leaders Samuel Martin Mar Esperanza Hélène Budzinski Céline Lagarrigue 28 REFERENCES Micropollutants: what efficiency can we expect from WWTP? WS&T 63(1), Advanced and conventional supplementary treatments. WS&T 63(11), Metals through municipal WWTP. WS&T 63(9), Estrogens and beta blockers through WWTP. STOTEN 408(19), Micropollutants through ASP. WS&T 62(12), Litterature review for pharmaceuticals in WWTP. Env Poll 157, Litteratre review for priority substances in WWTP. WS&T 57(12),