15 Oct 2009 MI WEA Meeting

Transcription

1 Occurrence and Treatment of EDCs and PPCPs in New England Waters Dave Reckhow & Kathleen Arcaro Department of Civil & Environmental Engineering and Veterinary and Animal Science University of Massachusetts Partners: EarthTech & Mass DEP 1 EDCs & PPCPs Endocrine Disrupting Compounds (EDCs) Estrogens: regulate and sustain female sexual development and reproductive function Androgen: male sex hormones Mimics: estrogenic and androgenic compounds Also anti-estrogenic and anti-androgenic androgenic Pharmaceuticals and Personal Care Products (PPCPs) Non-steroidal anti-inflammatory Anti-epileptic Antibiotics Anti-anxiety Antioxidants Pain reliever Anti-cholesterol Sun Screen 2 PPCPs in the Environment USGS Survey 138 stream sampling sites Kolpin et al., PPCPs: Chemical Analysis Boston Globe March 1, 28; page 2 LC/MS/MS The most widely used approach GC/MS/MS may be needed for some compounds Requires SPE for isolation and concentration 1 x Isotope dilution? Published methods: many EPA method 1694 Snyder methods 5 6 1

2 Existing Funded Project Establishing Guidelines for the Use of Ozone- GAC for Control of Endocrine Disruptors and Related Compounds in Water Water Research Foundation Formerly AWWARF Broad Project Goals WRF & utilities/researchers Ozone-GAC What is the effectiveness of the ozone-gac process in removing prototypical EDCs and PPCPs? Can we establish preliminary design criteria for full-scale use in water and wastewater applications. Conventional Processes How well do conventional treatment processes perform? With respect to parent PPCPs? Daughter PPCPs? Estrogenic activity? To what extent is treatment effectiveness location dependent or dependent on raw water quality? 7 8 Local Project Goals For Participating Utilities How well does your treatment plant remove PPCPs, should they find their way into the raw water? Could other forms of oxidation improve PPCP control in your plant? What about daughter products? What are the impacts on estrogenic activity? What are the concentrations currently found in your raw water? Selected Compounds EDC PhAC WW associated N-N-diethyltoluamide Atorvastatin N-Nitrosodimethylamine (DEET) Ti Tris(2- Naproxen chloroethyl)phosphate (TCEP) Sulfamethoxazole Trimethoprim Perchlorate Atenolol Ranitidine Ciprofloxacin 9 1 Utilities: Treatment Trains Scope # Lab Treatment 1 1 Chlorination-alum coagulation & filtration-adsorption2 - chlorination Alum coagulation & filtration-ozonation-filtration 3-2 chlorination 3 Adsorption 2 -chlorination 4 ph adjustment-chlorination 5 Ultrafiltration 6 Alum coagulation & filtration-chlorination 7 Ozonation-chlorination-ammonia addition 8 Alum coagulation & filtration Chlorine Dioxide, chlorine-alum coagulation & 9 filtration-chlorination Alum coagulation & settling-ozonation-filtration 3-1 chlorination-ammonia addition 11 Chlorination-filtration 3 12 Alum coagulation & filtration [1] Lead utility 13 chlorination [2] Using plant GAC [3] Plant media, freshly collected, and transported to UMass for immediate bench-scale treatment Task 1: literature update Task 2: Raw Water Occurrence Survey Anonymous: Double Blind design Task 3: Site-specific Removal On spiked raw water 3a: Existing treatment 3b: Oxidation: O 3, HOCl, NH 2 Cl Task 4: O 3 /Biofiltration Lab pilot (next slide)

3 Lab Analysis Conventional parameters DOC, UV, DBPs, etc. PPCP Analysis LC/MS/MS HPLC or UPLC Following HLB SPE; off-line and integrated Parent Compound & Daughter Products NDMA GC/MS/MS, following charcoal SPE Perchlorate Biological Activity: Estrogenic/Anti-estrogenic Measuring changes in gene expression in the Japanese medaka fish and the fathead minnow Analytical Methods Development LC/MS compounds Adaptation of 1694 to target compounds using UPLC/MS/MS Changes in analytes, LC system, isotopes Comparison of manual SPE to automated FMS Powerprep system: on-going work Assessment of integrated system Waters AquaAnalysis Kirsten Studer: estrogenic compounds Adam Graichen: broad-spectrum PPCPs #1694 Solid Phase Extraction Four analytical groups Extraction of organic contaminants from water and adsorb onto solid phase to concentrate Sample pretreatment method used to quantitatively analyze contaminants with Liquid Chromatography/Mass Spectroscopy Solid phase contained in cartridges or barrels Condition/ Equilibrate Load Wash Elute 15 Solid Phase Extraction Extraction of EDCs from environmental matrixes Method comparison Manual versus automated t EPA 1694 Method: Pharmaceuticals and Personal Care Products in Water, Soil, Sediment and Biosolids by HPLC/MS/MS (27) Off-line Manual SPE Method 5 ml to 1 ml sample size concentrated to 1 ml One-time use HLB extraction cartridges 6 hour extraction method time 16 min instrument run time HPLC-MS/MS 3

4 Off-line FMS Power-Prep Automated sample extraction, cleanup and evaporation Integrated SPE AquaAnalysis Parallel on-line sample prep plus separation and detection system 2 min extraction and instrument run time Reusable HLB cartridges (>4 injections) 5 ml to 2 ml sample size Kirsten Studer: Estrogens Diethylstilbestrol MW 268 g/mol 17β-Ethinylestradiol MW 296 g/mol Estriol MW 288 g/mol MW 27 g/mol Estradiol MW 272 g/mol SPE Method Comparison HLB Oasis cartridges On-line Single use C-18 analytical column (Atlantis) LC/MS/MS (ESI-) Parent/Daughter (m/z) Cone/Collision (V) / / / / / / / / / / 25 Manual SPE Method 2 ppt 2 ppt 7 Estriol 6 Estradiol 5 Ethinylestradiol 4 Diethylstilbestrol Automated SPE Many automated SPE devices available Two distinct types of automated SPE Automated off-line SPE excluding detection system Automated online SPE including detection system Comparison of manual to automated online SPE including detection system was used in this analysis 4

5 8 7 Estriol Estradiol Ethinylestradiol Diethylstilbestrol Estriol Estradiol Ethinylestradiol Diethylstilbestrol

6 Cost Comparison Cost Comparison Capital Costs Capital Costs Instrument Costs Operations and Maintenance Costs Labor Consumables Capital Costs Total Instrument Costs Annualized Instrument Costs AquaAnalysis - Automated $349, $47, Alliance/Micro Manual $281, $38, n = 1 yrs i = 5.5 % Cost Comparison Operations & Maintenance Method Comparison Manual SPE Method Labor intensive extraction method (8 hours for 24 samples) MDLs of 2 ppt or lower O&M Costs per Sample AquaAnalysis Automated Alliance/Micro Manual Extraction Columns Analyst Time Instrument Time $.84 5 min 15 min $5.3 2 min 16 min AquaAnalysis Faster turn-around on samples MDLs of or lower Potential for much lower MDLs with automated cartridge loading Automated with ability to run over night Discussion on Automated Method Contribution to Environmental Engineering Decreases error with all-in-one unit Increases efficiency in sample preparation Eliminates need for large sample volumes Comparable cost to manual extraction with lower O&M costs Potentially lower MDLs Biological Activity Tests Estrogenic and antiestrogenic activity will be assessed by measuring changes in gene expression in the Japanese medaka fish. expose fish to 1-L water sample for 96 hours sacrifice the fish; livers removed other tissues, e.g. gonads and brain also will be removed, stored in RNAlater and archived for potential future studies or examination of expression of other genes measure vitellogen in mrna in the liver using real time reverse transciptase PCR (Roche Light Cycler). Detection limit is typically 1 femtomolar Vitellogenin, the precursor egg yolk protein normally produced only in female fish - but male fish exposed to xenoestrogens will also produce it. 36 6

7 Bio Testing Sample Data Conventional Drinking Water Treatment Most common for surface water Coagulation & solids separation rapid mix, flocculation, settling, filtration Disinfection including clearwell for contact time Not effective for PPCPs Destroys and Modifies many PPCPs Corrosion Control Fluoride 37 Coagulant Disinfectant Clear well Dist. Sys. raw water rapid flocculation Settling Filtration mix David Reckhow A. 38 Removal by Conventional Drinking Water Treatment Coagulation & conventional filtration Generally not effective Nearly all EDCs and PPCPs are too small or too soluble to be susceptible Oxidation and Disinfection Effective for some - issue of daughter products Chlorination: works well for primary amines, activated aromatics (especially phenolics) and activated aliphatics Chloramination: not as effective as chlorine Ozonation: generally good especially if doses are high and hydrogen peroxide is added too 39 Ozone Plant Many types Simplest type: ozone, non-filtration shown below examples: MWRA (Boston), Portland ME Effective as long as the ozone dose and contact times are high Cl 2 O 3 Cl2 NH 3 4 Dist. Sys. Wachusett & Boston System Advanced Water Treatment 1 Water Treatment Plants at Walnut Hill in Marlborough and at the Quabbin Reservoir (no filtration) 2 MetroWest Water Supply Tunnel connects the new treatment plant and storage tanks and provide a back-up to the aging Hultman Aqueduct David A. 3 Reckhow Covered Water Storage MI Tanks WEA meeting at five locations 41 May Include: Granular Activated Carbon Filtration Can be effective if run in adsorption mode Expensive Ozonation and Biofiltration Can be effective if filters are in place and allowed to operate biologically Membranes Only the high pressure types are effective (e.g., reverse osmosis) These are quite expensive to operate 42 7

8 Early Dataset Chemical Addition 3L of #14A Raw Water Add HL Target Compounds 3.5 mg/l KMnO mg/l NaOCl 61 mg/l KOH 3 min Analytical tests Raw: TOC, DOC, TN, DN, UV abs, ph, Fe, Mn, turbidity Spiked: Target cmpds w/o pre conc. Some treatment schematics Good removal of most Filter with GF/F Aeration Filtered: TOC, DOC, UV abs, Cl 2 resid. ph, Fe, Mn, turbidity Target cmpds w/o pre conc. ad NaF NaOCl.9 mg/l.5 mg/l Aerated: TOC, DOC, UV abs, ph, Cl 2 resid hrs 1 Percent Remaining mg/l Na 2SO 3 Atenolol Ranitidine Sulfamethoxazole Trimethoprim Ciprofloxacin DEET Naproxen TCEP Atorvastatin Naproxen-Neg Quench Finished Water Finished1: Cl 2 resid. Finished2: TOC, DOC, UV abs, ph, Fe, Mn, turbidity, THMs, HAAs Target cmpds w/o pre conc. 2 1 filtered finished 43 Treatment 44 Aromatic EDCs (cont.) Rates Deborde et al., 24 + k1 EDC + HOCl + H products EDC + 2 k HOCl products k3 EDC + HOCl products Chlorination ph dependence of the apparent second-order rate constants and the half-life times for chlorine reaction with selected endocrine disruptors and pharmaceuticals 2 25 C Half-lives are calculated for a chlorine concentration of 1mgL 1 (14.1 μm). From: Deborde & von Gunten, 28 [Wat. Res. 42(1)13] 1 hour 1 day Removal by Residual Disinfectants Snyder et al., 27 [AwwaRF report] Ozonation Removal by Chloramines 5-8% >8% <2% 2-5% Androstenedione Atrazine g-bhc Caffeine Ibuprofen Carbamazepine Iopromide DDT Meprobamate DEET Metolachlor Dilantin Progesterone Fluorene TCEP Fluoxetine Testosterone Galaxolide Diazepam Pentoxifylline Gemfibrozil Acetaminophen Estradiol Estriol Ethynyestradiol Triclosan Benzo(a)pyrene Diclofenac Oxybenzone Hydrocodone Erythromycin Musk Ketone Naproxen Sulfamethoxazole Trimethoprim Removal by ozone <2% 2-5% 5-8% >8% Removal by Free Chlorine 47 Westerhoff David et A. al., Reckhow 25 [EST 39:17:6649] 48 8

9 Oxidation of PPCPs Average percentage removal of LC/MS/MS and GC/MS/MS compounds by ozone and chlorine across four waters spiked with EDC/PPCPs (PVW, ORW, SRW, CRW). Solid line represents 1:1 removal between ozonation and chlorination experiments. Error bars represent one standard deviation in percentage removal based on experiments in the four waters. Cleaning up PPCPs and daughters Ozone/biofiltration with controls No-O 3 No bio Constant Head Tank O 3 Generator Pumps GAC Filters To vent Westerhoff et al., 25 [ES&T, 39:6649] Raw Water Reservoir Filtrate Collection 49 5 Pilot Operation One year duration 3 months initial acclimation 9 months testing Target 1 min EBCT Spike raw water with PPCPs Run until stable removals under varying conditions Ozone doses Temperatures Others: EBCT, backwash? Daughters Chlorine substitution probably occurs here first with the formation of 2-chloro-estrone and 4-chloro-estrone. Neither of these two initial products showed substantially reduced estrogenic activity (Nakamura et al., 26). Nakamura also identified the expected 2,4-dichloroestrone as well as a tetrachloro product (2,4,16 and 16 position) and a quinone-like form that was singly chlorinated Estradiol: loss means what? Sulfamethoxazole daughters Proposed pathway from Dodd & Huang, 24 chlorination

10 Getting rid of unused drugs Which is best? To Landfill To Incinerator Landfill Liners Modern composite liner systems 2 feet clay & 6 mil HDPE liner includes leachate collection & dosposal Expectation: >99.9% of leachate captured to WWTP? <.1% lost to groundwater via holes in liner system To wastewater treatment plant Conventional Biological Wastewater Treatment Effective for many PPCPs Exceptions include: Organophosphate flame retardants TCEP (and others?) Nitrogen heterocycles Atrazine (herbacide) Dilantin & Primidone (antiepileptics) Unsubstituted benzenes on an imidizolidine Carbamazepine (anticonvulsant & mood stabilizer) X-ray contrast media Iopromide Summary: Natural & Engineered Attenuation Some are removed by 99%+ Most estrogens Daughter products? Some are removed by 5-9% Wide range of pharmaceuticals Some are barely removed at all Some pharmaceuticals & EDCs Flame retardants Propranolol: beta blocker The End 59 1