Danielle Westerman, Hannah K. Liberatore, Kristin H. Cochran Cassiana Montagner, Dion D. Dionysiou, Leslie H. Cizmas, Susan Richardson

Transcription

1 Danielle Westerman, Hannah K. Liberatore, Kristin H. Cochran Cassiana Montagner, Dion D. Dionysiou, Leslie H. Cizmas, Susan Richardson Department of Chemistry and Biochemistry University of South Carolina Congaree National Park, SC

2 What s in my water? These chemicals may or may not be in your drinking water But there is always something that is in your water Pesticides Pharmaceuticals PFA Lead

3 H Disinfection byproducts are always in your drinking water (usually at ppb levels) H C Br H H 3C C Br N C H Br N N H C

4 DBPs can also form from pollutants Pesticides Pharmaceuticals Antibacterial agents Estrogens Textile dyes Bisphenol A Parabens (swimming pools) Alkylphenol ethoxylate surfactants Algal toxins Musks Postigo and Richardson, J. Hazardous Materials 2014, 279,

5 Drinking Water DBPs What are the Issues? Concern over possible human health risk: Epidemiologic studies: risk of bladder cancer, miscarriage, and birth defects New: Cardiac birth defects (Wright et al. 2016)

6 nly 11 DBPs Regulated in U.S. DBP MCL (µg/l) Total THMs 80 5 Haloacetic acids 60 Bromate 10 Chlorite 1000 But >700 DBPs now known Little known about occurrence, toxicity of unregulated DBPs Regulated DBPs do not cause bladder cancer in animals!

7 Bromo and Iodo DBPs are important Halogenated DBP Relative Toxicity: I > Br >> Iodoacetic acid is the most genotoxic DBP and is tumorigenic in mice Yang, et al. Environ. Sci. Technol. 2014, 48,

8 New Issues New impacts (hydrofracking, coal fired power plants) imate Change -> drought Growing populations, water scarcity New water resources: Wastewater reuse Lake Lanier (Atlanta, GA), 2009

9 Part 1: Hydraulic Fracturing Lots going on in the U.S.! (and in other countries!) High pressure water, sand, surfactants, biocides, and other proprietary stuff injected deep into the ground to enhance extraction of oil and natural gas Produced waters high in Br and I

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11 Hydraulic Fracturing What would happen if HF waters entered our drinking water supplies? Hannah Liberatore H NH 2 DBPs 0.1 µm 2 µm Concern: Formation of toxic Br- and I-DBPs

12 Results: New Iodo-DBPs Chloraminated (NH 2 ): XIC 127 (I + ) Homologous series of iodophenols n = 1 m/z 220 n = 2 m/z 346 n = 3 m/z 472 Key: Raw Feed Pretreated Nanofiltered Microfiltered

13 New Iodo-DBPs: Chloraminated Water XIC 127 (I + ) Homologous series of unknowns; Either a) iodobenzoquinones or b) iodocresols n = 1 m/z 234 n = 2 m/z 360 n = 3 m/z 486 Key: Raw Feed Pretreated Nanofiltered Microfiltered

14 High Resolution Accurate Mass MS bserved m/z Iodobenzoquinone Da VS. Iodocresol Da Da Diiodobenzoquinone Da VS. Diiodocresol Da Da Triiodobenzoquinone Da VS. Triiodocresol Da Da

15 High Resolution Accurate Mass MS Compound Formula bserved Mass Theoretical Mass Iodophenol C 6 H 5 I Diiodophenol C 6 H 4 I Triiodophenol C 6 H 3 I Iodocresol C 7 H 7 I Diiodocresol C 7 H 6 I Triiodocresol C 7 H 5 I Iodoxylenol C 8 H 9 I Diiodoxylenol C 8 H 8 I Triiodoxylenol C 8 H 7 I LEC Pegasus GC-HRT 50,000 resolution Another class identified: iodoxylenols

16 Isomer Identification: Retention Time Confirmation H I Abundance 2-iodophenol NF + NH 2 Abundance 2,4,6-triiodophenol NF + NH 2 Time (min.) Time (min.)

17 Mammalian Cell Cytotoxicity of Iodophenols 2-Iodophenol (2-IP) 3-Iodophenol (3-IP) 3-IP 4-IP 2-IP Lethal Concentration, 50% (LC 50 ) Concentration required to kill half of the population Measured as cell density, in relation to that of the negative control 4-Iodophenol (4-IP)

18 Part 2: Wastewater Reuse range County, CA: Indirect Potable Water Reuse (Jan 2008) Largest in the World ur focus: 21 Priority ECs Groundwater Recharge 2 Wastewater Treatment Microfiltration Reverse smosis Advanced xidation El Paso, TX is building the largest direct WW reuse plant in the world 18

19 PFA, PFS Pharmaceuticals Hormones Flame retardants Pesticides DBP (NDMA) Antimicrobial (Triclosan) Plastics (BPA, phthalates)

20 Advanced xidation for Removing 21 Priority Emerging Contaminants Advanced xidation Cytotoxicity Triclosan Diclofenac BPA Ibuprofen Estrone ER AhR Unconventional advanced oxidation of EC spiked C treated waters (carbonate radicals, Ti 2 /UV) Cytotoxicity and estrogen activity analyzed using estrogen receptor and aryl hydrocarbon receptor assays

21 Using LC-MS/MS to determine reaction pathways Triclosan H UV m/z T 253a-c, m/z H H H N H 2 T 235a-c,m/z H H N 2 T 280,m/z H Kristin Cochran H H N 2 T 264,m/z H or UV H H T 161,m/z UV H T 127a-b,m/z H H H T 143,m/z H H T 303 H H and UV T 249,m/z T 301 H H H H T 317,m/z T 283,m/z

22 Chlorination: Simulating further drinking water treatment 2 Na (w/without Br ) 150 ml H2 Sample Rxn Glass Filter 48 Hr Room Temp Solid Phase Extraction H 2 S 4 Vacuum Filter 1. Condition 2. Load 3. Wash 4. Dry (N 2 ) H2 + Br TPs? Acidify Cytotoxicity and Estrogen Activity and LC-MS/MS

23 The goal: ean and Safe Drinking Water

24 Funding: Thank you! Dion Dionysiou Dan Schlenk Thanks to Waters, Agilent, and LEC My research group at USC Michael Plewa