Determination of Trace Metals, Volatile Organic Compounds, and Other Water Standards in WMU Drinking Water By: Tyler Walter Thesis Chair: Dr. Carla M. Koretsky Thesis Committee: Dr. Michael Barcelona, Dr. Steven Bertman

Background U.S. Water Footprint = 2100 – 2500 m 3 /capita/year Among the highest in the world EPA (Environmental Protection Agency) DEQ (Department of Environmental Quality) CDC (Center for Disease Control) Kalamazoo City Water Department Treatment processes (Pulsipher, 2011; Department of Public Service, 2011)

Objectives Determine the concentrations of various contaminants in on campus drinking water Trace metals (Cu, Zn, Fe, Mn, Ni, Pb and As) Average hardness, pH, E. coli levels, and concentrations of select pesticides (atrazine/simazine), NO3-, NO2- (as N), and Cl A suite of volatile organic compounds (toluene, ethylbenzene, xylene, and chlorobenzene) Compare the contaminant concentrations among select building Influence of building age on concentration Influence of water source distance from the buildings water supply entrance on concentration Compare measured concentrations to EPA standards

Hypothesis Concentrations of trace metals, volatile organic compounds, pesticides, NO 3 -, NO 2 -, and Cl will increase with increasing distance of the water source from the initial water supply point Concentrations will also increase with increased building age Levels of hardness, pH, and bacteria will not be affected by distance from the initial water supply point Levels will increase with building age

Inductively Coupled Plasma Optical Emission Spectroscopy Multi-element technique Radio frequency ICP torch Polychromator wavelength selector Photomultiplier detector Axial vs. radial axial = lower detection limits (Baysal et al., 2013)

Watersafe ® Drinking Water Test kits Silver Lake Research Corporation (discovertesting.com) Cheap, yet effective Child safety Lead levels in drinking water Center for Disease Control (CDC) Escherichia coli (City Water Test Kit, 2013)

Solid Phase Microextraction (SPME) Direct (immersion) SPME vs. Headspace SPME Fused Silica fiber Absorbs target compounds Split vs. Splitless (Pecoraino et al., 2008)

SPME using Gas Chromatography Vaporization Mobile (gas) phase vs. Stationary (liquid) phase Temperature gradient effects compound affinity Flame Ionization Detector (FID) Amplification and integration (Christie, 1989)

Sample Collection Sources Locations: Davis Hall (1954) ground floor drinking fountain e * first floor dorm room faucet d * second floor lounge faucet third floor dorm room faucet d The Chemistry Building (2007) First floor drinking fountain ed * Second floor drinking fountain Third floor drinking fountain d * The Dalton Center (1982) First floor drinking fountain (NE) e First floor drinking fountain (SE)* Second floor drinking fountain (NE) d * e = entry point d = duplicate * = Watersafe® Source

Sample Collection ICP-OES 20 mL polyvinyl vials Acidified with 5% nitric acid Watersafe Drinking Water Test On site sample collection and analysis SPME using Gas Chromatography 20 mL vials Neoprene-containing cap

ICP-OES Analysis Trace metal solutions – 0, 25, 50, 100, 250, 500, 1000 ppb Cu, Zn, Fe, Mn, Ni, and As Yttrium used as internal standard Acidified (5% nitric acid) Diluted with Ultrapure water Axial Mode

Watersafe ® Drinking Water Test Bacteria Test – growth medium test Lead/Pesticides Test – indicator test Nitrate/Nitrite Test – colorimetric test pH/hardness/chlorine Test – colorimetric test (City Water Test Kit, 2013)

SPME Calibration Standards 20 ppm stock solutions: Toluene (99.97% purity) Ethylbenzene/Total xylene (≥98.5 % purity) 25 ppm stock solution: Chlorobenzene (100% purity) ~1 mL of solution added to each vial Magnetic stir bar added

SPME and GC Parameters 40°C thermostatic bath (5 min) 85 m Carboxen/polydimethylsiloxane fiber 20 min absorption (Headspace SPME method) GC inlet (250°C) for 5 min desorption in splitless mode GC column: 30 m long Coated with 0.32 mm I.D. (internal diameter) 1.5 µm thick Maximum temperature: 260°C Temperature Program: 40°C initial temperature (2 min) Rises 8°C/min until reaching 210°C Carrier gas: Helium with 50.8 mL/min flow rate Average velocity of 29 cm/s (Pecoraino et al., 2008)

ASME/ASTM Piping Standards ASTM Piping Regulations: Galvanized Pipe (A53/A53M-12): Contains Fe, C, Mn, P, S, Cu, Ni, Cr, Mo, V Zn-coating Older building = more corrosion (higher Zn concentration) Copper Pipe (B88-09): Contains Cu (w/Au) and trace amounts of P Plastic Piping: CPVC (chlorinated polyvinyl chloride) Schedule 40 rating (ASTM, 2009; ASTM, 2012)

(T. Spitzner, personal communication, April 10, 2013; USEPA, 2009) Trace Metal Contaminants

(T. Spitzer, personal communication, April 10, 2013; USEPA, 2009) Commonly Tested Contaminants

Volatile Organic Contaminants (T. Spitzer, personal communication, April 12, 2013; USEPA, 2009)

ICP-OES Determination for Davis Hall (As & Ni not shown) Fe, Mn, and Cu shows decreasing trend with distance Zn presents too many outliers Fe and Mn are above EPA secondary standards May affect taste, odor, and color of water Also may present corrosion and staining affects Explained by MDEQ data Trace Metal Concentrations in Drinking Water from Davis Hall Location Trace Metal Concentration (in ppb) FeMnCuZn Davis blankBDL BDL Davis control Davis 1a Davis 1b Davis Davis 3a BDL379.3 Davis 3b BDL301.4 CompoundObserved RangeEPA Limits Fe528 – 1390 ppb300 ppb Mn63.8 – 193 ppb50 ppm Cu<20 – 22.5 ppb1000 ppb (T. Spitzner, personal communication, April 10, 2013; USEPA, 2009)

ICP-OES Determination for the Chemistry Building (As & Ni not shown) Fe and Cu shows increasing trends with distance Mn shows decreasing trend Zn is too inconsistent Fe and Cu are above EPA secondary standards Fe levels explained by MDEQ data Cu may be explained by the presence of copper piping near water outlets Trace Metal Concentrations in Drinking Water from the Chemistry building Location Trace Metal Concentration (in ppb) FeMnCuZn Chem blankBDL0.470BDL Chem control a BDL Chem control b BDL Chem Chem 3a BDL Chem 3b BDL CompoundObserved RangeEPA Limits Fe528 – 1390 ppb300 ppb Mn63.8 – 193 ppb50 ppm Cu<20 – 22.5 ppb1000 ppb (T. Spitzner, personal communication, April 10, 2013; USEPA, 2009)

ICP-OES Determination for the Dalton Center (As & Ni not shown) Cu shows increasing trend with distance Zn shows inverse trend Fe and Mn show no significant trend Fe and Mn are above EPA secondary standards Same as Davis Hall Trace Metal Concentrations in Drinking Water from the Dalton Center Location Trace Metal Concentration (in ppb) FeMnCuZn Dalton blankBDL BDL Dalton control Dalton 1 (SE) Dalton 2a (NE) Dalton 2b (NE) (T. Spitzner, personal communication, April 10, 2013; USEPA, 2009) CompoundObserved RangeEPA Limits Fe528 – 1390 ppb300 ppb Mn63.8 – 193 ppb50 ppm Cu<20 – 22.5 ppb1000 ppb

Watersafe ® Drinking Water Tests ConditionObserved RangeEPA Limits pH6.72 – – 8.5 Hardness324 – 368 ppm50 ppm Cl1.10 – 1.64 ppm4 ppm (T. Spitzer, personal communication, April 10, 2013; USEPA, 2009)

SPME Determination of Toluene

SPME Determination of Ethylbenzene

SPME Determination of Total Xylene

SPME Determination of Chlorobenzene

SPME/GC Determination Ethylbenzene, total xylene, and chlorobenzene All samples were below detection limits Ethylbenzene: below 0.2 ppm Total Xylene: below 0.2 ppm Chlorobenzene: below 0.05 ppm Toluene Most samples were below detection limits Toluene: below 0.2 ppm 4 samples produced peaks

SPME: Toluene Determination 4 samples produced peaks 2 were calculated to below detection limits 1 was calculated to ppm (Davis 1) Below EPA limits 1 was calculated to ppm (Dalton 1 NE) Above EPA limits, warranted further testing Second test produced no peaks Possibly explained by evaporation over time Chronic consumption produces serious health affects

Conclusions Some slight trends observed between distance from initial water supply and concentration Most samples showed inverse trends Contradicts hypothesis Zinc showed strong trend between concentration and building age Increased age = increased corrosion No other contaminants showed any trends Contradicts hypothesis Several compounds were above EPA limits and standards Most were secondary standards explained by MDEQ data Presence of toluene above EPA limits Absence in second test may be due to evaporation over time

Recommendations Monitor water temperature more closely Water temperature for ICP-OES and SPME analysis was never measured Work with a partner Most of the Watersafe Drinking Water Test kit procedures involve comparative judgment A second person could alleviate result bias Fresh Samples for SPME analysis Evaporation may have produced different data Nearby GC detected target chemicals Use more calibration points for SPME analysis

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