Ensuring the Safety of Recycled Water

(1)

1

Ensuring the Safety of Recycled Water

Shane Snyder, Ph.D.

Professor & Co-Director University of Arizona Distinguished Adjunct Professor

King Abdulaziz University

Senior Research Specialist Armando Durazo – UCLA Post-Doctoral Associates Sylvain Merel - U. of Rennes Ai Jia – Peking University Hye-Weon Yu – GIST Korea Sonia Dagnino – US EPA Jian Gong – Guangzhou U.

Ph.D. Students

Tarun Anumol - Carnegie Mellon Shimin Wu – Peking University Minkyu Park – GIST Korea Sheena Young – U. Maryland Shuwen Yan – Fudan University M.S. Students

Darcy VanDervort – U. Ohio JoAnne Barcellano – N. AZ U.

Xuhao Nie – U. of Arizona

snyderlab.arizona.edu

(2)

(3)

3 Arizona Laboratory for Emerging Contaminants - NORTH

LC-MS/MS LC-QTOF GC-MS/MS

Arizona Laboratory for Emerging Contaminants - SOUTH

LC-FLD/DAD ICP-MS GC-ECD/FID

(4)

WEST Center

Opening Fall 2014 KAU Collaboration Desired!

(5)

5

(6)

Peter Smith (University of Arizona) Principal Investigator:

The Imager for Mars Pathfinder (IMP)

Robert Brown (University of Arizona) Principle Investigator,

Visual and Infrared Mapping Spectrometer (VIMS) on

NASA's Cassini spacecraft

(7)

7

Advanced Detection Capability

(8)

Water, Power, and Food: Intimately Related

US agriculture withdraws 485 million m

³

water/day

(9)

9

The largest US atomic power plant is located in the desert of Arizona

In USA, >750,000 m

³

water/day used for electrical generation

U.S. Population Could Exceed 400,000,000 by 2050

≈ 2.5M people/year for the next 40 years

≈ the population of Houston TX each year

(10)

Top 10 US Cities Running Out of Water Top 10 US Cities Running Out of Water

10. Orlando 9. Atlanta 8. Tucson 7. Las Vegas 6. Fort Worth 5. San Francisco 4. San Antonio 3. Phoenix 2. Houston 1. Los Angeles

Source: http://247wallst.com/2010/10/29/the-ten-great-american-cities-that-are-dying-of-thirst/3/

540 Km distance &

600 meters elevation

(11)

11

(12)

The Texas Drought

http://www.economist.com/node/14222305

The Economist 13^thAugust 2009 The Economist 12^thNovember 2011

http://www.economist.com/node/21538196

Lake Spence - Texas

(13)

13

(14)

(15)

15

Fishing Dock at Lake Mead Fishing Dock at Lake Mead

X X

X

Three Advanced WWTPs Three Advanced WWTPs

Drinking Water

(16)

(17)

17

0 2 4 6 8 10 12 14 16

Estrone (ng/L)

-150 -130 -110 -90 -70 -50 -30 -10

Depth(m)

0 5 10 15 20 25 30

0 2 4 6 8 10 12 14 16

Kilometers from WWTP effluent confluence to Hoover Dam DEET (ng/L)

-150 -130 -110 -90 -70 -50 -30 -10

Depth(m)

0 5 10 15 20 25 30

(18)

0 2 4 6 8 10 12 14 16 Meprobamate (ng/L)

-150 -130 -110 -90 -70 -50 -30 -10

Depth(m)

0 10 20 30 40 50

0 2 4 6 8 10 12 14 16

Sulfamethoxazole (ng/L)

-150 -130 -110 -90 -70 -50 -30 -10

Depth(m)

0 5 10 15 20 25 30

LV Wash kilometers Hoover Dam

S

HN O

O N O

N H₂ O

O

H₂N O

NH2

O

Las Vegas Wash monitoring – 5 years

0 200 400 600 800 1000 1200

6/2/2004 6/2/2005 6/2/2006 6/2/2007 6/2/2008 6/2/2009

Concentration (ng/L)

Carbamazepine Dilantin Meprobamate Sulfamethoxazole

(19)

19

• About 5‐6% of

US wastewater is reused

– 1/3

^rd

of all US

wastewater discharged to oceans

• California is mandating increased reuse

• Arizona, Florida and Texas also high growth

5-6%

Reclaimed

USA Wastewater Resources

Source: Wade Miller – WateReuse Association

(20)

Source: http://www.hcn.org/issues/354/17227

Can treatment make this drinkable???

(21)

21

Contaminants potentially detectable in reclaimed water

Pharmaceuticals

Pesticides

Industrial chemicals Natural chemicals

Personal care

products Household

chemicals Transformation

products

Viruses

Bacteria

Protozoa Helminths

Anions

Cations Metals

Chemical origins

Microbial origins

Primary Contaminant Removal Mechanisms

Separation Biological Oxidation

(22)

Surrogates and Indicators

Health‐relevant CECs

Performance indicator CECs

Surrogates

CECs of toxicological relevance to human health

Useful for monitoring treatment process efficacy

Bulk parameters that are

indicative of occurrence and/or

attenuation of trace organic

compounds

(23)

23

Ozone Oxidation of Trace Contaminants

Difficult to

Oxidize Moderate Easily Oxidized

Percent Removal

(24)

Application of Fluorescence indexes as surrogates for water quality

1.5 ppm Control

3 ppm 4.5 ppm 6 ppm

Wastewater Effluent on Ozone treatment

~50% of TOX >1000 Da: Khiari, et al., Proc. 1996 AWWA Water Quality

More than 60% of DBPs are still not known….

Unknown 69.9%

THMs 13.5%

HAAs 11.8%

Halofuranones 0.1%

IodoTHMs 0.2%

HANs 0.8%

HALDs 1.8%

HKs 0.9%

HACEs 0.5%HNMs 0.5%

Nationwide Occurrence Study, Krasner et al., Environ. Sci. Technol. 2006, 40, 7175-7185.

(25)

25 NDMA-FP with Ozone

Ozone Reaction Products

Atenolol

C₁₄H₂₂N₂O₃ m/z267.1703 (m+H)⁺ Ozone

Addition

Ozone Addition

Transformation Product

C₆H₁₅NO₂(Calculated) m/z134.1173 (m+H)⁺

(26)

Benzotriazole + Ozone

m/z118, 1H‐benzotriazole

m/z124, transformation product

m/z124.01522 (meas.) m/z124.01525 (calc.) C₄H₃N₃O₂ O3/ ._OH

N N N H

H H

H

1H-benzotriazole

1H-1,2,3-triazole-4,5-dicarbaldehyde

N N N

H O

O H H

Intermediates and minor products

Mawhinney, DB, BJ Vanderford, and SA Snyder. (2012) Environmental Science &

Technology46 (13):7102-7111.

LC-QTOF (Agilent 6540)

(27)

27 Searching for unknown in water

Chromatograms Very Similar

Extraction of Molecular Features

Reveals Almost 1,000 compounds in each chromatogram

Further Data Processing Requires

Specific Software Raw Water

Ozone (1.5 ppm)

Ozone (3 ppm)

Ozone (4.5 ppm)

Ozone (5.6 ppm)

WATER TREATMENT &

ANALYSIS OF UNKNOWNS

Untreated water

Ozonated water (3 mg/L)

Ozonated water (1.5 mg/L)

PCA Plot for Different Ozone Doses

Although chromatograms were

all similar for the analyst

Software identifies features able to discriminate the different water quality

WATER TREATMENT &

(28)

A

Ozonated water (3 mg/L)

Blank color reflects compounds not found

BCD

Untreated water

Although chromatograms were

all similar for the analyst, clear differences appear on

the heatmap A & C are group of compounds in the raw

water but at lower concentration or absent

in ozonated water (removed by ozone) B & D are compounds absent in raw water but present in treated water

(ozone by-products)

Increasing removal with increasing O₃dose

Formation after exposure to O₃

WATER TREATMENT &

MBR Aeration Basin MBR Filtrate

Ozone Effluent Reverse Osmosis Permeate

Treatment can make this

drinkable!!!

(29)

29

“About two years ago, very small traces of an antibiotic, an anti-seizure medication and a possible cancer-causing agent appeared in four groundwater wells in northwest Tucson.

All of the wells are located downstream of the local sewage treatment plant, which releases its treated sewage water into a riverbed.

When tested, some of Flagstaff's drinking water wells downstream of the Rio de Flag wastewater treatment plant have also shown tiny traces of other

pharmaceuticals and hormones, which have an ability to influence growth in amphibians.”

Analytical Chemistry VS Bioassay

Targeted Analytical Mechanistic Bioassay Known compounds

Quantitative

Individual compounds

Knowns/unknowns

Semi‐quantitative

Synergism/Antagonism

(30)

HPLC Fractionation

AMES II/CALUX test/RTCA

Analyte Identification

LC/GC ICPMS GC‐QTOF

LC‐QTOF Sample Preparation

TA98, TAmix Nrf2 cell lines

Fraction Collector Extraction

16HBE14o‐cell

UV Transformation Products

(31)

31 New mutagenic DBPs detected!

LC-QTOF

GC-QTOF

(32)

Five Day Embryonic Exposure to Organic Constituents in Tucson WWTP Effluent

0.25X

1X 5X

DMSO Control

Five Day Embryonic Exposure to Organic Constituents in Tucson WWTP Effluent

(33)

33

Lab-on-a-chip (LOC)

A microfluidic device that integrates one or several laboratory functions, such as sampling, mixing, reaction, and separation into a small single chip (only millimeters to a few square centimeters in size)

www.popsci.com scopeblog.stanford.edu

(34)

Physical/Chemical sensor

A device that transforms chemical information, ranging from the concentration of a specific sample component to total composition analysis, into an analytically useful signal

•Ion-selective electrode

•Organic

carbon sensor •Fluorometer

•Turbidity

•UV/VIS spectrometer

•ORP meter •Conductivity •Temperature

Biosensor

Analytical device that combines a biological sensing

element

with a transducer to produce a signal proportional to the analyte concentration

Ultra-Sensitive Electrical Biosensor for Instant

(35)

35 Sensors are

at the forefront of a multidisciplinary science that marries

the biological world and the electronic world

Smart Water Grid

• High‐tech sensor‐based monitoring

• Data analysis system

• Integrated operation system

sensus.com

(36)

Thank You for Your Attention & Kindness!

Contact: [email protected]

Visit Us: snyderlab.arizona.edu

(37)

37

Today, Tomorrow, and Beyond

Analytical Approaches for Unknowns

Krewski et al. (2011). New Directions in Toxicity Testing. Ann Rev Public Health, 32, 161-178.