April 13 2006UI ECE Research Colloqiuim1 Water Treatment Using Ultrasound-Induced Cavitation Michael...

April 13 2006 UI ECE Research Colloqiuim 1

Water Treatment Using Water Treatment Using Ultrasound-Induced Ultrasound-Induced

CavitationCavitation

Michael AndersonMichael AndersonMechanical Engineering

Center for Intelligent Systems Research

Greg MöllerGreg Möller Food Science and Toxicology

http://isgc.uidaho.edu/Information.php?Page=2


Experts consider options over sources of city water Associated Press, September 20, 2004

TWIN FALLS, Idaho – After years of drought and a declining Snake River Aquifer, experts are not ruling out any local lakes or even wastewater plant effluent as a source of city water.

Just five years ago, Twin Falls thought it had accumulated enough water sources to last for 50 years. Considering that diminishing supply, the city now finds itself pretty much starting over.

But since the first plan was devised, rounding up that water has become more complicated. The federal government recently said Twin Falls must lower naturally occurring arsenic levels in about 40 percent of its supply.

A committee is looking at a number of sources for water along the Snake River Canyon, including Devil's Corral, Rock Creek, seepage tunnels and wastewater treatment plant effluent. It's also working with state officials to change the use of certain water rights to purchase them.


Problem StatementProblem Statement

• Water quality and quantity is vitally linked to public health, environmental quality and economic opportunity.

• Many communities are now “development limited” due to limited water supply and limited wastewater discharge opportunity.

• New science suggests bioactive substances in human wastewater and other discharges are a direct threat.


Pump & ScreenPump & Screen

Primary SettlingPrimary Settling

SecondaryAeration

SecondaryAeration

ClarifiersClarifiers

Solids DigestionSolids Digestion

DisinfectionDisinfection

NPDES Permit to Pollute

NPDES Permit to Pollute


ChallengesChallenges• Pharmaceuticals, endocrine disrupting substances,

personal care products, and various pesticides and herbicides are found in many natural waters.– Wastewater discharge and non-point source pollution. – Micropollutants, PPCPs, PhAS, Biocidals.

• Concern about environmental and public health impact of these substances.

• Need for better science and technology.– Disposal and treatment options.– Detection of chemicals and biological impacts.– Green science and engineering.


Example: Antibiotic SoapExample: Antibiotic Soap

• Triclosan, the common antiseptic, was found in 57.6% of the United States water resources surveyed (USGS).

• A broad-spectrum antibacterial - antimicrobial agent classified as a Class III drug by the FDA.

• Bacteriostatic activity against a wide range of bacteria has lead to popular use in: – Personal care products, cosmetics, antimicrobial creams,

acne treatment, lotions and hand soaps, plastics, polymers and textiles.

• Linked to estrogenic effectsin fish.

O

OHCl Cl

Cl


Micropollutants in U.S. WatersMicropollutants in U.S. Waters

• USGS study tested U.S. waters for 95 chemicals ranging from perfumes to antidepressants.

• Of 139 streams tested, 80% had at least one of the chemicals and 50% had seven or more.

• Continual introduction “persistence”.• Threat to water reuse and to “captive”

aquatic biota.


ExcretionExcretion

• When we take medication, our bodies excrete the active chemicals with as much as 90% of the ingested drug still in a potent form.


Endocrine DisruptersEndocrine Disrupters

• Chemicals which interfere with endocrine system function.

• Endocrine system consists of glands and the hormones they produce. – Pituitary, thyroid, and adrenal glands, the female

ovaries and male testes.

Estradiol


Male-to-Female Sex ReversalMale-to-Female Sex Reversal

• Salmon: “a high incidence (84%) of a genetic marker for the Y chromosome in phenotypic females sampled from the wild... It appears likely that female salmon with a male genotype have been sex reversed, creating the potential for an abnormal YY genotype in the wild that would produce all-male offspring and alter sex ratios significantly.”

• High Incidence of a Male-Specific Genetic Marker in Phenotypic Female Chinook Salmon from the Columbia River. Nagler, JJ; Bouma, J; Thorgaard, GH; Dauble, DD Environmental Health Perspectives. Vol. 109, no. 1, pp. 67-69. Jan 2001


HypospadiasHypospadiasIncomplete Masculinization of the Reproductive Tract

• Paulozzi LJ, Erickson JD, Jackson RJ. 1997. Hypospadias trends in two U.S. surveillance systems. Pediatrics 100:831-834.

• Paulozzi LJ 1999. International trends in rates of hypospadias and cryptorchidism. Environmental Health Perspectives 107:297-302.

• Gray, LE, C Wolf, C Lambright, P Mann, M Price, RL Cooper and J Ostby. 1999. Administration of potentially antiandrogenic pesticides (procymidone, linuron, iprodione, chlozolinate, p,p'-DDE, and ketoconazole) and toxic substances (dibutyl- and diethylhexyl phthalate, PCB 169, and ethane dimethane sulphonate) during sexual differentiation produces diverse profiles of reproductive malformations in the male rat. Toxicology and Industrial Health. 15:94-118.


CavitationCavitation

• Oscillating pressure field (ultrasonic) or fluctuating pressure in shear layer of water jets (hydrodynamic) cause pre-existing microscopic bubble nuclei to grow explosively and then collapse violently.


11 22

33 44

Simulated Cavitation Bubble Simulated Cavitation Bubble DynamicsDynamics

• Sequence from high speed film of ~1cm cavitation bubble collapse.

• Note formation of high speed re-entrant jet (3,4)


Pressure Field Associated with Pressure Field Associated with Bubble CollapseBubble Collapse

Cavitational activity is directly proportional to the number density of particles present in the medium (Madanshetty and Apfel, 1991).


Ultrasonic Water Treatment:Ultrasonic Water Treatment:How Does It Work?How Does It Work?

•Acoustic waves in water can resonantly vibrate gas bubbles

•Resonant vibration can result in violent bubble collapse, causing temperatures and pressures as high as 5000K and 1700atm

•High pressures and temperatures cause chemical reactions among the gas in the bubble and water vapor, one of them the dissolution of water into H● and OH● (free radicals).

•Free radicals diffuse into the water and oxidize harmful chemicals.


New York Times, “Tiny Bubbles Implode With the Heat of a Star”,March 15 2005

How Hot?How Hot?


SonochemistrySonochemistry

• Free radicals are formed as a result of the cavitation microbubbles which are created during the negative pressure period of sound waves– Acoustic vs hydrodynamic

• Dissolved gas & nucleation sites needed– Ozone

• Milder operating conditions– Lower T, P


Postulated Reaction Postulated Reaction Mechanisms and LocationsMechanisms and Locations

• Within bubble.– Hydroxyl and other radical attack in gas phase.– Pyrolysis in gas phase.– Ion reactions.

• At or near bubble surface in liquid.– Hydroxyl and other radical attack in liquid phase. – Formation and reaction with supercritical water.

• In bulk liquid solution.– Hydroxyl and other radicals attack in liquid phase.

• Intermediate reactions and reaction products.


Mechanism of Cavitation OxidationMechanism of Cavitation OxidationAdvanced oxidation process

• Water dissociates under extreme physical conditions generated at cavitation bubble collapse.– Calculated up to ~5-10,000°K and 500-1200 atm

(sec lifetime).

• Forms free radicals:

H2O H + OH

H + H H2

OH + OH H2O2

OH + ORGANIC CO2 + H2O + …


Higher Frequency UltrasonicsHigher Frequency UltrasonicsMegasonics ~1MHz

• Current research is finding that for oxidations higher frequencies may lead to higher reaction rates.

• More, smaller, faster collapsing bubbles– Less OH radical recombination?


PPR

PR

RR og

21

2

3 2

2

2

22 422

31

ov

ov

oo

oo R

PR

PR

PR

Rayleigh-Plesset EquationRayleigh-Plesset Equation


Resonance Frequencies Resonance Frequencies Air Bubbles in Water Air Bubbles in Water


Moderate Vibration Moderate Vibration

Source: Leighton, “The Acoustic Bubble”, Academic Press, 1994

Ro= 2 mm, fo=1.7 kHzf = 10 kHzPA = 2.4 bar = 0.27 MPa


Stable Cavitation Stable Cavitation


Ro= 0.10 mm, fo 10 kHzf = 10 kHzPA = 2.4 bar = 0.24 MPa


Stable Cavitation Stable Cavitation

Made by Tom Matula, Applied Physics Laboratory, University of Washington, available on Wikipedia


Transient Cavitation Transient Cavitation


Ro = 60 m

Ro = 50 m

Ro = 10 m

Ro = 1 m

f = 10 kHzPA = 0.24 MPa


Spectra for Stable and Spectra for Stable and Transient Cavitation Transient Cavitation

Source: Frohly, et al.,JASA, 108(5), 2012-2020, 2000


0 0.2 0.4 0.6 0.8 1 1.20

2

4

6

8

10

12

14

16

18

RMS Pressure (MPa)

Bub

ble

Rad

ius

(m

)980 kHz

PRD

PB

PTC

713 mV672 mV

600 mV

521 mV

Effect of Pressure Amplitude onEffect of Pressure Amplitude onAcoustic Cavitation Acoustic Cavitation


State of the Art- Water TreatmentState of the Art- Water Treatment

Source: Destaillats, et al., “Ind. Eng. Chem. Res., 40, pp. 3855-3860, 2001

3096 J/Liter for ½ “removal” MO @ 67 W/Liter


Diffusion of Ultrasound in Tube Diffusion of Ultrasound in Tube ReactorReactor

Measurement PortsO-Ring Piston CollimatorMeasurement PortsO-Ring Piston Measurement PortsO-Ring Piston Collimator

Total Length of Tube = 120 cm

Tube Diameter = 9 cm


PZT TransducerCollimatorElectrode

PZT TransducerCollimatorElectrode

Copper Backing

Collimator to Diffuse Ultrasound Collimator to Diffuse Ultrasound


Pilot Scale Flow Ultrasonic CavitationPilot Scale Flow Ultrasonic Cavitation 5 Cell Apparatus and Filter Radiator Design


High Achievable Energy Densities High Achievable Energy Densities


Luminol Chemi-Lumeniscence Luminol Chemi-Lumeniscence



Ultrasound DistributionUltrasound Distribution

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8-3

-2

-1

0

+1

+2

+3

+4

RMS Pressure (MPa)

Loca

tion

Fro

m C

ente

r (c

m)

100% Drive

70% Drive

100% Drive= 100 Watts

= 15.1 W/Liter

70% Drive = 43 Watts

Length of Tube = 55 cm

Measurement 15 cm from transducer


0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 510

-6

10-4

10-2

100

102

PZT Response Set 1 - 0.0068568 Watts - 0.47038 Volts RMS

Frequency(MHz)

Vol

tage

(V

)

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

10-5

100

Hydrophone Response Set 1 - 0.0033221 MPa

Frequency(MHz)

Pre

ssur

e (M

Pa)

1st Harmonic, A1

Ultraharmonics

Noise Level, NS

Fundamental, A0

Fundamental, B01st Harmonic, B

1Ultraharmonics

Noise Level, NH

Spectra at Low PowerSpectra at Low Power


0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 510

-6

10-4

10-2

100

102

PZT Response Set 6 - 109.8652 Watts - 59.5413 Volts RMS

Frequency(MHz)

Vol

tage

(V

)

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

10-5

100

Hydrophone Response Set 6 - 0.66475 MPa

Frequency(MHz)

Pre

ssur

e (M

Pa)

Spectra at High PowerSpectra at High Power


Test ReactorTest ReactorSonochemical Measurements Sonochemical Measurements

Diameter = 7.5 cm

Length = 27 cm

Volume = 1.2 Liter

0.7 MPa at 95 WattsTypical = 80 Watts/Liter


Relative Oxidizing StrengthRelative Oxidizing Strength

Standard Potential (V)

Hydroxyl radical 2.80

Ozone 2.18

Chlorine 1.68


0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8500

550

600

650

700

750

RMS Pressure (MPa)

Eh

(mV

)

Redox Potential: 18 MΩ-cm Water


0 50 100 150400

450

500

550

600

650

700

Time (Minutes)

Eh

(mV

)

20M Fe2+ 0.7 MPa

20M Fe2+ 0.4 MPa

Reagent Water 0.7 MPa

Reagent Water 0.4 MPa

20M Mn2+ 0.7 MPa

20M Mn2+ 0.4 MPa

Fe2+/Mn2+ Oxidation


0 10 20 30 40 50 60 70-0.05

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

Time (Minutes)

Abs

orpt

ion

(AU

)0.2M KI 0.49 MPa

0.2M KI 0.23 MPa

0.2M KI 0.13 MPa

Potassium Iodide


0 10 20 30 40 50 60 70-0.05

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

Time (Minutes)

Abs

orpt

ion

(AU

)0.2M KI 0.49 MPa

0.2M KI 0.23 MPa

0.2M KI 0.13 MPa

Potassium Iodide

Pressure Power k t 1/2 Eff

MPa W/l 103 min-1 min J/l for 1/20.13 17.61 0.07 9902 1743290.23 41.92 0.7 990 415070.49 56.17 6.3 110 6180


0 10 20 30 40 50 60 70-0.05

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

Time (Minutes)

Abs

orpt

ion

(AU

)0.2M KI 0.49 MPa

0.2M KI 0.23 MPa

0.2M KI 0.13 MPa

Potassium Iodide





0 100 200 300 400 500 60010

-3

10-2

10-1

100

Time (Minutes)

Abs

orpt

ion

(AU

)0.64 MPa

0.45 MPa

0.31 MPa

Indigo Carmine Dye Bleaching


Observations/Conclusions

• 0.7 MPa achieved at 15 W/Liter in 3.5 Liter volume.

•Sonochemical activity caused by stable cavitation. Potential for increased performance with transient cavitation.

•At 0.7 MPa and 56 W/Liter, measured

6180 J/Liter for t1/2 KI in 1 Liter volume (possibility for 15 W/Liter with tube reactor).

•Compares with unknown pressure, 67

Watt/Liter, 3096 J/Liter for t1/2 MO in 45 Liter volume.



UI Intellectual PropertyUI Intellectual Property

• Parabolic transducer source (6,818,128)

• Radiator tube reactor array (6,911,153)

• Biphasic/triphasic US/ozone/metal-oxide catalytic water filter (patent pending)


0 100 200 300 400 500 60010

-3

10-2

10-1

100

Time (Minutes)

Abs

orpt

ion

(AU

)0.64 MPa

0.45 MPa

0.31 MPa





Sec # Pressure (Mpa) Power (Watts) W/L5.3.2 - Eh of DI Water at 980 kHz 0.16 25 20.96

0.3 43 36.050.41 62 51.980.71 94 78.8

5.3.2 Eh of Fe, Mn, and DI 0.7 95 79.640.4 59 49.46

5.3.3 Indigo Carmine Kinetics 0.64 92 77.130.45 65 54.490.31 43 36.05

5.3.4 Potassium Iodide 0.49 67 56.170.23 50 41.920.13 21 17.61

Acoustic Measurements Acoustic Measurements


Chemical and Engineering News, “Bubble Inferno”, 2005, 83, 10.

How Hot?How Hot?


Science, 2002, 295, 1868.

How Hot?How Hot?


Science News, 2005, 167, 147.

How Hot?How Hot?


0 5 10 15 20 25 30 350

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4H

ydro

phon

e F

unda

men

tal,

B0 (

MP

a)

Source Fundamental, A0 (Volts)

Amplitude of FundamentalAmplitude of Fundamental


0 5 10 15 20 25 300

0.05

0.1

0.15

0.2

0.25

Hyd

roph

one

1st

Har

mon

ic,

B 1 (M

Pa)

Source 1st Harmonic, A1 (Volts)

Amplitude of 1Amplitude of 1stst Harmonic Harmonic


Endocrine DisruptersEndocrine Disrupters

• Hormones are biochemicals.– Produced by endocrine glands.– Travel through the bloodstream and cause

responses in other parts of the body.

• Hormones of primary concern.– Estrogen, androgen

and thyroid hormones.


AntidepressantsAntidepressants• With the introduction of a host of new anti-depression

drugs in the late 80s, antidepressant prescriptions grew from 40 million in 1988 to more than 120 million in 1998.

• According to the CDC National Center for Health Statistics, more than 61 million new prescriptions for antidepressants were given by U.S. doctors in 2001.


Antidepressants in BiotaAntidepressants in Biota

• Prozac, Zoloft, Paxil and Celexa (selective serotonin reuptake inhibitors) are found in biota downstream of WWTPs (B. Brooks, Baylor U.)

• Levels of antidepressants as low as 1.5 ppb delays frog metamorphosis and cause development problems in fish (M. Black, U. GA).


Newton, Iowa WWTPNewton, Iowa WWTP


PharmaceuticalsPharmaceuticals

• Prescription drug sales in the U.S. have increased by 16.9% to $172 billion in 2003, plus $18 billon in over-the-counter medicines.

• The Union of Concerned Scientists estimates that in the U.S., 25 million pounds of antibiotics are fed to animals each year compared to 8 million pounds for people.

April 13 2006UI ECE Research Colloqiuim1 Water Treatment Using Ultrasound-Induced Cavitation Michael...

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