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Risto OikariDirector, CEMIS
26.11.2015
Reliable On-Line Sensing
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CONTENTS
1. CEMIS – Centre for Measurement and Information Systems
2. Sosio-Economic-Environmental Benefits of Reliable On-line Sensing
3. Examples of on-line sensors developed at CEMIS
4. Vision for Future Sensor
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CEMIS in a nutshellCEMIS is a contract based joint centre of University of Oulu, University of Jyväskylä, Technical Research Centre of Finland VTT and Kajaani University of Applied Sciences.CEMIS is founded Kajaani in 2010 and employs around 110 professionals.CEMIS specialises in research and higher education in the field of measurement and information systems.
CEMIS´s mission is to provide r&d –services, training and education, new technology and innovations for companies and research organizations developing and applying measurement and information systems.
••
• Oulu
Jyväskylä
Espoo
• Kajaani
Helsinki•
•Finland
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Why automatic on-line monitoring is a good solution?
To save money and save time (less people are needed to control process or pollution) More real information is available for process control and for reporting (on-line monitoring gives
possibility to know continuously, what is really happening, reporting to the authorities/owners is easier => less need to explain!
Possibility to avoid environmental accidents and problems, since you can react immediately, when something happens – no long delays for reactions => Early Warning System
Possibility to adjust and optimize the process Big savings! monitor process and pollution everywhere, where is the need (no need to worry about electricity
and communication cables Monitoring is possible all year around - heat or coldness are not making any problems (operates -
40….+80 °C The data is sent to automation system or to Internet wirelessly => very pleasant and fast system
vs.
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On-line monitoring system and wireless data transfer
Video on environmental monitoring by EHP-Tekniikka Solutions:http://www.youtube.com/watch?v=IvItLVyH_i8&feature=youtu.be
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Economic Value of On-line Monitoring
From EHP-Tekniikka Ltd. marketing material
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Parameters to be monitored...
Measurand Lower limit ⃰ Upper limit ⃰ Accuracy ⃰Level of surface water (mm) 0 250 000 0.1 %Level of ground water (mm) 0 250 000 0.1 %Discharge (flow) of the water (l/s) 0 > 1 000 l/s 0.1 %Oil in water (μg/l) 0 200pH 0 14Conductivity (mS/m) 0 > 1 000 0.5-1 %Redox (mV) - 2 000 + 2 000 0.5 %Oxygen (mg/l) 0 20 0.1 mg/lTemperature (°C) 0 80 ± 0.25 ° C COD/TOC/DOC (mg/l) 0 > 100NO3-N and NO2-N (mg/l) 0 1 000 0.1 %NH4-N (mg/l) 0 1 000 0.1 %PO4-P and NO2-N (mg/l) : analyser 0.1 25Total P and total N (mg/l) : analyser 0.01 3 000Suspended solids (mg/l) 1 1 000Turbidity (NTU) 0 3 000Toxic metals (mg/l): Cu, Ni, Zn, Pb, Cd … 0.01 1 000Sulfates (mg/l)BacteriaDrugs residues, hormone-like subtances etc. Others...Totally
about 45 parameters !
Under development at CEMIS
�⃰ Typical values
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Need: Ability to measure simultaneously different trace metals at concentration levels down to the fractional parts per billion (sub-ppb), using inexpensive, versatile, reliable, small size instrumentation, with no requirement of special installationConventional electrochemical detection: Stripping voltametry based on amalgamation on a mercury electrodeOur key solution is anodic stripping voltametry by1) Screen printed mercury electrode2) Screen printed mercury-free electrode (based on graphene or bismuth)3) Gold wire electrode
We have also expertise on:4) Amperometric method based on an enzyme biosensor for complex forming metal
ions like nickel5) Strip test with colormetric analysis6) Plasma discharge atomic absortion and emission spectroscopy7) Plasma, spark or laser induced breakdown spectroscopy8) Optical transmission spectroscopy with complex forming reagents
On-line detection of toxic metals in waste water streams
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Anodic stripping voltametry by screen printed electrodesBased on screen printed electrodes developed originally by University of Rome
Detection limit: ppb -level
•WORKING ELECTRODE
•COUNTER ELECTRODE
•REFERENCE ELECTRODE
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Gold wire electrodeBased on a 3-electrode configuration with microwire technology originally developed
by University of Liverpool. The solution has an integrated solution to prevent contamination of the sensor surface and to increase the selectivity, sensitivity and stability
First prototype
Detection limit: sub-ppbPotential
Cur
rent
tap water
0.00 0.05 0.10 0.15 0.20 0.25
V
20
40
60
80
nA
Cu 104,37 ± 5,85 ppb
Three metal simultaneously5, 10, 20 ja 50 ppb
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Calibration curve for Ni
[Ni] (ppm)
0 1 2 3 4 5 6
Rel
ativ
e cu
rren
t (%
)
0
20
40
60
80
100
120
140
Calibration curve for Ni using sarcosine oxidaseLinear regression
Enzyme-based sensorsEnzyme (Sarcosine oxidase) produces hydorgen peroxide that can be measured amperometrically using a modified electrode (Prussian Blue). Nickel
inhibits enzyme activity, resulting in lower response detected.
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Ni sensorNi detection based on regenerable bismuth coated electro chemical sensor
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Field usable optic online measuring instrument for liquids
The instrument can be used to measure metal concentrations in liquid samples with a reagent that forms complexes with metals. The formed complexes absorb light in the visible area. Measurements are based on optical spectroscopy within wavelength range 200 … 850 nm. Fouling of optical surfaces is controlled with a cleaning solution.
Figure shows the spectra of several concentrations of nickel with PAR (4-(2-pyridylazo)resorcinol) reagent.
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2011
2012
2014
CEMIS has develop a fast and reliable on-line measurement system for determination of trace metal content in water. The measurement device has passed several field tests in order to evaluate the compatibility of the technique in harsh conditions. The solution will be commercialized by the end of year 2015. Key features: Analysis is based on electrochemical technique (square
wave anodic stripping voltammetry/potentiometry/electrical impedance spectroscopy)
Several metal analytes (e.g. Cu, Pb, Zn, Ni, Hg …) Low detection limit < µg/L (sub-ppb) for metals Fast analysis < 5 minutes No toxic reagents used, Mercury-free operation Automated sampling Integrated sample pre-treatment technology Low maintenance and running costs Wireless data transfer + remote control Battery-operated Robust design, suitable for field use
Automated online analyzer
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Teollisuuden metallipäästöjen mittaamisessa läpimurto - Pienten metallipitoisuuksien on line mittaaminen teollisuusvesistä on nyt totta Tiedote. Julkaistu: 19.11.2015 klo 13:02 Julkaisija: EHP-Tekniikka Heinäkuussa 2014 käynnistyi kehitystyö, jonka tuloksena luvattiin olevan siirrettävä, jatkuvatoiminen (on line) metallimittausratkaisu teollisuusvesille - kaivoksille, metallitehtaille, kemiantehtaille ja energiateollisuuteen - on saavuttanut tavoitteeseensa ja läpimurto on saavutettu suomalais-norjalaisen yhteistyönä.
Liukoisten metallipitoisuuksien mittaamistoive on toteutunut ja todella pieniä, mikrogrammatason liukoisia metallipitoisuuksia voidaan mitata teollisuuden kuivatusvesistä, jäähdytysvesistä ja jätevesistä jatkuvatoimisesti paikasta ja ajasta riippumatta vuodet ympäri äärimmäisissä olosuhteissa. Metallipäästöt vesistöihin kuormittavat herkkiä vesistöjä ja metallien mittaamisen avulla päästöjä voidaan vähentää merkittävästi. Käyttöön on otettu mittausratkaisu, jolla ensimmäisenä maailmassa voidaan maastossa mitata useiden metallien päästöjä ympärivuotisesti paikasta ja ajasta riippumatta. Jatkuvatoiminen mittaus voidaan viedä ojaan, purku-uomaan, lampeen, jokeen, järveen tai altaaseen ja täysin reaaliaikaisesti mitata metallien määrää vedessä. Tämä mahdollistaa metallipäästöjen kiinnisaamisen heti - esim. onnettomuustilanteessa on tärkeää havaita päästö heti alkuvaiheessa, jolloin voidaan välittömästi reagoida ja estää suurten metallimäärien joutumisen vesistöön. Tämä säästää rahaa sekä ympäristöä.
Mitatut metallipitoisuustiedot lähetetään langattomasti eteenpäin ja näin voidaan metallipitoisuuksien noususta saada välittömästi tieto ja ryhtyä saman tien korjaaviin toimenpiteisiin. Ratkaisuun kuuluu myös vesimäärän ja muiden vedenlaatutietojen samanaikainen mittaaminen, joten ratkaisu on globaalisti täysin ainutlaatuinen. Ratkaisun toimivuus on todettu vuoden 2015 aikana kaivos- ja metallikonserni Bolidenin kaivoksella ja metallisulattamolla tehdyissä täyden mittakaavan koejoissa ja ensimmäiset kaupalliset sopimukset asiakkaiden kanssa on solmittu marraskuussa 2015. Ratkaisun takana ovat EHP-Tekniikka Oy, oululainen ympäristömittaustekniikan yhtiö, CEMIS-Oulu, Kajaanissa toimiva Oulun yliopiston tutkimusyksikkö ja EnviTech AS, norjalainen ympäristöalan yhtiö.
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Mobile Monitoring Station
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Interoperability Reliability
Sensitivity
Selectivity
Specificity
Detection speed
Remote use
Wide detection
rangeLow
invest.&oper. costs
Small size
Minimal energy
consumption
Reagent free
No moving
parts
Real-time
Multisensing
Robustness
”Ultimate”Sensor
Vision of Future Sensor…
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Just one dream…
… wireless, self-powered, robust, reliable, self-calibrating sensor network for water quality.
…Vision of Future Sensor
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Implementing Results of Cleen/MMEA -Programme
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Director Risto OikariCEMIS (Ketunpolku 3, FIN-87101 KAJAANI, FINLAND)
Tel.: +358-44-7101410, e-mail: [email protected]
Thank you!
Reliable On-line Measurements for Demanding Conditions