MMEA (The Measurement, Monitoring and Environmental Efficiency Assessment) research program final seminar presentation by Dr. Risto Oikari, CEMIS

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Risto Oikari
Director, 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 nutshell
CEMIS 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 limit⃰ Upper limit⃰ Accuracy⃰
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) 0 200
pH 0 14
Conductivity (mS/m) 0 > 1 000 0.5-1 %
Redox (mV) - 2 000 + 2 000 0.5 %
Oxygen (mg/l) 0 20 0.1 mg/l
Temperature (°C) 0 80 ± 0.25 ° C
COD/TOC/DOC (mg/l) 0 > 100
NO3-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 25
Total P and total N (mg/l) : analyser 0.01 3 000
Suspended solids (mg/l) 1 1 000
Turbidity (NTU) 0 3 000
Toxic metals (mg/l): Cu, Ni, Zn, Pb, Cd … 0.01 1 000
Sulfates (mg/l)
Bacteria
Drugs 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 installation
Conventional electrochemical detection: Stripping voltametry based on amalgamation on a
mercury electrode
Our key solution is anodic stripping voltametry by
1) Screen printed mercury electrode
2) Screen printed mercury-free electrode (based on graphene or bismuth)
3) Gold wire electrode
We have also expertise on:
1) Amperometric method based on an enzyme biosensor for complex forming metal ions like nickel
2) Strip test with colormetric analysis
3) Plasma discharge atomic absortion and emission spectroscopy
4) Plasma, spark or laser induced breakdown spectroscopy
5) 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 electrodes
Based 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 electrode
Based 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-ppb
Potential
Current
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 simultaneously
5, 10, 20 ja 50 ppb

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Calibration curve for Ni
[Ni] (ppm)
0 1 2 3 4 5 6
Relativecurrent(%)
0
20
40
60
80
100
120
140
Calibration curve for Ni using sarcosine oxidase
Linear regression
Enzyme-based sensors
Enzyme (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 sensor
Ni 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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Interoper
ability
Reliability
Sensitivity
Selectivity
Specificity
Detection
speed
Remote
use
Wide
detection
range
Low
invest.&o
per. costs
Small size
Minimal
energy
consumpti
on
Reagent
free
No
moving
parts
Real-time
Multi
sensing
Robust
ness
”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 Oikari
CEMIS (Ketunpolku 3, FIN-87101 KAJAANI, FINLAND)
Tel.: +358-44-7101410, e-mail: risto.oikari@cemis.fi
Thank you!
Reliable On-line Measurements for
Demanding Conditions