MMEA Wastewater treatment seminar presentation by Risto Oikari, CEMIS

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Risto Oikari
Director, CEMIS
17.9.2015
Reliable On-Line Sensing

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CONTENTS
1. CEMIS – Centre for Measurement and Information
Systems
2. Sosio-Economic 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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Its worth to measure: More than 2 % of the GDP is spent for measurements in developed
countries worldwide (3-4 billion euros in Finland), 80 % of global trade includes action
requiring measurements certificates, more than 50 % of EC directives contain requirements
for measurements.
Economic impact of measurements exceeds the cost many times, even several tens of times
Measurements build the better society: Reliable measurements improve competence,
efficiency and safety
Measurement is business: More than 200 measurement technology companies in Finland
(combined turnover around 2 billion euros, i.e. 1 % of GDP). 70 % of the companies are small
or medium in size (SME) (Statistics Finland 2009).
Investments in metrology research is worthwhile: Average number of new research –based
measurement technology companies per year is two (K. Kankaala et al., Sitra reports 72,
2007: 15 new research –based measurement technology companies were founded in years
2000-2006). In past few years much more thanks to Tekes TuTLI –funding!
Introduction

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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)
 You really know your current situation and process status, when you measure it on-line =>
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!
vs.

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 monitor process and pollution everywhere, where is the need (no need to worry about
electricity and communication cables)
 monitor even once a minute and thus you can really on-line control your process and
emissions…and save money…!
 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
Kari Ennola 2012

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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
2013
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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0
0,5
1
1,5
2
2,5
3
6.10. 7.10. 7.10. 8.10. 8.10.
Continuous Chloride Measurement
mg/
l
0
10
20
30
40
50
60
70
6.10. 7.10. 7.10. 8.10. 8.10.
Continuous Sulfate Measurement
mg/
n=244 SO₄²¯ mg/l
Average 57,5
StDev 1,79
%StDev 3 %
Min 54,0
Max 62,8
On-line Capillar Electrophoresis
Analyzer
n=244 Cl¯ mg/l
Average 2,2
StDev 0,25
%StDev 11 %
Min 1,7
Max 2,8

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A technique to detect fouling on optical sensors
A technique has been developed to detect contamination on optical surfaces and correct the
optical measurement signal accordingly.
Measured reflectance Index of contamination
0 20 40 60 80
0.15
0.2
0.25
0.3
0.35
Aika
R
37
likaantunut puhdas
0 20 40 60 80
0
0.01
0.02
0.03
Aika
Likaindeksi
0.0058

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Mobile Monitoring Station

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Focus on reliable measurements
Evaluation of the combined measurement uncertainty of Cu-sensor

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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