innovative modular sensing systems for autonomous …

Mary-Lou Tercier-Waeber

Groups of Chemical sensors & Analytical and Environmental Chemistry

Dept. of Inorganic and Analytical Chemistry University of Geneva - Switzerland

INNOVATIVE MODULAR SENSING SYSTEMS FOR AUTONOMOUS IN SITU MONITORING

OF TRACE METALS AND (HARMFUL) ALGAE

AEI2019–9to11July2019-Lille(PolytechLille)-France

Oceanmonitoringandriskassessment

IntegratedMultifunctionalAutonomousInsituSensorObservationSystem

WEBinterfacesforwirelessbi-directionalinteraction

WEBinformationsystem

http://www.schema-ocean.eu/Data-Portal

THE OCEAN OF TOMORROW

METALS

NUTRIENTS NO3

-, NO2-, Ca) O2

DEPLETION

PHYCOTOXINS

EUTROPHICATION

(HARMFUL) ALGAE

Time

BIO-ACCUMULATION

BIO-MAGNIFICATION

CARBONATE CO2 pH

Targetanalytes

Analytical approach:

Sensorsandprobefortracemetals(UNIGE, EPFL)

Antifouling gel

Si 3 N 4 Ir Si 3 N 4

Silicon 5 µm

Hg

GIME: Cd(II), Pb(II), Cu(II), Zn(II)

SEM

5 µm

AuNP Antifouling gel

Si 3 N 4 Ir Si 3 N 4

Silicon

AuNP-GIME: As(III), Hg(II) As tot = As(V)+As(III)

Sensorsandprobefortracemetals(UNIGE, EPFL)

Mn(II)Mn(0)As(V)+Mn(0)As(III)+Mn(II)

e-

Detection technique: subtractive SWASV

Sensorsandprobefortracemetals

Detection technique: subtractive SWASV

preconcentration equilibration

stripping time

pote

ntia

l

Mn+

M0

Mn+

- e

Mn+

M0

cleaning

background equilibration

peakpositionspecifictoametalpeakcurrent~Meconcentrationandpreconc.t

curren

t

potential

-0,30

-0,25

-0,20

-0,15

-0,10

-0,05

0,00

-1200 -1000 -800 -600 -400 -200 0 200

Δi /

µA

E / mV

i stripping i background i stripping-i background

Zn 4 nM

Cd 3.6 nM

Pb 4 nM

Cu 10 nM

J. Buffle, M.-L. Tercier-Waeber, Trends in Analytical Chemistry 24 (2005) 172-191.

Main features related to the characteristics of micro-sized electrodes (r ≤ 10 µm)

Specific measurements of the dynamic M species i.e. max conc. of M potentially available for bio-uptake

SensorsandprobefortracemetalsGIME features

Sensorsandprobefortracemetals(UNIGE, IDRO, EPFL)

Antifouling gel

5 µm

AuNPs

Antifouling gel

5 µm

AuNPs

Rawsignals

Sensorsandprobesfortracemetals(UNIGE, IDRO)

Channel1

Channel2

Channel3

TMSM

Me LOD 500-GIME / nM (ng/L)

Preconc.: 10 min Preconc.: 30 min

Hg(II) 0.017 (3) 0.006 (1.2)

As(III) 0.20 (15) 0.08 (6)

Cu(II) 0.10 (6.3) 0.04 (2.5)

Pb(II) 0.01 (1.6) 0.005 (1)

Cd(II) 0.015 (1.5) 0.005 (0.6)

Zn(II) 0.15 (10) 0.05 (3)



Hg(II) 0.04 (8) 0.01 (2.5)

As(III) 0.50 (35) 0.20 (15)

Cu(II) 0.25 (15) 0.10 (6.3)

Pb(II) 0.02 (4) 0.01 (2)

Cd(II) 0.03 (3) 0.01 (1)

Zn(II) 0.40 (25) 0.15 (10)

Sensorsandprobesfortracemetals(UNIGE, IDRO, EPFL)

Ø  TMSManalyticalperformanceandpotentialityforenvironmentalandwaterqualitymonitoring

Pigment-basedtaxonomicclassificationAnalyticalapproach:

Thephotosyntheticapparatusofalgaeconsistsoftwotypesofpigment-proteincomplexes:•  light-harvestingcomplexes•  reactioncentersLHCcontainpigments:absorblight,transferringittophotosystemreactioncentersReactioncenters:turnsolarenergyintochemicalenergy.•  Chlorophyllpigmentsomnipresentinallreactioncenters(RC)•  Pigmentsoflight-harvesting-complex(LHC)differsfordifferentalgalgroups

Ø  CombiningLEDswithrelevantwavelengthrangestosignaldeconvolutionenabletodetectthedifferenciesinthealgalgroupLHCrelativepigmentpatterns

Miniaturized fully Integrated Algae Detection Module - ASM (TUGraz)

Ø  Algaecultivationandcharacterization(fluorescenceexcitationspectrastudy;markerpigmentsanalyzedviaHPLC)

Ø  Generationofdatabankforsignalanalysis:ü  76coastalalgaespeciesbelongingto8differentphyla•  Cyanobacteriatoxinproductivealgae•  Dinophyta(Dinoflagellates)toxinproductivealgae•  Bacillariophyta(Diatoms)•  Haptophyta•  Chlorophyta•  Ochrophyta

•  Cryptophyta•  Euglenophyta.

Ø  Selectionof

ü  Selectionofopticalcomponentsü  Referencedatamatrixfordataevaluation

Analyticalapproach:

Miniaturized fully Integrated Algae Detection Module - ASM (TUGraz) Challenge:Lackofinformationaboutalgalpigmentpatterninliterature

14

Miniaturized fully Integrated Algal Detection Module - ASM (TUGraz)

Ø  MaterialandDimensions

Material:AluminumSize:28x34.8x15.8mm3

Capillary:Quartz,ID=1.94mm,OD=3mmMeasurementvolume:5.91µL

Ø  Opticalcomponents

8Excitationsources:LEDs380-650nm4Photodetectors:Siliconpinphotodiode

ASM detection module:

S.Ziegeretall,Env.Sci.Tech.,2018

Miniaturized fully Integrated Algae Detection Module - ASM (TUGraz, IDRO) Algae detection system: portable and submersible

CSM

Dedicated software

Ø  Detection of single cell events - quantification of average cell density

0 5

10 15 20 25 30 35 40

Rel

. alg

ae c

ompo

sitio

n

Semi-quantification of the various algal phylum


In situ application and validation (UNIGE, UBx, UNIGe-IT)

Ø  Girondeestuary–June2017•  Reliabilityofmeasurementsinsalinitygradientandhighlyturbidsystem(SPM:55to1600mg/L)

(19stations)

SensorsandprobesfortracemetalsIn situ application and validation (UNIGE, UBx)

GIMETMSMchannels1and3:copper,lead,cadmium,zincØ  Girondeestuary–June2017

•  ReliabilityofGIMEmeasurementsinhighlyturbidsystems

0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80

0 5 10 15 20 25 30 35 C

onc.

nM

Salinity

Cd(II)dyn -Ch1 / nM Cd(II) dyn -Ch3 / nM Cd(II) dyn av. / nM

0,00

0,02

0,04

0,06

0,08

0,10

0,12

0 5 10 15 20 25 30 35

Con

c. /

nM

Salinity

Pb(II) dyn - Ch1 / nM Pb(II) dyn -Ch3 / nM Pb(II) dyn av. / nM

0

0,01

0,02

0,03

0,04

0,05

0,06

0 5 10 15 20 25 30 35

Pb(II) -ch1 / nM

Pb(II) -ch3 / nM

Av.

Gironde18.06.201714h(L413:SPM75.4mg/L)

-0,16

-0,11

-0,06

-0,01

0,04 -1200 -1000 -800 -600 -400 -200 0

Δi /

µA

E / mV

Zn 0.53 nM

Cd 0.18 nM

Pb 0.08 nM

Cu 0.36 nM


Ø  Girondeestuary–June2017•  Variationofbioavailablefraction,underdifferenttrends,anduptooneorderofmagnitude

alongthesalinitygradient

Hg-GIMETMSM:copper,lead,cadmium,zinc


Ø  Mespeciation-Girondeestuary–June2017Hg-GIMETMSM:copper,lead,cadmium,zinc


Ø  SalinitygradientAuNP-GIMETMSM:As(III)GirondeEstuary–June2017

As(III)dyn:1.2to2.8nM

As(III)dyn:1to2nM

EffluxAs(III)

As(V)Internalisation

via phosphate channel

+ e-

Ø  30hcyclecoastalarea

Miniaturized fully Integrated Algae Detection Module - ASM

In situ application and validation (TUGraz, UNIGe-IT, ETT)

Girondecoastalarea24hcycle–June2017

Deviationfrommicroscopeanalysis<15%

28

32

Sal.

0

20

40

60

80

100

8h

10h

12h

14h

16h

18:0

0

20:0

0

22:0

0

00:0

0

02:0

0

04:0

0

06:0

0

Rel

. Alg

al c

ompo

sitio

n

Other algae

Cyanobacteria

Diatom & Ochrophyta

Haptophyta

Dinophyta

In situ application and validation (UNIGE, UBx, ETT)MEPHY

Ø  Elbe Estuary mouth: 7-16 May 2019


AuNP-GIMETMSMchannel3:95measurementswithoutrenewaloftheAuNPlayers

HT LT


AuNP-GIMETMSMchannel2:150measurementswithoutrenewaloftheAuNPlayers


GIMETMSMchannel1:150measurementswithoutrenewaloftheHglayers

HT LT


HT LT


Phytoplanktoncommunities

http://www.schema-ocean.eu

Ø Visit the SCHeMA web site

Università degli Studidi Genova


For more information

MaritimeSensorTechnologiesfortheEuropeanMarket:Research,DevelopmentandImplementation.Goodpracticeguide.Horizon2020:COLUMBUSandAtlantosprojectsFP7:OceanofTomorrowprojects



For more information

EU publications

Theoceanoftomorrowprojects(2010-2013)Jointresearchforcestomeetchallengesinoceanmanagement


Main contributors DevelopmentTMSMsensorsandprobe

UNIGEGuyLecoultreStéphaneJeanneretEPFLMariannaFigheraIdronautFabioConfalonieriGiulianoBrandini

DevelopmentASM

TUGrazIngoKlimant SilviaZieger,LukasTroiAlexanderLangGünterMistlbergerChristianHollyIdronautFabioConfalonieri

FieldtestsGironde(SCHeMA)

UBxJörgSchäferMélinaAbdouCécileBossyLionelDutruchUNIGEAbraPenezic

FieldtestsElbe(MEPHY)UNIGEMélinaAbdouPierreGroc*UBxJörgSchäferMaevaLabassa*ThibaultDevanne*LionelDutruchETTLucaBonofiglioSusannaAlloisioHZGWilliPetersenDanielBlandfort*Masterstudents

Financial support European Commission:

SCHeMA (FP7 – Ocean of Tomorrow)

MEPHY (FP7 – JERICO-NEXT NTA


MEPHY


Oligoelements, i.e. essential to living organisms, or toxic depending on their concentrations

Motivation and Challenges:

Response depends on: Element Chemical species Biological target

Toxic even at very low conc. (Hg, As, Pb, U, Tl)

Motivation and Challenges: - Direct monitoring at natural pH and in presence fouling materials and oxygen - Detection limit: nM to pM -  Selectivity to relevant, in term of toxicity, metal species


M.-L. Tercier-Waeber, M. Taillefert, J. Environ. Monit., 10, 2008, 30-54.


Ø  Occurrence and intensity increase Ø  Production of various toxins

§  Physical threat to fish and human §  Fish and shellfish poisoning

Ø  Relevant as screening and alarm system for: §  Recreational facilities §  Fish farming industry

Dinoflagellates(Dynophyta)

Saxitoxin(STX)

https://www.whoi.edu/website/redtide/regions/world-distribution/

Motivation and Challenges:

ExcitationspectrumCyanobacteriasp.Lightintensityspectra

ExcitationspectrumAmphorasp.

Dedicated software:

Ø  identification/classification of the various algae Ø  clear separation of common toxin producing Cyanobacteria and Dinophyta (Fisher’s linear

discriminant analysis)

SeparationintheLDAsubspace


Miniaturized fully Integrated Algae Detection Module - ASM

Ø  Evaluation:Genoalong-termfieldtests(15February-7March2017)

In situ evaluation and validation (TUGraz, UNIGe-IT, ETT)

In situ application and validation (UNIGE, UBx, ETT, HZG)MEPHY

Hg-GIMETMSM:copper,leadcadmium,zinc

(TMSM:1GIMEs;2AuNP-GIMEs)

M.Abdoua,P.Groca*,J.Schäferb,M.Labassab*,T.Devanneb*,A. Novellinoc,S.Alloisioc,L.Bonofiglioc,B. W.Petersend,D.Blandfortd

FieldtestsElbe(MEPHY)UNIGEMélinaAbdouPierreGroc*UBxJörgSchäferMaevaLabassa*ThibaultDevanne*LionelDutruchETTLucaBonofiglioSusannaAlloisioHZGWilliPetersenDanielBlandfort*Masterstudents

Marineecosystems:cradleoflifeontheEarth

Ø  94percentoflifeonEarthisaquatic

ThemainBluesectors TheEU'blue'economyrepresentsroughly5.4millionjobsandgeneratesagrossaddedvalueofalmost€500billionayear.

http://ec.europa.eu/maritimeaffairs/policy/blue_growth/index_en.htm

Oceanresourcesandcontributiontoeconomy:Wellbeingofbillionsofpeople

Oceanmonitoringandriskassessment

Ø  Detailedspatialandtemporalmeasurementsrequiredforefficientü  waterqualitymonitoringü  riskassessmentü  todefineappropriateactiontoensurefurthersustainablemanagementandthereforeBlueGrowthEconomy

ü  Innovativesensorswithimproved:

-sensitivity,selectivityandreliability-robustness

ü  Miniaturizationü  Minimumreagentsrequirements

ü  Lowpowerconsumptionandcost

ü  Standardizationof:-wiredandwirelessnetworkingsolutions-web-baseddatainformationsystem

Chemicalsensorprobenetworkdevelopment:CriteriaofcurrentR&D



Hg(II) 0.017 (3) 0.006 (1.2)

As(III) 0.20 (15) 0.08 (6)

Cu(II) 0.10 (6.3) 0.04 (2.5)

Pb(II) 0.01 (1.6) 0.005 (1)

Cd(II) 0.015 (1.5) 0.005 (0.6)

Zn(II) 0.15 (10) 0.05 (3)



Hg(II) 0.04 (8) 0.01 (2.5)

As(III) 0.50 (35) 0.20 (15)

Cu(II) 0.25 (15) 0.10 (6.3)

Pb(II) 0.02 (4) 0.01 (2)

Cd(II) 0.03 (3) 0.01 (1)

Zn(II) 0.40 (25) 0.15 (10)

Parameter Units Open Sea Coastal / surface water AA-WQS

Dissolved Inorganic Mercury (II) nM 0.0002-0.0015 0.001 - 15 1.50 Dissolved Inorganic Arsenic (III) nM 0.3-0.6 1 - 500 130.00 Dissolved Copper (Cu) nM 0.5-5 1 - 235 80.00 Dissolved Lead (Pb) nM 0.005-0.09 0.03 - 200 120.00 Dissolved Cadmium (Cd) nM 0.001-1.2 0.005 - 25 22.00 Dissolved Zinc (Zn) nM 0.1 - 8 0.3 - 680 610.00

Sensorsandprobesfortracemetals(UNIGE, IDRO, EPFL)

Ø  TMSManalyticalperformanceandpotentialityforenvironmentalandwaterqualitymonitoring

47

Macro / micronutrients and light: parameters that ensure or limit the development and maintenance of life in aquatic environments


AuNP-GIMETMSM:As(V),Astot-GirondeEstuary–June2017

0 5

10 15 20 25 30 35 40

0 5 10 15 20 25 30 35

As(tot) dyn (nM) As tot 0.02 (nM)/ nM As tot 0.2 (nM)

0 5

10 15 20 25 30 35 40

0 5 10 15 20 25 30 35

As(V) dyn (nM) As(V) diss 0.02 (nM) As(V) diss 0.2 (nM)

R² = 0,84193

0

5

10

15

20

25

0 4 8 12 16

As(

V) d

yn (n

M)

Mn 0.02 (nM)

MnO2

IntegratedMultifunctionalIntonomousInsituSensorObservationSystem

50

MEPHYSources,behaviour,fateandsynergicinteraction

METALS

NUTRIENTS O2 DEPLETION

PHYCOTOXINS

EUTROPHICATION

(HARMFUL) ALGAE

Time

BIO-ACCUMULATION

BIO-MAGNIFICATION

Targetanalytes

In situ application and validation (UNIGE, UBx, UNIGe-IT)

Ø  Girondeestuary–June2017•  ReliabilityofGIMEmeasurementinsalinitygradientandhighlyturbidsystem(SPM:55to1600mg/L)

(19stations)

(2Hg-GIMEs;1AuNP-GIME)

Ø  9Partnersfrom6differentcountries(5Universities,3SMEs,1FederalInstituteof

Technology)

Ø  Startingdate:1stOctober2013(48months)

Ø  Totalbudget:€6.74Million

Ø  EUcontribution:€5.2Million

FP7:OceanofTomorrowprojectsTHE OCEAN OF TOMORROW

Metal role, behavior and fate are very complex:

-  inherently persistent (i.e. non bio-degradable) -  involved in bio-geochemical processes

Réactivité ?Biodisponibility ?

Ecotoxicité ?Propagation?

SensorsandprobesfortracemetalsIn situ application and validation (UNIGE, UBx, UNIGe-IT)

Hg-GIMETMSM:copper,leadcadmium,zinc

Ø  Girondeestuary–June2017•  ReliabilityofGIMEmeasurementinsalinitygradientandhighlyturbidsystem(SPM:55to1600mg/L)

-0,16 -0,14 -0,12

-0,1 -0,08 -0,06 -0,04 -0,02

0 0,02 0,04

-1200 -1000 -800 -600 -400 -200 0 Δ

i / µ

A

E / mV

Gironde18.06.201714h(L413:SPM75.4mg/L)

Zn 0.53 nM

Cd 0.18 nM

Pb 0.08 nM

Cu 0.36 nM

(2GIMEs;1AuNP-GIME)

innovative modular sensing systems for autonomous …

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