DETECTION OF TOXIC AGENTS IN WATER SYSTEMS

J. (ART) JANATA

School of Chemistry and BiochemistryGeorgia Institute of Technology

E-mail: jiri.janata@chemistry.gatech.eduPhone: 404 256 0186

OUTLINE

• OVERVIEW OF SENSORS/SYSTEMS - BASICS

• CHARACTERISTICS OF THE APPLICATION

• CONCLUSIONS

Workshop: “NEW TECHNOLOGIES”, Newark, June 27-28,2002

• SENSORS ACQUIRE INFORMATION CONTINUOUSLY

• SENSING SYSTEMS (ASSAYS) ARE DISCONTINUOUS,CONTAIN DISCRETE STEPS

SENSORS ARE DIFFERENT THAN SENSING SYSTEMS

OR

TRANSDUCER DATA PROCESSOR

RESPONSE

SELECTIVE SURFACE SENSOR

RE

SP

ON

SE

TIME

TRANSDUCER TYPES • THERMAL • MASS • ELECTROCHEMICAL • OPTICAL

BULK SELECTIVE LAYER SENSOR

SELECTIVE LAYER TRANSDUCER DATA PROCESSOR

RESPONSE

CONTINUOUS SENSORS

ANALYTE

ANALYTE

DYNAMIC RANGE

SATURATION

SENSITIVITY

INTERFERENCESR

ES

PO

NS

E

CONCENTRATION

DETECTION LIMIT

INT

ER

FE

RE

NC

ES

SENSOR BASICS

TIME

RE

SP

ON

SE

63%

del

GENERAL LIMITATIONS OF CONTINUOUS OPERATION

• BASELINE STABILITY

• LOSS OF SENSITIVITY

• POWER CONSUMPTION

minutes for bulk< seconds for surface

RESPONSE TIME

SAMPLE

INTRODUCTION

REAGENTADDITION INCUBATION MEASUREMENT

READOUTEVALUATION

TIME

INF

OR

MA

TIO

N

BIOSENSING SYSTEM (ASSAY)

DISCRETE STEPS

CALIBRATION POINT

Solution: Lab-on-a-Chip Technology

Miniaturization, Integration, AutomationRevolutionary Advance in Laboratory Technology

An integrated microfluidic device Nanoliter internal Nanoliter internal volumes, channel cross-volumes, channel cross-sections in the 10 to 100 sections in the 10 to 100 µm range (needed for fast µm range (needed for fast diffusion times)diffusion times)

Electrokinetic movement Electrokinetic movement of liquids and samples of liquids and samples (allows for control at (allows for control at many wells)many wells)

Personal Laboratory Workstation

http://www.chem.agilent.com/cag/products/intro_g.htm

The Microfluidic Toolbox

•11 Separations: DNA, RNA, ProteinsSeparations: DNA, RNA, Proteins

•22 Enzyme Activity AssaysEnzyme Activity Assays

•33 Joule Heating on a ChipJoule Heating on a Chip

•44 PCR on a ChipPCR on a Chip

•55 Solid Phase Reagent StorageSolid Phase Reagent Storage

•66 Cell and Bead AssaysCell and Bead Assays

•77 ViscometerViscometer

•88 Sample Preparation Sample Preparation

FLOW INJECTION ANALYSIS (FIA)

a marriage of wet analytical chemistry and automation for microscale analysis

APPLICATIONS

Groundwater and soil analysis

Radiochemical analysis

Health effects research

Biomedical research/technology

Extraction/process simulation

Sample introduction to ICP-MS

Flow injection methods providea microscale toolkit forcombining various sampleprocessing stepsinto one integrated andautomated flow system.

ADVANTAGES

Flexibility

Small sample volumes

Fast analysis time

Minimal reagent consumption

Minimal waste generation

Automated

Field-portable

Carrier

Sample(s)

Reagents(s)

MixDilute

ExtractDialyze

Concentrate

pHElectrochemicalChemical sensor

SpectrophotometricCounterICP-MS

DETECTOR

Waste

PROCESSING ANALYTICALRESPONSE

INJECTION

Pump(s)Valve(s)

FIELD-DEPLOYABLE SYSTEMFOR Cr(VI) ANALYSIS

D

Sample

Purge Line

CarrierAcidColorFormingReagent

10 20 30

1100

1350

1600

Multi-positionValve

SyringePump

ControlComputer

Spectrophotometer

Sample Size: < 500 microliters50 microliters analyzed

< 2 minutes per sample

total volume of waste1.5 milliliters per sample

10 ppb to 5 ppm range

CHARACTERISTICS OF DETECTION IN WATER SYSTEMS

• LARGE SAMPLE VOLUME

• DILUTION

• LONG TIME CONSTANT

• WATER AS A MEDIUM

• HYDROLYSIS

• BIOLOGICAL AGENTS

• LIMITED ACCESIBILITY OF WATER TOWERS

• EASY ACCESS TO RESERVOIRS

RESPIRATORY PERCUTANEOUS TOXICITIES (REL)Chlorine (Cl2) l0,000 - 1

Phosgene (CG) 3,000 - 3

Hydrogene Cyanide (AC) 5,000 200,000 2

Cyanogen Chloride (CK) 11,000 - 1

Mustard (Sulfur) (HD) 1,500 10,000 7

Mustard (Nitrogen) (HN-1) 1,200 100,000 8

GA (Tabun) 400 40,000 251,000 mg(L)/ Man

GB (Sarin) 100 15,000 1001,700 mg(L)/ Man

GD (Soman) 70 1,000 1501,000 mg(L)/ Man

Tammelin Esters (IV-0.56) - -

EA 5365 40 35 mg(L) 250

LCT50 [mg-min/m3] Lethal concentration at which 50% of the test animals are killed

TOXICITIES OF LETHAL GASES

CYA

NO

GEN

CH

LO

RID

E

CH

LO

RIN

E

HY

DR

OG

EN

CYA

NID

E

PH

OS

GEN

E

HD

HN

-1

TA

BU

N

SA

RIN

SO

MA

N

EA

5365

TA

MM

ELIN

ES

TER

S

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

LOG

TO

XIC

ITY

TOXICITY RELATIVE TO CHLORINE

CYA

NO

GE

N C

HLO

RID

E

CH

LOR

INE

HY

DR

OG

EN

CYA

NID

E

PH

OS

GE

NE

HD

HN

-1

TAB

UN

SA

RIN

SO

MA

N

EA

53

65

TAM

ME

LIN

ES

TE

RS0.0

1.0

2.0

3.0

4.0

5.0

6.0LO

G (

TO

X *

RE

L.

DE

NS

ITY

)

DOWNDRAFT APPLICATION

CYA

NO

GE

N C

HLO

RID

E

CH

LOR

INE

HY

DR

OG

EN

CYA

NID

E

PH

OS

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HD

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-1

TAB

UN

SA

RIN

SO

MA

N

EA

53

65

TAM

ME

LIN

ES

TE

RS0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0LO

G (

TO

XIC

ITY

* V

OLA

TIL

ITY

)

UPDRAFT APPLICATION

HARMFUL AGENTS

• INORGANIC POISONS: HEAVY METALS; CYANIDE...

• INFECTIOUS BACTERIAL/VIRAL AGENTS

• TOXINS: AFLATOXINS, RICINE, ANTHRAX,...

• RADIONUCLIDES: Cs-137; Sr-90; Tc-99m; Np-237,...

DETECTION

• ASSAYS• RADIATION DETECTORS

IMPORTANT DIFFERENCES BETWEEN DETECTION

OF THREAT AGENTS IN AIR AND IN WATER

GAS WATER

REQUIRED RESPONSE TIME SHORT LONG

BIOAGENTS DIFFICULT EASY

DISTRIBUTION PATTERNS COMPLEX PREDICTABLE

REMEDIAL ACTION COMPLEX SIMPLE

MODES OF ATTACK MANY FEW

AVAILABLE SPACE LIMITED AMPLE

IMPACT LIMITED LARGE

DEPLOY DISTRIBUTED SENSING SYSTEMS

CONSTRUCT RELEVANT SCENARIOS

THERE IS NO SUCH THING AS “UNTHINKABLE FORM OF ATTACK”

DESIGN REALISTIC CRISIS MANAGEMENT PLAN

DESIGN MULTIPLE LEVEL RESPONSE

DESIGN MITIGATION OPTIONS

DEFINE QUALITY CONTROL & MAINTENANCE

REQUIREMENTS

CONCLUSIONS(PROTECTION OF WATER SYSTEMS)

NSF Workshop: “New Challenges in Chemical and Biosensing”, January 9-10, 2002

http://www.chemistry.gatech.edu/sensingforum-02/