Automated Wet Chemistry Analysis – New Green Applications

Hari Narayanan Ph.D.

Product Marketing Manager
Discrete Industrial Analyzer

The world leader in serving science

 Agenda 1 Introduction to automated wet chemical analysis

2 Traditional workflow and limitations

3 Green workflow and advantages

4 Environmental applications

5 Summary

2
Sample Analysis

Assay Chromatography

Elemental analysis Impurities ID Molecular spectroscopy

3
Wet Chemistry Analysis

Volumetric
• Classical

• Liquids samples
Colorimetric

• Manual methods

• Visual detection
Gravimetric
• Labor intensive

• Time consuming
Other
Methods

4
Automated Wet Chemical Analysis – Standalone Instruments

Analytical labs •Automated wet chemical

Few samples per day analyzers

Few parameters per sample

5
 Industrial Water, Dinking Water and Waste Water – Multiparameter Analysis

Total Kjeldal Nitrogen (TKN), Total pH &

Conductivity
Phosphate, Total Phenol, Total Alkalinity, Total hardness
Oxidizable Nitrogen (TON), Cyanide,
Waste Water Basic Water
Total Cyanide, Boron, Aluminium Testing Testing

Corrosion F,Cl,NO2,NO3,SO4,PO4, Thiocyanate, Sulfide

Anions
Indicators

Hexavalent Chromium, Zinc,

Manganese, Iron,

Scale Forming
Nutrients TP, TKN, TN, Nitrate, Ammonia, K,
Species
Silica, Calcium, Magnesium
Corrosion
Inhibitors

Ammonia, Zinc, Nitrite, Molybdenum

Single Sample – Many Parameters

6
Traditional Wet Chemistry Workflow –Water Analysis
Multiple Instruments Multiple Users +
Samples for Multiple Reagents & Calibration, Training Long Turnaround Time
Multiple Standards Maintenance, time Profit
&
Analytes Preparation Consumables Money

=
Basic Water
Analysis Traditional Wet chemistry: Titration+ISE, Flow Analyzers
• 50-100 mL Samples per test
• mL Reagents
• Liters of Waste Generation
• Multiple Instruments
Conductivity pH
• Sequential
• Typically Single or max 4 Parameters per sample
• High cost per analysis

Alkalinity

Hardness

7
Traditional Wet Chemistry Workflow – Water Analysis

Limitations of Multi Parameter setup with ISE, pH and Conductivity

• Periodic calibration and sensor maintenance
• Sequential measurements
• Large sample volume
• Multiple burettes and Sensors
• Large reagent consumption and waste
• ISE – Shelf life, matrix effect and
generation
sensitivity
• Complex systems to work and maintain
• Carry over -time consuming – Rinsing
and cleaning after each tests • Needs skilled operators
• Large bench space
• Limited number of parameters
• Low throughput

8
Traditional Wet Chemistry Workflow –Water Analysis

Limitations of Flow Injection Analyzers (FIA) or Segmented Flow Analyzer (SFA)

• Batch Analyzers
• Limited number of parameters limited by
number of channels
• Large sample, reagent consumption and
waste generation
• Complex systems to work
• Periodical tube change and maintenance
• Needs expert users

9
Dinking Water, Industrial Process Water and Waste Water – Multiparameter Analysis
• Problems
Auto pH/Cond.
Titration Meter
• Multiple testing methods for a sample
• Large sample volume, excessive reagent consumption
Flow
Injection
and waste generation
Analyzer
(FIA) or
• Multiple instruments
Segmented
Flow
• Skilled users
Analyzer
(SFA)
• Labor intensive

• Impact
Ion
Meter • Long Hands on Sample Time
• Throughput, Response time, Results accuracy
• Cost per Analysis
• Frequent maintenance
Spectro
photometer • Users Training

Multiple parameters – Multiple instruments

10
Dinking Water, Industrial Process Water and Waste Water – Multiparameter Analysis
• Problems

• Multiple testing methods for a sample

• Large sample volume, excessive reagent consumption
and waste generation
• Multiple instruments
• Skilled users
• Labor intensive

• Impact
• Long Hands on Sample Time
• Throughput, Response time, Results accuracy
• Cost per Analysis
• Frequent maintenance
• Users Training

Multiple parameters –Multiple operators

11
 Dinking Water, Industrial Process Water and Waste Water – Multiparameter Analysis

Total Kjeldal Nitrogen (TKN), Total pH &

Conductivity
Phosphate, Total Phenol, Total Alkalinity, Total hardness
Oxidizable Nitrogen (TON), Cyanide,
Waste Water Basic Water
Total Cyanide, Boron, Aluminium Testing Testing

Corrosion F,Cl,NO2,NO3,SO4,PO4, Thiocyanate, Sulfide

Anions
Indicators

Hexavalent Chromium, Zinc,

Manganese, Iron,

Scale Forming
Nutrients TP, TKN, TN, Nitrate, Ammonia, K,
Species
Silica, Calcium, Magnesium
Corrosion
Inhibitors

Ammonia, Zinc, Nitrite, Molybdenum

Single Instrument – Single Operator – Many Parameters

12
Consolidate Your Water Analysis

pH pH
Auto Conductivity
Conductivity Titration
Alkalinity Alkalinity
Total Hardness Total Hardness
Silica Flow
Silica
Chloride, Sulfate, Injection Chloride, Sulfate,
Fluoride, Phosphate, Analyzer Fluoride, Phosphate,
(FIA) or Nitrite, Nitrate
Nitrite, Nitrate Segmented
Ammonia, Calcium, Flow Ammonia, Calcium,
Magnesium Analyzer Magnesium
(SFA)
Total Iron Total Iron
Hexavalent Chromium Hexavalent Chromium
Zinc, Molybdenum Zinc, Molybdenum
pH/Cond/
Total Phosphate Total Phosphate
Ion Meter
Cyanide, Total Cyanide, Total
Cyanide Cyanide
Total Phenol Total Phenol
Total Kjeldal Nitrogen Total Kjeldal Nitrogen
Total Oxidizable Total Oxidizable
Spectro Nitrogen
Nitrogen photometer
Boron Boron

Single Instrument – Many Parameters

Multiple Parameters – Multiple Instruments
13
Green Workflow – Consolidated Water Analysis

Gallery Platform
Water Analysis
- Parallel Measurements
• 2µL to 120 µL Reagents
• Max 200µL per test
• Few mL of Waste
Conductivity/pH Alkalinity Hardness Ions
Other • Single Platform
parameters
• Fully Automated
• Parallel & Simultaneous analysis
• Multiple parameters per sample
• Reduced cost per analysis

Samples for Multiple Ready to use Reagents Fast Multiparameter

Single Instrument Single Operator Productivity Profitability
Analytes & Standards Analysis

14
Thermo Scientific™ Gallery™ Discrete Analyzer Platform
Consolidated testing - Rapid Multiparameter
Wet Chemical Analyzer

Single platform – Parallel analysis

1 Colorimetric/turbidimetric

2 Enzymatic

3 Electrochemical

15
How Does a Discrete Analyzer Work? Method Test Flow

16
How Does a Discrete Analyzer work? Method Test Flow

For a basic assay, in this case sulphate

• Add an aliquot of sample
• Shine 420 nm light through the sample and measure the intensity in Absorbance units (AU)
• Add an aliquot of reagent (Barium chloride)
• Wait for and period of time for the reaction to occur (300 seconds)
• Shine 420 nm light through again and the difference in intensity is the absorbance ΔA for each
sample

Individual discrete
reaction cell

Measurement area

17
Gallery Discrete Analyzer USEPA Methods
ANALYTE METHOD DESCRIPTION METHOD NUMBER

Alkalinity Buffered methyl orange 310.2 (Rev. 1974)

Ammonia Alkaline phenate with hypochlorite and sodium nitroprusside 350.1, Rev. 2.0 (1993)
Ammonia Alkaline dichloroisocyanurate with salicylate and sodium nitroprusside 350.1, Rev. 2.0 (1993)
Chloride Mercuric thiocyanate in the presence of ferric nitrate SM4500‐Cl E
Chlorine Phosphate buffer DPD SM4500‐Cl G
Chromium VI Diphenylcarbazide SM3500‐Cr B
COD Off line dichromate digestion 410.4, Rev. 2.0 (1993)
Conductivity Eleectrochemical method 120.1
Copper Bathocuprione SM3500‐Cu C
Cyanide Chloramine‐T and pyridine barbituric acid 335.4, Rev. 1.0 (1993)
Fluoride SPADNS SM4500‐F D
Hardness (Total) Calmagite indicator reaction 130.1 (Issued 1971)
Iron (Ferrous) Phenanthroline SM3500‐Fe B
Iron (Total) Phenanthroline SM3500‐Fe B
Nitrate+Nitrite Hydrazine reduction SM4500‐NO3 H
Nitrate+Nitrite Vanadium reduction CFR Part 136.3
Nitrate+Nitrite Enzymatic reduction N07‐0003
Nitrite Bypass Enzymatic reduction N07‐0003
Nitrite Sulphanilamide/NEDD SM4500‐NO2 B
Orthophosphate Acidic molybdate/antimony with ascorbic acid reduction 365.1, Rev. 2.0 (1993)
Orthophosphate Acidic molybdate/antimony with ascorbic acid reduction SM4500‐P E
pH Electrochemical method 150.2
Phenol Buffered KFCN and 4‐AAP 420.1 (Rev. 1978)
Silica Molybdate/Oxalic/Ascorbic SM4500‐SiO2 C
Sulfate Turbidimetric barium chloride ASTM D516‐11
Sulfide Acidic DMPD/Ferric chloride SM4500‐S2 D
Thiocyanate Acidic ferric nitrate SM4500‐CN M
TKN Alkaline salicylate with hypochlorite and sodium nitroprusside 351.2, Rev. 2.0 (1993)
TKP Kjeldahl digested sample molybdate/antimony with ascorbic acid reduction 365.4 (Issued 1974)

18
Environmental Applications: Parallel pH and Conductivity Measurements

• Integrated Conductivity and pH measurements

• Measuring range for

•Conductivity 20 µS/cm - 112 mS/cm
•pH 2 – 12

• Sample types
•Raw water, ground water, sea water, rain water,
municipal water, drinking water and Wastewater

• Not suitable for DI water or steam condensate

19
Environmental Applications: Alkalinity

Chemistry: Bromophenol Blue and phthalate buffer

pH 3.5
Sample matrix: Drinking, ground, surface, waste
and saline water

20
Environmental Applications: Total Hardness

Chemistry: Calmagite
Sample matrix: Drinking, ground, surface, waste
and saline water

References: EPA 130.1

21
Environmental Applications: Total Oxidized Nitrogen (TON Enzymatic)

Chemistry: Nitrate reductase • A rapid, non-toxic alternative

Sample matrix: Drinking, ground, surface, waste
and saline water •Sample preparation is simplified
•Detection range is flexible
•Reduce costs in reagent usage and
waste disposal

References: ASTM D7781-14, EPA 40 CFR Part 141

22
Environmental Applications: Total Oxidized Nitrogen (TON Enzymatic)

Chemistry: Nitrate reductase Method Comparison: TON Hydrazine

Sample matrix: Drinking, ground, surface, waste
and saline water

Resource: Automated nutrient analysis and water quality monitoring

23
Green Workflow – Consolidated Water Analysis
--------------------------------- How -------------------------------------------------
Why Gallery Analyzer
Speed of analysis
• Parallel pH and conductivity measurements
• Walkaway solution
• Integrated analytics – multiparameter by single instrument

Get more done with less

• Very low sample volume
• Reduced cost per analysis • Reduced reagent consumption - 1/100th to 1/1000th
compared to traditional wet chemistry
• Reduced waste disposal cost

• System uptime and reliability Robust instrument

• No cross contamination due to disposable cuvettes
• Long life Xenon source lamp

• Ease of use Workflow based operation

• Don’t need skilled operator
• Built in barcode reader
• Bi-directional LMS

24
Consolidate Your Water Analysis

Special Limited Time Offer pH

Conductivity
Alkalinity
Total Hardness
Silica
Chloride, Sulfate,
Fluoride, Phosphate,
Nitrite, Nitrate
Ammonia, Calcium,
Magnesium
Total Iron
Hexavalent Chromium
Zinc, Molybdenum
Total Phosphate
Cyanide, Total
Cyanide
Total Phenol
Total Kjeldal Nitrogen
Total Oxidizable
Nitrogen
Boron

Single Instrument – Many Parameters

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Thank You

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