Real Time Monitoring – The Real Time Monitoring – The Installation and Continuous Installation and Continuous

Operation of Organic Carbon and Operation of Organic Carbon and Liquid Chromatography Analyzers Liquid Chromatography Analyzers

at Remote Field Stations in the at Remote Field Stations in the Sacramento – San Joaquin DeltaSacramento – San Joaquin Delta

David GonzalezDavid GonzalezCalifornia Department of Water ResourcesCalifornia Department of Water Resources

Division of Environmental ServicesDivision of Environmental ServicesMunicipal Water Quality Investigations Municipal Water Quality Investigations

Field Support UnitField Support Unit

Drinking Water and Organic Carbon – Drinking Water and Organic Carbon – What are some of the Issues?What are some of the Issues?

Organic carbon reacts with chlorine Organic carbon reacts with chlorine during disinfection to form suspected during disinfection to form suspected carcinogenic compounds such as carcinogenic compounds such as trihalomethanes and haloacetic acids.trihalomethanes and haloacetic acids.

The majority of Delta islands are The majority of Delta islands are composed of peat soils rich in organic composed of peat soils rich in organic carbon.carbon.

The complex Delta system makes it The complex Delta system makes it difficult to assess the relative carbon difficult to assess the relative carbon contributions from riverine inputs and in-contributions from riverine inputs and in-Delta sources, and to develop accurate Delta sources, and to develop accurate models of water quality fluctuations in the models of water quality fluctuations in the Delta.Delta.

Real Time Monitoring StationsReal Time Monitoring Stations

Banks Station

Hood Station

McCune Station

Real Time Monitoring of Organic Carbon Real Time Monitoring of Organic Carbon with a Dedicated Field Analyzer – with a Dedicated Field Analyzer –

Feasibility StudyFeasibility Study

The MWQI Field Unit The MWQI Field Unit conducted a feasibility conducted a feasibility study in 1999 – 2000 to study in 1999 – 2000 to evaluate the evaluate the performance of a performance of a Sievers 800 Sievers 800 UV/Oxidation based UV/Oxidation based carbon analyzer carbon analyzer installed in a field installed in a field station on the station on the Sacramento River. Sacramento River.

We learned what is needed to make the We learned what is needed to make the system work and provide representative datasystem work and provide representative data

Secure location with accessibility, power, Secure location with accessibility, power, and phone serviceand phone service

Water delivery system including pump and Water delivery system including pump and water lineswater lines

Water flow control and flow diversion Water flow control and flow diversion systemsystem

Water Sampling portsWater Sampling ports Data Logger communicationData Logger communication Develop SOP’s and a QA/QC planDevelop SOP’s and a QA/QC plan

The Next Phase: The Installation of a The Next Phase: The Installation of a Shimadzu 4100 TOC analyzer at Banks Shimadzu 4100 TOC analyzer at Banks

HeadworksHeadworks

Shimadzu 4100 is a catalyzed Shimadzu 4100 is a catalyzed combustion based analyzer.combustion based analyzer.

Dual stream – can do both Total Dual stream – can do both Total Organic and Dissolved Organic CarbonOrganic and Dissolved Organic Carbon

Filtration system required for DOC Filtration system required for DOC analysisanalysis

Pressurized air supply requiredPressurized air supply required

Data SystemData System

TOC Analyzer

Datalogger Phone Modem

Access Database QA/QC Data

World Wide Web

FTP

DWR California Data

Exchange

A Shimadzu 4100 unit was installed A Shimadzu 4100 unit was installed at Hood facility in April 2002at Hood facility in April 2002

The only station The only station with both with both UV/oxidation and UV/oxidation and catalyzed catalyzed combustion combustion based analyzers.based analyzers.

Sievers 900 TOC analyzer installed in Sievers 900 TOC analyzer installed in May 2005May 2005

Touch screen Touch screen programmingprogramming

Integrated on-line Integrated on-line sampling systemsampling system

Integrated inorganic Integrated inorganic carbon removal unitcarbon removal unit

USB port for data USB port for data transfertransfer

Increased rate of Increased rate of analysisanalysis

The Next Step - The addition of a Dionex DX-The Next Step - The addition of a Dionex DX-800 Ion Chromatography Analyzer at the 800 Ion Chromatography Analyzer at the

Banks station for anion analysisBanks station for anion analysis

Parameters of Interest - Parameters of Interest -

Chloride – Trihalomethane Formation PotentialChloride – Trihalomethane Formation Potential

Bromide - Trihalomethane Formation PotentialBromide - Trihalomethane Formation Potential

Nitrate – Nutrient loadingNitrate – Nutrient loading

Sulfate – Drinking water regulatory standardsSulfate – Drinking water regulatory standards

The Anion Analyzers Operational The Anion Analyzers Operational RequirementsRequirements::

Need supply of both pressurize nitrogen Need supply of both pressurize nitrogen and clean air.and clean air.

T1 line needed for remote operation of T1 line needed for remote operation of analyzer’s computer.analyzer’s computer.

Sample stream must be filtered to 0.45Sample stream must be filtered to 0.45m.m. Requires 18 MRequires 18 M DI Water DI Water

New building needed to house anion New building needed to house anion and carbon analyzersand carbon analyzers

The New SystemThe New System

Required ComponentsRequired Components

Our newest facility: The San Joaquin Our newest facility: The San Joaquin River McCune Station near VernalisRiver McCune Station near Vernalis

New AnalyzersNew Analyzers

Dionex system and Pump float Dionex system and Pump float componentscomponents

TOC/DOC Daily Average ComparisonTOC/DOC Daily Average Comparison

San Joaquin River near Vernalis Daily Average of Organic Carbon

0

1

2

3

4

5

6

7

8/7/

05

8/21

/05

9/4/

05

9/18

/05

10/2

/05

10/1

6/05

10/3

0/05

11/1

3/05

11/2

7/05

12/1

1/05

12/2

5/05

1/8/

06

1/22

/06

2/5/

06

2/19

/06

3/5/

06

3/19

/06

mg

/l

Shimadzu TOC Shimadzu DOC

Organic Carbon concentration and its relation Organic Carbon concentration and its relation to flow in the San Joaquin River near Vernalisto flow in the San Joaquin River near Vernalis

0

1

2

3

4

5

6

7

8

3/9/06 3/14/06 3/19/06 3/24/06 3/29/06 4/3/06 4/8/06 4/13/06 4/18/06

mg/

L of

C

10000

15000

20000

25000

30000

35000

40000

cfs

TOC DOC FLOW

Sievers/Shimadzu Daily TOC Averages on Sievers/Shimadzu Daily TOC Averages on the Sacramento River at Hoodthe Sacramento River at Hood

Shimadzu/Sievers Daily TOC Averages at Hood

0

1

2

3

4

5

6

7

10/2

0/05

10/2

7/05

11/3

/05

11/1

0/05

11/1

7/05

11/2

4/05

12/1

/05

12/8

/05

12/1

5/05

12/2

2/05

12/2

9/05

1/5/

06

1/12

/06

1/19

/06

1/26

/06

2/2/

06

2/9/

06

2/16

/06

2/23

/06

3/2/

06

3/9/

06

3/16

/06

3/23

/06

mg/

L

Sievers Shimadzu

Banks Headworks: Online vs. Grab TOC Banks Headworks: Online vs. Grab TOC Samples – Relative Percent DifferenceSamples – Relative Percent Difference

0123456789

mg/

L

0102030405060708090100

RPD

TOC Online TOC Grab RPD

Banks Headworks: Online vs. Grab DOC Banks Headworks: Online vs. Grab DOC Samples – Relative Percent DifferenceSamples – Relative Percent Difference

0.001.002.003.004.005.006.007.008.009.00

8/12

/03

10/1

2/03

12/1

2/03

2/12

/04

4/12

/04

6/12

/04

8/12

/04

10/1

2/04

12/1

2/04

2/12

/05

4/12

/05

6/12

/05

8/12

/05

10/1

2/05

12/1

2/05

2/12

/06

mg

/L

0.0010.0020.0030.0040.0050.0060.0070.0080.0090.00100.00

RP

D

DOC Online

DOC Canal Grab

RPD of DOC

Sample Name: SanJoaquin River at Vernalis Inj. Vol.: 100.0 Sample Type: unknown Dilution Factor: 1.0000Program: AS19 Grad 10-45mM OH Grad 10mL Sample_0 Operator: n.a.Inj. Date/Time: 23.08.05 10:35 Run Time: 35.00

No. Time Peak Name Type Area Height Amount min µS*min µS ppm

1 5.65 Fluoride BMB 0.630 1.634 0.09942 9.94 Chloride BMB 257.872 673.538 52.35353 15.24 Bromide BMB 0.411 1.278 0.19934 16.57 Nitrate BMB 20.749 61.453 7.20026 21.14 Sulfate bMB 192.974 316.667 54.37377 29.19 Phosphate BMB 0.373 0.291 0.0549

TOTAL: 473.01 1054.86 114.28

0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0-100

0

100

200

300

400

500

600

700

800

900

1,000 000000 #3 SanJoaquin River at Vernalis ECD_1µS

min

1 - F

luorid

e - 5.650

2 - C

hlo

rid

e - 9.937

3 - B

rom

ide - 15.243

4 - N

itrate - 16.570

5 - 20.310

6 - S

ulfate - 21.140

7 - P

hosphate - 29.193

chloride

Bromide

Nitrate

Sulfate

In ConclusionIn Conclusion

Continual operation of remotely installed Continual operation of remotely installed organic carbon analyzers is achievable.organic carbon analyzers is achievable.

With proper maintenance, servicing, and With proper maintenance, servicing, and operation these systems produce representative operation these systems produce representative data .data .

Remote analyzers can be very labor intensive at Remote analyzers can be very labor intensive at times and require frequent monitoring of times and require frequent monitoring of operational statusoperational status

The remote operation of anion analyzers has a The remote operation of anion analyzers has a steep learning curve.steep learning curve.

Still developing operational procedures and Still developing operational procedures and techniques for anion units that work in field techniques for anion units that work in field setting.setting.