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Accurate Measurement of Particulate Nitrogen and Phosphorus in - - PowerPoint PPT Presentation

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Accurate Measurement of Particulate Nitrogen and Phosphorus in Environmental Phosphorus in Environmental Water Samples Carl Zimmermann Carolyn Keefe Carl Zimmermann, Carolyn Keefe and Jerome Frank UMCES, Chesapeake Biological g Laboratory

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SLIDE 1

Accurate Measurement of Particulate Nitrogen and Phosphorus in Environmental Phosphorus in Environmental Water Samples

Carl Zimmermann Carolyn Keefe Carl Zimmermann, Carolyn Keefe and Jerome Frank UMCES, Chesapeake Biological g Laboratory

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SLIDE 2

Outline

  • Total Versus Particulate and Dissolved

Methods Used

  • Methods Used
  • Examples of Data Using Direct

Measurements

– Chesapeake Bay – Near Coastal – Fresh Water Ponds

  • SRM, Chesapeake Bay Split Sample

Program

  • Chesapeake Bay Blind Audit Program
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SLIDE 3

Components Of A Whole Water S l Sample

Particulate Whole Water Sample Dissolved Sample Advantages of Direct Particulate Analysis Advantages of Direct Particulate Analysis

  • 1. A representative sample can always be obtained.
  • 2. Additional Information is Obtained
  • 1. Contribution of biological community
  • 2. How the various fractions may shift spatially and temporally
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SLIDE 4

“By-Difference” vs Direct Analysis f P i l

  • f Particulates

A B A B “By Difference”….. Total – Dissolved= Particulate Consequences: Opportunity for negative particulate values. Direct Measurement: Can always obtain a representative sample

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SLIDE 5

Methods Methods

  • Particulate Nitrogen: EPA Method 440 0

Particulate Nitrogen: EPA Method 440.0… (high temperature combustion, using thermal conductivity detection) Exeter thermal conductivity detection). Exeter Analytical CE440 Elemental Analyzer.

  • Particulate Phosphorus: Aspila et al 1976
  • Particulate Phosphorus: Aspila, et al. 1976

(high temperature ashing/acid extraction)

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SLIDE 6

Examples of Particulate and Di l d Di ib i Dissolved Distributions

  • Coastal

DNR Coastal Survey May Coastal …. DNR Coastal Survey May 2011

  • Estuarine

Chesapeake Bay 2001 2003

  • Estuarine… Chesapeake Bay 2001-2003
  • Agricultural Ponds… Calvert County, MD
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SLIDE 7

Total P Near Coastal May 2011

Total P Near Coastal May 2011 Mid Total P Near Coastal May 2011 Surface

Total P Near Coastal May 2011

Surface Mid

0.0250 0.0300 0.0350 0.0400 0.0450 0.0500 g P/L 0.0200 0.0250 0.0300 0.0350 0.0400 g P/L

Dissolved

0.0000 0.0050 0.0100 0.0150 0.0200 0.0250 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 mg 0.0000 0.0050 0.0100 0.0150 0.0200 1 4 7 10 13 16 19 22 25 28 31 34 37 mg

sso ed Particulate Dissolved Particulate

Total P Near Coastal May 2011 Bottom

0.0600 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 Stations 1 4 7 10 13 16 19 22 25 28 31 34 37 Stations

Bottom

0.0200 0.0300 0.0400 0.0500 mg P/L

Surface: Particulate: 39% Mid: Particulate 37.8% Bottom (10 m): 37% Dissolved Bottom

0.0000 0.0100 0 0 00 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 Stations

Bottom (10 m): 37% Particulate

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SLIDE 8

Total N Near Coastal May 2011 Total N Near Coastal May 2011

Surface Mid

Total N Near Coastal May 2011 Surface

0 2000 0.2500 0.3000 0.3500 0.4000 0.4500 m g N / L

Total N Near Coastal May 2011 Mid

0 2000 0.2500 0.3000 0.3500 0.4000 0.4500 0.5000 m g N / L

Dissolved Dissolved

0.0000 0.0500 0.1000 0.1500 0.2000 1 4 7 10 13 16 19 22 25 28 31 34 37 Stations m 0.0000 0.0500 0.1000 0.1500 0.2000 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 Stations

Particulate Particulate

Total N Near Coastal May 2011 Bottom

0.3000 0.3500 0.4000 0.4500

Surface Particulate: 32.9% Mid Particulate: 32.6% Dissolved

0.0000 0.0500 0.1000 0.1500 0.2000 0.2500 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 mg N/L

Bottom (10 m): 31.1% Dissolved Particulate

1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 Stations

Bottom

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SLIDE 9

Chesapeake Bay 2001-2003 U B T l N Upper Bay Total N

Total N CB5.2 Surface 2001-2003

1 1.2

Total N CB5.2 2001-2003 Bottom

1.2 1.4

Surface Bottom

0 4 0.6 0.8 1 mg N/L 0.4 0.6 0.8 1 mg N/L

Dissolved Dissolved

0.2 0.4 0.2

Particulate Particulate 2001 2003 2001 2003 Particulate Fraction Mean: 30 1% Particulate Fraction Mean: 23.3% Mean: 30.1% Range: 15-50% Range: 10-65%

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SLIDE 10

Chesapeake Bay 2001-2003 U B T l P Upper Bay Total P

Total P CB5.2 2001-2003 Surface

0.06

Total P CB5.2 2001-2003 Bottom

0.14

Surface Bottom

0.04 0.05 /L

0.08 0.1 0.12 L

Dissolved Dissolved Surface

  • o

0.01 0.02 0.03 mg P/

0 02 0.04 0.06 mg P/L 0.02

Particulate Particulate Particulate Fraction Particulate Fraction 2001 2003 2001 2003 Mean: 50% Range: 18-70% Mean: 39.8% Range: 10-90%

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SLIDE 11

Nitrogen Partitioning Fresh Water Pond

Nitrogen Partitioning November Nitrogen Partitioning August

25.5% 16% 1.8% 36.2% 58.5% 36 % 62% DIN= Blue DON= Purple Particulate N= Beige Particulate N= Beige

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SLIDE 12

Phosphorus Partitioning Fresh Water Pond

Phosphorus Partitioning November Phosphorus Partitioning August Phosphorus Partitioning November Phosphorus Partitioning August

20% 8% 8% 60% 20% 84% DIP= Blue 84% DIP= Blue DOP= Purple Particulate P= Beige

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SLIDE 13

Determining Accuracy and Precision of Di t P ti l t M t Direct Particulate Measurements

  • Determining Accuracy in the Lab

Determining Accuracy in the Lab

  • Chesapeake Bay Split Sample Program

Ch k B Bli d A dit P

  • Chesapeake Bay Blind Audit Program
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SLIDE 14

No Commercially Available SRM for Particulate N and P BCSS-1 Marine Sediment (Gulf of St. Lawrence) National Research Board of Canada. Hi t i l V l f N 0 2% R li bl V l f P 0 0672% Historical Value of N: 0.2% Reliable Value of P: 0.0672%

BCSS-1 Sediment N 2009-2010

BCSS-1 %P 2010

0.22 0.23 0.24 0.25

0 0800 0.1000 0.1200

Nitrogen Phosphorus

0 17 0.18 0.19 0.20 0.21 %N

0.0400 0.0600 0.0800 %P

0.15 0.16 0.17 Occurrences

Mean= 0 20%

0.0000 0.0200

Mean= 0 068% Mean= 0.20%

  • Std. Dev.= 0.0057

%CV= 2.8 Mean= 0.068%

  • Std. Dev.: 0.0059

%CV= 8.7

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SLIDE 15

Chesapeake Bay Coordinated Split S l P Sample Program

  • Quarterly split samples collected

Quarterly split samples collected

  • Delivered to laboratories same day

S l d b th

  • Samples processed by groups the

following day

  • Results indicative of processing and

analytical variability

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SLIDE 16

Particulate N and P Mainstem CSSP 2010 CSSP 2010

0 25 0.15 0.2 0.25 L

0 015 0.02 0.025

0.05 0.1 mg N/L

0.005 0.01 0.015 mg P/L

Feb. May Aug Nov Feb. Feb. May Aug Nov Feb.

Particulate N Particulate P

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SLIDE 17

Chesapeake Bay Blind Audit Program

  • Particulate and Dissolved Unknowns Sent

Particulate and Dissolved Unknowns Sent to Participating Laboratories Semi- annually annually.

  • Prepared Concentrations Approximate

Estuarine Levels Estuarine Levels

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SLIDE 18

Blind Audit Particulates Blind Audit Particulates

  • Natural Population Samples Collected

Natural Population Samples Collected From End of CBL Pier.

  • Filtered and Dried
  • Filtered and Dried
  • Several Replicates Analyzed At CBL To

P id E ti t f A l ti l d Provide Estimate of Analytical and Processing Variablility.

  • Eliminates other laboratories processing

variability

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SLIDE 19

Apparent vs Reported Apparent vs Reported

Particulate N

0.3

Particulate P

0 035

Blue: Multiple

0.1 0.15 0.2 0.25 0.3 mg N/L 0 01 0.015 0.02 0.025 0.03 0.035 mg P/L

Multiple Replicates Purple: Laboratory

0.05 0.005 0.01

Particulate P CBL Labs

1998 2003 2011 2011 2003 1998

Laboratory Results

Particulate N CBL Labs 1998 Mean 0.0318 0.0316 SD 0.001 0.0005 %CV 3.1 1.6 1998 Mean 0.078 0.0733 SD 0.004 0.0087 %CV 5.1 11.9 2003 Mean 0.0159 0.014 SD 0.001 0.0008 %CV 3.1 1.6 2003 Mean 0.26 0.243 SD 0.0048 0.0223 %CV 1.8 9.2 2011 Mean 0.0203 0.0197 SD 0.0018 0.0026 %CV 8.9 13.2 2011 Mean 0.23 0.221 SD 0.0079 0.0131 %CV 3.4 5.9

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SLIDE 20

CBP Blind Audit S 2010 Summer 2010

Summer 2010 Blind Audit Particulate Nitrogen Summer 2010 Blind Audit Particulate Phosphorus 0 25 0.3 0.35 0.4 0.45 0.5 N/L 0 02 0.025 0.03 0.035 0.04 P/L 0.05 0.1 0.15 0.2 0.25 Laboratories mg 0.005 0.01 0.015 0.02 Laboratories mg Laboratories Laboratories

Particulate N Mean: 0.255 mg N/L Particulate P Mean: 0.0298 mg P/L

  • Std. Dev.: 0.068

%CV: 26.9

  • Std. Dev.: 0.0036

%CV: 12.03

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SLIDE 21

CBP Blind Audit Wi 2011 Winter 2011

Winter 2011 Particulate P

0 025

Winter 2011 Particulate N

0 3 0.015 0.02 0.025 P/L 0 15 0.2 0.25 0.3 N/L 0.005 0.01 mg 0.05 0.1 0.15 mg

Particulate N Particulate P Mean: 0.221 mg N/L

  • Std. Dev.: 0.014

%CV: 5 9 Mean: 0.0197

  • Std. Dev.: 0.0026

%CV: 13 %CV: 5.9 %CV: 13

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SLIDE 22

Conclusions

  • Direct measurement of particulates

Direct measurement of particulates preferred over the “by-difference” technique. q

  • Particulate analysis gives an estimate of

biological fraction g

  • Cost
  • Chesapeake Bay Program has programs

Chesapeake Bay Program has programs in place to adequately address precision and accuracy of these fractions y