A Dialogue on Phosphorus Measurements 4/8/2014 Upstate Freshwater [PDF]

SLIDE 1

A Dialogue on Phosphorus Measurements

4/8/2014 Upstate Freshwater Institute 1

SLIDE 2

Outline

1. review of forms of phosphorus (P) 2. triplicate sample performance, Cayuga Lake 2013 study 3. phosphorus fraction comparisons among different systems 4. phosphorus fraction comparisons: different certified labs 5. consistency of P forms with limnological paradigms 6. UFI’s P resume 7. evaluation of two SRP methods (selected features)

4/8/2014 Upstate Freshwater Institute 2

SLIDE 3

Partitioning P Fractions

 contemporary methods for large sample number studies remain operationally-based  particulate vs. dissolved partitioning – 0.45 µm pore size filtration – imperfect – colloidal and ruptured cell passage – convenient and replicable  total P fractions – following digestion – without filtration – total P (TP) – following filtration – total “dissolved” P (TDP) – particulate P (PP) usually by calculation

4/8/2014 Upstate Freshwater Institute 3

𝑄𝑄 = 𝑈𝑄 − 𝑈𝐸𝑄

SLIDE 4

Partitioning Dissolved P Fractions

 nomenclature

– soluble reactive P (SRP)

operationally defined – responsive to “mixed” reagent
also MRP – molybdate reactive; PO4

3-—P (not good alternative)

PO4

3- actually a small fraction of SRP

– soluble unreactive P (SUP)

commonly and heretofore, dissolved organic P (DOP)
henceforth SUP

 wide array of P-containing chemical entities contribute to fractions

– system specific differences and temporal variation reasonable expectations – variations in relative contributions of SRP and SUP to be expected

TDP SRP SUP

PO4

3-

heterogeneous array of forms

condensed phosphates

rganic P

colloidal particles

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SLIDE 5

References for P: Limitations of Common Operative Measurements

 selective

– Lean, D.R.S. 1973. Science. 179:678-680 – Fisher, T.R. and Lean, D.R.S. 1992. Can. J. Fish. Aquat. Sci. 49:252-259 – Baldwin, D.S. 1998. Wat. Res. 2265-2270 – Hudson, J.J., Taylor W.D., and Schindler, D.W. 2000. Nature. 406:54-56 – Dodds, W.K. 2003. J. N. Am. Benthol. Soc. 22:171-181 – Hudson, J.J. and Taylor, W.D. 2005. Aquat. Sci. 67:316-325

 UFI’s synthesis

– see Introduction of Effler and O’Donnell (2010). Fundam. Appl.

Limnol. 177:1-18

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SLIDE 6

References for P: SUP(DOP) – Characterizations, Etc.

 Turner, B.L., E. Frossard, and D.S. Baldwin. (2005) Organic Phosphorus in the

Environment. CABI, Oxfordshire UK, 399pp.

– various examples of elegant isolations of specific groups

 selected articles

– Francko, D.A. and Heath, R.T. 1979. Limnol.

Oceanogr. 24: 463-473

– Cotner, J.B. and Wetzel, R.G. 1992. Limnol.

Oceanogr. 37: 232-243

– Betzen, E. and Taylor, W.D. 1992. Limnol. Oceanogr. 37: 217-231 – Baldwin, D.S. 1998. Wat. Res. 32:2265-2270 – Bjorkman, K.M. and Karl, D.M. 2003. Limnol.

Oceanogr. 48: 1049-1057

– Stets, E.G. and Cotner, J.B. 2008. Limnol. Oceanogr. 53: 137-147

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Outline

1. review of forms of phosphorus (P) 2. triplicate sample performance, Cayuga Lake 2013 study 3. phosphorus fraction comparisons among different systems 4. phosphorus fraction comparisons: different certified labs 5. consistency of P forms with limnological paradigms 6. UFI’s P resume 7. evaluation of two SRP methods (selected features)

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SLIDE 8

Analysis of Field Triplicate Samples

 3 discrete samples collected over a short time interval  combined test of – representativeness of individual samples – laboratory performance  not a NELAC requirement  conducted in addition to lab QA protocols  UFI policy to include – limnological QA – included in Cayuga L. QAPP  coefficient of variation (CV=stand. dev. ÷ mean) adopted as a summary statistic  acceptable thresholds rarely set – one example, CV ≤ 20% for Onondaga L. Superfund site – some guidance in the literature

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SLIDE 9

Analysis of Field Triplicate Samples: Salmon Creek, P

 based on UFI’s experience a case of good performance

– low variability

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SLIDE 10

Analysis of Field Triplicate Samples: Onondaga Creek, P

example year, 2006, TP,

TDP, and SRP

generally consistent with

Salmon Creek

bservations, 2013

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Count

4 8 12

Count

4 8

CV (%)

4 8 12 16 20

Count

4 8

(a) TP (b) TDP (c) SRP

>20

n=27 mean=10% n=27 mean=10% n=27 mean=8%

SLIDE 11

Peer-Reviewed Literature Support for Field Triplicate Performance

UFI reported average CV =

10% for TP, biweekly collection for 19 years (supported as appropriate in the peer-reviewed literature)

Effler, S.W., Prestigiacomo,

A.R., Matthews, D.A., Michalenko, E.M., and Hughes, D.J. 2009. Partitioning phosphorus concentrations and loads in tributaries of a recovering urban lake. Lake Reservoir

Manag. 25: 225-239.

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SLIDE 12

Peer-Reviewed Literature Support for UFI Performance on Field Triplicates P Analyses: Onondaga Lake

 note CV higher for SRP because many samples approached detection limit  Effler, S.W. and S.M. O’Donnell. 2010. A long-term record of epilimnetic phosphorus patterns in recovering Onondaga Lake, New

York. Fundam. Appl. Limnol. Vol. 177/1, 1–18.

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Phosphorus Concentration (µg·L-1) Forms of Phosphorus SRP TDP TP n median CV % n median CV % n median CV % 1-5 157 15.5 56 7.3

5-20

83 2.7 263 7.5 49 3.1 20-50 86 1.6 148 6.3 220 3.4 50-100 39 1.0 99 2.8 231 3.1

SLIDE 13

Comparison of Cayuga Lake Field Triplicate Performance to Onondaga Lake Performance

 consistent, good, performance

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Phosphorus Concentration (µg·L-1) Forms of Phosphorus SRP TDP TP n median CV % n median CV % n median CV % 1-5 On.Lk. 157 15.5 56 7.3

1-5 Cay. Lk. 2013

9 8.5 5 8.4

1-5 Cay. Lk. 98-06

90 4.5 144 12.4 1

5-20 On. Lk.

83 2.7 263 7.5 49 3.1 5-20 Cay. Lk. 2013 2 3.2 11 5.7 16 3.9 5-20 Cay. Lk. 98-06

48 3.2

113 9.6 171 5.2 20-50 On. Lk. 86 1.6 148 6.3 220 3.4 20-50 Cay. Lk. 2013

20-50 Cay. Lk. 98-06
4

3.1 99 7.4 50-100 On. Lk. 39 1.0 99 2.8 231 3.1 50-100 Cay. Lk. 2013

50-100 Cay. Lk. 98-06
6

6.9

general consistency in performance between lake programs

SLIDE 14

Analysis of Field Triplicate Samples: Salmon Creek, Other Constituents

low variability for these other constituents

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SLIDE 15

Outline

1. review of forms of phosphorus (P) 2. triplicate sample performance, Cayuga Lake 2013 study 3. phosphorus fraction comparisons among different systems 4. phosphorus fraction comparisons: different certified labs 5. consistency of P forms with limnological paradigms 6. UFI’s P resume 7. evaluation of two SRP methods (selected features)

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SLIDE 16

Phosphorus Fractions

where : TP = total phosphorus PP = particulate phosphorus TDP = total dissolved phosphorus

𝑈𝑄 = 𝑄𝑄 + 𝑈𝐸𝑄

where : SRP = soluble reactive phosphorus SUP = soluble unreactive phosphorus

𝑈𝐸𝑄 = 𝑇𝑆𝑄 + 𝑇𝑉𝑄

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SLIDE 17

Phosphorus Ratios as Diagnostics Supporting Data Analysis 𝑈𝑄 = 𝑄𝑄 + 𝑈𝐸𝑄 𝑈𝐸𝑄 = 𝑇𝑆𝑄 + 𝑇𝑉𝑄 𝑄𝑄 𝑈𝑄 𝑇𝑆𝑄 𝑈𝐸𝑄 𝑇𝑉𝑄 𝑈𝐸𝑄

 to represent contributions of fractions

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SLIDE 18

SRP/TDP : Tributary Cross System Comparison

 tributaries, averages and variability bars (1 std. dev.)  UFI measurements

4/8/2014 Upstate Freshwater Institute 18 C-WBDR95 C-WBDR98 AW-ESO97 P-EBDR97 S-Sch98 N-NevR98

SRP/TDP (%)

20 40 60 80 100 A-MR 99 Cr-Cross99 M-AngFly99 M-AngFly00 M-Plum99 M-Plum00 M-Stone99 M-Stone00 N-Hunt99 N-Hunt00 N-Kiscot99 N-Kisco00 O-Nm06 O-Nm07 O-Nm08 O-Nm09 O-Nm10 O-Ock06 O-Ock07 O-Ock08 O-Ock09 O-Ock10

Onon. L.

NYC WOH NYC EOH

SLIDE 19

SRP/TDP : Tributary Cross System Comparison Including Cayuga Lake

 tributaries, averages and variability bars (1 std. dev.)  UFI measurements  Cayuga tribs not widely different – similar temporal variability

4/8/2014 Upstate Freshwater Institute 19 C-WBDR95 C-WBDR98 AW-ESO97 P-EBDR97 S-Sch98 N-NevR98

SRP/TDP (%)

20 40 60 80 100 A-MR 99 Cr-Cross99 M-AngFly99 M-AngFly00 M-Plum99 M-Plum00 M-Stone99 M-Stone00 N-Hunt99 N-Hunt00 N-Kiscot99 N-Kisco00 O-Nm06 O-Nm07 O-Nm08 O-Nm09 O-Nm10 O-Ock06 O-Ock07 O-Ock08 O-Ock09 O-Ock10 Cay-FallCk Cay-CayInlet Cay-Salmon Cay-SixMile Cay-TaughCk

Onon. L.

NYC WOH NYC EOH Cayuga Tribs

SLIDE 20

PP/TP : Tributary Cross System Comparison

 tributaries, averages and variability bars (1 std. dev.)  UFI measurements

C-WBDR95 C-WBDR98 AW-ESO97 P-EBDR97 S-Sch98 N-NevR98

PP/TP (%)

20 40 60 80 100 A-MR 99 Cr-Cross99 M-AngFly99 M-AngFly00 M-Plum99 M-Plum00 M-Stone99 M-Stone00 N-Hunt99 N-Hunt00 N-Kiscot99 N-Kisco00 O-Nm06 O-Nm07 O-Nm08 O-Nm09 O-Nm10 O-Ock06 O-Ock07 O-Ock08 O-Ock09 O-Ock10

Onon. L.

NYC WOH NYC EOH

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SLIDE 21

PP/TP: Tributary Cross System Comparison, Including Cayuga Lake

 tributaries, averages and variability bars (1 std. dev.)  UFI measurements  Cayuga tributaries not widely different – similar to sediment-rich Onondaga Lake tributaries – similar temporal variability

C-WBDR95 C-WBDR98 AW-ESO97 P-EBDR97 S-Sch98 N-NevR98

PP/TP (%)

20 40 60 80 100 A-MR 99 Cr-Cross99 M-AngFly99 M-AngFly00 M-Plum99 M-Plum00 M-Stone99 M-Stone00 N-Hunt99 N-Hunt00 N-Kiscot99 N-Kisco00 O-Nm06 O-Nm07 O-Nm08 O-Nm09 O-Nm10 O-Ock06 O-Ock07 O-Ock08 O-Ock09 O-Ock10 Cay-FallCk Cay-CayInlet Cay-Salmon Cay-SixMile Cay-TaughCk

Onon. L.

NYC WOH NYC EOH Cayuga Tribs

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SLIDE 22

SUP/TDP: Upper Waters Cross System Comparison

 epilimnion, averages (spring-fall) and variability bars (1

std. dev.)

 UFI measurements

ASE-97 ASW-97 PEP-97 RON-97 CAN-95 CAN-98 NEV-98 SCH-98 WBR-98

SUPe/TDPe (%)

20 40 60 80 100

Onondaga Cat/Del EOH

AWR-99 CRR-99 CFR-99 DVR-99 TCR-99 MCR-99 MCR-00 NCR-99 NCR-00 ONL-06 ONL-07 ONL-08 ONL-09 ONL-10 ONL-11 ONL-12 4/8/2014 Upstate Freshwater Institute 22

SLIDE 23

SUP/TDP: Upper Waters Cross System Comparison, Including Cayuga Lake

 epilimnion, averages (spring-fall) and variability bars (1 std. dev.)  Cayuga Lake 0-4m composite sample (1999 -2006), site LSC8 or site 3  UFI measurements  Cayuga Lake generally consistent, SUP dominates

ASE-97 ASW-97 PEP-97 RON-97 CAN-95 CAN-98 NEV-98 SCH-98 WBR-98

SUPe/TDPe (%)

20 40 60 80 100

Onondaga Cat/Del EOH

AWR-99 CRR-99 CFR-99 DVR-99 TCR-99 MCR-99 MCR-00 NCR-99 NCR-00 ONL-06 ONL-07 ONL-08 ONL-09 ONL-10 ONL-11 ONL-12 CAY-99 CAY-00 CAY-01 CAY-02 CAY-03 CAY-04 CAY-05 CAY-06

Cayuga

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SLIDE 24

PP/TP: Upper Waters Cross System Comparison

 epilimnion, averages (spring-fall) and variability bars (1

std. dev.)

 UFI measurements

ASE-97 ASW-97 PEP-97 RON-97 CAN-95 CAN-98 NEV-98 SCH-98 WBR-98

PPe/TPe (%)

20 40 60 80 100

Onondaga Cat/Del EOH

AWR-99 CRR-99 CFR-99 DVR-99 TCR-99 MCR-99 MCR-00 NCR-99 NCR-00 ONL-06 ONL-07 ONL-08 ONL-09 ONL-10 ONL-11 ONL-12 4/8/2014 Upstate Freshwater Institute 24

SLIDE 25

PP/TP: Upper Waters Cross System Comparison, Including Cayuga Lake

 epilimnion, averages (spring-fall) and variability bars (1 std. dev.)  Cayuga Lake 0-4m composite sample (1999 -2006), site LSC8 or site 3  Cayuga Lake generally consistent

ASE-97 ASW-97 PEP-97 RON-97 CAN-95 CAN-98 NEV-98 SCH-98 WBR-98

PPe/TPe (%)

20 40 60 80 100

Onondaga Cat/Del EOH

AWR-99 CRR-99 CFR-99 DVR-99 TCR-99 MCR-99 MCR-00 NCR-99 NCR-00 ONL-06 ONL-07 ONL-08 ONL-09 ONL-10 ONL-11 ONL-12 CAY-99 CAY-00 CAY-01 CAY-02 CAY-03 CAY-04 CAY-05 CAY-06

Cayuga

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SLIDE 26

Outline

1. review of forms of phosphorus (P) 2. triplicate sample performance, Cayuga Lake 2013 study 3. phosphorus fraction comparisons among different systems 4. phosphorus fraction comparisons: different certified labs 5. consistency of P forms with limnological paradigms 6. UFI’s P resume 7. evaluation of two SRP methods (selected features)

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SLIDE 27

SRP/TDP Ratio: Comparison Between Labs

 West Branch Delaware River  2002  UFI versus NYSDEP lab  samples not paired  similar distribution

(a) UFI n = 17

med. = 0.80

% Occurrence

10 20 30 40 50 (b) DEP n = 24

med. = 0.72

SRP/TDP

0.0 0.2 0.4 0.6 0.8 1.0 10 20 30 40

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SRP/TDP Ratio: Comparison Between Labs

 Onondaga Creek @ Kirkpatrick St.  2006-2012  UFI versus WEP lab  samples not paired  similar distributions

(a) UFI n = 271

med. = 0.67

% Occurrence

10 20 30 40 50 (b) WEP n = 185

med. = 0.64

SRP/TDP

0.0 0.2 0.4 0.6 0.8 1.0 10 20 30 40

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SLIDE 29

SRP/TDP Ratio: Comparison Between Labs

 Ninemile Creek @ Route 48  2006-2012  UFI versus WEP lab  samples not paired  similar distribution

(b) WEP n = 261

med. = 0.53

SRP/TDP

0.0 0.2 0.4 0.6 0.8 1.0 5 10 15 20 25 (a) UFI n = 179

med. = 0.53

% Occurrence

5 10 15 20 25 30

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SLIDE 30

SRP/TDP Ratio: Comparison Between Labs

 Ley Creek @ Park Street  2006-2012  UFI versus WEP lab  samples not paired  similar distribution

(b) WEP n = 180

med. = 0.57

SRP/TDP

0.0 0.2 0.4 0.6 0.8 1.0 5 10 15 20 25 (a) UFI n = 177

med. = 0.60

% Occurrence

5 10 15 20 25 30

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SLIDE 31

Outline

1. review of forms of phosphorus (P) 2. triplicate sample performance, Cayuga Lake 2013 study 3. phosphorus fraction comparisons among different systems 4. phosphorus fraction comparisons: different certified labs 5. consistency of P forms with limnological paradigms 6. UFI’s P resume 7. evaluation of two SRP methods (selected features)

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SLIDE 32

Utility of Monitoring Operationally Defined Forms of P: The Onondaga Lake Example

 demonstrated widely as an effective basis of management  long-term trends for Onondaga Lake (a UFI product) a good example (Effler and O’Donnell 2010)

TPL (kg·d-1)

100 200 300 400

TPMetro (µgP·L-1)

500 1000 1500

(a)

(µgP·L (µgP·L (µgP·L

TPL TPMetro

70 75 80 85

TPMetro

6 12

87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 07 08 09

decreasing loads (WEP data) severe eutrophy upper mesotrophy

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Utility of Monitoring Operationally Defined Forms of P: The Onondaga Lake Example

 demonstrated widely as an effective basis of management  long-term trends for Onondaga Lake (a UFI product) a good example (Effler and O’Donnell 2010)

TPL (kg·d-1)

100 200 300 400

TPMetro (µgP·L-1)

500 1000 1500

(a) (b)

TPe (µgP·L-1)

50 100 150

(µgP·L (µgP·L

TPL TPMetro

70 75 80 85

TPMetro

6 12

87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 07 08 09

decreasing loads (WEP data) decreasing epilimnetic concentrations severe eutrophy upper mesotrophy

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Utility of Monitoring Operationally Defined Forms of P: The Onondaga Lake Example

 demonstrated widely as an effective basis of management  long-term trends for Onondaga Lake (a UFI product) a good example (Effler and O’Donnell 2010)

TPL (kg·d-1)

100 200 300 400

TPMetro (µgP·L-1)

500 1000 1500

(a) (b) (c)

TPe (µgP·L-1)

50 100 150

(µgP·L SRPe (µgP·L-1)

0.0 12.5 25.0 37.5 50.0

TPL TPMetro

70 75 80 85

TPMetro

6 12

87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 07 08 09

decreasing loads (WEP data) decreasing epilimnetic concentrations shift to distinct P-limitation severe eutrophy upper mesotrophy

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SLIDE 35

Utility of Monitoring Operationally Defined Forms of P: The Onondaga Lake Example

 demonstrated widely as an effective basis of management  long-term trends for Onondaga Lake (a UFI product) a good example (Effler and O’Donnell 2010)

TPL (kg·d-1)

100 200 300 400

TPMetro (µgP·L-1)

500 1000 1500

(a) (b) (c) (d)

TPe (µgP·L-1)

50 100 150

SUPe (µgP·L-1)

0.0 12.5 25.0 37.5 50.0

% of TDPe

25 50 75 100

SRPe (µgP·L-1)

0.0 12.5 25.0 37.5 50.0

SUPe %SUPe of TDPe TPL TPMetro

70 75 80 85

TPMetro

6 12

87 88 89 90 91 92 93 94 95 96 97 98 99 00 01 02 03 04 05 06 07 08 09

decreasing loads (WEP data) decreasing epilimnetic concentrations shift to distinct P-limitation decreases reflect increased enzymatic uptake severe eutrophy upper mesotrophy

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SLIDE 36

Limnological Consistency Checks: SUP to DOC Ratio, Hypolimnion, Cayuga Lake

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 dissolved organic material (DOM) pool

– primary proxy – dissolved organic carbon (DOC) – expected to have associated dissolved

rganic phosphorus

(DOP) - e.g. SUP

 hypolimnetic temporal pattern  lack of noteworthy trend, consistent 2013

Apr May Jun Jul Aug Sep Oct

SUP/DOC (µgP/mgC)

0.0 0.5 1.0 1.5 2.0 2.5

95 5 90 10 75 25 50 key

SLIDE 37

Limnological Consistency Checks: Hypolimnetic Pools of SUP, SRP and DOC, in the Vertical

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profiles mid-lake early May profiles mid-lake Sept.

T (°C)

10 20

Depth (m)

20 40 60 80 100 120

P (µgP/L)

5 10 15

DOC (mg/L)

1 2 3 4

T (°C)

0 5 101520

Depth (m)

20 40 60 80 100 120

P (µgP/L)

5 10 15

DOC (mg/L)

1 2 3 4

SRP SUP

little vertical structure DOC and SUP
SRP seasonally variable structure – source

and sink processes

SLIDE 38

Limnological Consistency Checks: Hypolimnetic Pools of SUP, SRP, and DOC Temporally

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 as mass estimates – volumes for depth interval from hypsographic data 𝑛𝑏𝑡𝑡 = 𝑑𝑝𝑜𝑑 𝑛𝑕 𝑛3 · 𝑤𝑝𝑚(𝑛3) 𝑢𝑝𝑢𝑏𝑚 𝑛𝑏𝑡𝑡 =

𝑗=1 𝑜

𝑤𝑗 · 𝑑𝑝𝑜𝑑.𝑗  temporal patterns of mass

2013

Apr May Jun Jul Aug Sep Oct

Hypolimnion Mass (mgP)

1e+10 2e+10 3e+10 4e+10

Hypolimnion Mass (gC)

1e+10 2e+10 3e+10 4e+10

SRP SUP DOC

SLIDE 39

Cayuga vs. Finger Lakes

 2004 Finger Lakes survey  Chl and TP, TDP, PP  average measurements, bars are 1

std. dev. (temporal variations)

 UFI lake data – collected 1/month – May – Sept. 2004 – samples 0-2m composite – laboratory fluorometric Chl  Cayuga LSC8 (presently Site 3) – collected 2/month – 2 cases

May-Sept. 2004
May-Sept. 1998-2006

– samples 0-4m composite – laboratory spectrophotometric Chl

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Chl a (µg/L)

5 10 15 20

TP (µgP/L)

10 20 30

TDP (µg/L)

10 20 30

System

Conesus Hemlock Canadice Honeoye Canandaigua Keuka Seneca Cayuga Cayuga LSC8 CayugaLSCl98-06 Owasco Skaneateles Otisco

PP (µg/L)

10 20 30

SLIDE 40

TDP (µgP/L)

5 10 15

SUP (µgP/L)

5 10

System

Conesus Hemlock Canadice Honeoye Canandaigua Keuka Seneca Cayuga Cayuga LSC8 CayugaLSC98-06 Owasco Skaneateles Otisco

SRP (µgP/L)

5 10

Cayuga vs. Finger Lakes

 2004 Finger Lakes survey  TDP, SUP, SRP  average measurements, bars are 1 std. dev. (temporal variations)  UFI lake data – collected 1/month – May – Sept. 2004 – samples 0-2m composite  Cayuga LSC8 (presently Site 3) – collected 2/month – 2 cases

May-Sept. 2004
May-Sept. 1998-2006

samples 0-4m composite

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SLIDE 41

Cayuga vs. Finger Lakes

 2004 Finger Lakes survey  Chl and SD  average measurements, bars are 1

std. dev. (temporal variations)

 UFI lake data – collected 1/month – May – Sept. 2004 – samples 0-2m composite – Chl fluorometric  Cayuga LSC8 (presently Site 3) – collected 2/month – 2 cases

May-Sept. 2004
May-Sept. 1998-2006 samples

0-4m composite – samples 0-4m composite – Chl spectrophotometric

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Chl a (µg/L)

5 10 15 20

System

Conesus Hemlock Canadice Honeoye Canandaigua Keuka Seneca Cayuga Cayuga LSC8 CayugaLSC98-06 Owasco Skaneateles Otisco

SD (m)

2 4 6 8 10

SLIDE 42

Outline

1. review of forms of phosphorus (P) 2. triplicate sample performance, Cayuga Lake 2013 study 3. phosphorus fraction comparisons among different systems 4. phosphorus fraction comparisons: different certified labs 5. consistency of P forms with limnological paradigms 6. UFI’s P resume 7. evaluation of two SRP methods (selected features)

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SLIDE 43

UFI’s Phosphorus Resume

 years making P measurements: 1980 - 2013 (34 years)  years certified by NYS DOH for TP and SRP: 1994 – 2014 (20 years)  measurements in the limnological range of interest  estimated number of samples analyzed for P: a conservative estimate – TP ~ 31,400 – TDP ~ 13,930 – SRP ~ 20,810 total analyses run > 67,000

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SLIDE 44

UFI Phosphorus Resume: Analyses Supporting Research and Long-term Monitoring

Key Studies/Systems  CSLAP program - 14 years; NYSDEC  NYC Reservoirs - 19 years; FAD work

(Cannonsville, Pepacton, Rondout, Neversink, Ashokan, Schoharie, West Branch, Middle Branch, East Branch, Diverting, Titicus, Amawalk, Bog Brook, Cross River, Croton, Muscoot, Boyds Corners, Kensico)

 Onondaga Lake - 34 years; Phosphorus TMDL  Finger Lakes Surveys (11 lakes) – 1996 & 1997; 2001 & 2002 (in collaboration with NYSDEC)  Lake Source Cooling (Cornell) monitoring (facility & in- lake) - 18 years  Cornell Shackelton Point - 8 years; Oneida Lake  ESF Thousand Islands Biological Station - 5 years

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SLIDE 45

UFI-Phosphorus Resume: Publications in the Peer-Reviewed Literature

 based on UFI P analyses  papers for which UFI P data are central – 43  national and international peer-reviewed journals – 20  aspects of phosphorus (P) assessed with UFI P data – vertical transport from enriched hypolimnia to productive epilimnia – deposition – effects of pollution on cycling – sediment-water exchange (e.g., release) – sediment diagenesis (legacy effects) – limitation of algae growth

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SLIDE 46

UFI-Phosphorus Resume: Publications in the Peer-Reviewed Literature

 aspects of phosphorus (P) assessed with UFI P data – models

water column P
nutrient-eutropication
sediments

– effects of dreissenid mussels on cycling – eutrophication effects on other constituents – bioavailability assessments – effects of minerogenic particles – external loading calculations – long-term trend analysis – Cayuga Lake – specific analyses

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SLIDE 47

Outline

1. review of forms of phosphorus (P) 2. triplicate sample performance, Cayuga Lake 2013 study 3. phosphorus fraction comparisons among different systems 4. phosphorus fraction comparisons: different certified labs 5. consistency of P forms with limnological paradigms 6. UFI’s P resume 7. evaluation of two SRP methods (selected features)

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SLIDE 48

Approved Methods for NELAC Certification for SRP

Process SM 4500 P E & 4500 P b.5 EPA 1978 (365.3) Container acid washed glass

r plastic

Acid washed pyrex

r plastic

Filtering 0.45 um membrane 0.45 um membrane Colormetric method ascorbic acid ascorbic acid Filtration immediately after collection, store at 4C, analyze within 48 hrs day of collection

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 UFI uses SM 4500 P E & 4500 P b.5

SLIDE 49

Process SM 4500 P E & 4500 P b.5 EPA 1978 (365.3) Reagents 5N H2SO4 (50 ml) + potassium antimonyl tartrate (PAT) (5 ml) + ammonium molybdate (15 ml) + ascorbic acid (30 ml) = “mixed reagent” (8 mls added to sample) 11 N H2SO4 (1 ml) + PAT + ammonium molybdate (4 ml) + ascorbic acid (2 ml) Reagents added sequentially to sample Sample volume 50 ml 50 ml

Approved Methods for NELAC Certification for SRP (continued)

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SLIDE 50

Process SM 4500 P E & 4500 P b.5 EPA 1978 (365.3) Calibration curve(s) Prepared weekly; verified daily Prepared with each run pH adjustment yes Color development 10 minutes 5 minutes Read sample 10 – 30 minutes after adding “mixed reagent” 5 - 60 minutes after sequential addition

f reagents

Wavelength 880 nm 650 nm (660/880) Glassware cleaning 1:1 Nitric acid 1:1 HCL & all reagents Precision & Bias (DI water) 100 ug/L, 3 labs RSD = 9.1%, RE = 10.0%

Approved Methods for NELAC Certification for SRP (continued)

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SLIDE 51

Color Development Experiment Sample Results

 comparison of Methods (Feb 2014) – Standard Methods 18-21; 4500-P E – EPA 1978  Cayuga Lake system samples  EPA method consistently reads higher but both methods are relatively close (RPD 4 – 23%) at 15 minutes  divergence with time

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a) Inlet 2 4 6 8 Standard Methods EPA 1978 b) Cayuga near LSC

SRP (µg·L-1)

17 19 21 23 c) Salmon Cr

Time (minutes)

20 40 60 80 100 8 10 12 14

RPD = 23% RPD = 4% RPD = 7%

SLIDE 52

Color Development Experiment: Quality Control

 both methods had continuing calibration blanks (CCB) that were below UFI’s Level of Detection (LOD)  the continuing calibration verification (CCV; 25 µg·L-1) is phosphorus in DI water and should remain relatively constant over time. – EPA method increases

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a) CCB

0.25

0.00 0.25 0.50 b) CCV

Time (minutes)

20 40 60 80 100

SRP (µg·L-1)

24 25 26 Standard Methods EPA 1978

UFI LOD

SLIDE 53

Color Development Experiment

for Onondaga Lake and Tributaries Standard Methods 18-21 4500-P E

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 color stability over time  dissolved phosphorus components stable

Time after adding mixed reagent (min)

20 40 60 80 100

SRP ( g·L-1)

2 4 6 8 10 Ninemile Cr Onon Cr Ley Cr Onon Lk Marina

SLIDE 54

Color Development Experiment

for Onondaga Lake and Tributaries

initial sample values for SM and USEPA had a RPD ranging from 6 to 11%

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Time after adding mixed reagent (min)

20 40 60 80 100

SRP (g·L-1)

2 4 6 8 10 SM 18-21 4500 PE Ninemile Cr (EPA 1978) Onon Cr (EPA 1978) Ley Cr (EPA 1978) Onon Lk Marina (EPA 1978)

 USEPA 1978, with time  initial Standard Methods results also

SLIDE 55

Summary

 UFI presented – a review of P forms, according to the operationally based methods, and presented related literature citations – a description of UFI’s triplicate sample program, and a review of performance for Cayuga Lake in a comparative context – a selective review of P fractions for different systems in New York

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SLIDE 56

Summary

 UFI presented – a selective comparison of P fractions according to UFI

vs. other certified labs

– examples of consistent patterns of forms of P in multiple lakes – a review of UFI’s P resume

durations, lake programs
P related topics in peer-reviewed literature

– an evaluation of selected features of the NELAC- approved SRP methods

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