a dialogue on phosphorus measurements · 5-20 cay. lk. 2013 2 3.2 11 5.7 16 3.9 5-20 cay. lk. 98-06...

A Dialogue on Phosphorus

Measurements

4/8/2014 Upstate Freshwater Institute 1

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)


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


𝑃𝑃 = 𝑇𝑃 − 𝑇𝐷𝑃

Partitioning Dissolved P Fractions

nomenclature– soluble reactive P (SRP)

• operationally defined – responsive to “mixed” reagent

• also MRP – molybdate reactive; PO43-—P (not good alternative)

• PO43- 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

TDPSRP SUP

PO43- heterogeneous array of forms

condensed phosphates

organic P

colloidal particles


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


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


Outline






6. UFI’s P resume



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


Analysis of Field Triplicate

Samples: Salmon Creek, P

based on UFI’s experience

a case of good performance

– low variability


Analysis of Field Triplicate

Samples: Onondaga Creek, P

• example year, 2006, TP,

TDP, and SRP

• generally consistent with

Salmon Creek

observations, 2013


Count

0

4

8

12

Count

0

4

8

CV (%)

0 4 8 12 16 20

Count

0

4

8

(a) TP

(b) TDP

(c) SRP

>20

n=27mean=10%

n=27mean=10%

n=27mean=8%

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.


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, 1–18.4/8/2014 Upstate Freshwater Institute 12

Phosphorus

Concentration

(µg·L-1)

Forms of Phosphorus

SRP TDP TP

nmedian

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

Comparison of Cayuga Lake Field Triplicate

Performance to Onondaga Lake Performance

consistent, good, performance4/8/2014 Upstate Freshwater Institute 13

Phosphorus

Concentration

(µg·L-1)

Forms of Phosphorus

SRP TDP TP

nmedian 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 0 --

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 0 -- 0 -- 0 --

20-50 Cay. Lk. 98-06 0 -- 4 3.1 99 7.4

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

50-100 Cay. Lk. 2013 0 -- 0 -- 0 --

50-100 Cay. Lk. 98-06 0 -- 0 -- 6 6.9

general consistencyin performance

between lake programs

Analysis of Field Triplicate Samples:

Salmon Creek, Other Constituents• low variability for these other constituents


Outline






6. UFI’s P resume



Phosphorus Fractions

where : TP = total phosphorus

PP = particulatephosphorus

TDP = total dissolvedphosphorus

𝑇𝑃 = 𝑃𝑃 + 𝑇𝐷𝑃where : SRP = soluble reactive

phosphorus

SUP = soluble unreactive

phosphorus

𝑇𝐷𝑃 = 𝑆𝑅𝑃 + 𝑆𝑈𝑃


Phosphorus Ratios as Diagnostics

Supporting Data Analysis

𝑇𝑃 = 𝑃𝑃 + 𝑇𝐷𝑃

𝑇𝐷𝑃 = 𝑆𝑅𝑃 + 𝑆𝑈𝑃

𝑃𝑃

𝑇𝑃

𝑆𝑅𝑃

𝑇𝐷𝑃

𝑆𝑈𝑃

𝑇𝐷𝑃

to represent contributions of fractions


SRP/TDP : Tributary Cross System

Comparison

tributaries, averages and variability bars (1 std. dev.)

UFI measurements


C-W

BD

R95

C-W

BD

R98

AW

-ES

O97

P-E

BD

R97

S-S

ch98

N-N

evR

98

SR

P/T

DP

(%

)

0

20

40

60

80

100A

-MR

99

Cr-

Cro

ss99

M-A

ngF

ly99

M-A

ngF

ly00

M-P

lum

99

M-P

lum

00

M-S

tone

99

M-S

tone

00

N-H

unt9

9N

-Hunt0

0N

-Kis

cot9

9N

-Kis

co00

O-N

m06

O-N

m07

O-N

m08

O-N

m09

O-N

m10

O-O

ck06

O-O

ck07

O-O

ck08

O-O

ck09

O-O

ck10

Onon. L.

NYCWOH

NYCEOH

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


C-W

BD

R95

C-W

BD

R98

AW

-ES

O97

P-E

BD

R97

S-S

ch98

N-N

evR

98

SR

P/T

DP

(%

)

0

20

40

60

80

100

A-M

R 9

9C

r-C

ross99

M-A

ngF

ly99

M-A

ngF

ly00

M-P

lum

99

M-P

lum

00

M-S

tone

99

M-S

tone

00

N-H

unt9

9N

-Hunt0

0N

-Kis

cot9

9N

-Kis

co00

O-N

m06

O-N

m07

O-N

m08

O-N

m09

O-N

m10

O-O

ck06

O-O

ck07

O-O

ck08

O-O

ck09

O-O

ck10

Cay-F

allC

kC

ay-C

ayIn

let

Cay-S

alm

on

Cay-S

ixM

ile

Cay-T

aug

hC

k

Onon. L.

NYCWOH

NYCEOH

CayugaTribs

PP/TP : Tributary Cross System

Comparison

tributaries, averages and variability bars (1 std. dev.)

UFI measurements

C-W

BD

R95

C-W

BD

R98

AW

-ES

O97

P-E

BD

R97

S-S

ch98

N-N

evR

98

PP

/TP

(%

)

0

20

40

60

80

100A

-MR

99

Cr-

Cro

ss99

M-A

ngF

ly99

M-A

ngF

ly00

M-P

lum

99

M-P

lum

00

M-S

tone

99

M-S

tone

00

N-H

unt9

9N

-Hunt0

0N

-Kis

cot9

9N

-Kis

co00

O-N

m06

O-N

m07

O-N

m08

O-N

m09

O-N

m10

O-O

ck06

O-O

ck07

O-O

ck08

O-O

ck09

O-O

ck10

Onon. L.

NYCWOH

NYCEOH


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-W

BD

R95

C-W

BD

R98

AW

-ES

O97

P-E

BD

R97

S-S

ch98

N-N

evR

98

PP

/TP

(%

)

0

20

40

60

80

100

A-M

R 9

9C

r-C

ross99

M-A

ngF

ly99

M-A

ngF

ly00

M-P

lum

99

M-P

lum

00

M-S

tone

99

M-S

tone

00

N-H

unt9

9N

-Hunt0

0N

-Kis

cot9

9N

-Kis

co00

O-N

m06

O-N

m07

O-N

m08

O-N

m09

O-N

m10

O-O

ck06

O-O

ck07

O-O

ck08

O-O

ck09

O-O

ck10

Cay-F

allC

kC

ay-C

ayIn

let

Cay-S

alm

on

Cay-S

ixM

ile

Cay-T

aug

hC

k

Onon. L.

NYCWOH

NYCEOH

CayugaTribs


SUP/TDP: Upper Waters Cross

System Comparison epilimnion, averages (spring-fall) and variability bars (1

std. dev.)

UFI measurements

AS

E-9

7A

SW

-97

PE

P-9

7R

ON

-97

CA

N-9

5C

AN

-98

NE

V-9

8S

CH

-98

WB

R-9

8

SU

Pe/T

DP

e

(%)

0

20

40

60

80

100OnondagaCat/Del EOH

AW

R-9

9C

RR

-99

CF

R-9

9D

VR

-99

TC

R-9

9M

CR

-99

MC

R-0

0N

CR

-99

NC

R-0

0

ON

L-0

6O

NL

-07

ON

L-0

8O

NL

-09

ON

L-1

0O

NL

-11

ON

L-1

2


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

AS

E-9

7A

SW

-97

PE

P-9

7R

ON

-97

CA

N-9

5C

AN

-98

NE

V-9

8S

CH

-98

WB

R-9

8

SU

Pe/T

DP

e

(%)

0

20

40

60

80


AW

R-9

9C

RR

-99

CF

R-9

9D

VR

-99

TC

R-9

9M

CR

-99

MC

R-0

0N

CR

-99

NC

R-0

0

ON

L-0

6O

NL-0

7O

NL-0

8O

NL-0

9O

NL-1

0O

NL-1

1O

NL-1

2

CA

Y-9

9C

AY

-00

CA

Y-0

1C

AY

-02

CA

Y-0

3C

AY

-04

CA

Y-0

5C

AY

-06

Cayuga


PP/TP: Upper Waters Cross

System Comparison

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

std. dev.)

UFI measurements

AS

E-9

7A

SW

-97

PE

P-9

7R

ON

-97

CA

N-9

5C

AN

-98

NE

V-9

8S

CH

-98

WB

R-9

8

PP

e/T

Pe

(%)

0

20

40

60

80


AW

R-9

9C

RR

-99

CF

R-9

9D

VR

-99

TC

R-9

9M

CR

-99

MC

R-0

0N

CR

-99

NC

R-0

0

ON

L-0

6O

NL

-07

ON

L-0

8O

NL

-09

ON

L-1

0O

NL

-11

ON

L-1

2


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

AS

E-9

7A

SW

-97

PE

P-9

7R

ON

-97

CA

N-9

5C

AN

-98

NE

V-9

8S

CH

-98

WB

R-9

8

PP

e/T

Pe

(%)

0

20

40

60

80


AW

R-9

9C

RR

-99

CF

R-9

9D

VR

-99

TC

R-9

9M

CR

-99

MC

R-0

0N

CR

-99

NC

R-0

0

ON

L-0

6O

NL-0

7O

NL-0

8O

NL-0

9O

NL-1

0O

NL-1

1O

NL-1

2

CA

Y-9

9C

AY

-00

CA

Y-0

1C

AY

-02

CA

Y-0

3C

AY

-04

CA

Y-0

5C

AY

-06

Cayuga


Outline






6. UFI’s P resume



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

% O

ccurr

ence

0

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

0

10

20

30

40



Between Labs

Onondaga Creek @ Kirkpatrick St.

2006-2012

UFI versus WEP lab

samples not paired

similar distributions

(a) UFI n = 271 med. = 0.67

% O

ccurr

ence

0

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

0

10

20

30

40



Between Labs

Ninemile Creek @

Route 48

2006-2012

UFI versus WEP lab

samples not paired


(b) WEP

n = 261

med. = 0.53

SRP/TDP

0.0 0.2 0.4 0.6 0.8 1.0

0

5

10

15

20

25

(a) UFI n = 179 med. = 0.53

% O

ccurr

ence

0

5

10

15

20

25

30



Between Labs

Ley Creek @ Park Street

2006-2012

UFI versus WEP lab

samples not paired


(b) WEP n = 180 med. = 0.57

SRP/TDP

0.0 0.2 0.4 0.6 0.8 1.0

0

5

10

15

20

25

(a) UFI n = 177 med. = 0.60

% O

ccurr

ence

0

5

10

15

20

25

30


Outline






6. UFI’s P resume



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)

TP

L

(kg

·d-1

)

0

100

200

300

400

TP

Metr

o

(µ

gP

·L-1

)

0

500

1000

1500(a)

(b)

(c)

(d)

TP

e

(µ

gP

·L-1

)

0

50

100

150

SU

Pe

(µ

gP

·L-1

)

0.0

12.5

25.0

37.5

50.0

% o

f T

DP

e

0

25

50

75

100

SR

Pe

(µ

gP

·L-1

)

0.0

12.5

25.0

37.5

50.0

SUPe

%SUPe of TDPe

TPL

TPMetro

70 75 80 85

TP

Metr

o

0

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

decreasingloads

(WEP data)

severe eutrophy upper mesotrophy





2010)

TP

L

(kg·d

-1)

0

100

200

300

400

TP

Metr

o

(µ

gP

·L-1

)

0

500

1000

1500(a)

(b)

(c)

(d)

TP

e

(µ

gP

·L-1

)

0

50

100

150

SU

Pe

(µ

gP

·L-1

)

0.0

12.5

25.0

37.5

50.0

% o

f T

DP

e

0

25

50

75

100

SR

Pe

(µ

gP

·L-1

)

0.0

12.5

25.0

37.5

50.0

SUPe

%SUPe of TDPe

TPL

TPMetro

70 75 80 85

TP

Me

tro

0

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

decreasingloads

(WEP data)

decreasingepilimnetic

concentrations






2010)

TP

L

(kg·d

-1)

0

100

200

300

400

TP

Metr

o

(µ

gP

·L-1

)

0

500

1000

1500(a)

(b)

(c)

(d)

TP

e

(µ

gP

·L-1

)

0

50

100

150

SU

Pe

(µ

gP

·L-1

)

0.0

12.5

25.0

37.5

50.0

% o

f T

DP

e

0

25

50

75

100

SR

Pe

(µ

gP

·L-1

)

0.0

12.5

25.0

37.5

50.0

SUPe

%SUPe of TDPe

TPL

TPMetro

70 75 80 85

TP

Me

tro

0

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

decreasingloads

(WEP data)


concentrations

shift to distinctP-limitation






2010)

TP

L

(kg

·d-1

)

0

100

200

300

400

TP

Metr

o

(µ

gP

·L-1

)

0

500

1000

1500(a)

(b)

(c)

(d)

TP

e

(µ

gP

·L-1

)

0

50

100

150

SU

Pe

(µ

gP

·L-1

)

0.0

12.5

25.0

37.5

50.0

% o

f T

DP

e

0

25

50

75

100

SR

Pe

(µ

gP

·L-1

)

0.0

12.5

25.0

37.5

50.0

SUPe

%SUPe of TDPe

TPL

TPMetro

70 75 80 85

TP

Metr

o

0

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

decreasingloads

(WEP data)


concentrations

shift to distinctP-limitation

decreases reflectincreasedenzymatic

uptake

severe eutrophy upper mesotrophy4/8/2014 Upstate Freshwater Institute 35

Limnological Consistency Checks:

SUP to DOC Ratio, Hypolimnion,

Cayuga Lake


dissolved organic

material (DOM) pool

– primary proxy –dissolved organic carbon (DOC)

– expected to have associated dissolved organic phosphorus (DOP) - e.g. SUP

hypolimnetic temporal

pattern

lack of noteworthy

trend, consistent

2013

Apr May Jun Jul Aug Sep Oct

SU

P/D

OC

(µg

P/m

gC

)

0.0

0.5

1.0

1.5

2.0

2.5

95

5

90

10

75

2550

key

Limnological Consistency Checks: Hypolimnetic

Pools of SUP, SRP and DOC, in the Vertical


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

(°C)

0 10 20

De

pth

(m

)

0

20

40

60

80

100

120

P(µgP/L)

0 5 10 15

DOC(mg/L)

1 2 3 4

T(°C)

0 5 101520

Dep

th (

m)

0

20

40

60

80

100

120

P(µgP/L)

0 5 10 15

DOC(mg/L)

1 2 3 4

SRPSUP

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

and sink processes

Limnological Consistency Checks:

Hypolimnetic Pools of SUP, SRP, and

DOC Temporally


as mass estimates

– volumes for depth interval from hypsographic data

𝑚𝑎𝑠𝑠 = 𝑐𝑜𝑛𝑐𝑚𝑔

𝑚3· 𝑣𝑜𝑙(𝑚3)

𝑡𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 =

𝑖=1

𝑛

𝑣𝑖 · 𝑐𝑜𝑛𝑐.𝑖

temporal patterns of mass

2013

Apr May Jun Jul Aug Sep Oct

Hyp

olim

nio

n M

ass (

mg

P)

0

1e+10

2e+10

3e+10

4e+10

Hyp

olim

nio

n M

ass (

gC

)

0

1e+10

2e+10

3e+10

4e+10SRP

SUP

DOC

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)


– 2 cases

• May-Sept. 2004

• May-Sept. 1998-2006


– laboratory spectrophotometric Chl


Ch

l a

(µg

/L)

0

5

10

15

20

TP

(µg

P/L

)

0

10

20

30

TD

P(µ

g/L

)

0

10

20

30

System

Conesus

Hem

lock

Canadic

e

Honeoye

Canandaig

ua

Keuka

Seneca

Cayu

ga

Cayu

ga L

SC

8

Cayu

gaLS

Cl9

8-0

6

Ow

asco

Skaneate

les

Otisco

PP

(µg

/L)

0

10

20

30

TD

P(µ

gP

/L)

0

5

10

15

SU

P(µ

gP

/L)

0

5

10

SystemC

onesus

Hem

lock

Canadic

e

Honeoye

Canandaig

ua

Keuka

Seneca

Cayu

ga

Cayu

ga L

SC

8

Cayu

gaLS

C98-0

6

Ow

asco

Skaneate

les

Otisco

SR

P(µ

gP

/L)

0

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


– May – Sept. 2004




– 2 cases

• May-Sept. 2004

• May-Sept. 1998-2006

samples 0-4m composite


Cayuga vs. Finger Lakes 2004 Finger Lakes survey

Chl and SD

average measurements, bars are 1

std. dev. (temporal variations)

UFI lake data


– May – Sept. 2004


– Chl fluorometric



– 2 cases

• May-Sept. 2004

• May-Sept. 1998-2006 samples

0-4m composite


– Chl spectrophotometric


Chl a

(µg

/L)

0

5

10

15

20

SystemC

onesus

Hem

lock

Canadic

e

Honeoye

Canandaig

ua

Keuka

Seneca

Cayu

ga

Cayu

ga L

SC

8

Cayu

gaLS

C98-0

6

Ow

asco

Skaneate

les

Otisco

SD

(m)

0

2

4

6

8

10

Outline






6. UFI’s P resume



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


UFI Phosphorus Resume: Analyses

Supporting Research and Long-term

MonitoringKey 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 years4/8/2014 Upstate Freshwater Institute 44

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


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


Outline






6. UFI’s P resume



Approved Methods for NELAC

Certification for SRP

Process SM 4500 P E & 4500 P b.5

EPA 1978 (365.3)

Container acid washed glass or plastic

Acid washed pyrexor plastic

Filtering 0.45 um membrane 0.45 um membrane

Colormetric method ascorbic acid ascorbic acid

Filtration immediately after collection, store at 4C, analyze within 48 hrs

day of collection


UFI uses 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


Certification for SRP (continued)



EPA 1978 (365.3)

Calibration curve(s) Prepared weekly;verified daily

Prepared with eachrun

pH adjustment yes

Color development 10 minutes 5 minutes

Read sample 10 – 30 minutes after adding “mixed reagent”

5 - 60 minutes after sequential addition of 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 labsRSD = 9.1%, RE = 10.0%


Certification for SRP (continued)


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


a) Inlet

0

2

4

6

8

Standard Methods

EPA 1978

b) Cayuga near LSC

SR

P (

µg·L

-1)

17

19

21

23

c) Salmon Cr

Time (minutes)

0 20 40 60 80 100

8

10

12

14

RPD = 23%

RPD = 4%

RPD = 7%

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


a) CCB

-0.25

0.00

0.25

0.50

b) CCV

Time (minutes)

0 20 40 60 80 100S

RP

(µ

g·L

-1)

24

25

26

Standard Methods

EPA 1978

UFI LOD

Color Development Experimentfor Onondaga Lake and Tributaries

Standard Methods 18-21 4500-P E


color stability over time

dissolved phosphorus components stable

Time after adding mixed reagent (min)

0 20 40 60 80 100

SR

P (

g·L

-1)

0

2

4

6

8

10

Ninemile Cr

Onon Cr

Ley Cr

Onon Lk Marina

Color Development Experimentfor Onondaga Lake and Tributaries

initial sample values for SM and USEPA

had a RPD ranging from 6 to 11%


Time after adding mixed reagent (min)

0 20 40 60 80 100

SR

P (

g·L

-1)

0

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

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


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


a dialogue on phosphorus measurements · 5-20 cay. lk. 2013 2 3.2 11 5.7 16 3.9 5-20 cay. lk. 98-06...

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