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importance, recent history, and variability D. Phosphorus Bioavailability and Loads 10/22/2015 Upstate Freshwater Institute 1

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Page 1: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

importance, recent history, and variability

D. Phosphorus Bioavailability and

Loads

10/22/2015 Upstate Freshwater Institute 1

Page 2: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Outline

10/22/2015 Upstate Freshwater Institute 2

1. Phosphorus importance and forms

2. Runoff events, phosphorus loading, and variability

3. Bioavailability: Background and results

4. Applying the bioavailability concept to phosphorus loads

5. Point source reductions to the shelf

6. Bioavailable loads to Cayuga Lake: LSC context

7. Summary

* see attached slides for added information on estimates of variability and uncertainty

Page 3: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Outline

10/22/2015 Upstate Freshwater Institute 3

1. Phosphorus importance and forms

2. Runoff events, phosphorus loading, and variability

3. Bioavailability: Background and results

4. Applying the bioavailability concept to phosphorus loads

5. Point source reductions to the shelf

6. Bioavailable loads to Cayuga Lake: LSC context

7. Summary

Page 4: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Importance of phosphorus (P) loads to

lakes

10/22/2015 Upstate Freshwater Institute 4

cultural eutrophication and associated water quality problems continue to be an important issue

P is the limiting nutrient for algae growth in most inland waters, least available constituent necessary to support growth Cayuga Lake is P-limited

control of the supply of P (PL; loads e.g., kg) is a primary management approach for lakes with excessive algal growth, described as culturally eutrophic

earlier this was based on the concentration of total P (TP), and the development of TP loading rates (TPL = Q·TP; where Q is the flow rate of the input)

focus here: the evolution to the development of bioavailable P loads (BAPL)

Page 5: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Forms of phosphorus (P)

10/22/2015 Upstate Freshwater Institute 5

Total phosphorus (TP)

TP = PP + TDP (m)

Particulate P (PP) (m)

organic PP (PPo)

minerogenic PP (PPm)

PPm = PPm/u + PPm/a

Total dissolved P (TDP) (m)

TDP = SRP + SUP (m)

Soluble reactive P (SRP) (m)

Soluble unreactive P (SUP) (m)

(m) – directly, or indirectly

from measurement

advanced

here

Page 6: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Outline

10/22/2015 Upstate Freshwater Institute 6

1. Phosphorus importance and forms

2. Runoff events, phosphorus loading, and variability

3. Bioavailability: Background and results

4. Applying the bioavailability concept to phosphorus loads

5. Point source reductions to the shelf

6. Bioavailable loads to Cayuga Lake: LSC context

7. Summary

Page 7: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Q (

m3/s

)

0

20

40

60

80

100

BB B

B B B B B B

B

B BB

B B B B

EEEEEEEEEEEEEEEEEEEEEEEEEEEE

E EEEEEE

EEEE

EEEE

E

EE

EE E

EEEEEE

EEE

EEE EEEEEEEEEE EEE

flow

biweekly obs.B

event obs.E

(a)

2013

SR

P (

µg/L

)

0

20

40

SU

P (

µg/L

)0

20

40

PP

g/L

)

0

200

400

est. conc.

obs. conc.

0

20

40

(b)

(c)

(d)

00 06 12 18 00

Aug 9

0

20

40

00 06 12 18 00

Aug 9

0250500750

00 06 12 18 00

Aug 9

0

40

80

120

00 06 12 18 00

Apr May Jun Jul Aug Sep Oct

Inclusion of runoff-event based sampling was critical to

support development of representative loading estimates

and the overall P-eutrophication modeling initiative

10/22/2015 Upstate Freshwater Institute 7

strong dynamics in concentrations of forms

of P are observed in most tributaries during

runoff events

these need to be resolved and parameterized

to support credible loading estimates and

related modeling

as promoted by NYSDEC (automated

sampling equipment, and program

support)

PL as a major model driver has important

management implications

apportionment according to sources is

critical

- Figure 3 (Fall Cr.) from Prestigiacomo et al., 2015

Page 8: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Sixmile Creek during high flow

10/22/2015 Upstate Freshwater Institute 8

Page 9: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Approach used for phosphorus load

estimation: Independently for each stream

10/22/2015 Upstate Freshwater Institute 9

TP

PP

SUP

SRP

PP-driver

expression

SUP-driver

expression

SRP-driver

expression

PPL

SUPL

SRPL

TPL=PPL+SUPL+SRPL

concentrations

runoff event

based sampling

conc.-driver

relationships

(Q,T)

loading rate

calculations

(kg·d-1)

2013 Q

records

non-point

interannual

variability

long-term

Q records

Page 10: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Loading estimates for the Cayuga Lake system: Context,

importance of runoff event tributary monitoring

10/22/2015 Upstate Freshwater Institute 10

tributary P loading methods and quantification – reported in Prestigiacomo et al. (2015), previous presentations

PL strongly dependent on P/Q relationships (stream, P-form dependent) developed from 2013 program

P/Q relationships were the sole basis for estimates for previous years interannual differences in P loading –

driven by interannual variations in Q support from CSI program (Community

Science Institute) ─ based on monitoring since early 2000s, no systematic

changes in TP/Q relationships indicated, supporting the approach for historic PL estimation

─ other historic PL validations ongoing

positive dependency,

but substantial variance

Page 11: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Sources of uncertainty in the estimation of P loads (PL)

10/22/2015 Upstate Freshwater Institute 11

1. methods of load estimation numerous protocols available

daily estimates required

2. dependencies of tributary P concentrations (various forms) stream flow rate (Q) other environmental conditions,

i.e., season

3. monitoring coverage adjoining tributary mouths number, frequency of sample

collection

4. application of bioavailability results

uncertainty and variability common to loading analyses

detailed treatment of variability

(uncertainty) for Fall Cr.

available at end of presentation

and for all tribs in Prestigiacomo

et al. 2015

Page 12: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Outline

10/22/2015 Upstate Freshwater Institute 12

1. Phosphorus importance and forms

2. Runoff events, phosphorus loading, and variability

3. Bioavailability: Background and results

4. Applying the bioavailability concept to phosphorus loads

5. Point source reductions to the shelf

6. Bioavailable loads to Cayuga Lake: LSC context

7. Summary

Page 13: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Phosphorus bioavailability: An established protocol

10/22/2015 Upstate Freshwater Institute 13

1. established bioassay protocol

a. review by Auer 2015, others

2. applications in New York

a. NYC – reservoir tributaries

b. Onondaga Lake – NYSDEC Metro/Actiflo

tributaries

3. Cayuga Lake (NYSDEC) 4 main tributaries

IAWWTP/Actiflo

CHWWTP

LSC

PP

Page 14: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Importance of the bioavailability of

phosphorus loads delivered to lakes

10/22/2015 Upstate Freshwater Institute 14

a major problem has emerged for the simple approach of focusing strictly on TP

P exists in multiple chemical forms that differ substantially in their availability to

support algal growth

differences in availability according to P forms

TP = PP + TDP (PP – particulate P ; TDP – total dissolved P)

TDP = SRP + SUP (SRP – soluble reactive P; SUP – soluble unreactive P)

PP = PPo and PPm (PPo – organic PP; PPm – minerogenic PP)

P form bioavailability

SRP ~ completely

SUP mostly

PP low

PPo intermediate, variable

PPm low (<< PPo)

Page 15: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Consideration of bioavailability causes the effective

external P loads (BAPL) to be diminished relative to the TP

load (TPL)

10/22/2015 Upstate Freshwater Institute 15

the failure to consider bioavailability in most contemporary

mechanistic P-eutrophication models is problematic

TP loads overestimate the amount of P that grow algae and that

leads to compensating by misrepresentation of source and/or

sink processes for P as part of model calibration

key examples of the importance of appropriate

representation of BAPL are emerging for prominent cases

re-eutrophication of western Lake Erie

Onondaga Lake –Metro discharge and rehabilitation

Cayuga Lake – emerging in these analyses, based on related

NYSDEC recommendations

Page 16: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Phosphorus (P) associated with clay particles:

Simple concepts

10/22/2015 Upstate Freshwater Institute 16

red border – strongly bound

red dots – strongly bound

such P would not be mobilized following delivery to the

lake and thus is uncoupled from trophic state

• not bioavailable

1.

adsorption/desorption processes

• driven by ambient SRP

• potential bioavailability

2.

a.

b.

adsorption – in tributaries where SRP is higher

desorption, low SRP – in lakes, bioavailable P

released, where SRP is lower

- giving up the green layer

green layer

subject to

release

Page 17: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

The BAPL initiative for Cayuga Lake

10/22/2015 Upstate Freshwater Institute 17

supporting components monitoring forms of P in critical inputs development of empirical concentration-Q

relationships, supported by runoff event sampling

bioassay-based bioavailability (fraction fBAP) assessments of PP, SUP, and SRP – multiple sources

estimates and apportionment of BAPL

estimates of interannual variation in loads associated with variations in stream flow

importance apportionment of BAPL according to sources model credibility management deliberations/transferability

Page 18: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

External loading to shelf of bioavailable P, 2013: Sites

10/22/2015 Upstate Freshwater Institute 18

April through October, 2013

tributaries

Fall Cr.

Cayuga Inlet mouth

Cayuga Inl. Cr.

Sixmile Cr.

Cascadilla Cr. (estimates)

point sources

IAWWTP

CHWWTP

LSC

minors (estimates)

Page 19: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

10/22/2015 Upstate Freshwater Institute 19

Methods for assessing P-bioavailability: Soluble

phase assays

Adopts the procedure of W.E.Miller and J.C. Greene. 1978.

The Selenastrum capricornutum Printz Algal Assay Bottle Test: Experimental Design,

Application, and Data Interpretation Protocol. U.S. Environmental Protection Agency,

Office of Research and Development, Corvallis Environmental Research Laboratory.

0

20

40

60

80

0 2 4 6 8 10 12

Solu

ble

Pho

spho

rus

(µgP

/L

)

Time of Incubation (days)

Precision: <11%, n=3

Soluble Phase Assay Setup

SUP (63% BAP)

SRP (100% BAP

Page 20: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

10/22/2015 Upstate Freshwater Institute 20

Methods for assessing P-bioavailability: Particulate

phase assays

Adopts the procedure of J.V. DePinto. 1982.

An experimental apparatus for evaluating kinetics of available phosphorous release from

aquatic particulates. Water Research, 16: 1065-1070.

Dual Culture Diffusion Apparatus

0

50

100

150

200

250

0 7 14 21

Cum

ulat

ive

P U

ptak

e (µ

PP (25% BAP)

PPinitial = 871 µgP/L

Precision: <4%, n=3

Page 21: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

10/22/2015 Upstate Freshwater Institute 21

Application of P-bioavailability assays

89 bioassays performed on 13 systems

Page 22: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

0.0

0.2

0.4

0.6

0.8

1.0

Frac

tion

Bio

avai

labl

e, f bi

o (d

’les

s) Cayuga

Other Sites

10/22/2015 Upstate Freshwater Institute 22

Range in P-bioavailability: Soluble unreactive

phosphorus (SUP)

0.0

Page 23: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

10/22/2015 Upstate Freshwater Institute 23

Range in P-bioavailability: Particulate phosphorus

(PP)

Cayuga

Other Sites

Frac

tion

Bio

avai

labl

e, f bi

o (d

’les

s)

0.0

0.2

0.4

0.6

0.8

1.0

0.0

Page 24: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

0.0

0.2

0.4

0.6

0.8

1.0

10/22/2015 Upstate Freshwater Institute 24

P-bioavailability: Particulate phosphorus (PP), by

discharge type

Cayuga

Other Sites

Frac

tion

Bio

avai

labl

e, f bi

o (d

’les

s)

0.0

Tributaries

WWTP Effluents

Page 25: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Cayuga Lake and tributaries: Sediment loading and

bioavailability information

10/22/2015 Upstate Freshwater Institute 25

Tributary

Watershed

(%)

PAVm

Load

(%)1

ISPM

Load

(%) 1

ISPM:SPM

(%) 1

PP

Load

(%)1

fBAP

PP

(%) 2

Fall Cr. 17.7 94 96 90 85 9

Inlet 22.0 89 87 90 78 -

Cayuga Inlet Cr. 12.9 96 99 93 98 6

Six Mile Cr. 7.20 97 90 97 89 6

Salmon Cr. 12.5 98 98 87 95 21

Unmonitored3 49.7 96 95 91 90 -

1 fraction received during high runoff intervals

2 fraction of PP bioavailable, average of three bioassays (Prestigiacomo et al., 2015)

3 estimated, based on monitored portion

minerogenic particles dominate in

runoff event samples

Page 26: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Bioavailability assay results (fBAP) for P forms

from multiple sources to Cayuga Lake

10/22/2015 Upstate Freshwater Institute 26

fBAP

Source PP SUP SRP

Fall Cr. 9 77 94

Cayuga Inl. Cr. 6 64 89

Salmon Cr. 21 84 98

Sixmile Cr. 6 62 94

IAWWTP 1 72 93

CHWWTP 26 63 98

LSC not avail 10 97

shelf 2 95 97

noteworthy features tributary PP fBAP - low,

Salmon highest on average some limited evidence that

PP fBAP correlated with land-use

LSC SUP - low in-lake processing effect,

enzymatic activity

IAWWTP PP fBAP – low Actiflo

(similar to Syracuse Metro)

shelf, post event fBAP – low dominated by mineral

particles

Page 27: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Bioavailability results for Cayuga Lake

system: Context

10/22/2015 Upstate Freshwater Institute 27

1. Salmon Cr. vs shelf tributaries a. Salmon Cr. SRP ~ 25 µg/L b. shelf tribs SRP ~ 5-10 µg/L c. lake SRP ~ 1 µg/L

2. important implications of low shelf fBAP (~ 1.7%), following the major runoff event of early July 2013

PP = 368 µg/L; i.e., not related to trophic state TP = 387 µg/L

Salmon Cr.

shelf

PP received by the shelf from

major runoff events is nearly

completely unavailable

Page 28: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Salmon Creek during high flow

10/22/2015 Upstate Freshwater Institute 28

Page 29: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Outline

10/22/2015 Upstate Freshwater Institute 29

1. Phosphorus importance and forms

2. Runoff events, phosphorus loading, and variability

3. Bioavailability: Background and results

4. Applying the bioavailability concept to phosphorus loads

5. Point source reductions to the shelf

6. Bioavailable loads to Cayuga Lake: LSC context

7. Summary

Page 30: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Application of the bioavailability concept

10/22/2015 Upstate Freshwater Institute 30

TP

PP

SUP

SRP

PP-driver

expression

SUP-driver

expression

SRP-driver

expression

PPL

SUPL

SRPL

x fBAP/PP

x fBAP/SUP

x fBAP/SRP

PPL/B

SUPL/B

SRPL/B

TPL = PPL+SUPL+SRPL BAPL=PPL/B+SUPL/B+SRPL/B

concentrations

runoff event

based sampling

conc.-driver

relationships

(Q,T)

loading rate

calculations

(kg·d-1)

fBAP

bioavailability

assays

bioavailable loads, P

fractions

2013 Q

records

non-point

interannual

variability

long-term

Q records

Page 31: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Phosphorus and bioavailability results

for Cayuga Lake system: Context

10/22/2015 Upstate Freshwater Institute 31

tributary P loading – totals, according to forms TP = PP + SUP + SRP

PP dominant (~84%)

2013 study results (Apr.-Oct.) documented in Prestigiacomo et al.

(2015) scope, NYSDEC input, event sampling

daily loads generated summaries for different intervals (e.g.,

summer)

BAPL ~ 26% of TPL PPL/B ~ 40% SRPL/B ~ 41% SUPL/B ~ 19%

PL (

mt)

0

25

50

75

PPL

SUPL

SRPL

TPL

BAPL

54.2 mt(±7.1 mt)

14.0 mt(±2.1 mt)

Page 32: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

PL (

mt)

0

5

10

15

20

25

PPL

SUPL

SRPL

TPL

BAPL

15.8 mt(±3.4 mt)

3.9 mt(±0.4 mt)

PL (

mt)

0

25

50

75

PPL

SUPL

SRPL

TPL

BAPL

54.2 mt(±7.1 mt)

14.0 mt(±2.1 mt)

Comparison of total (TPL) and bioavailable (BAPL) load

estimates to Cayuga Lake: Entire lake vs. shelf

10/22/2015 Upstate Freshwater Institute 32

dominant contribution of PPL to

TPL, received mostly during

runoff events

BAPL <<TPL; ~25% due to

low fBAP of PP

caution for related local interpretations, because of rapid flushing of shelf (subsequently)

BAPL remains much smaller (~ 22%) than TPL locally

entire

lake

shelf

* includes point and non-point sources

Page 33: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

BAPL Shelf

Non-point source

IAWWTP + CHWWTP

LSC

BAPL to Whole Lake

Comparison of BAPL to the shelf and

lake as a whole, 2013 conditions

10/22/2015 Upstate Freshwater Institute 33

tributaries ~87%

LSC ~6% IA,CH ~7%

tributaries ~95.5%

LSC ~1.6%

other PtS ~2.9%

Page 34: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Apportionment of BAP loads, 2013

10/22/2015 Upstate Freshwater Institute 34

BAPL (mt) Percent Contribution to

total BAPL (%)

Fall Cr. 2.10 15

Cayuga In. 0.79 5.6

Salmon Cr. 2.18 15.6

Six Mile Cr. 0.47 3.4

Taugh. Cr. 1.10 7.9

Unmon. Tribs. 6.75 48.1

summed (%) 13.4 95.5

IAWWTP 0.21 1.5

CHWWTP 0.08 0.5

minor WWTP 0.14 1.0

LSC 0.22 1.6

summed (%) 0.64 4.5

summed (%) 14.0 100

non-point

sources

point

sources

Page 35: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Outline

10/22/2015 Upstate Freshwater Institute 35

1. Phosphorus importance and forms

2. Runoff events, phosphorus loading, and variability

3. Bioavailability: Background and results

4. Applying the bioavailability concept to phosphorus loads

5. Point source reductions to the shelf

6. Bioavailable loads to Cayuga Lake: LSC context

7. Summary

Page 36: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Reductions in P loading to the shelf

from point sources

10/22/2015 Upstate Freshwater Institute 36

April-October loads

LSC (blue bar)

initiated in 2000

notable point source contributor in 2013

small relative to the overall decrease in point source inputs

TP

L (

mt)

0.0

2.5

5.0

7.5

0.2

0.3

0.4

WWTPs directly

to shelf

including LSC discharge

(added in 2000)

IA

CH

4.8

0.93

4.8

1.2

81% dec. 75% dec.

LSC variability

max=0.36

min=0.30

BA

PL (

mt)

0.0

2.5

5.0

7.5

0.2

0.3

0.4

3.4

0.28

3.4

0.5

92% dec. 85% dec.

max=0.25

min=0.22

1990s* 1990s 2013 2013

1990s 1990s 2013 2013

* 1990s point source assumptions detailed in Prestigiacomo et al. 2015

Page 37: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Outline

10/22/2015 Upstate Freshwater Institute 37

1. Phosphorus importance and forms

2. Runoff events, phosphorus loading, and variability

3. Bioavailability: Background and results

4. Applying the bioavailability concept to phosphorus loads

5. Point source reductions to the shelf

6. Bioavailable loads to Cayuga Lake: LSC context

7. Summary

Page 38: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

Representation of interannual variations in

whole lake BAPL, results

10/22/2015 Upstate Freshwater Institute 38

Prestigiacomo et al. 2015 (Figure 8)

• BAPL variations according to source (± 1 std. dev.)

variations in tributary loading dominate;

potential climate change effects should

be considered

1. ± 1 std. dev. ~ 4.5 % of LSC load

2. ± 3.6 % of total PtS load

3. ± 0.07 % of total local 2013 load

4. ± 0.04 % of total estimated variability in BAPL

comparative features of LSC variability

BA

PL (

mt)

0

10

20

30

40

19.6 ± 23.1

13.4

0.28

0.46 ± 0.11

0.22

0.23 ± 0.01

‘13 ’00-’12 tribs

BA

PL (m

t)

0.0

0.2

0.4

0.6

0.8

1.0

0.28

0.46 ± 0.11

0.22

0.23 ± 0.01

Pt. S

ou

rce

PtS ‘13 ’09-’12 ‘13 ’06-’12

LSC

different y-axis

scaling for tribs vs.

PtS

± std. dev. annual ests. (estimate of interannual availability)

Page 39: Phosphorus Bioavailability and Loads · D. Phosphorus Bioavailability and Loads 1 Upstate Freshwater Institute 10/22/2015 . Outline 2 Upstate Freshwater Institute 10/22/2015 1. Phosphorus

BA

PL (

mt)

0

1

2

3

4

5

Representation of interannual variations in

local lake BAPL, results

10/22/2015 Upstate Freshwater Institute 39

variations in tributary loading dominate;

potential climate change effects should

be considered

1. ± 1 std. dev. ~ 4.5 % of LSC load

2. ± 3.6 % of total PtS load

3. ± 0.3 % of total local 2013 load

4. ± 0.3 % of total estimated variability in BAPL

comparative features of LSC variability

5.0 ± 3.6 3.4

0.28

0.46 ± 0.11

0.22

0.23 ± 0.01

‘13 ’00-’12 tribs PtS*

‘13 ’09-’12 ‘13 ’06-’12 LSC

*summation of point sources

Prestigiacomo et al. 2015 (Figure 8)

• BAPL variations according to source (± 1 std. dev.)

± std. dev. annual ests. (estimate of interannual availability)

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98 99 00 01 02 03 04 05 06 07 08 09 10 11 12 13

Ch

l-a

(µg

/L)

0

3

6

9

Representation of interannual

variations in local lake BAPL, results

10/22/2015 Upstate Freshwater Institute 40

local BAPL for the April –

October interval

1998-2013 period

systematic decrease in the

WWTP BAPL (IA nd CH) in ~

2006

increase in LSC BAPL starting

2004-2005 evident

Shelf Chl-a (avg. 1 & 2) B

AP

L (m

t)

0

1

2

3

4

IA+CH

LSC

no significant trends in Chl-a (or TP) despite those in

point source BAPL

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98 99 00 01 02 03 04 05 06 07 08 09 10 11 12 13

Ch

l-a

(µg

/L)

0

3

6

9

Representation of interannual

variations in local lake BAPL, results

10/22/2015 Upstate Freshwater Institute 41

local BAPL for the April –

October interval

1998-2013 period

systematic decrease in the

WWTP BAPL (IA nd CH) in ~

2006

increase in LSC BAPL starting

2004-2005 evident

the tributary usually dominates

overall loading

exceptions, dry years, 2012

highly variable, dependent

on hydrology

Prestigiacomo et al. 2015

no significant trends in Chl-a (or TP) despite those in

point source BAPL

Shelf Chl-a (avg. 1 & 2)

flow-based

tribs

BA

PL

(m

t)

0

4

8

12

16IA+CH

LSC

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The increase in the LSC SRP levels: A limnological

signature, but only a small increase in BAPL

10/22/2015 Upstate Freshwater Institute 42

distinct increase in 2004 SRP concentration was 4-6 µg/L, now 8-10 µg/L

current conditions represent, on average, an increase in the LSC BAPL of ~0.1 mt ~2.7% increase in BAPL to shelf

small component of overall load (all tribs, non-point sources)

indicative of shift in system metabolism

zebra to quagga mussels?

2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013

SR

P (

µgP

/L)

0

2

4

6

8

10

LSC effluent

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Outline

10/22/2015 Upstate Freshwater Institute 43

1. Phosphorus importance and forms

2. Runoff events, phosphorus loading, and variability

3. Bioavailability: Background and results

4. Applying the bioavailability concept to phosphorus loads

5. Point source reductions to the shelf

6. Bioavailable loads to Cayuga Lake: LSC context

7. Summary

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Summary: Phosphorus bioavailability

and loads

10/22/2015 Upstate Freshwater Institute 44

runoff event monitoring and P concentration-flow (P/Q) relationships critical to support loading estimates

bioavailability concept (fBAP) integrated into P loading analysis for Cayuga Lake

components multiple fractions of P monitored algal bioassays of PP, SUP, and SRP – multiple sources and events development of load estimates (TPL and BAPL)

including historic estimates (~late 1990s) and contemporary

bioavailability findings for tributary inputs PP (mostly minerogenic particles) – low (6-21%) SUP – mostly (60-85%) SRP – ~ completely (>90%) other contrasting conditions – LSC/SUP, Actiflo/PP, Salmon Cr./PP, shelf

post events/PP

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Summary: Phosphorus bioavailability

and loads

10/22/2015 Upstate Freshwater Institute 45

tributary sources of BAPL dominate the overall BAPL to the entire lake and shelf ~ 95% on a lake-wide basis ~ 87% on the shelf

April-October 2013 BAPL was substantially lower than TPL

~ 26% of TPL

received mostly during runoff events large interannual variations anticipated from variations in hydrology -

complications

point source upgrades reduced BAPL contributions lake-wide from ~20% (late 1990s) to ~5% (2013) obvious benefits, quantification of benefits difficult due to tribs

dominance

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Questions

10/22/2015 Upstate Freshwater Institute 46

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Detailed uncertainty and variability

analyses

10/22/2015 Upstate Freshwater Institute 47

1. methods of load estimation numerous protocols evaluated

results for Fall Creek

2. dependencies of tributary P concentrations (various forms) stream flow rate (Q) loading calculations, FLUX32 Jackknifing

3. monitoring coverage adjoining tributary mouths loading calculations, FLUX32 Jackknifing

4. application of bioavailability results temporal, site specific variability in bioavailability

Monte Carlo analysis

5. estimates of interannual variations in tributary BAPL

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1. Variability in Fall Creek PL estimation: Calculation protocol

10/22/2015 Upstate Freshwater Institute 48

Method PP Load

(kg)

SUP Load

(kg)

SRP Load

(kg)

TP Load

(kg)

F32 method 6 C/Q interpolated, seasonal

8,032 741 876 9,649

F32 method 6 C/Q interpolated, flow 8,010 742 855 9,607

F32 method 6 C/Q 11,289 770 1,202 13,261

F32 method 5 C/Q adj. 8,156 755 893 9,804

F32 method 4 C/Q flow wtd. adj. 8,300 759 907 9,966

F32 Rising/Falling limb 8,008 739 850 9,597

Manual regr. 10,251 746 1,108 12,105

Manual regr. with events 10,223 645 1,153 12,021

Multiple Linear Regression 8,896 784 971 10,651

range (regression methods) 8,008-11,289 645-784 850-1,202 9,597-13,261

• demonstration of some dependence of load estimates on the specifics of the

loading calculation protocol adopted

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Best Est. Avg. Regr. Methods

2013

Fall

Cr.

PL (

mt)

0.0

2.5

5.0

7.5

10.0

12.5

15.0

PP

SUP

SRP

10/22/2015 Upstate Freshwater Institute 49

best estimate Fall Cr. TPL = 9.6 mt

PPL = 8.0 mt;

SRPL = 0.88 mt;

SUPL = 0.74 mt

range in estimates from regression protocols is typical

TPL range = 3.7 mt (38% of best estimate TPL)

PPL = 3.3 mt;

SRPL = 0.35 mt;

SUPL = 0.14 mt

protocol uncertainty due to:

uncertainty in C/Q

assumptions embedded in individual protocols

methodological uncertainty similar for other tributaries

most uncertain

most certain

range in TPL

3.7 mt

- April – October, 2013

1. Variability in Fall Creek PL estimation: Calculation protocol

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Phosphorus Form

PP SUP SRP TP

PL (

mt)

0

2

4

6

8

10

12

PPL

SUPL

SRPL

TPL

2-3. Uncertainty in Fall Creek load estimation

associated with adopted method: Jackknife analysis

10/22/2015 Upstate Freshwater Institute 50

unavoidable, associated with variability in the C/Q relationships and number of observations

greatest uncertainty associated with PP, the dominant P component

magnitudes of jackknife uncertainty

TPL = 2.2 mt

PPL 2.7 mt

SRPL = 0.23 mt

SUPL = 0.06

± 2 standard

deviations of

jackknife analysis

Jackknife procedure (FLUX32)

1. calculates the best estimate load using all observed concentration data

2. excludes one measured concentration one at a time, and recalculates the loads

3. repeated for n-1 number of iterations, where n is the total number of concentration observations

4. uncertainty statistics calculated on the n-1 number of load estimates

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4. Uncertainty in BAPL estimates: Monte Carlo analysis

10/22/2015 Upstate Freshwater Institute 51

fully summarized in Prestigiacomo et al. 2015

associated with temporal variations in fBAP in the tributaries beta distribution (StatSoft, 2003) was established for fBAP for each tributary

based on the three observations for each P form values of fBAP were selected randomly from these distributions for each day

over the April-October interval of 2013 for each tributary (and P form) and associated loads were calculated (summed to BAPL), as conducted for the original overall best estimate

process repeated for 2000 simulated April-October intervals uncertainty in PL/B for each tributary and together is represented by 95%

confidence limits of the calculated 2000 seasonal distributions

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Phosphorus Form

PP SUP SRP TP

PL/B

(m

t)

0.0

0.5

1.0

1.5

2.0

2.5

PPL/B

SUPL/B

SRPL/B

BAPL/B

10/22/2015 Upstate Freshwater Institute 52

Fall Cr. results

greatest uncertainty

associated with PP,

magnitudes of Monte

Carlo uncertainty

BAPL/B = 0.24 mt

PPL/B = 0.24 mt

SRPL/B = 0.04 mt

SUPL/B = 0.003 mt

PP is the dominant

component

4. Uncertainty in BAPL estimates: Monte Carlo analysis

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5. Representation of interannual variations in

local PL and BAPL, methods (2000-2012)

10/22/2015 Upstate Freshwater Institute 53

1. analyses of loads for tributaries a. evaluation of concentration-flow (C/Q)

relationships logarithmic relationships

positive, reasonably strong

“power law” format

important support for position that these dependencies have not systematically changed in recent years (historical CSI, UFI monitoring)

b. FLUX32 calculations of PL a. application of bioassay fBAP results to daily PL estimates

c. enhanced credibility of load estimates from NYSDEC’s call for event-based tributary monitoring

d. uncertainty in estimates unavoidable, from real variations in P/Q relationships

2. point sources – discharge monitoring

3. uncertainty – estimates, real variations

- Prestigiacomo et al., 2015

Q (m3/s)

1 10 100

PP

BA

P (

µg/L

)

1

10

100

e.g., high flow years

will have higher

concentrations and

associated loads

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Potential for interannual variations in local BAPL to

mask systematic benefits from reductions in point

source loads

10/22/2015 Upstate Freshwater Institute 54

the executed experiment:

Prestigiacomo et al. 2015

“Point source contributions to the total bioavailable P load (BAPL)

are minor (5%), reflecting the benefit of reductions from recent

treatment upgrades. The BAPL represented only about 26% of the

total P load, because of the large contribution of the low bioavailable

PP component. Most of BAPL (> 70%) is received during high flow

intervals. Large interannual variations in tributary flow and coupled

BAPL will tend to mask future responses to changes in individual

inputs.”