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...
Transcript of 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)
4/8/2014 Upstate Freshwater Institute 2
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
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
4/8/2014 Upstate Freshwater Institute 4
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
4/8/2014 Upstate Freshwater Institute 5
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
4/8/2014 Upstate Freshwater Institute 6
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 7
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
4/8/2014 Upstate Freshwater Institute 8
Analysis of Field Triplicate
Samples: Salmon Creek, P
based on UFI’s experience
a case of good performance
– low variability
4/8/2014 Upstate Freshwater Institute 9
Analysis of Field Triplicate
Samples: Onondaga Creek, P
• example year, 2006, TP,
TDP, and SRP
• generally consistent with
Salmon Creek
observations, 2013
4/8/2014 Upstate Freshwater Institute 10
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.
4/8/2014 Upstate Freshwater Institute 11
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
4/8/2014 Upstate Freshwater Institute 14
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 15
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
4/8/2014 Upstate Freshwater Institute 16
Phosphorus Ratios as Diagnostics
Supporting Data Analysis
𝑇𝑃 = 𝑃𝑃 + 𝑇𝐷𝑃
𝑇𝐷𝑃 = 𝑆𝑅𝑃 + 𝑆𝑈𝑃
𝑃𝑃
𝑇𝑃
𝑆𝑅𝑃
𝑇𝐷𝑃
𝑆𝑈𝑃
𝑇𝐷𝑃
to represent contributions of fractions
4/8/2014 Upstate Freshwater Institute 17
SRP/TDP : Tributary Cross System
Comparison
tributaries, averages and variability bars (1 std. dev.)
UFI measurements
4/8/2014 Upstate Freshwater Institute 18
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
4/8/2014 Upstate Freshwater Institute 19
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
4/8/2014 Upstate Freshwater Institute 20
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
4/8/2014 Upstate Freshwater Institute 21
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
4/8/2014 Upstate Freshwater Institute 22
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
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-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
4/8/2014 Upstate Freshwater Institute 23
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
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
4/8/2014 Upstate Freshwater Institute 24
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
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-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
4/8/2014 Upstate Freshwater Institute 25
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 26
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
4/8/2014 Upstate Freshwater Institute 27
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
% 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
4/8/2014 Upstate Freshwater Institute 28
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
0
5
10
15
20
25
(a) UFI n = 179 med. = 0.53
% O
ccurr
ence
0
5
10
15
20
25
30
4/8/2014 Upstate Freshwater Institute 29
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
0
5
10
15
20
25
(a) UFI n = 177 med. = 0.60
% O
ccurr
ence
0
5
10
15
20
25
30
4/8/2014 Upstate Freshwater Institute 30
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 31
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
4/8/2014 Upstate Freshwater Institute 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)
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
severe eutrophy upper mesotrophy
4/8/2014 Upstate Freshwater Institute 33
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
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
shift to distinctP-limitation
severe eutrophy upper mesotrophy
4/8/2014 Upstate Freshwater Institute 34
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)
decreasingepilimnetic
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
4/8/2014 Upstate Freshwater Institute 36
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
4/8/2014 Upstate Freshwater Institute 37
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
4/8/2014 Upstate Freshwater Institute 38
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)
– collected 2/month
– 2 cases
• May-Sept. 2004
• May-Sept. 1998-2006
– samples 0-4m composite
– laboratory spectrophotometric Chl
4/8/2014 Upstate Freshwater Institute 39
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
– 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
4/8/2014 Upstate Freshwater Institute 40
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
4/8/2014 Upstate Freshwater Institute 41
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
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 42
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
4/8/2014 Upstate Freshwater Institute 43
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
4/8/2014 Upstate Freshwater Institute 45
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
4/8/2014 Upstate Freshwater Institute 46
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 47
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
4/8/2014 Upstate Freshwater Institute 48
UFI uses SM 4500 P E &
4500 P b.5
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)
4/8/2014 Upstate Freshwater Institute 49
Process SM 4500 P E & 4500 P b.5
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%
Approved Methods for NELAC
Certification for SRP (continued)
4/8/2014 Upstate Freshwater Institute 50
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
4/8/2014 Upstate Freshwater Institute 51
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
4/8/2014 Upstate Freshwater Institute 52
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
4/8/2014 Upstate Freshwater Institute 53
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%
4/8/2014 Upstate Freshwater Institute 54
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
4/8/2014 Upstate Freshwater Institute 55
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
4/8/2014 Upstate Freshwater Institute 56