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 UFI’s P resume 6. 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 𝑄𝑄 = 𝑈𝑄 − 𝑈𝐸𝑄 4/8/2014 Upstate Freshwater Institute 3
Partitioning Dissolved P Fractions TDP SRP SUP heterogeneous array of forms 3- PO 4 condensed phosphates organic P colloidal particles nomenclature – soluble reactive P ( SRP ) • operationally defined – responsive to “mixed” reagent • also MRP – molybdate reactive; PO 4 3- — P (not good alternative) 3- actually a small fraction of SRP • PO 4 – 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 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 UFI’s P resume 6. 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 12 n=27 (a) TP Count mean=10% 8 4 • example year, 2006, TP, 0 TDP, and SRP n=27 (b) TDP Count mean=10% 8 • generally consistent with 4 Salmon Creek 0 observations, 2013 (c) SRP n=27 Count mean=8% 8 4 0 >20 0 4 8 12 16 20 CV (%) 4/8/2014 Upstate Freshwater Institute 10
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 Forms of Phosphorus Phosphorus SRP TDP TP Concentration median median median (µg·L -1 ) n n n CV % CV % 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 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
Comparison of Cayuga Lake Field Triplicate Performance to Onondaga Lake Performance Forms of Phosphorus Phosphorus SRP TDP TP Concentration (µg·L -1 ) median CV median CV median CV n n n % % % 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 general consistency 90 4.5 144 12.4 1 -- in performance 5-20 On. Lk. 83 2.7 263 7.5 49 3.1 between lake programs 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 -- 0 -- 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 consistent, good, performance 50-100 Cay. Lk. 2013 0 -- 0 -- 0 -- 4/8/2014 Upstate Freshwater Institute 13 50-100 Cay. Lk. 98-06 0 -- 0 -- 6 6.9
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 UFI’s P resume 6. 7. evaluation of two SRP methods (selected features) 4/8/2014 Upstate Freshwater Institute 15
Phosphorus Fractions 𝑈𝐸𝑄 = 𝑇𝑆𝑄 + 𝑇𝑉𝑄 𝑈𝑄 = 𝑄𝑄 + 𝑈𝐸𝑄 where : TP = total phosphorus where : SRP = soluble reactive phosphorus PP = particulate phosphorus SUP = soluble unreactive TDP = total dissolved phosphorus phosphorus 4/8/2014 Upstate Freshwater Institute 16
Phosphorus Ratios as Diagnostics Supporting Data Analysis to represent contributions of fractions 𝑈𝑄 = 𝑄𝑄 + 𝑈𝐸𝑄 𝑄𝑄 𝑈𝑄 𝑈𝐸𝑄 = 𝑇𝑆𝑄 + 𝑇𝑉𝑄 𝑇𝑉𝑄 𝑇𝑆𝑄 𝑈𝐸𝑄 𝑈𝐸𝑄 4/8/2014 Upstate Freshwater Institute 17
4/8/2014 UFI measurements tributaries, averages and variability bars ( 1 std. dev.) SRP/TDP : Tributary Cross System SRP/TDP (%) 100 20 40 60 80 0 C-WBDR95 C-WBDR98 WOH AW-ESO97 NYC P-EBDR97 S-Sch98 N-NevR98 A-MR 99 Comparison Cr-Cross99 M-AngFly99 Upstate Freshwater Institute M-AngFly00 M-Plum99 EOH NYC M-Plum00 M-Stone99 M-Stone00 N-Hunt99 N-Hunt00 N-Kiscot99 N-Kisco00 O-Nm06 O-Nm07 O-Nm08 Onon. L. O-Nm09 O-Nm10 O-Ock06 O-Ock07 O-Ock08 O-Ock09 O-Ock10 18
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 Cayuga NYC NYC Tribs WOH EOH Onon. L. 100 SRP/TDP (%) 80 60 40 20 0 C-WBDR95 C-WBDR98 AW-ESO97 P-EBDR97 S-Sch98 N-NevR98 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 4/8/2014 Upstate Freshwater Institute 19
4/8/2014 UFI measurements tributaries, averages and variability bars ( 1 std. dev.) PP/TP (%) PP/TP : Tributary Cross System 100 20 40 60 80 0 C-WBDR95 C-WBDR98 WOH NYC AW-ESO97 P-EBDR97 S-Sch98 N-NevR98 A-MR 99 Comparison Cr-Cross99 M-AngFly99 Upstate Freshwater Institute M-AngFly00 M-Plum99 EOH NYC M-Plum00 M-Stone99 M-Stone00 N-Hunt99 N-Hunt00 N-Kiscot99 N-Kisco00 O-Nm06 O-Nm07 O-Nm08 Onon. L. O-Nm09 O-Nm10 O-Ock06 O-Ock07 O-Ock08 O-Ock09 O-Ock10 20
Recommend
More recommend
