Catskill Trends Mike McHale, Doug Burns, Jason Siemion, Mike Antidormi, Greg Lawrence U.S. Geological Survey, Troy NY New York Catskill LTM Network New York NADP and MDN Station Mean Acidity 1991-2014 60 40 Neversink River 20 Biscuit Brook 0 Rondout Creek -20 Tison's Creek in micromoles per liter Acid Neutralizing Capacity, Winnisook -40 4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4 pH, in pH units Catskill Sampling Water sampling at 5 streams in the Catskill Mountains Monthly sampling plus storms ~ 35 samples per year Winnisook soils were sampled in 1993 (Javier Ruiz) and 2012 (McHale). Fall Brook Soils were sampled in 2001 (Lawrence) and 2011 (Lawrence and others). There is an NADP site at Biscuit Brook Rondout Creek above Peekamoose (RC) Winnisook Watershed (WN) on the slopes of Slide Mountain in the headwaters of the Neversink River basin Biscuit Brook eq/L) 16 50140 eq/L) ARP Emmissions 14 NY68 Deposition 120 Biscuit Brook ( conc. 40 2- 4 12 100 30 10 80 8 60 20 6 40 10 4 20 2 0 1990 1995 2000 2005 2010 20152015 Biscuit NTN annual volume-weighted SO annual volume-weighted NTN Biscuit Biscuit NTN annual volume-weighted ( SO42- conc. annual volume-weighted NTN Biscuit EPA Acid Rain Program SO2 annual emissions (million tons) SO2(million EPA annual emissions Rain Program Acid EPA Acid Rain Program SO2 annual emissions (million tons) EPA Acid Rain Program SO2 annual emissions (million tons)EPASO2 (million annual Rain Program emissions Acid Year Biscuit Brook 7 2860 eq/L) ARP Emmissions 26 NY68 Deposition 6 Biscuit Brook 50 conc. ( 24 - 3 22 5 40 20 4 1830 annual emissions (million tons) (million annual emissions annual (millionemissions tons) X X 16 3 20 14 12 2 10 10 1 80 1990 1995 2000 2005 2010 2015 Biscuit NTN annual volume-weighted NO Biscuit NTN annual volume-weighted EPA Acid Rain Program NO Program EPA Rain Acid EPA Acid Rain NO Program Year Biscuit Brook Biscuit Brook eq/L) eq/L) 50 120 conc. ( conc. conc. ( 2- 2- 40 4 100 4 30 80 20 60 Deposition b[0] = 29.5 b[0] = 2.99 Water Stream b[1] = 4.88 b[1] = 2.46 10 40 r ² = 0.85 r ² = 0.84 0 20 2 4 6 8 10 12 14 16 2 4 6 8 10 12 14 16 Biscuit NTN annual volume-weighted SO NTN annualBiscuit volume-weighted Emissions SOBiscuit Brook annual volume-weighted Emissions EPA Acid Rain Program SO2 annual emissions (million tons) EPA Acid Rain Program SO2 annual emissions (million tons) Biscuit Brook eq/L) 120 b[0] = 27.7 b[1] = 1.83 conc. ( r ² = 0.86 2- 4 100 80 60 40 Stream Water Stream 20 0 10 20 30 40 50 Biscuit Brook annual volume-weighted SOBiscuit Brook annual volume-weighted Deposition 2- Biscuit NTN annual volume-weighted SO4 conc. (eq/L) Biscuit Brook Biscuit Brook eq/L) eq/L) 28 60 b[0] = 25.8 26 b[1] = 0.016 r ² = 8.75e-6 conc. ( conc. - 24 50 3 22 20 40 18 16 30 14 Deposition b[0] = 6.11 b[1] = 2.76 12 r ² = 0.81 Water Stream 20 10 8 10 1 2 3 4 5 6 7 1 2 3 4 5 6 7 Biscuit NTN annual volume-weighted NO volume-weighted annual NTN Biscuit Emissions ( conc. NO3- volume-weighted annual Brook Biscuit Emissions EPA Acid Rain Program NOX annual emissions (million tons) EPA Acid Rain Program NOX annual emissions (million tons) Biscuit Brook eq/L) 60 b[0] = 26.5 b[1] = -0.033 r ² = 3.5e-4 conc. ( conc. - 3 50 40 30 20 Stream Water Stream 10 8 10 12 14 16 18 20 22 24 26 28 Biscuit Brook annual volume-weighted NO annualBrook volume-weighted Biscuit Deposition - Biscuit NTN annual volume-weighted NO3 conc. (eq/L) Mean Annual Sulfate Concentration 140 Deposition 120 Biscuit Brook eq/l Rondout Creek Tison's Creek 100 Winnisook Creek Neversink River 80 60 40 20 Vol. Wt. Annual Mean Sulfate, in 0 1990 1995 2000 2005 2010 2015 Water Year Mean Annual Nitrate Concentration 70 Deposition 60 Biscuit Brook eq/l Rondout Creek Tison's Creek 50 Winnisook Creek Neversink River 40 30 20 10 Vol. Wt. Annual Mean Nitrate, in 0 1990 1995 2000 2005 2010 2015 Water Year Forest Floor Forest Floor Oa Spodosol Cake E Bs Winnisook Oa Calcium Magnesium Potassium Sodium 4.0 1.2 3.5 1.0 3.5 3.0 1.0 0.8 3.0 2.5 2.5 0.6 0.8 2.0 2.0 0.4 1.5 1.5 0.6 1.0 0.2 per kilogram per 1.0 0.4 0.5 0.5 0.0 Centimoles of charge of Centimoles 0.0 0.2 0.0 * 1993 2012 1993 2012 1993 2012 1993 2012 Fall Brook Oa/A Calcium Magnesium Potassium Sodium 20 2.5 1.4 0.06 1.2 0.05 15 2.0 1.0 0.04 10 1.5 0.8 0.03 5 1.0 0.6 0.02 0.4 0.01 per kilogram per 0 0.5 0.2 0.00 Centimoles of charge of Centimoles * 0.0 0.0 2001 2011 2001 2011 2001 2011 2001 2011 Winnisook Oa Aluminum Hydrogen pH-H20 Original 14 10 4.6 12 4.4 8 4.2 10 4.0 6 8 3.8 Reanalysis 3.6 6 4 3.4 4 per kilogram per 2 3.2 2 3.0 * Centimoles of charge of Centimoles 0 0 2.8 1993 2012 1993 2012 1993 2012 Fall Brook Oa/A Aluminum Hydrogen pH-H20 6 14 5.0 4.8 5 12 10 4.6 4 4.4 8 4.2 3 6 4.0 2 4 3.8 per kilogram per 2 3.6 1 0 3.4 Centimoles of charge of Centimoles 0 3.2 * 2001 2011 2001 2011 2001 2011 Winnisook Oa Carbon Nitrogen 60 3.0 50 2.5 40 2.0 30 1.5 Percent 20 1.0 10 0.5 1993 2012 1993 2012 Fall Brook Oa/A Carbon Nitrogen 50 2.5 40 2.0 30 1.5 20 1.0 Percent 10 0.5 0 * 0.0 2001 2011 2001 2011 Winnisook Oa CEC % Base Saturation 20 40 18 35 30 16 25 14 20 12 15 per kilogram per 10 10 Centimoles of charge of Centimoles 8 5 1993 2012 1993 2012 Fall Brook Oa/A CEC % Base Saturation 26 100 24 22 80 20 18 60 16 14 12 40 10 per kilogram per 8 20 6 Centimoles of charge of Centimoles 4 0 2001 2011 2001 2011 Winnisook B Calcium Magnesium Potassium Sodium 0.22 0.16 0.40 0.25 0.20 0.35 0.18 0.14 0.20 0.16 0.12 0.30 0.14 0.25 0.15 0.12 0.10 0.20 0.10 0.10 0.08 0.15 0.08 0.05 0.06 0.06 per kilogram per 0.10 0.04 0.04 0.00 0.02 0.05 Centimoles of charge of Centimoles 0.00 0.02 0.00 1993 2012 1993 2012 1993 2012 1993 2012 Fall Brook B Calcium Magnesium Potassium Sodium 4 0.5 0.22 0.014 0.20 0.012 3 0.4 0.18 0.010 0.16 0.3 2 0.14 0.008 0.12 1 0.2 0.006 0.10 0.004 per kilogram per 0 0.1 0.08 0.06 0.002 Centimoles of charge of Centimoles 0.0 0.04 * 0.000 * 2001 2011 2001 2011 2001 2011 2001 2011 Winnisook B Aluminum Hydrogen pH-H20 Original 7 1.8 5.2 1.6 5.0 6 1.4 4.8 5 1.2 4.6 4.4 1.0 4 4.2 Reanalysis 0.8 4.0 3 0.6 3.8 per kilogram per 0.4 2 3.6 0.2 3.4 Centimoles of charge of Centimoles 1 0.0 * 3.2 * 1993 2012 1993 2012 1993 2012 Fall Brook B Aluminum Hydrogen pH-H20 6 14 5.0 4.8 5 12 10 4.6 4 4.4 8 4.2 3 6 4.0 2 4 3.8 per kilogram per 2 3.6 1 0 3.4 Centimoles of charge of Centimoles 0 3.2 2001 2011 2001 2011 2001 2011 Winnisook B Carbon Nitrogen 5.0 3.0 4.5 2.5 4.0 3.5 2.0 3.0 2.5 1.5 Percent 2.0 1.0 1.5 1.0 0.5 1993 2012 1993 2012 Fall Brook B Carbon Nitrogen 7 2.5 6 2.0 5 4 1.5 3 1.0 Percent 2 0.5 1 0 0.0 2001 2011 2001 2011 Winnisook B CEC % Base Saturation 8 14 7 12 10 6 8 5 6 4 4 per kilogram per 3 2 Centimoles of charge of Centimoles 2 0 * 1993 2012 1993 2012 Fall Brook B CEC % Base Saturation 10 70 9 60 8 50 40 7 30 6 20 5 per kilogram per 10 4 0 Centimoles of charge of Centimoles 3 2001 2011 2001 2011 Sulfate NY68 * WN * RC Stream Water * Station TS * Trends BS * MB * -3 -2 -1 0 1 2 3 Sen Slope in eq/L/yr Nitrate NY68 * WN RC Station TS BS MB -2 -1 0 1 2 Sen Slope in eq/L/yr ANC NY68 WN * Stream Water RC * Station TS * Trends BS MB * -3 -2 -1 0 1 2 3 Sen Slope in eq/L/yr H+ NY68 * WN * RC * Station TS * BS MB * -2 -1 0 1 2 Sen Slope in eq/L/yr Mg NY68 WN * RC * Stream Water Station TS * Trends BS * MB * -1.0 -0.5 0.0 0.5 1.0 Sen Slope in eq/L/yr SiO2 NY68 WN * RC * Station TS * BS * MB * -1.0 -0.5 0.0 0.5 1.0 Sen Slope in eq/L/yr Base Cation- Si Correlations (r2) Site Mg-Si Ca-Si Na-Si K-Si Biscuit 0.934 0.873 0.625 0.843 Rondout 0.847 0.839 0.718 0.525 Tison 0.884 0.867 0.623 0.702 Winnisook 0.863 0.633 0.497 0.637 Claryville 0.755 0.141 -0.733 0.588 Is this an indication of a decreasing weathering rate? Conclusions The Clean Air Act and its amendments have decreased emissions and deposition Stream sulfate concentrations have decreased significantly, nitrate concentrations have not At the most acidic sites stream water ANC is increasing and H+ is decreasing The stream water trends results may indicate a decreasing weathering rate in response to decreased acid deposition.