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.  There little or no signs of recovery in either Fall Brook or Winnisook soils. Mean Annual DOC Concentration

1000 Biscuit Brook Rondout Creek Tison's Creek 800

mol/l Winnisook Creek

 Neversink River

600

400

200

0

Vol. Wt. in Annual Mean DOC,

1990 1995 2000 2005 2010 2015 WaterDOC Year

NY68

WN * RC *

Station TS

BS

MB

-2 -1 0 1 2 Sen Slope in mol/L/yr Chloride

NY68

WN * RC *

Station TS *

BS *

MB *

-2 -1 0 1 2 Sen Slope in eq/L/yr Na

NY68

WN

RC

Station TS

BS

MB *

-2 -1 0 1 2 Sen Slope in eq/L/yr