PART ONE A Valuable Resource for CERM ICP-MS in Catskills Research Presented by Alison Keimowitz Associate Professor of Chemistry, Vassar College

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1 PART ONE A Valuable Resource for CERM ICP-MS in Catskills Research Presented by Alison Keimowitz Associate Professor of Chemistry, Vassar College PART TWO A Collaborative Research Example Chemistry of Special Soils in the Catskills Presented by Steven Parisio Geologist (retired), NYSDEC Catskill Environmental Research & Monitoring (CERM) Conference October 24, 2018 Belleayre Mountain Ski Center, Highmount, NY

2 ICP-MS in Catskills Research Alison Keimowitz Vassar College

3 The Instrument Inductively coupled plasma mass spectrometer Elements from 6 Li à 238 U Solutions up to 0.2% TDS Linear over 5+ orders of magnitude Interference reduction from collision cell Coupled to ion chromatograph for arsenic speciation

4 Example: teaching laboratory mg in tablet mg in tablet from ICP-MS from label % difference Ca 38.0 ± % Cr ± % Fe 0.10 ± % Mn 7.7 ± % Cu 1.9 ± % Zn 2.1 ± % Se 15.5 ± % Mo ± % Mg ± % ±1 std dev shown

5 Examples: student research projects Hg in sediments downstream from a former hat factory Hg (+others?) As cycling in shallow contaminated lakes (includes speciation) As, Fe, Mn, S 400 mg As/kg sediment SL VA VV

6 Current Projects Release of trace elements from simulated fracking fluid Fracking puts huge volumes of chemically modified water in contact with shale Flowback water may contain high concentrations of contaminants of concern Noura Abualfaraj, Patrick L. Gurian, and Mira S. Olson. Environmental Engineering Science. Sep 2014.

7 Current Projects Depositional history of Pb and Hg in the Catskills Bog cores Depth (cm) Lake cores West Kill Mtn Peat Pb (mg/kg) samples North Mountain Pb (mg/kg) Dry Brook Ridge Pb (mg/kg) Balsam Lake Mountain Pb (mg/kg)

8 Current projects Catskill soils My role: extract Ca, Na, Mg, K with an NH 4 Cl solution; analyze by ICP-MS Eutrudepts Spodosols Dysrudepts mg Ca/kg soil Kelly Hollow A Pakatakan Mt 1 A Pakatakan Mt 2 A Plateau Mtn Spur A Romer Mtn 2 A mg Ca/kg soil Hunter Mtn - E Hunter Mtn - Bs1 Hunter Mtn - Bs2 Millbrook Valley - Oa Millbrook Valley - E Millbrook Valley - Bs Slide Mtn - Oa Slide Mtn - E Slide Mtn - Bhs mg Ca/kg soil Bear Pen Mtn - O/A Bear Pen Mtn - E Bear Pen Mtn - Bw2 Cherry Ridge/DblTop Cherry Ridge/DblTop - E Cherry Ridge/DblTop - Bw2 Panther Mtn - O/A Panther Mtn - E Panther Mtn - Bw

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10 Your turn! CERM was a big part of the grant application What would you like to analyze?

11 Chemistry of Special Soils in the Catskills Presented by Steven Parisio Geologist (Retired) New York State Dept. of Environmental Conservation

12 Three Contrasting Soil-Plant Associations Hemlock Ash Characteristic Dominant Canopy or Maple Beech Maple Vegetation Species: Spruce-Fir Birch Basswood and Soil Soil Taxonomy: Spodosol Dystrudept Eutrudept Morphology Soil Humus Form: Mor Moder Mull (Observed in Herbaceous Flora the Field) Species Richness: Low Medium High Soil Chemistry (Predicted) Extremely Soil Reaction: Acid Basic Cation Availability: Very Low Acid Circumneutral Low High Study Objectives: To relate soil chemical properties to observed associations between plant communities and soil humus forms. To see whether characteristics of soil morphology and site vegetation, which are easily observable in the field, can be used to predict certain soil chemical properties.

13 Data sorted by Soil Type, Site and Soil Horizon: Soil Humus Form Total Exch. Bases Total Exch. Acidity, meq/100g Site Name Horizon Soil Profile Type CEC, meq/100g % Base Saturation ph in Water Kelly Hollow A Eutrudept Mull Pakatakan Mt 1 A Eutrudept Mull Pakatakan Mt 2 A Eutrudept Mull Plateau Mt Spur A Eutrudept Mull Romer Mt 1 A Eutrudept Mull Romer Mt 2 A Eutrudept Mull Hunter Mt O Spodosol Mor Hunter Mt E Spodosol Mor Hunter Mt Bs1 Spodosol Mor Hunter Mt Bs2 Spodosol Mor Millbrook Valley O Spodosol Mor Millbrook Valley E Spodosol Mor Millbrook Valley Bs Spodosol Mor Slide Mt O Spodosol Mor Slide Mt E Spodosol Mor Slide Mt Bhs Spodosol Mor Bearpen Mt O/A Dystrudept Moder Bearpen Mt E Dystrudept Moder Bearpen Mt Bw2 Dystrudept Moder Doubletop Spur A Dystrudept Moder Doubletop Spur E Dystrudept Moder Doubletop Spur Bw2 Dystrudept Moder Panther Mt O/A Dystrudept Moder Panther Mt E Dystrudept Moder Panther Mt Bw Dystrudept Moder soil samples from 12 different soil profiles. Three distinct soil types/humus forms (color coded), each associated with a distinct plant community: Spodosol/Mor (gold) Eutrudepts/Mull (green) Dystrudepts/Moder (red) Profiles sampled by soil genetic horizon Samples analyzed for ph, Exchangeable Bases and Exchangeable Acidity Methods used follow those used by Chris Johnson

14 Data sorted by ph, decreasing from top to bottom: Soil Humus Form Total Exch. Bases Total Exch. Acidity, meq/100g Site Name Soil Profile Horizon Type CEC, meq/100g % Base Saturation ph in Water Plateau Mt Spur A Eutrudept Mull Romer Mt 2 A Eutrudept Mull Romer Mt 1 A Eutrudept Mull Pakatakan Mt 2 A Eutrudept Mull Pakatakan Mt 1 A Eutrudept Mull Kelly Hollow A Eutrudept Mull Doubletop Spur Bw2 Dystrudept Moder Bearpen Mt Bw2 Dystrudept Moder Slide Mt Bhs Spodosol Mor Bearpen Mt O/A Dystrudept Moder Doubletop Spur E Dystrudept Moder Panther Mt Bw Dystrudept Moder Hunter Mt Bs1 Spodosol Mor Slide Mt O Spodosol Mor Hunter Mt Bs2 Spodosol Mor Hunter Mt O Spodosol Mor Slide Mt E Spodosol Mor Panther Mt O/A Dystrudept Moder Bearpen Mt E Dystrudept Moder Doubletop Spur A Dystrudept Moder Millbrook Valley Bs Spodosol Mor Panther Mt E Dystrudept Moder Hunter Mt E Spodosol Mor Millbrook Valley O Spodosol Mor Millbrook Valley E Spodosol Mor Soil humus forms and soil profile types group well when the data is sorted by soil ph. A horizons of Eutrudepts with the mull humus form have ph values higher than all other samples. Samples from Spodosol profiles make up 4 of the 5 most acid samples. Samples Dystrudept profile morphology and moder humus form are concentrated near the center of the range.

15 Data sorted by % Base Saturation, decreasing from top to bottom Soil Humus Form Total Exch. Bases Total Exch. Acidity, meq/100g Site Name Horizon Soil Profile Type CEC, meq/100g % Base Saturation ph in Water Romer Mt 1 A Eutrudept Mull Pakatakan Mt 2 A Eutrudept Mull Pakatakan Mt 1 A Eutrudept Mull Kelly Hollow A Eutrudept Mull Hunter Mt Bs1 Spodosol Mor Hunter Mt E Spodosol Mor Plateau Mt Spur A Eutrudept Mull Millbrook Valley E Spodosol Mor Romer Mt 2 A Eutrudept Mull Hunter Mt Bs2 Spodosol Mor Bearpen Mt Bw2 Dystrudept Moder Millbrook Valley O Spodosol Mor Bearpen Mt O/A Dystrudept Moder Bearpen Mt E Dystrudept Moder Slide Mt E Spodosol Mor Doubletop Spur A Dystrudept Moder Slide Mt O Spodosol Mor Panther Mt E Dystrudept Moder Slide Mt Bhs Spodosol Mor Millbrook Valley Bs Spodosol Mor Hunter Mt O Spodosol Mor Panther Mt Bw Dystrudept Moder Panther Mt O/A Dystrudept Moder Doubletop Spur Bw2 Dystrudept Moder Doubletop Spur E Dystrudept Moder When the data is sorted by % base saturation, the Eutrudept A horizons still group together at the top of the chart (highest values) but there are anomalies (circled) and no clear separation between the other two groups of samples.

16 When ph and PBS are plotted together, Eutrudept samples plot together as a group. Spodosol data has some anomalies (high base saturation with low ph). Dystrudepts and Spodosols plot as one group.

17 Special Soils data superimposed over Chris Johnson data With the exception of 5 anomalous data points (circled), our data (colored circles) follows the same general pattern as the Chris Johnson data (black circles). Range of ph values extends farther to the left (more acid) and farther to the right (more circumneutral) due to our focus on special soils including Spodosols and Eutrudepts.