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Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands Bruce Vasilas, soil scientist (hydric soils) University of Delaware Yan Jin, soil physicist (colloid transport) Anastasia Chirnside, engineer (water chemistry) Ronald Manelski, M.S. candidate Jing Yan, Ph.D. candidate

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Page 1: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Bruce Vasilas, soil scientist (hydric soils)University of Delaware

Yan Jin, soil physicist (colloid transport)

Anastasia Chirnside, engineer (water chemistry)Ronald Manelski, M.S. candidate

Jing Yan, Ph.D. candidate

Page 2: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Acknowledgements

• This project is supported by a Agriculture and Food Research Initiative Competitive Grant (National Integrated Water Quality Grant Program #2013-67019-21361) from the USDA National Institute of Food and Agriculture.

• USDA NRCS Cooperative Soil Survey-soil characterizations

• EPA & MDE-funding for previous projects• DE DNREC & DE DA-field sites on state lands

Page 3: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Background & Hypotheses

• Wetlands can serve as sources, sinks, or conduits for surface water contaminants.

• Literature indicates that mobilization and export of DOM, Fe, N, and P from wetlands do not result from independent processes.

• We hypothesize that colloid mobilization plays a key role in these processes.

• We hypothesis is that soil Eh shifts in redox-dynamic wetlands can cause wide shifts in [colloids] and dissolved materials due to Fe mineral dissolution and pH shifts associated with Fe oxidation state changes.

Page 4: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Background

1. Water table rises2. Soil Eh drops=reducing conditions

3. Fe3+ → Fe2+

4. Clays disperse5. Transient spike in DOC

6. Increased colloids

Page 5: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Previous Research

• Field studies at these sites– Long term water table and soil Eh data– Site variability in Ni & OP removal from

groundwater– Seasonal fluctuations in [Ni] & [OP] in

groundwater• Previous lab studies: Onset of reducing conditions

coincides with a transient spike in DOC

Page 6: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Objectives

• To quantify temporal & spatial variability in groundwater [colloid] in freshwater wetlands.

• To evaluate the impact of soil Eh & Fe on [colloid].• To assess the role of colloids on mobilization &

export of DOM, N, & P.

Page 7: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Wetland Hydrology Criteria

The water table is ≤30 cm below the soil surface for ≥14 consecutive days during the growing season, at a minimum frequency of 5 years in 10 (USACE, 2005).

Page 8: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Hydroperiod: seasonal pattern of water table depth in a soil or wetland.

Hydrodynamics: direction and energy of water flow

winterwinter

Page 9: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Devil’s HolePiedmont; Toeslope seepPermanently inundatedVertically steady state, laterally static

Page 10: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

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Devil’s Hole HydroperiodPermanently Inundated

Dept

h cm

25

0

-25

Page 11: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Possum HillPiedmont; Backslope seepPermanently saturatedVertically static, laterally dynamic

Page 12: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

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Possum Hill HydroperiodPermanently SaturatedDe

pth

cm

25

0

-25

-50

Page 13: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

BlackbirdCoastal PlainMineral soil flat + depressionSeasonally saturatedVertically dynamic, laterally low energy

Page 14: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

3824338275

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Blackbird Flat HydroperiodSeasonally Saturated

Dept

h cm

25

0

-25

-50

-75

Page 15: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Sampling Well Placement Across a Hydrologic Gradient

InletCenter

Outlet

Page 16: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Groundwater Sampling Scheme

winterwinter

Page 17: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Groundwater Parameters

• Water table depth• Soil Eh (Pt & reference electrodes, alpha-alpha

dipyridyl strips, IRIS tubes) • Electrical conductivity• [Colloid] (dispersed phase particles)• [Dissolved organic carbon]• [Fe2+]• [soluble reactive phosphorous (OP)]• [NO3

-, NH4+]

Page 18: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Challenges

• Groundwater sampling wells typically sealed near the soil surface with bentonite (shrink-swell clays): contamination of colloidal clay minerals– Wells sealed with polyurethane foam & plastic sheeting

• Well purging & groundwater sampling with a pump could increase colloid levels through agitation.– Purge and sample at low flow rate (~100ml/min) to avoid

suspending immobilized colloids • Exposure of groundwater sample to air: Fe2+ → Fe3+ – Argon

Page 19: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Mean Groundwater [Colloid]

P.H. D.H. BB0

50

100

150

200

250

InletWet. OutletDepr.

mg/

L

Page 20: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Groundwater [Colloid] at Possum Hill in 2015

Dec. Mar. June0

20

40

60

80

100

InletWet. Outletm

g/L

Page 21: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Groundwater [Colloid] at Blackbird in 2014

Dec. Mar. June0

25

50

75

100

125

150

175

200

InletFlatDepr.Outlet

mg/

L

Page 22: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Summary

• Water chemistry is the most consistent at Possum Hill (short residence time & static water table) & changes slightly over time and as water moves through the wetland.

• Water chemistry changed the most as water moved through Blackbird (long residence time & dynamic water table).

• Data collected to date supports our contention that hydrologic characteristics have major impacts on water chemistry in wetlands.

Page 23: Colloid Mobilization and Biogeochemical Cycling of Organic Carbon, Nitrogen and Phosphorous in Wetlands

Questions