DOC

Geochemical Model of Redox Reactions in a Tropical Rain Forest Stream Riparian Zone: DOC Oxidation, Respiration and Denitrification

Jiménez R.A., Geochemical Model of Redox Reactions in a Tropical Rain Forest Stream Riparian Zone: DOC Oxidation, Respiration and Denitrification. Master's Capstone and Thesis. University of Pennsylvania, 2011.

Abstract: 
A geochemical equilibrium model was used to quantify Dissolved Organic Carbon (DOC) electron donors during aerobic respiration and denitrification in a tropical stream riparian zone of the Luquillo Experimental Forest, Puerto Rico. DOC electron donors were measured across three general redox zones (Oxic: slope, Transitional: slope-riparian interface and Anoxic: riparian-floodplain) of the Icacos watershed. Model results suggest that nitrate and oxygen are completely reduced after approximately 10.1 mg/L of DOC have reacted with an initial ground water solution. In order to reach the observed mean oxygen concentration of 3.79 mg/L in the Oxic zone from the modeled equilibrium oxygen concentration of 9.46 mg/L, approximately 5.33 mg/L of DOC need to be oxidized. Additionally, 2.06 mg/L of DOC are oxidized in order to reach the observed mean oxygen concentration of 1.6 mg/L in the Transitional zone. In order to reach the observed mean Anoxic zone oxygen concentration of 1.27 mg/L from the observed mean Transitional zone oxygen concentration, an additional 0.309 mg/L of DOC are oxidized. From modeled equilibrium concentrations of oxygen (9.46 mg/L), approximately 8.8 mg/L of DOC are oxidized by oxygen before nitrate becomes more thermodynamically favorable as the electron acceptor and begins decreasing in concentration. Model simulations suggest that 1.19 mg/L of DOC reduce the observed mean nitrate concentration of 0.47 mg/L found in the Oxic zone to the lowest observed mean nitrate concentration of 0.01mg/L found in the Transitional zone. Differences between the observed DOC concentrations in the field and the modeled DOC concentrations needed to reach zone levels of oxygen and nitrate suggest that field reported values for DOC electron donors could represent residual or unused electron donors. Results also indicate that between 8.68 mg/L and 10.7 mg/L of DOC oxidation, 0.42 mg/L of dissolved N2 are produced, HCO3 increases from 0.33 mg/L to 2.64 mg/L and CO2 concentrations decrease from 13.8 mg/L to 13.7 mg/L before continuing to increase. This pronounced interval of DOC oxidation at which denitrification occurs and beyond which CO2 continues increasing suggests a specific range at which denitrifiers metabolize versus a larger range at which a general heterotrophic population metabolizes.

Long‐term patterns and short‐term dynamics of stream solutes and suspended sediment in a rapidly weathering tropical watershed

Shanley, J. B., W. H. McDowell, and R. F. Stallard (2011), Long‐term patterns and short‐term dynamics of stream solutes and suspended sediment in a rapidly weathering tropical watershed, Water Resour. Res., 47, W07515, doi:10.1029/2010WR009788.

Abstract: 
The 326 ha Río Icacos watershed in the tropical wet forest of the Luquillo Mountains, northeastern Puerto Rico, is underlain by granodiorite bedrock with weathering rates among the highest in the world. We pooled stream chemistry and total suspended sediment (TSS) data sets from three discrete periods: 1983–1987, 1991–1997, and 2000–2008. During this period three major hurricanes crossed the site: Hugo in 1989, Hortense in 1996, and Georges in 1998. Stream chemistry reflects sea salt inputs (Na, Cl, and SO4), and high weathering rates of the granodiorite (Ca, Mg, Si, and alkalinity). During rainfall, stream composition shifts toward that of precipitation, diluting 90% or more in the largest storms, but maintains a biogeochemical watershed signal marked by elevated K and dissolved organic carbon (DOC) concentration. DOC exhibits an unusual “boomerang” pattern, initially increasing with flow but then decreasing at the highest flows as it becomes depleted and/or vigorous overland flow minimizes contact with watershed surfaces. TSS increased markedly with discharge (power function slope 1.54), reflecting the erosive power of large storms in a landslide‐prone landscape. The relations of TSS and most solute concentrations with stream discharge were stable through time, suggesting minimal long‐term effects from repeated hurricane disturbance. Nitrate concentration, however, increased about threefold in response to hurricanes then returned to baseline over several years following a pseudo first‐order decay pattern. The combined data sets provide insight about important hydrologic pathways, a long‐term perspective to assess response to hurricanes, and a framework to evaluate future climate change in tropical ecosystems.

Long‐term patterns and short‐term dynamics of stream solutes and suspended sediment in a rapidly weathering tropical watershed

Shanley, J. B., W. H. McDowell, and R. F. Stallard (2011), Long‐term patterns and short‐term dynamics of stream
solutes and suspended sediment in a rapidly weathering tropical watershed, Water Resour. Res., 47, W07515,
doi:10.1029/2010WR009788

Abstract: 
The 326 ha Río Icacos watershed in the tropical wet forest of the Luquillo Mountains, northeastern Puerto Rico, is underlain by granodiorite bedrock with weathering rates among the highest in the world. We pooled stream chemistry and total suspended sediment (TSS) data sets from three discrete periods: 1983–1987, 1991–1997, and 2000–2008. During this period three major hurricanes crossed the site: Hugo in 1989, Hortense in 1996, and Georges in 1998. Stream chemistry reflects sea salt inputs (Na, Cl, and SO4), and high weathering rates of the granodiorite (Ca, Mg, Si, and alkalinity). During rainfall, stream composition shifts toward that of precipitation, diluting 90% or more in the largest storms, but maintains a biogeochemical watershed signal marked by elevated K and dissolved organic carbon (DOC) concentration. DOC exhibits an unusual “boomerang” pattern, initially increasing with flow but then decreasing at the highest flows as it becomes depleted and/or vigorous overland flow minimizes contact with watershed surfaces. TSS increased markedly with discharge (power function slope 1.54), reflecting the erosive power of large storms in a landslide‐prone landscape. The relations of TSS and most solute concentrations with stream discharge were stable through time, suggesting minimal long‐term effects from repeated hurricane disturbance. Nitrate concentration, however, increased about threefold in response to hurricanes then returned to baseline over several years following a pseudo first‐order decay pattern. The combined data sets provide insight about important hydrologic pathways, a long‐term perspective to assess response to hurricanes, and a framework to evaluate future climate change in tropical ecosystems.

Patterns of Dissolved Organic Carbon in Transport

Patterns of Dissolved Organic Carbon in Transport
Louis A. Kaplan, Richard A. Larson and Thomas L. Bott
Limnology and Oceanography
Vol. 25, No. 6 (Nov., 1980), pp. 1034-1043

Abstract: 
Two distinct patterns of dissolved organic carbon (DOC) in transport were observed in a southeastern Pennsylvania piedmont drainage basin under low flow conditions. In relatively undisturbed woodland spring seeps, DOC concentrations increased with distance from the groundwater sources as did the apparent percentage of high molecular weight DOC. Changes in pH, color, and phenolic-C paralleled those for total DOC in a seep, while the concentration of carbohydrate-C remained relatively constant. In headwater areas perturbed by humans, cattle, or waterfowl, elevated DOC concentrations decreased rapidly from point source inputs.

Diel Fluctuations of DOC Generated by Algae in a Piedmont Stream

Diel Fluctuations of DOC Generated by Algae in a Piedmont Stream
Louis A. Kaplan and Thomas L. Bott
Limnology and Oceanography
Vol. 27, No. 6 (Nov., 1982), pp. 1091-1100

Abstract: 
Diel fluctuations in dissolved organic carbon (DOC) were measured in White Clay Creek, a piedmont stream in SE Pennsylvania. DOC concentrations, measured on 16 days from late March to early June and on 2 days in early November, 1978 and 1979, showed rapid increases from predawn minima to late afternoon maxima and gradual decreases after sunset. Concentrations increased during a single day by as much as 40% of the daily minimum. These measurements were made during periods of constant discharge and were not related to volume of flow or changes in groundwater DOC concentrations. Laboratory and microcosm experiments suggested that benthic algae excreted most of the DOM and that bacterial uptake modified its concentration and composition. When the diel pulse was strongest, net algal DOC excretion accounted for 20% of the total DOC exported from the watershed that day. Additional data show that the 14C method of measuring algal excretion is quantitatively and qualitatively inaccurate for periphyton incubated for 2-4 h.

Export of Carbon, Nitrogen, and Major Ions from Three Tropical Montane Watersheds

Export of Carbon, Nitrogen, and Major Ions from Three Tropical Montane Watersheds
William H. McDowell and Clyde E. Asbury
Limnology and Oceanography
Vol. 39, No. 1 (Jan., 1994), pp. 111-125

Abstract: 
Annual exports of suspended sediment, dissolved and particulate C and N, dissolved N and P, and major cations and anions were measured in three montane tropical rain forest watersheds in Puerto Rico during 1983-1986. Organic C was primarily exported in the form of DOC, and DOC export (33-94 kg ha-1 yr-1) was similar to values in larger tropical watersheds with similar runoff. Particulate and dissolved organic N accounted for 60-70% of the 4-9 kg ha-1 yr-1 of total N exported. Export of base cations and rates of weathering varied with bedrock geology in the three watersheds. Concentrations of suspended sediment, particulate C and N, and DOC increased as a function of discharge in all three streams. NH4+, NO3-, SO42-, and K+ concentrations showed little or no response to variations in discharge; Na-, Ca2+, Mg2+, Cl-, HCO3-, and SiO2 all decreased at high flows. After removing the effects of discharge, residual NO, concentrations in each stream were inversely related to estimated rates of leaf fall. On a watershed basis, export and accumulation of N in biomass were greater than precipitation inputs, suggesting that unmeasured inputs (8-16 kg ha-1 yr-1) were large.

C and N dynamics in the riparian and hyporheic zones of a tropical stream, Luquillo Mountains, Puerto Rico

C and N Dynamics in the Riparian and Hyporheic Zones of a Tropical Stream, Luquillo Mountains, Puerto Rico
Tamara J. Chestnut and William H. McDowell
Journal of the North American Benthological Society
Vol. 19, No. 2 (Jun., 2000), pp. 199-214

Abstract: 
Hydrologic and chemical characteristics were determined for both riparian and hyporheic subsurface flow along a 100-m reach of a sandy-bottom tributary of the Rio Icacos in the Luquillo Experimental Forest, Puerto Rico. Hydrologic data (vertical hydraulic gradient and hydraulic conductivity of streambed sediments) and the topographic and morphological features of the watershed indicated diffuse inputs of groundwater from the near-stream riparian zone along this site. Cumulative groundwater discharge, determined by tracer dilution techniques, was ∼1.5 L/s or 10% of the total stream discharge. Spatial heterogeneity in hydrologic and chemical properties of riparian and hyporheic sediments was large. Hydraulic conductivity explained much of the variation in NH<sub>4</sub>-N and dissolved organic carbon (DOC) concentrations, with highest concentrations in sites having low conductivity. A mass-balance approach was used to examine the influence of the near-stream zone on nutrient transport and retention. Outwelling riparian groundwater had the potential to increase stream N concentrations by up to 84% and DOC concentrations by up to 38% along our 100-m reach. Because stream concentrations were constant downstream despite this input, we conclude that significant N and C retention or loss were occurring in the near-stream zone. Lotic ecosystems and their associated riparian groundwater can have a quantitatively significant impact on the nutrient budgets of tropical headwater catchments.
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