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.

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.

Twelve testable hypotheses on the Geobiology of weathering

Brantley S.L., Megonigal J.P., Scatena F.N. et al 2010. Twelve testable hypotheses on the Geobiology of weathering. Geobiology. DOI: 10.1111/j.1472-4669.2010.00264.x

Critical Zone (CZ) research investigates the chemical, physical, and biological processes that modulate the Earth’s surface. Here, we advance 12 hypotheses that must be tested to improve our understanding of the CZ: (1) Solar-to-chemical conversion of energy by plants regulates flows of carbon, water, and nutrients through plant-microbe soil networks, thereby controlling the location and extent of biological weathering. (2) Biological stoichiometry drives changes in mineral stoichiometry and distribution through weathering. (3) On landscapes experiencing little erosion, biology drives weathering during initial succession, whereas weathering drives biology over the long term.(4) In eroding landscapes, weathering-front advance at depth is coupled to surface denudation via biotic processes.(5) Biology shapes the topography of the Critical Zone.(6) The impact of climate forcing on denudation rates in natural systems can be predicted from models incorporating biogeochemical reaction rates and geomorphological transport laws.(7) Rising global temperatures will increase carbon losses from the Critical Zone.(8) Rising atmospheric PCO2 will increase rates and extents of mineral weathering in soils.(9) Riverine solute fluxes will respond to changes in climate primarily due to changes in water fluxes and secondarily through changes in biologically mediated weathering.(10) Land use change will impact Critical Zone processes and exports more than climate change. (11) In many severely altered settings, restoration of hydrological processes is possible in decades or less, whereas restoration of biodiversity and biogeochemical processes requires longer timescales.(12) Biogeochemical properties impart thresholds or tipping points beyond which rapid and irreversible losses of ecosystem health, function, and services can occur.

Urban influences on the nitrogen cycle in Puerto Rico

Ortiz-Zayas, J. R., E. Cuevas, O. L. Mayol-Bracero, L.
Donoso, I. Trebs, D. Figueroa-Nieves, and W. H. Mcdowell.
2006. Urban influences on the nitrogen cycle in Puerto Rico.
Biogeochemistry 79:109–133.

Anthropogenic actions are altering fluxes of nitrogen (N) in the biosphere at unprecedented rates. Efforts to study these impacts have concentrated in the Northern hemisphere, where experimental data are available. In tropical developing countries, however, experimental studies are lacking. This paper summarizes available data and assesses the impacts of human activities on N fluxes in Puerto Rico, a densely populated Caribbean island that has experienced drastic landscape transformations over the last century associated with rapid socioeconomic changes. N yield calculations conducted in several watersheds of different anthropogenic influences revealed that disturbed watersheds export more N per unit area than undisturbed forested watersheds. Export of N from urban watersheds ranged from 4.8 kg ha)1 year)1 in the Rı´o Bayamo´ n watershed to 32.9 kg ha)1 year)1 in the highly urbanized Rı´o Piedras watershed and 33.3 kg ha)1 year)1 in the rural-agricultural Rı´o Grande de An˜ asco watershed. Along with land use, mean annual runoff explained most of the variance in fluvial N yield. Wastewater generated in the San Juan Metropolitan Area receives primary treatment before it is discharged into the Atlantic Ocean. These discharges are N-rich and export large amounts of N to the ocean at a rate of about 140 kg ha)1 year)1. Data on wet deposition of inorganic N (NHþ4 þ NO 3 ) suggest that rates of atmospheric N deposition are increasing in the pristine forests of Puerto Rico. Stationary and mobile sources of NOx (NO+NO2) and N2O generated in the large urban centers may be responsible for this trend. Comprehensive measurements are required in Puerto Rico to quantitatively characterize the local N cycle. More research is required to assess rates of atmospheric N deposition, N fixation in natural and human-dominated landscapes, N-balance associated with food and feed trade, and denitrification.

Nutrient relations of dwarf Rhizophora mangle L. mangroves on peat in eastern Puerto Rico

Medina E, Cuevas E, Lugo AE (2010) Nutrient relations of
dwarf Rhizophora mangle L. mangroves on peat in eastern
Puerto Rico. Plant Ecol 207:13–24

Dwarf mangroves on peat substrate growing in eastern Puerto Rico (Los Machos, Ceiba State Forest) were analyzed for element concentration, leaf sap osmolality, and isotopic signatures of C and N in leaves and substrate. Mangrove communities behind the fringe presented poor structural development with maximum height below 1.5 m, lacked a main stem, and produced horizontal stems from which rhizophores developed. This growth form departs from other dwarf mangrove sites in Belize, Panama, and Florida. The dwarf mangroves were not stressed by salinity but by the low P availability reflected in low P concentrations in adult and senescent leaves. Low P availability was associated with reduced remobilization of N and accumulation of K in senescent leaves, contrasting with the behavior of this cation in terrestrial plants. Remobilization of N and P before leaf abscission on a weight basis indicated complete resorption of these nutrients. On an area basis, resorption was complete for P but not for N. Sulfur accumulated markedly with leaf age, reaching values up to 400%, compared with relatively modest accumulation of Na (40%) in the same leaves. This suggests a more effective rejection of Na than sulfate at the root level. Dwarf mangrove leaves had more positive d13C values, which were not related to salinity, but possibly to drought during the dry season due to reduced flooding, and/or reduced hydraulic conductance under P limitation. Negative leaf d15N values were associated with low leaf P concentrations. Comparison with other R. mangle communities showed that P concentration in adult leaves below 13 mmol kg-1 is associated with negative d15N values, whereas leaves with P concentrations above 30 mmol kg-1 in non-polluted environments had positive d15N values.

Chemical and mineral control of soil carbon turnover in abandoned tropical pastures

Marín-Spiotta, Erika; Swanston, Christopher W.; Torn, Margaret S.; Silver, Whendee L.; Burton, Sarah D. 2007. Chemical and mineral control of soil carbon turnover in abandoned tropical pastures.. Geoderma, doi:10.1016/j.geoderma.2007.10.001.

We investigated changes in soil carbon (C) cycling with reforestation across a long-term, replicated chronosequence of tropical secondary forests regrowing on abandoned pastures. We applied CP MAS 13C NMR spectroscopy and radiocarbon modeling to soil density fractions from the top 10 cm to track changes in C chemistry and turnover during secondary forest establishment on former pastures. Our results showed that interaggregate, unattached, particulate organic C (free light fraction) and particulate C located inside soil aggregates (occluded light fraction) represent distinct soil C pools with different chemical composition and turnover rates. The signal intensity of the O-alkyl region, primarily representing carbohydrates, decreased, and alkyl C, attributed to recalcitrant waxy compounds and microbially resynthesized lipids, increased from plant litter to soil organic matter and with incorporation into soil aggregates. The alkyl/O-alkyl ratio, a common index of humification, was higher in the occluded than in the free light fraction. Greater variability in the chemical makeup of the occluded light fraction suggests that it represents material in varied stages of decomposition. Mean residence times (14C-based) of the free light fraction were significantly shorter (4±1 years) than for the heavy fraction. We report two scenarios for the occluded light fraction, one fast-cycling in which the occluded and free light fractions have similar turnover rates, and one slow-cycling, in which the occluded light fraction resembles the heavy fraction. Mean residence times of the occluded light fraction and heavy fraction in active pastures and 10-year old secondary forests in the earliest stage of succession were longer than in older secondary forests and primary forests. This is likely due to a preferential loss of physically unprotected C of more labile composition in the pastures and in the youngest successional forests, resulting in an increase in the dominance of slow-cycling C pools. Soil carbon turnover rates of the mineral-associated C in secondary forests recovering from abandoned pasture resembled those of primary forests in as little as 20 years of succession.

Trends and scenarios of the carbon budget in postagricultural Puerto Rico (1936–2060)

Grau, H. R., T. M. Aide, J. K. Zimmerman, and J. R.
Thomlinson. 2004. Trends and scenarios of the carbon
budget in post-agricultural Puerto Rico (1936–2060). Global
Change Biology 10:1163–1179.

Contrary to the general trend in the tropics, Puerto Rico underwent a process of agriculture abandonment during the second half of the 20th century as a consequence of socioeconomic changes toward urbanization and industrialization. Using data on landuse change, biomass accumulation in secondary forests, and ratios between gross domestic product (GDP) and carbon emissions, we developed a model of the carbon budget for Puerto Rico between 1936 and 2060. As a consequence of land abandonment, forests have expanded rapidly since 1950, achieving the highest sequestration rates between 1980 and 1990. Regardless of future scenarios of demography and land use, sequestration rates will decrease in the future because biomass accumulation decreases with forest age and there is little agricultural land remaining to be abandoned. Due to high per-capita consumption and population density, carbon emissions of Puerto Rico have increased dramatically and exceeded carbon sequestration during the second half of the 20th century. Although Puerto Rico had the highest percent of reforestation for a tropical country, emissions during the period 1950–2000 were approximately 3.5 times higher than sequestration, and current annual emission is almost nine times the rate of sequestration. Additionally, while sequestration will decrease over the next six decades, current socioeconomic trends suggest increasing emissions unless there are significant changes in energy technology or consumption patterns. In conclusion, socioeconomic changes leading to urbanization and industrialization in tropical countries may promote high rates of carbon sequestration during the decades following land abandonment. Initial high rates of carbon sequestration can balance emissions of developing countries with low emission/GDP ratio. In Puerto Rico, the socioeconomic changes that promoted reforestation also promoted high-energy consumption, and resulted in a net increase in carbon emissions.

The problem of co-production in environmental accounting by emergy analysis

Bastianoni, S. and Marchettini, N., 2000. The problem of co-production in environmental accounting
by emergy analysis. Ecol. Model. 129: 187-193.

This paper deals with the application of emergy analysis to systems with co-productions. Emergy is a measure of how much work the biosphere has done in order to provide a product, in terms of solar energy joules. For this reason, especially by means of the emergy-based indices, emergy analysis is a one of the key functions for assessing sustainability. However the application of emergy analysis to processes with co-production can be misleading. Usually some inputs have to be added in order to obtain a ‘useful’ product from a by-product. This would lead to penalizing a co-production with respect to two (or more) independent processes, since the fact of having another output is neglected in calculations. To have a better comparison, we introduce the concept of joint transformity and the weighted a6erage of the transformities. The same reasoning is applied to other emergy-based indices. These new indexes should be added to the set of the existing ones to enlarge the possibilities of application. A case study of a dairy farm in Puerto Rico was analyzed from this viewpoint, showing that co-production of milk and methane (or electricity) is more efficient and less impacting on the environment with respect to separate productions, while two separate processes would be more effective in using local resources. © 2000 Elsevier Science B.V. All rights reserved.

Nitrogen Immobilization by Decomposing Woody Debris and the Recovery of Tropical Wet Forest from Hurricane Damage

Nitrogen Immobilization by Decomposing Woody Debris and the Recovery of Tropical Wet Forest from Hurricane Damage
J. K. Zimmerman, W. M. Pulliam, D. J. Lodge, V. Quiñones-Orfila, N. Fetcher, S. Guzmán-Grajales, J. A. Parrotta, C. E. Asbury, L. R. Walker and R. B. Waide
Vol. 72, No. 3 (Apr., 1995), pp. 314-322

Following damage caused by Hurricane Hugo (September 1989) we monitored inorganic nitrogen availability in soil twice in 1990, leaf area index in 1991 and 1993, and litter production from 1990 through 1992 in subtropical wet forest of eastern Puerto Rico. Experimental removal of litter and woody debris generated by the hurricane (plus any standing stocks present before the hurricane) increased soil nitrogen availability and above-ground productivity by as much as 40% compared to unmanipulated control plots. These increases were similar to those created by quarterly fertilization with inorganic nutrients. Approximately 85% of hurricane-generated debris was woody debris >5 cm diameter. Thus, it appeared that woody debris stimulated nutrient immobilization, resulting in depression of soil nitrogen availability and productivity in control plots. This was further suggested by simulations of an ecosystem model (CENTURY) calibrated for our site that indicated that only the large wood component of hurricane-generated debris was of sufficiently low quality and of great enough mass to cause the observed effects on productivity. The model predicted that nutrient immobilization by decaying wood should suppress net primary productivity for 13 yr and total live biomass for almost 30 yr following the hurricane. Our findings emphasize the substantial influence that woody debris has upon nutrient cycling and productivity in forest ecosystems through its effects on the activity of decomposers. We suggest that the manner in which woody debris regulates ecosystem function in different forests is significantly affected by disturbance regime.

Base saturation, nutrient cation, and organic matter increases during early pedogenesis on landslide scars in the Luquillo Experimental Forest, Puerto Rico

ZARIN, D. J. 1993. Nutrient accumulation during succession in subtropical lower montane wet forests, Puerto Rico.
Ph.D. dissertation. University of Pennsylvania, Philadelphia, Pennsylvania.
———, AND A. H. JOHNSON. 1995a. Nutrient accumulation during primary succession in a montane tropical forest,
Puerto Rico. Soil Sci. Soc. Am. J. 59: 1444–1452.
———, AND ———. 1995b. Base saturation, nutrient cation, and organic matter increases during early pedogenesis
on landslide scars in the Luquillo Experimental Forest, Puerto Rico. Geoderma 65: 317–330.

We evaluate data from a chronosequence study of landslide scars, ranging in age from 1-55 + yr, in the Luquillo Experimental Forest (LEF) a subtropical lower montane wet forest (sensu Holdridge) in eastern Puerto Rico. Surface mineral soil (0-10 cm) base saturation index (BSI) values increase during primary succession in the LEF (R=0.85, P<0.001 ). Both BSI values and major nutrient cation concentrations are extremely low on new landslide scars. During the course of the 55 + yr chronosequence, major nutrient cation concentrations are positively correlated with soil organic matter (SOM) content (P = 0.079) and not with clay content (P = 0.794). When data collected from plots representing the two dominant late-succession vegetation associations are added to the analysis, nutrient cation concentrations correlate significantly with both SOM (P= 0.001) and clay content (P=0.033). Our data show that when initial conditions are oligotrophic, both nutrient cation pools and BSI values can increase in the surface mineral soil during early pedogenesis. We discuss exogenic litter input, substrate weathering, and precipitation as potential sources for nutrient cations in these soils. We further suggest that production and decomposition of SOM is the dominant process controlling capture, retention and intra-ecosystem cycling of nutrient cations in these forests.

Impact of experimental drought on greenhouse gas emissions and nutrient availability in a humid tropical forest

We excluded throughfall from humid tropical forests in Puerto Rico for a period of three months to determine how drought affects greenhouse gas emissions from tropical forest soils. We established five 1.24 m2 throughfall exclusion and five control plots of equal size in three sites located on ridges, slopes, and an upland valley dominated by palms (total of 30 plots). We measured weekly changes in carbon dioxide (CO2) and bi-weekly changes in nitrous oxide (N2O) and methane (CH4) in response to manipulation. We additionally measured the effects of throughfall exclusion on soil temperature and moisture, nutrient availability, and pH. Rainout shelters significantly reduced throughfall by 22 to 32 % and decreased soil moisture by 16 to 36% (top 10 cm). Rates of CO2 emissions decreased significantly in the ridge and slope sites (30%, 28%, respectively), but not the palm during the experimental drought. In contrast, the palm site became a significantly stronger sink for CH4 in response to drying (480% decline relative to controls), while CH4 fluxes in the ridge and slope sites did not respond to drought. Both the palm and ridge site became a sink for N2O in response to drought and the slope site followed a similar trend. Soil pH and available P decreased significantly in response to soil drying; however, available N was not affected. Variability in the response of greenhouse gas emissions to drought among the three sites highlights the complexity of biogeochemical cycling in tropical forested ecosystems, as well as the need for research that incorporates the high degree of spatial heterogeneity in experimental designs. Our results show that humid tropical forests are sensitive to climate change and that short-term declines in rainfall could result in a negative feedback to climate change via lowered greenhouse gas emissions and increased greenhouse gas consumption by soils.
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