Convergent evidence for widespread rock nitrogen sources in Earth's surface environment.

Nitrogen availability is a pivotal control on terrestrial carbon sequestration and global climate change. Historical and contemporary views assume that nitrogen enters Earth's land-surface ecosystems from the atmosphere. Here we demonstrate that bedrock is a nitrogen source that rivals atmospheric nitrogen inputs across major sectors of the global terrestrial environment. Evidence drawn from the planet's nitrogen balance, geochemical proxies, and our spatial weathering model reveal that ~19 to 31 teragrams of nitrogen are mobilized from near-surface rocks annually. About 11 to 18 teragrams of this nitrogen are chemically weathered in situ, thereby increasing the unmanaged (preindustrial) terrestrial nitrogen balance from 8 to 26%. These findings provide a global perspective to reconcile Earth's nitrogen budget, with implications for nutrient-driven controls over the terrestrial carbon sink.

Capturing Spatial Variability of Biogeochemical Mass Exchanges and Reaction Rates in Wetland Water and Soil through Model Compartmentalization.

A common phenomenon observed in natural and constructed wetlands is short-circuiting of flow and formation of stagnant zones that are only indirectly connected with the incoming water. Biogeochemistry of passive areas is potentially much different than that of active zones. In the research reported in this paper, the spatial resolution of a previously developed wetland nutrient cycling model was improved in order to capture the spatial variability of concentrations and reaction rates regarding nitrogen and carbon cycles throughout active and passive zones of wetlands. The upgraded model allows for several compartments in the horizontal domain, with all neighboring compartments connected through advective and dispersive/diffusive mass transport. The model was applied to data collected from a restored wetland in California that was characterized by the formation of a large stagnant zone at the southern end of the wetland due to close vicinity of the inlet and outlet structures in the northern end. Mass balance analysis revealed that over the course of the research period, about 23.4±3.9% of the incoming total nitrogen load was removed or retained by the wetland. It was observed that mass of all exchanges (physical and biogeochemical) regarding nitrogen cycling decreased along the activity gradient from active to passive zones. Model results also revealed that anaerobic processes become more significant along the activity gradient towards passive areas.

Efficacy of natural wetlands to retain nutrient, sediment and microbial pollutants.

Wetlands can improve water quality through natural processes including sedimentation, nutrient transformations, and microbial and plant uptake. Tailwater from irrigated pastures may contribute to nonpoint source water pollution in the form of sediments, nutrients, and pathogens that degrade downstream water quality. We examined benefits to water quality provided by a natural, flow-through wetland and a degraded, channelized wetland situated within the flood-irrigation agricultural landscape of the Sierra Nevada foothills of Northern California. The non-degraded, reference wetland significantly improved water quality by reducing loads of total suspended sediments, nitrate, and Escherichia coli on average by 77, 60, and 68%, respectively. Retention of total N, total P, and soluble reactive P (SRP) was between 35 and 42% of loads entering the reference wetland. Retention of pollutant loads by the channelized wetland was significantly lower than by the reference wetland for all pollutants except SRP. A net export of sediment and nitrate was observed from the channelized wetland. Decreased irrigation inflow rates significantly improved retention efficiencies for nitrate, E. coli, and sediments in the reference wetland. We suggest that maintenance of these natural wetlands and regulation of inflow rates can be important aspects of a best management plan to improve water quality as water runs off of irrigated pastures.

Chemical status of selenium in evaporation basins for disposal of agricultural drainage.

Evaporation basins (or ponds) are the most commonly used facilities for disposal of selenium-laden saline agricultural drainage in the closed hydrologic basin portion of the San Joaquin Valley, California. However concerns remain for potential risk from selenium (Se) toxicity to water fowl in these evaporation basins. In this study, we examined the chemical status of Se in both waters and sediments in two currently operating evaporation pond facilities in the Tulare Lake Drainage District. Some of the saline ponds have been colonized by brine-shrimp (Artemia), which have been harvested since 2001. We evaluated Se concentration and speciation, including selenate [Se(VI)], selenite [Se(IV)], and organic Se [org-Se or Se(-II)] in waters and sediment extracts, and fractionation (soluble, adsorbed, organic matter (OM)-associated, and Se(0) and other resistant forms) in sediments and organic-rich surface detrital layers from the decay of algal blooms. Selenium in ponds without vascular plants exhibited similar behavior to wetlands with vascular plant present, indicating that similar Se transformation processes and mechanisms had resulted in Se immobilization and an increase of reduced Se species [Se(IV), org-Se, and Se(0)] from Se(VI)-dominated input waters. Selenium concentrations in most pond waters were significantly lower than the influent drainage water. This decrease of dissolved Se concentration was accompanied by the increase of reduced Se species. Selenium accumulated preferentially in sediments of the initial pond cell receiving drainage water. Brine-shrimp harvesting activities did not affect Se speciation but may have reduced Se accumulation in surface detrital and sediments.

Efficacy of constructed wetlands to mitigate non-point source pollution from irrigation tailwaters in the San Joaquin Valley, California, USA.

The efficacy of using constructed wetlands (CWs) to sequester organic carbon and nutrients from irrigation tailwaters was studied in the San Joaquin Valley, California. Two CWs were monitored during the 2004 irrigation season, a new CW (W-1) and 10-year-old CW (W-2). Input/output waters from CW were collected weekly and analyzed for a variety of water quality contaminants. Organic carbon, nutrient and sediment retention efficiencies were evaluated from input/output concentrations. Characteristics of sediment were examined spatially at W-2. Results indicate that W-2 was more efficient at contaminant removal. Average particulate organic carbon retention, was 70+/-13% (mean +/-standard deviation) in W-2 and 48+/-32% in W-1. Chlorophyll-a, a measure of algal biomass, was higher at W-1, especially in input waters. Initially, output concentration of chlorophyll-a increased 15-fold in W-2, however over time, as emergent vegetation established, chlorophyll-a decreased to 35% of input levels. Average total N removal efficiency was 45 +/-18% for W-2 compared to 22 +/-32% in W-1. Total P removal efficiency was 72+/-14% at W-2 compared to 18+/-26% at W-1. CWs were most effective at removing total suspended solids, 84 +/-15% and 97+/-2% for W-1 and W-2, respectively. Results demonstrate that CWs are effective at capturing POC, sediment and nutrients from irrigation tailwaters.

Linking chemical reactivity and protein precipitation to structural characteristics of foliar tannins.

Tannins influence ecosystem function by affecting decomposition rates, nutrient cycling, and herbivory. To determine the role of tannins in ecological processes, it is important to quantify their abundance and understand how structural properties affect reactivity. In this study, purified tannins from the foliage of nine species growing in the pygmy forest of the northern California coast were examined for chemical reactivity, protein precipitation capacity (PPC), and structural characteristics (13C NMR). Reactivity of purified tannins varied among species 1.5-fold for the Folin total phenol assay, and 7-fold and 3-fold, respectively, for the acid butanol and vanillin condensed tannin assays. There was about a 5-fold difference in PPC. Variation in chemical reactivity and PPC can be largely explained by differences in structural characteristics of the tannins determined by 13C NMR. In particular, the condensed versus hydrolyzable tannin content, as well as the hydroxylation pattern of the B-ring and stereochemistry at the C-2-C-3 position appear to influence reactivity. Due to the large differences in chemical reactivity among species, it is necessary to use a well-characterized purified tannin from the species of interest to convert assay values to concentrations. Our results suggest that structural characteristics of tannins play an important role in regulating their reactivity in ecological processes.