Equilibrium isotope fractionation factors of H exchange between steam and soil clay fractions.

RATIONALE: Steam equilibration overcomes the problem of the traditional measurements of H isotope compositions, which leave an arbitrary amount of adsorbed water in the sample, by controlling for the entire exchangeable H pool, including adsorbed water and hydroxyl-H. However, the use of steam equilibration to determine nonexchangeable stable H isotope compositions in environmental media (expressed as δ2 Hn values) by mathematically eliminating the influence of exchangeable H after sample equilibration with waters of known H-isotopic composition requires the knowledge of the equilibrium isotope fractionation factor between steam-H and exchangeable H of the sample (αex-w ), which is frequently unknown. METHODS: We developed a new method to determine the αex-w values for clay minerals, topsoil clay fractions, and mica by manipulating the contributions of exchangeable H to the total H pool via different degrees of post-equilibration sample drying. We measured the δ2 H values of steam-equilibrated mineral and soil samples using elemental analyzer-pyrolysis-isotope ratio mass spectrometry. RESULTS: The αex-w values of seven clay minerals ranged from 1.071 to 1.140, and those of 19 topsoil clay fractions ranged from 0.885 to 1.216. The αex-w value of USGS57 biotite, USGS58 muscovite, and of cellulose was 0.965, 0.871, and 1.175, respectively. The method did not work for kaolinite, because its small exchangeable H pool did not respond to the selected drying conditions. Structurally different mineral groups such as two- and three-layer clay minerals or mica showed systematically different αex-w values. The αex-w value of the topsoil clay fractions correlated with the soil clay content (r = 0.63, P = 0.004), the local mean annual temperature (r = 0.68, P = 0.001), and the δ2 H values of local precipitation (r = 0.72, P < 0.001), likely to reflect the different clay mineralogy under different weathering regimes. CONCLUSIONS: Our new αex-w determination method yielded realistic results in line with the few previously published values for cellulose. The determined αex-w values were similar to the widely assumed values of 1.00-1.08 in the literature, suggesting that the adoption of one of these values in steam equilibration approaches is appropriate.

Carbon Stable Isotope Ratio of Dissolved Organic Matter as a Tool To Identify Its Sources and Transformations in a Tropical Montane Forest in Ecuador.

Dissolved organic matter (DOM) contributes to forest C cycling. We assessed temporal variability, sources, and transformations of DOM during four years in a tropical montane forest with the help of stable C isotope ratios (δ13C values). We measured δ13C values of DOM in rainfall (RF), throughfall (TF), stemflow (SF), litter leachate (LL), soil solutions at the 0.15 and 0.30 m depths (SS15, SS30), and streamflow (ST) with TOC-IRMS. The δ13C values of DOM did not vary seasonally. We detected an event with a high δ13C value likely attributable to black carbon from local pasture fires. The mean δ13C values of DOM outside the event decreased in the order, RF (-26.0 ± 1.3‰) > TF (-28.7 ± 0.3‰) > SF (-29.2 ± 0.2‰) > LL (-29.6 ± 0.2‰) because of increasing leaching of C-isotopically light compounds. The higher δ13C values of DOM in SS15 (-27.8 ± 1.0‰), SS30 (-27.6 ± 1.1‰), and ST (-27.9 ± 1.1‰) than in the above-ground solutions suggested that roots and root exudates are major belowground DOM sources. Although in DOM the C/N ratios correlated with the δ13C values when all solutions were considered, this was not the case for SS15, SS30, and ST alone. Thus, the δ13C values of DOM provide an additional tool to assess the sources and turnover of DOM.

Land-use intensity alters networks between biodiversity, ecosystem functions, and services.

Land-use intensification can increase provisioning ecosystem services, such as food and timber production, but it also drives changes in ecosystem functioning and biodiversity loss, which may ultimately compromise human wellbeing. To understand how changes in land-use intensity affect the relationships between biodiversity, ecosystem functions, and services, we built networks from correlations between the species richness of 16 trophic groups, 10 ecosystem functions, and 15 ecosystem services. We evaluated how the properties of these networks varied across land-use intensity gradients for 150 forests and 150 grasslands. Land-use intensity significantly affected network structure in both habitats. Changes in connectance were larger in forests, while changes in modularity and evenness were more evident in grasslands. Our results show that increasing land-use intensity leads to more homogeneous networks with less integration within modules in both habitats, driven by the belowground compartment in grasslands, while forest responses to land management were more complex. Land-use intensity strongly altered hub identity and module composition in both habitats, showing that the positive correlations of provisioning services with biodiversity and ecosystem functions found at low land-use intensity levels, decline at higher intensity levels. Our approach provides a comprehensive view of the relationships between multiple components of biodiversity, ecosystem functions, and ecosystem services and how they respond to land use. This can be used to identify overall changes in the ecosystem, to derive mechanistic hypotheses, and it can be readily applied to further global change drivers.

Nutrient cycling drives plant community trait assembly and ecosystem functioning in a tropical mountain biodiversity hotspot.

Community trait assembly in highly diverse tropical rainforests is still poorly understood. Based on more than a decade of field measurements in a biodiversity hotspot of southern Ecuador, we implemented plant trait variation and improved soil organic matter dynamics in a widely used dynamic vegetation model (the Lund-Potsdam-Jena General Ecosystem Simulator, LPJ-GUESS) to explore the main drivers of community assembly along an elevational gradient. In the model used here (LPJ-GUESS-NTD, where NTD stands for nutrient-trait dynamics), each plant individual can possess different trait combinations, and the community trait composition emerges via ecological sorting. Further model developments include plant growth limitation by phosphorous (P) and mycorrhizal nutrient uptake. The new model version reproduced the main observed community trait shift and related vegetation processes along the elevational gradient, but only if nutrient limitations to plant growth were activated. In turn, when traits were fixed, low productivity communities emerged due to reduced nutrient-use efficiency. Mycorrhizal nutrient uptake, when deactivated, reduced net primary production (NPP) by 61-72% along the gradient. Our results strongly suggest that the elevational temperature gradient drives community assembly and ecosystem functioning indirectly through its effect on soil nutrient dynamics and vegetation traits. This illustrates the importance of considering these processes to yield realistic model predictions.

A research framework for projecting ecosystem change in highly diverse tropical mountain ecosystems.

Tropical mountain ecosystems are threatened by climate and land-use changes. Their diversity and complexity make projections how they respond to environmental changes challenging. A suitable way are trait-based approaches, by distinguishing between response traits that determine the resistance of species to environmental changes and effect traits that are relevant for species' interactions, biotic processes, and ecosystem functions. The combination of those approaches with land surface models (LSM) linking the functional community composition to ecosystem functions provides new ways to project the response of ecosystems to environmental changes. With the interdisciplinary project RESPECT, we propose a research framework that uses a trait-based response-effect-framework (REF) to quantify relationships between abiotic conditions, the diversity of functional traits in communities, and associated biotic processes, informing a biodiversity-LSM. We apply the framework to a megadiverse tropical mountain forest. We use a plot design along an elevation and a land-use gradient to collect data on abiotic drivers, functional traits, and biotic processes. We integrate these data to build the biodiversity-LSM and illustrate how to test the model. REF results show that aboveground biomass production is not directly related to changing climatic conditions, but indirectly through associated changes in functional traits. Herbivory is directly related to changing abiotic conditions. The biodiversity-LSM informed by local functional trait and soil data improved the simulation of biomass production substantially. We conclude that local data, also derived from previous projects (platform Ecuador), are key elements of the research framework. We specify essential datasets to apply this framework to other mountain ecosystems.

Polycyclic aromatic hydrocarbons (PAHs) in soils of an industrial area in semi-arid Uzbekistan: spatial distribution, relationship with trace metals and risk assessment.

The concentrations, composition patterns, transport and fate of PAHs in semi-arid and arid soils such as in Central Asia are not well known. Such knowledge is required to manage the risk posed by these toxic chemicals to humans and ecosystems in these regions. To fill this knowledge gap, we determined the concentrations of 21 parent PAHs, 4,5-methylenephenanthrene, 6 alkylated PAHs, and biphenyl in soils from 11 sampling locations (0-10, 10-20 cm soil depths) along a 20-km transect downwind from the Almalyk metal mining and metallurgical industrial complex (Almalyk MMC), Uzbekistan. The concentrations of Σ29 PAHs and Σ16 US-EPA PAHs were 41-2670 ng g-1 and 29-1940 ng g-1, respectively. The highest concentration of Σ29 PAHs occurred in the immediate vicinity of the copper smelting factory of the Almalyk MMC. The concentrations in topsoil decreased substantially to a value of ≤ 200 ng g-1 (considered as background concentration) at ≥ 2 km away from the factory. Low molecular weight PAHs dominated the PAH mixtures at less contaminated sites and high molecular weight PAHs at the most contaminated site. The concentration of Σ16 US-EPA PAHs did not exceed the precautionary values set by the soil quality guidelines of, e.g., Switzerland and Germany. Similarly, the benzo[a]pyrene equivalent concentration in soils near the Almalyk MMC did not exceed the value set by the Canadian guidelines for the protection of humans from carcinogenic PAHs in soils. Consequently, the cancer risk due to exposure to PAHs in these soils can be considered as low.

Total organic carbon concentrations in ecosystem solutions of a remote tropical montane forest respond to global environmental change.

The response of organic carbon (C) concentrations in ecosystem solutions to environmental change affects the release of dissolved organic matter (DOM) from forests to surface and groundwaters. We determined the total organic C (TOC) concentrations (filtered <1-7 µm) and the ratios of TOC/dissolved organic nitrogen (DON) concentrations, electrical conductivity (EC), and pH in all major ecosystem solutions of a tropical montane forest from 1998 to 2013. The forest was located on the rim of the Amazon basin in Ecuador and experienced increasing numbers of days with >25°C, decreasing soil moisture, and rising nitrogen (N) deposition from the atmosphere during the study period. In rainfall, throughfall, mineral soil solutions (at the 0.15- and 0.30-m depths), and streamflow, TOC concentrations and fluxes decreased significantly from 1998 to 2013, while they increased in stemflow. TOC/DON ratios decreased significantly in rainfall, throughfall, soil solution at the 0.15-m depth, and streamflow. Based on Δ14 C values, the TOC in rainfall and mineral soil solutions was 1 year old and that of litter leachate was 10 years old. The pH in litter leachate decreased with time, that in mineral soil solutions increased, while those in the other ecosystem solutions did not change. Thus, reduced TOC solubility because of lower pH values cannot explain the negative trends in TOC concentrations in most ecosystem solutions. The increasing TOC concentrations and EC in stemflow pointed at an increased leaching of TOC and other ions from the bark. Our results suggest an accelerated degradation of DOM, particularly of young DOM, associated with the production of N-rich compounds simultaneously to changing climatic conditions and increasing N availability. Thus, environmental change increased the CO2 release to the atmosphere but reduced DOM export to surface and groundwater.

Accounting for multiple ecosystem services in a simulation of land-use decisions: Does it reduce tropical deforestation?

Conversion of tropical forests is among the primary causes of global environmental change. The loss of their important environmental services has prompted calls to integrate ecosystem services (ES) in addition to socio-economic objectives in decision-making. To test the effect of accounting for both ES and socio-economic objectives in land-use decisions, we develop a new dynamic approach to model deforestation scenarios for tropical mountain forests. We integrate multi-objective optimization of land allocation with an innovative approach to consider uncertainty spaces for each objective. These uncertainty spaces account for potential variability among decision-makers, who may have different expectations about the future. When optimizing only socio-economic objectives, the model continues the past trend in deforestation (1975-2015) in the projected land-use allocation (2015-2070). Based on indicators for biomass production, carbon storage, climate and water regulation, and soil quality, we show that considering multiple ES in addition to the socio-economic objectives has heterogeneous effects on land-use allocation. It saves some natural forest if the natural forest share is below 38%, and can stop deforestation once the natural forest share drops below 10%. For landscapes with high shares of forest (38%-80% in our study), accounting for multiple ES under high uncertainty of their indicators may, however, accelerate deforestation. For such multifunctional landscapes, two main effects prevail: (a) accelerated expansion of diversified non-natural areas to elevate the levels of the indicators and (b) increased landscape diversification to maintain multiple ES, reducing the proportion of natural forest. Only when accounting for vascular plant species richness as an explicit objective in the optimization, deforestation was consistently reduced. Aiming for multifunctional landscapes may therefore conflict with the aim of reducing deforestation, which we can quantify here for the first time. Our findings are relevant for identifying types of landscapes where this conflict may arise and to better align respective policies.

Plant diversity influenced gross nitrogen mineralization, microbial ammonium consumption and gross inorganic N immobilization in a grassland experiment.

Gross rates of nitrogen (N) turnover inform about the total N release and consumption. We investigated how plant diversity affects gross N mineralization, microbial ammonium (NH4+) consumption and gross inorganic N immobilization in grasslands via isotopic pool dilution. The field experiment included 74 plots with 1-16 plant species and 1-4 plant functional groups (legumes, grasses, tall herbs, small herbs). We determined soil pH, shoot height, root, shoot and microbial biomass, and C and N concentrations in soil, microbial biomass, roots and shoots. Structural equation modeling (SEM) showed that increasing plant species richness significantly decreased gross N mineralization and microbial NH4+ consumption rates via increased root C:N ratios. Root C:N ratios increased because of the replacement of legumes (low C:N ratios) by small herbs (high C:N ratios) and an increasing shoot height, which was positively related with root C:N ratios, with increasing species richness. However, in our SEM remained an unexplained direct negative path from species richness to both N turnover rates. The presence of legumes increased gross N mineralization, microbial NH4+ consumption and gross inorganic N immobilization rates likely because of improved N supply by N2 fixation. The positive effect of small herbs on microbial NH4+ consumption and gross inorganic N immobilization could be attributed to their increased rhizodeposition, stimulating microbial growth. Our results demonstrate that increasing root C:N ratios with increasing species richness slow down the N cycle but also that there must be additional, still unidentified processes behind the species richness effect potentially including changed microbial community composition.

The Fate of Zn in Agricultural Soils: A Stable Isotope Approach to Anthropogenic Impact, Soil Formation, and Soil-Plant Cycling.

The supplementation of Zn to farm animal feed and the excretion via manure leads to an unintended Zn input to agricultural systems, which might compromise the long-term soil fertility. The Zn fluxes at three grassland sites in Switzerland were determined by a detailed analysis of relevant inputs (atmospheric deposition, manure, weathering) and outputs (seepage water, biomass harvest) during one hydrological year. The most important Zn input occurred through animal manure (1076-1857 g ha-1 yr-1) and Zn mass balances revealed net Zn accumulations (456-1478 g ha-1 yr-1). We used Zn stable isotopes to assess the importance of anthropogenic impacts and natural long-term processes on the Zn distribution in soils. Soil-plant cycling and parent material weathering were identified as the most important processes, over the entire period of soil formation (13 700 years), whereas the soil pH strongly affected the direction of Zn isotopic fractionation. Recent anthropogenic inputs of Zn only had a smaller influence compared to the natural processes of the past 13 700 years. However, this will probably change in the future, as Zn stocks in the 0-20 cm layer will increase by 22-68% in the next 100 years, if Zn inputs remain on the same level as today.