Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

Performance of the WRF model to simulate the seasonal and interannual variability of hydrometeorological variables in East Africa: a case study for the Tana River basin in Kenya

This study investigates the ability of the regional climate model Weather Research and Forecasting (WRF) in simulating the seasonal and interannual variability of hydrometeorological variables in the Tana River basin (TRB) in Kenya, East Africa. The impact of two different land use classifications, i.e., the Moderate Resolution Imaging Spectroradiometer (MODIS) and the US Geological Survey (USGS) at two horizontal resolutions (50 and 25 km) is investigated. Simulated precipitation and temperature for the period 2011–2014 are compared with Tropical Rainfall Measuring Mission (TRMM), Climate Research Unit (CRU), and station data. The ability of Tropical Rainfall Measuring Mission (TRMM) and Climate Research Unit (CRU) data in reproducing in situ observation in the TRB is analyzed. All considered WRF simulations capture well the annual as well as the interannual and spatial distribution of precipitation in the TRB according to station data and the TRMM estimates. Our results demonstrate that the increase of horizontal resolution from 50 to 25 km, together with the use of the MODIS land use classification, significantly improves the precipitation results. In the case of temperature, spatial patterns and seasonal cycle are well reproduced, although there is a systematic cold bias with respect to both station and CRU data. Our results contribute to the identification of suitable and regionally adapted regional climate models (RCMs) for East Africa.

     

The relative importance of land use and climatic change in Alpine catchments

Carbon storage and catchment hydrology are influenced both by land use changes and climatic changes, but there are few studies addressing both responses under both driving forces. We investigated the relative importance of climate change vs. land use change for four Alpine catchments using the LPJ-GUESS model. Two scenarios of grassland management were calibrated based on the more detailed model PROGRASS. The simulations until 2100 show that only reforestation could lead to an increase of carbon storage under climatic change, whereby a cessation of carbon accumulation occurred in all catchments after 2050. The initial increase in carbon storage was attributable mainly to forest re-growth on abandoned land, whereas the stagnation and decline in the second half of the century was mainly driven by climate change. If land was used more intensively, i.e. as grassland, litter input to the soil decreased due to harvesting, resulting in a decline of soil carbon storage (1.2−2.9 kg C m^–2) that was larger than the climate-induced change (0.8–1.4 kg C m⁻²). Land use change influenced transpiration both directly and in interaction with climate change. The response of forested catchments diverged with climatic change (11–40 mm increase in AET), reflecting the differences in forest age, topography and water holding capacity within and between catchments. For grass-dominated catchments, however, transpiration responded in a similar manner to climate change (light management: 23–32 mm AET decrease, heavy management: 29–44 mm AET decrease), likely because grassroots are concentrated in the uppermost soil layers. Both the water and the carbon cycle were more strongly influenced by land use compared to climatic changes, as land use had not only a direct effect on carbon storage and transpiration, but also an indirect effect by modifying the climate change response of transpiration and carbon flux in the catchments. For the carbon cycle, climate change led to a cessation of the catchment response (sink/source strength is limited), whereas for the water cycle, the effect of land use change remains evident throughout the simulation period (changes in evapotranspiration do not attenuate). Thus we conclude that management will have a large potential to influence the carbon and water cycle, which needs to be considered in management planning as well as in climate and hydrological modelling.     

Biomonitoring of Atmospheric Heavy Metal Deposition by Mosses in the Vicinity of Industrial Sites

At four industrial regions, heavy metal concentrations and calculated depositions were investigated by sampling and analysing mosses. In each region, a special spatial pattern of heavy metal concentrations was detected, reflecting the industrial processes. Metals most likely originating from the industrial sites showed an exponential decrease of concentrations and depositions with increasing distance from the pollution source. The exponential deposition pattern was in some cases modified by a series of natural factors, like the main direction of winds or orographic conditions. The distance at which deposition dropped to background values was up to 20 km. Beside the fact that the moss-metho is a useful tool for deposition measurement in the vicinity of stationary sources, some improvements for using this method are discussed, highlighting factors such as a proper calculation of deposition from concentrations, or the better knowledge of correlations between heavy metal concentrations in mosses and effects on human health.     

Developing country perspectives on ‘mitigation actions’, ‘NAMAs’, and ‘LCDS’

The MAPS programme, which seeks to deepen mitigation ambition in developing countries, is engaged in exploring the concepts of Nationally Appropriate Mitigation Actions (NAMAs) and Low Carbon Development Strategies (LCDS) from a developing country perspective. Here, climate mitigation practitioners in six developing countries were surveyed for their understanding of these concepts (anonymous, personal communications with climate mitigation practitioners in Argentina, Brazil, Chile, Colombia, India, and South Africa). It is found that there is much scope for clarity and conceptual elaboration in this policy space. NAMAs are largely interpreted as mitigation activities packaged for submission to the United Nations Framework Convention on Climate Change (UNFCCC) registry, but are not held to constitute the full set of mitigation activity in a developing country. New terminology may be needed to describe this broader set. A tighter interpretation of LCDS to distinguish between a strategic or coordinating policy action may be useful. Other themes arising include the way ‘national appropriateness’ is reflected in the concepts, and the role of international policy in deepening mitigation action in developing countries.     

Current approaches to MRV in South Africa: a scoping study

It is shown that there are MRV-related activities underway in South Africa, particularly focusing on measuring electricity consumption and monitoring GHG emissions. Yet currently many of these activities happen in parallel systems within multi-polar governance structures. A bottom-up perspective of MRV in South Africa, informed by interviews, workshops, desktop research, and stakeholder consultations, is provided and the systems, data, methodologies, and the institutional environment relevant to a South African MRV system are examined. The development of the local monitoring and evaluation system, and its relevance within the international MRV context, is also discussed. Some recommendations are made: most importantly, there is a need for a coherent approach to be developed, one that is coordinated by government and built on existing MRV systems.     

A Review of Forest Gap Models

Forest gap models, initially conceived in 1969 as a special case of individual-tree based models, have become widely popular among forest ecologists for addressing a large number of applied research questions, including the impacts of global change on long-term dynamics of forest structure, biomass, and composition. However, they have been strongly criticized for a number of weaknesses inherent in the original model structure. In this paper, I review the fundamental assumptions underlying forest gap models, the structure of the parent model JABOWA, and examine these criticisms in the context of the many alternative formulations that have been developed over the past 30 years.Four assumptions originally underlie gap models: (1) The forest is abstracted as a composite of many small patches of land, where each can have a different age and successional stage; (2) patches are horizontally homogeneous, i.e., tree position within a patch is not considered; (3) the leaves of each tree are located in an indefinitely thin layer (disk) at the top of the stem; and (4) successional processes are described on each patch separately, i.e., there are no interactions between patches. These simplifications made it possible to consider mixed-species, mixed-age forests, which had been difficult previously mainly because of computing limitations.The structure of JABOWA is analysed in terms of the functional relationships used for formulating the processes of tree establishment, growth, and mortality. It is concluded that JABOWA contains a number of unrealistic assumptions that have not been questioned strongly to date. At the same time, some aspects of JABOWA that were criticized strongly in the past years are internally consistent given the objectives of this specific model.A wide variety of formulations for growth processes, establishment, and mortality factors have been developed in gap models over the past 30 years, and modern gap models include more robust parameterizations of environmental influences on tree growth and population dynamics as compared to JABOWA. Approaches taken in more recent models that led to the relaxation of one or several of the four basic assumptions are discussed. It is found that the original assumptions often have been replaced by alternatives; however, no systematic analysis of the behavioral effects of these conceptual changes has been attempted to date.The feasibility of including more physiological detail (instead of using relatively simple parameterizations) in forest gap models is discussed, and it is concluded that we often lack the data base to implement such approaches for more than a few commercially important tree species. Hence, it is important to find a compromise between using simplistic parameterizations and expanding gap models with physiology-based functions and parameters that are difficult to estimate. While the modeling of tree growth has received a lot of attention over the past years, much less effort has been spent on improving the formulations of tree establishment and mortality, although these processes are likely to be just as sensitive to global change as tree growth itself. Finally, model validation issues are discussed, and it is found that there is no single data source that can reliably be used for evaluating the behavior of forest gap models; instead, I propose a combination of sensitivity analyses, qualitative examinations of process formulations, and quantitative tests of gap models or selected submodels against various kinds of empirical data to evaluate the usefulness of these models for assessing their utility for predicting the impacts of global change on long-term forest dynamics.     

Hydrothermal alteration and tectonic evolution of an intermediate- to fast-spreading back-arc oceanic crust: Late Ordovician Solund-Stavfjord ophiolite, western Norway

Abstract The Solund‐Stavfjord ophiolite complex (SSOC) in western Norway represents a remnant of the Late Ordovician oceanic lithosphere, which developed in an intermediate‐ to fast‐spreading Caledonian back‐arc basin. The internal architecture and magmatic features of its crustal component suggest that the SSOC has a complex, multistage sea floor spreading history in a supra‐subduction zone environment. The youngest crustal section associated with the propagating rift tectonics consists of a relatively complete ophiolite pseudostratigraphy, including basaltic volcanic rocks, a transition zone between the sheeted dyke complex and the extrusive sequence, sheeted dykes, and high‐level isotropic gabbros. Large‐scale variations in major and trace element distributions indicate significant remobilization far beyond that which would result from magmatic processes, as a result of the hydrothermal alteration of crustal rocks. Whereas K₂O is strongly enriched in volcanic rocks of the extrusive sequence, Cu and Zn show the largest enrichment in the dyke complex near the dyke–volcanic transition zone or within this transition zone. The δ¹⁸O values of the whole‐rock samples show a general depletion structurally downwards in the ophiolite, with the largest and smallest variations observed in volcanic rocks and the transition zone, respectively. δ¹⁸O values of epidote–quartz mineral pairs indicate 260–290°C for volcanic rocks, 420°C for the transition zone, 280–345°C for the sheeted dyke complex and 290–475°C for the gabbros. The ⁸⁷Sr/⁸⁶Sr isotope ratios show the widest range and highest values in the extrusive rocks (0.70316–0.70495), and generally the lowest values and the narrowest range in the sheeted dyke complex (0.70338–0.70377). The minimum water/rock ratios calculated show the largest variations in volcanic rocks and gabbros (approximately 0–14), and generally the lowest values and range in the sheeted dyke complex (approximately 1–3). The δD values of epidote (?1 to ?12‰), together with the δ¹⁸O calculated for Ordovician seawater, are similar to those of present‐day seawater. Volcanic rocks experienced both cold and warm water circulation, resulting in the observed K₂O‐enrichment and the largest scatter in the δ¹⁸O values. As a result of metal leaching in the hot reaction zone above a magma chamber, Zn is strongly depleted in the gabbros but enriched in the sheeted dyke complex because of precipitation from upwelling of discharged hydrothermal fluids. The present study demonstrates that the near intact effect of ocean floor hydrothermal activity is preserved in the upper part of the SSOC crust, despite the influence of regional lower greenschist facies metamorphism.