Organic matter (OM) composition and dynamic in subsoils is thought to be significantly different from those in surface soils. This has been suggested by increasing apparent 14C ages of bulk soil OM with depth suggesting that the amount of fresh, more easily degradable components is declining. Compositional changes have been inferred from declining ä13C values and C/N ratios indicative for stronger OM transformation. Beside these bulk OM data more specific results on OM composition and preservation mechanisms are very limited but modelling studies and results from incubation experiments suggest the presence and mineralization of younger, 'reactive carbon pool in subsoils. Less refractory OM components may be protected against degradation by interaction with soil mineral particles and within aggregates as suggested by the very limited number of more specific OM analysis e.g., identification of organic compound in soil fractions. The objective of this project is to characterize the composition, transformation, stabilization and bioavailability of OM in subsurface horizons on the molecular level: 1) major sources and compositional changes with depth will be identified by analysis of different lipid compound classes in surface and subsoil horizons, 2) the origin and stabilization of 'reactive OM will be revealed by lipid distributions and 14C values of soil fractions and of selected plant-specific lipids, and 3) organic substrates metabolized by microbial communities in subsoils are identified by distributional and 14C analysis of microbial membrane lipids. Besides detailed analyses of three soil profiles at the subsoil observatory site (Grinderwald), information on regional variability will be gained from analyses of soil profiles at sites with different parent material.
During microbial turnover of organic chemicals in soil, non-extractable residues (NER) are formed frequently. Studies on NER formation usually performed with radioisotope labelled tracer compounds are limited to localisation and quantitative analyses but their chemical composition is left unknown. Recently, we could show for 2,4-dichlorophenoxyacetic acid and ibuprofen that during microbial turnover in soil nearly all NER were derived from microbial biomass, since degrading bacteria use the pollutant carbon for their biomass synthesis. Their cell debris is subsequently stabilised within soil organic matter (SOM) forming biogenic NER (bioNER). It is still unknown whether bioNER are also formed during biodegradation of other, structurally different compound classes of organic contaminants. Therefore, agricultural soil will be incubated with labelled compounds of five classes of commonly used and emerging pesticides: organophosphate, phenylurea, triazinone, benzothiadiazine and aryloxyphenoxypropionic acid. The fate of the label will be monitored in both living and non-living SOM pools and the formation of bioNER will be quantified for each compound over extended periods of time. In addition, soil samples from long-term lysimeter studies with 14C-labelled pesticide residues (e.g. triazine, benzothiazole and phenoxypropionic acid group) will be also analysed for bioNER formation. The results will be summarised to identify the metabolic conditions of microorganisms needed for bioNER formation and to develop an extended concept of risk assessment including bioNER formation in soils.
Organotin and especially butyltin compounds are used for a variety of applications, e.g. as biocides, stabilizers, catalysts and intermediates in chemical syntheses. Tributyltin (TBT) compounds exhibit the greatest toxicity of all organotins and have even been characterized as one of the most toxic groups of xenobiotics ever produced and deliberately introduced into the environment. TBT is not only used as an active biocidal compound in antifouling paints, which are designed to prevent marine and freshwater biota from settlement on ship hulls, harbour and offshore installations, but also as a biocide in wood preservatives, textiles, dispersion paints and agricultural pesticides. Additionally, it occurs as a by-product of mono- (MBT) and dibutyltin (DBT) compounds, which are used as UV stabilizer in many plastics and for other applications. Triphenyltin (TPT) compounds are also used as the active biocide in antifouling paints outside Europe and furthermore as an agricultural fungicide since the early 1960s to combat a range of fungal diseases in various crops, particularly potato blight, leaf spot and powdery mildew on sugar beet, peanuts and celery, other fungi on hop, brown rust on beans, grey moulds on onions, rice blast and coffee leaf rust. Although the use of TBT and TPT was regulated in many countries world-wide from restrictions for certain applications to a total ban, these compounds are still present in the environment. In the early 1970s the impact of TBT on nontarget organisms became apparent. Among the broad variety of malformations caused by TBT in aquatic animals, molluscs have been found to be an extremely sensitive group of invertebrates and no other pathological condition produced by TBT at relative low concentrations rivals that of the imposex phenomenon in prosobranch gastropods speaking in terms of sensitivity. TBT induces imposex in marine prosobranchs at concentrations as low as 0,5 ng TBT-Sn/L. Since 1993, for the littorinid snail Littorina littorea a second virilisation phenomenon, termed intersex, is known. In female specimens affected by intersex the pallial oviduct is transformed of towards a male morphology with a final supplanting of female organs by the corresponding male formations. Imposex and intersex are morphological alterations caused by a chronic exposure to ultra-trace concentrations of TBT. A biological effect monitoring offers the possibility to determine the degree of contamination with organotin compounds in the aquatic environment and especially in coastal waters without using any expensive analytical methods. Furthermore, the biological effect monitoring allows an assessment of the existing TBT pollution on the basis of biological effects. Such results are normally more relevant for the ecosystem than pure analytical data. usw.
For surface soils, the mechanisms controlling soil organic C turnover have been thoroughly investigated. The database on subsoil C dynamics, however, is scarce, although greater than 50 percent of SOC stocks are stored in deeper soil horizons. The transfer of results obtained from surface soil studies to deeper soil horizons is limited, because soil organic matter (SOM) in deeper soil layers is exposed to contrasting environmental conditions (e.g. more constant temperature and moisture regime, higher CO2 and lower O2 concentrations, increasing N and P limitation to C mineralization with soil depth) and differs in composition compared to SOM of the surface layer, which in turn entails differences in its decomposition. For a quantitative analysis of subsoil SOC dynamics, it is necessary to trace the origins of the soil organic compounds and the pathways of their transformations. Since SOM is composed of various C pools which turn over on different time scales, from hours to millennia, bulk measurements do not reflect the response of specific pools to both transient and long-term change and may significantly underestimate CO2 fluxes. More detailed information can be gained from the fractionation of subsoil SOM into different functional pools in combination with the use of stable and radioactive isotopes. Additionally, soil-respired CO2 isotopic signatures can be used to understand the role of environmental factors on the rate of SOM decomposition and the magnitude and source of CO2 fluxes. The aims of this study are to (i) determine CO2 production and subsoil C mineralization in situ, (ii) investigate the vertical distribution and origin of CO2 in the soil profile using 14CO2 and 13CO2 analyses in the Grinderwald, and to (iii) determine the effect of environmental controls (temperature, oxygen) on subsoil C turnover. We hypothesize that in-situ CO2 production in subsoils is mainly controlled by root distribution and activity and that CO2 produced in deeper soil depth derives to a large part from the mineralization of fresh root derived C inputs. Further, we hypothesize that a large part of the subsoil C is potentially degradable, but is mineralized slower compared with the surface soil due to possible temperature or oxygen limitation.
In order to understand the interlinked problems in the Nexus (Latin = connection, linkage, interrelation) of water, energy and food security, close cooperation between scientists and practitioners from different fields is necessary. The present and future challenge of a reliable supply with water, energy and food is an example, where isolated considerations do not lead to viable solutions. Sustainable action and meaningful research in these highly interconnected fields require a holistic and comprehensive perspective and a new approach. In this sense, a collaborative research structure with a holistic view on the Nexus of Water, Energy and Food security was established in 2013 at the Cologne University of Applied Sciences. The project bundles some of the research efforts of 11 professors from different faculties and institutes. The researchers jointly work on initiating new cooperation projects with partners from industry, academia and civil society. Together they aim at exploring new technologies and applying new approaches to solve major issues of efficiency and sustainability in resource use.
Due to the often practised uncontrolled disposal into the environment, olive oil production wastewater (OPWW) is presently a serious environmental problem in Palestine and Israel. The objectives of this interdisciplinary trilateral research project are (i) to understand the mechanisms of influence of the olive oil production wastewater on soil wettability, water storage, interaction with organic agrochemicals and pollutants; (ii) monitor short-term and long-term effects of OPWW land application in model laboratory and field experiments; (iii) identify the components responsible for unwanted changes in soil properties and (iv) analyse the mechanisms of association of OPWW OM with soil, the interplay between climatic conditions, pH, presence of multivalent cations and the resulting effects of land application. Laboratory incubation experiments, field experiments and new experiments to study heat-induced water repellency will be conducted to identify responsible OPWW compounds and mechanisms of interaction. Samples from field experiments and laboratory experiments are investigated using 3D excitation-emission fluorescence spectroscopy, thermogravimetry-differential thermal analysis-mass spectrometry (TGA-DSC-MS), LC-MS and GC-MS analyses. We will combine thermal decomposition profiles from OPWW and OPWW-treated soils in dependence of the incubation status using TGA-DSC-MS, contact angle measurements, sorption isotherms and the newly developed time dependent sessile drop method (TISED). The resulting process understanding will open a perspective for OPWW wastewater reuse in small-scale and family-scale olive oil production busi-nesses in the Mediterranean area and will further help to comprehend the until now not fully un-ravelled effects of wastewater irrigation on soil water repellency.
Chlorinated ethylenes are prevalent groundwater contaminants. Numerous studies have addressed the mechanism of their reductive dehalogenation during biodegradation and reaction with zero-valent iron. However, despite insight with purified enzymes and well-characterized chemical model systems, conclusive evidence has been missing that the same mechanisms do indeed prevail in real-world transformations. While dual kinetic isotope effect measurements can provide such lines of evidence, until now this approach has not been possible for chlorinated ethylenes because an adequate method for continuous flow compound specific chlorine isotope analysis has been missing. This study attempts to close this prevalent research gap by a combination of two complementary approaches. (1) A novel analytical method to measure isotope effects for carbon and chlorine. (2) A carefully chosen set of well-defined model reactants representing distinct dehalogenation mechanisms believed to be important in real-world systems. Isotope trends observed in biotic and abiotic environmental dehalogenation will be compared to these model reactions, and the respective mechanistic hypotheses will be confirmed or discarded. With this hypothesis-driven approach it is our goal to elucidate for the first timdehalogenation reactions.
Trassen aller Kreisstraßen mit Bezeichnung im Landkreis Leer
Comprehension of belowground competition between plant species is a central part in understanding the complex interactions in intercropped agricultural systems, between crops and weeds as well as in natural ecosystems. So far, no simple and rapid method for species discrimination of roots in the soil exists. We will be developing a method for root discrimination of various species based on Fourier Transform Infrared (FTIR)-Attenuated Total Reflexion (ATR) Spectroscopy and expanding its application to the field. The absorbance patterns of FTIR-ATR spectra represent the chemical sample composition like an individual fingerprint. By means of multivariate methods, spectra will be grouped according to spectral and chemical similarity in order to achieve species discrimination. We will investigate pea and oat roots as well as maize and barnyard grass roots using various cultivars/proveniences grown in the greenhouse. Pea and oat are recommendable species for intercropping to achieve superior grain and protein yields in an environmentally sustainable manner. To evaluate the effects of intercropping on root distribution in the field, root segments will be measured directly at the soil profile wall using a mobile FTIR spectrometer. By extracting the main root compounds (lipids, proteins, carbohydrates) and recording their FTIR-ATR spectra as references, we will elucidate the chemical basis of species-specific differences.
The aim of P2 within the Research Unit 'The Forgotten Part of Carbon Cycling: Organic Matter Storage and Turnover in Subsoils (SUBSOM)' is to contribute to the understanding of the different sources and stabilization processes of subsoil organic matter. This will be achieved by the analysis of the soil organic matter composition in topsoil versus subsoil by 13C NMR spectroscopy in bulk soils as well as organo-mineral associations. This will be done on a number of soil profiles differing in parent material and mineralogy and therefore also in the relevance of organo-mineral associations for subsoil C stabilization. In addition, a specific sampling approach will allow to differentiate three zones associated with the dominating effect of (1) leaching of DOC (the 'bulk soil' between trees), (2) root litter decomposition (the 'root-affected zone'), and (3) direct rhizodeposition of root exudates (the 'rhizosphere' sensu strictu). The contribution of above-ground versus below-ground litter is differentiated by the analysis of cutin and suberin biomarkers. Organic matter derived from microbial sources will be identified by the microbial signature of polysaccharides in the subsoil through the analysis of neutral sugars and amino sugars. Organo-mineral associations will be further characterized by N2-BET analyses to delineate the coverage of the mineral phase with organic matter. With these analyses and our specific analytical expertise at the submicron scale (nanoSIMS) we will participate in selected joint experiments of the research unit.
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