Showing papers by "Geological Survey of Denmark and Greenland published in 2010"

Devonian rise in atmospheric oxygen correlated to the radiations of terrestrial plants and large predatory fish

Abstract: The evolution of Earth’s biota is intimately linked to the oxygenation of the oceans and atmosphere. We use the isotopic composition and concentration of molybdenum (Mo) in sedimentary rocks to explore this relationship. Our results indicate two episodes of global ocean oxygenation. The first coincides with the emergence of the Ediacaran fauna, including large, motile bilaterian animals, ca. 550–560 million year ago (Ma), reinforcing previous geochemical indications that Earth surface oxygenation facilitated this radiation. The second, perhaps larger, oxygenation took place around 400 Ma, well after the initial rise of animals and, therefore, suggesting that early metazoans evolved in a relatively low oxygen environment. This later oxygenation correlates with the diversification of vascular plants, which likely contributed to increased oxygenation through the enhanced burial of organic carbon in sediments. It also correlates with a pronounced radiation of large predatory fish, animals with high oxygen demand. We thereby couple the redox history of the atmosphere and oceans to major events in animal evolution.

Deep-Sea Biodiversity in the Mediterranean Sea: The Known, the Unknown, and the Unknowable

Abstract: Deep-sea ecosystems represent the largest biome of the global biosphere, but knowledge of their biodiversity is still scant. The Mediterranean basin has been proposed as a hot spot of terrestrial and coastal marine biodiversity but has been supposed to be impoverished of deep-sea species richness. We summarized all available information on benthic biodiversity (Prokaryotes, Foraminifera, Meiofauna, Macrofauna, and Megafauna) in different deepsea ecosystems of the Mediterranean Sea (200 to more than 4,000 m depth), including open slopes, deep basins, canyons, cold seeps, seamounts, deep-water corals and deep-hypersaline anoxic basins and analyzed overall longitudinal and bathymetric patterns. We show that in contrast to what was expected from the sharp decrease in organic carbon fluxes and reduced faunal abundance, the deep-sea biodiversity of both the eastern and the western basins of the Mediterranean Sea is similarly high. All of the biodiversity components, except Bacteria and Archaea, displayed a decreasing pattern with increasing water depth, but to a different extent for each component. Unlike patterns observed for faunal abundance, highest negative values of the slopes of the biodiversity patterns were observed for Meiofauna, followed by Macrofauna and Megafauna. Comparison of the biodiversity associated with open slopes, deep basins, canyons, and deep-water corals showed that the deep basins were the least diverse. Rarefaction curves allowed us to estimate the expected number of species for each benthic component in different bathymetric ranges. A large fraction of exclusive species was associated with each specific habitat or ecosystem. Thus, each deep-sea ecosystem contributes significantly to overall biodiversity. From theoretical extrapolations we estimate that the overall deep-sea Mediterranean biodiversity (excluding prokaryotes) reaches approximately 2805 species of which about 66% is still undiscovered. Among the biotic components investigated (Prokaryotes excluded), most of the unknown species are within the phylum Nematoda, followed by Foraminifera, but an important fraction of macrofaunal and megafaunal species also remains unknown. Data reported here provide new insights into the patterns of biodiversity in the deep-sea Mediterranean and new clues for future investigations aimed at identifying the factors controlling and threatening deep-sea biodiversity.

A physically based calving model applied to marine outlet glaciers and implications for the glacier dynamics

Abstract: We present results from numerical ice-flow models that include calving criteria based on penetration of surface and basal crevasses, which in turn is a function of longitudinal strain rates near the glacier front. The position of the calving front is defined as the point where either (1) surface crevasses reach the waterline (model CDw), or (2) surface and basal crevasses penetrate the full thickness of the glacier (model CD). For comparison with previous studies, results are also presented for a height-above-buoyancy calving model. Qualitatively, both models CDw and CD produce similar behaviour. Unlike previous models for calving, the new calving criteria are applicable to both grounded termini and floating ice shelves and tongues. The numerical ice-flow model is applied to an idealized geometry characteristic of marine outlet glaciers. Results indicate that grounding-line dynamics are less sensitive to basal topography than previously suggested. Stable grounding-line positions can be obtained even on a reverse bed slope with or without floating termini. The proposed calving criteria also allow calving losses to be linked to surface melt and therefore climate. In contrast to previous studies in which calving rate or position of the terminus is linked to local water depth, the new calving criterion is able to produce seasonal cycles of retreat and advance as observed for Greenland marine outlet glaciers. The contrasting dynamical behaviour and stability found for different calving models suggests that a realistic parameterization for the process of calving is crucial for any predictions of marine outlet glacier change.

Evaluation of remote-sensing-based rainfall products through predictive capability in hydrological runoff modelling.

Abstract: The emergence of regional and global satellite-based rainfall products with high spatial and temporal resolution has opened up new large-scale hydrological applications in data-sparse or ungauged catchments. Particularly, distributed hydrological models can benefit from the good spatial coverage and distributed nature of satellite-based rainfall estimates (SRFE). In this study, five SRFEs with temporal resolution of 24 h and spatial resolution between 8 and 27 km have been evaluated through their predictive capability in a distributed hydrological model of the Senegal River basin in West Africa. The main advantage of this evaluation methodology is the integration of the rainfall model input in time and space when evaluated at the sub-catchment scale. An initial data analysis revealed significant biases in the SRFE products and large variations in rainfall amounts between SRFEs, although the spatial patterns were similar. The results showed that the Climate Prediction Center/Famine Early Warning System (CPC-FEWS) and cold cloud duration (CCD) products, which are partly based on rain gauge data and produced specifically for the African continent, performed better in the modelling context than the global SRFEs, Climate Prediction Center MORPHing technique (CMORPH), Tropical Rainfall Measuring Mission (TRMM) and Precipitation Estimation from Remotely Sensed Information using Artificial Neural Networks (PERSIANN). The best performing SRFE, CPC-FEWS, produced good results with values of R2NS between 0·84 and 0·87 after bias correction and model recalibration. This was comparable to model simulations based on traditional rain gauge data. The study highlights the need for input specific calibration of hydrological models, since major differences were observed in model performances even when all SRFEs were scaled to the same mean rainfall amounts. This is mainly attributed to differences in temporal dynamics between products. Copyright © 2009 John Wiley & Sons, Ltd.

Système Hydrologique Europeén (SHE): review and perspectives after 30 years development in distributed physically-based hydrological modelling

Abstract: The European Hydrological System (or Systeme Hydrologique Europeen , SHE) was initiated as a collaborative venture in 1976 between the Danish Hydraulic Institute (Denmark), Institute of Hydrology (UK) and SOGREAH (France). The present paper reviews the development history of the SHE and discusses the practical and scientific difficulties encountered during the different stages of the development. Comparison is made with eight other well-known model codes with respect to development stage and code dissemination among researchers and practitioners. Finally, the scientific developments and disputes on physically-based distributed modelling are discussed and the future perspectives outlined. The SHE venture has resulted in significant contributions to hydrological science, both in terms of model codes and new scientific insight. The fundamental scientific problems related to the inability to incorporate local scale spatial heterogeneity, scaling and uncertainty that were formulated are fundamentally still unresolved. Thus, in spite of the original visions, the hydrological community has not yet witnessed a model that in a universal sense (i.e. at all scales and for all internal variables) simulates accurate results for the right reasons. Instead, much of the scientific progress achieved during the recent years has dealt with how to live with these recognized problems.

The development of the Amazonian mega-wetland (Miocene; Brazil, Colombia, Peru, Bolivia)

Abstract: The scenery of Western Amazonia once consisted of fluvial systems that originated on the Amazonian Craton and were directed towards the sub-Andean zone and the Caribbean. In the course of the Early Miocene these fluvial systems were largely replaced by lakes, swamps, tidal channels and marginal marine embayments, forming a mega-wetland. In this chapter we will review the characteristics of this mega-wetland and its different phases of development. These aquatic environments hosted a diverse fauna whereas the shores of these systems were fringed by palm swamps, and a diverse rainforest occurred in the peripheral dry lands. The genesis of this wetland was primarily driven by geological mechanisms such as the Andean uplift, and an increase in accommodation space in the sub-Andean and intracratonic basins. Additionally, high precipitation rates also played an important role in wetland formation. The earliest phase of wetland development is recorded in boreholes drilled in the sub-Andean foreland basins of Peru and Colombia, and in the intracratonic Solimoes Basin of western Brazil. During the latest Oligocene to Early Miocene (~24 to 16 Ma) lacustrine conditions alternated with episodes of Andean and cratonic fluvial drainage as well as marginal marine influence. In Amazonia, marine incursions are intercalated as thin beds in the Middle to Upper Miocene fluvial strata and contain marine and coastal taxa (foraminifera, mangrove pollen). Lacustrine conditions expanded further during the Middle Miocene to early Late Miocene (~16 to 11.3 Ma; Pebas phase). During this period the lake-embayment and swamp systems - fringed by forested lowland - reached their maximum extension. This wetland was subject to marginal marine influence and sustained a large radiation of endemic aquatic invertebrate faunas. During its maximum extent the wetland covered an area of more than 1.5 × 106 km2 - comprising much of the Present western Amazonian lowlands. From the Late Miocene onwards uplift rates in the Eastern Cordillera, Cordillera Real and Cordillera de Merida substantially increased and the Andes became a continuous barrier. This barrier effectively separated lowland Amazonia from Orinoquia and the Magdalena Valley and closed off all lowland connections with the Pacific and the Caribbean. The wetland system became a complex environment where deltaic, estuarine and fluvial environments coexisted. This Late Miocene fluvial-tidal-dominated wetland (~11.3 to 7 Ma, Acre phase) hosted a species-rich vertebrate fauna, but (in contrast to the Pebas phase), the molluscan fauna was species poor and already strongly resembled the modern Amazonian fluvial fauna. This system represents the onset of the transcontinental Amazon River. From 11.3 Ma onwards, sediments of Andean origin reached the Atlantic continental shelf and initiated the build-up of the Amazon Fan.

U–Pb LA-SF-ICP-MS zircon geochronology of the Serbo-Macedonian Massif, Greece: palaeotectonic constraints for Gondwana-derived terranes in the Eastern Mediterranean

Abstract: The Pirgadikia Terrane in northern Greece forms tectonic inliers within the Vardar suture zone bordering the Serbo-Macedonian Massif to the southwest. It comprises Cadomian basement rocks of volcanic-arc origin and very mature quartz-rich metasedimentary rocks. U–Pb laser ablation sector-field inductively-coupled plasma mass spectrometry analyses of detrital zircons from the latter reveal a marked input from a Cadomian–Pan-African source with minor contribution from Mesoproterozoic, Palaeoproterozoic and Archaean sources. The metasedimentary rocks are correlated with Ordovician overlap sequences at the northern margin of Gondwana on the basis of their maturity and zircon age spectra. The Pirgadikia Terrane can be best interpreted as a peri-Gondwana terrane of Avalonian origin, which was situated close to the Cadomian terranes in the Late Neoproterozoic–Early Palaeozoic, very much like the Istanbul Terrane. The second unit investigated is the Vertiskos Terrane, which constitutes the major part of the Serbo-Macedonian Massif in Greece. It comprises predominantly igneous rocks of Silurian age and minor metasedimentary rocks of unknown age and provenance. U–Pb analyses of detrital zircons from a garnetiferous mica schist of the Vertiskos Terrane indicate derivation from 550 to 1,150 Ma-old source rocks with a major Cadomian peak. This, combined with minor input of >1,950 Ma-old zircons and the absence of ages between ca. 1.2 and 1.7 Ga suggests a NW Africa source. The protolith age of the garnetiferous mica schist is presumably Early Ordovician. One sample of garnet-bearing biotite gneiss, interpreted as meta-igneous rock, comprises predominantly subhedral zircons of igneous origin with late Middle Ordovician to Silurian ages. We suggest that the rock association of the Vertiskos Terrane is part of an ancient active-margin succession of the Hun superterrane, comparable to successions of the Austro- and Intra-Alpine Terranes. The new data of this study provide evidence of occurrences of Avalonia- and Armorica-derived terranes in the Eastern Mediterranean and moreover help to clarify palaeogeographic reconstructions for the peri-Gondwana realm in the Early Palaeozoic.

Drivers of metabolism and net heterotrophy in contrasting lakes

Abstract: We investigated the influence of light, nutrients, and organic matter on gross primary production (GPP), ecosystem respiration (R), and net ecosystem production (NEP 5 GPP 2 R) in a dystrophic forest lake and an open eutrophic lake. Forest vegetation reduced incoming irradiance (20%) and wind speed (34%) in dystrophic Gribso, having thermal stratification 1 month longer than in eutrophic Slotsso. While Gribso had nutrient-limited phytoplankton during most of the year, Slotsso only experienced nutrient depletion during algal blooms. Colored dissolved organic matter (CDOM) absorbed most light (average 82%) in dystrophic Gribso, while phytoplankton and other particles absorbed most light (45%) in eutrophic Slotsso. GPP and NEP were positively related to irradiance in both lakes. However, because of higher CDOM absorbance, three times more light was needed to attain autotrophy in Gribso, being net heterotrophic (NEP , 0) for 79% of all days, compared to 59% in Slotsso. This difference vanished when NEP was scaled to light absorption by pigments, although the eutrophic lake maintained a higher photon yield. Metabolic rates varied much more in Slotsso, where higher light and nutrient availability facilitated occasional phytoplankton blooms, while low light and nutrient availability in Gribso dampened temporal variability. Both lakes were annually net heterotrophic with similar annual areal rates (NEP, 214 mol C m22). Net heterotrophy in dystrophic Gribso derives from high import of organic carbon-rich water, while heterotrophy in eutrophic Slotsso is fueled by degradation of sediment pools of organic matter accumulated under previous hypereutrophic conditions, emphasizing the importance of lake history on the contemporary metabolic state.

Spatial and temporal melt variability at Helheim Glacier, East Greenland, and its effect on ice dynamics

Abstract: This is the publisher's version, also available electronically from "http://onlinelibrary.wiley.com".

Lithostratigraphy of the Upper Oligocene - Miocene succession of Denmark

Abstract: This paper presents a revised lithostratigraphic scheme for the uppermost Upper Oligocene – Miocene succession of Denmark. The marine Oligocene Brejning Clay Member is upgraded to formation status and includes the Sydklint Member and the Oksenrade Member (new). The shallow marine and deltaic deposits of mainly Early Miocene age are included in the Ribe Group (new) while the fully marine Middle and Upper Miocene clay-rich deposits are referred to the Made Group (new). The Ribe Group is subdivided into 6 formations: the Vejle Fjord Formation is revised and includes the Skansebakke Member, the Billund Formation (new) includes the Addit and Hvidbjerg Members (new), the Klintinghoved Formation is redefined formally and includes the Koldingfjord Member (new), the Bastrup Formation (new) includes the Resen Member (new), the Vandel Member is a new member in the Arnum Formation (revised), the Odderup Formation is redefined and includes the Stauning Member (new) and the coalbearing Fasterholt Member. The Made Group is subdivided into the Hodde, Ornhoj (new), Gram and Marbaek (new) Formations. Subdivision of the Upper Oligocene – Miocene succession into two groups, the Ribe and Made Groups, is compatible with the North Sea lithostratigraphic framework where they correlate with the upper part of the Hordaland Group and the Nordland Group, respectively. The revised lithostratigraphic framework correlated in three dimensions provides rigorous constraints on the palaeogeographic interpretation of the Late Oligocene – Miocene period. Three major deltaic units (Billund, Bastrup and Odderup Formations) prograded from the north and north-east into the North Sea Basin during the Early – early Middle Miocene. Delta progradation was punctuated by deposition of marine clay and silt associated with minor transgressive events (Vejle Fjord, Klintinghoved and Arnum Formations). During the Middle–Late Miocene, marine depositional conditions dominated (Hodde, Ornhoj and Gram Formations). A fourth and final progadational event (Marbaek Formation) commenced in the latest Tortonian heralding the emergence of present-day Denmark (including the North Sea sector).

Influence of Temperature and Predation on Survival of Salmonella enterica Serovar Typhimurium and Expression of invA in Soil and Manure-Amended Soil

Abstract: The effects of three temperatures (5, 15, and 25 degrees C) on the survival of Salmonella enterica serovar Typhimurium in topsoil were investigated in small microcosms by three different techniques: plate counting, invA gene quantification, and invA mRNA quantification. Differences in survival were related to the effect of protozoan predation. Tetracycline-resistant Salmonella serovar Typhimurium was inoculated into soil and manure-amended soil at 1.5 x 10(8) cells g soil(-1). Population densities were determined by plate counting and by molecular methods and monitored for 42 days. Simultaneous extraction of RNA and DNA, followed by quantitative PCR, was used to investigate invA gene levels and expression. Analysis by these three techniques showed that Salmonella serovar Typhimurium survived better at 5 degrees C. Comparing DNA and CFU levels, significantly higher values were determined by DNA-based techniques. invA mRNA levels showed a fast decrease in activity, with no detectable mRNA after an incubation period of less than 4 days in any of the soil scenarios. A negative correlation was found between Salmonella serovar Typhimurium CFU levels and protozoan most probable numbers, and we propose the role of the predator-prey interaction as a factor to explain the die-off of the introduced strain by both culture- and DNA quantification-based methods. The results indicate that temperature, manure, and protozoan predation are important factors influencing the survival of Salmonella serovar Typhimurium in soil.

Field evaluation of biological enhanced reductive dechlorination of chloroethenes in clayey till.

Abstract: The performance of enhanced reductive dechlorination (ERD) for in situ remediation of cis-1,2-dichloroethene (cDCE) and vinyl chloride in clayey till was investigated in a pilot test. A dilute groundwater solution containing emulsified soybean oil and Dehalococcoides bacteria was injected into a sand-filled hydraulic fracture. Fermentation of the ERD solution caused the establishment of a dechlorinating bioactive zone in the fracture within 1 month of injection. By 148 days, all the cDCE in the fracture was dechlorinated to ethene. Analysis of a clay core from Day 150 indicated that electron donor and fermentation products diffused from the fracture at least 10 cm into clay and that stimulated dechlorination occurred in the clay in the presence of Dehalococcoides (7.9·104 cells g−1). Comparison of chloroethene profiles in the Day 150 core to modeled diffusion profiles indicated degradation occurred in a bioactive zone extending approximately 5 to 6 cm into the clay matrix. These data suggest that a bioact...

Groundwater modeling in integrated water resources management - visions for 2020.

Abstract: Groundwater modeling is undergoing a change from traditional stand-alone studies toward being an integrated part of holistic water resources management procedures. This is illustrated by the development in Denmark, where comprehensive national databases for geologic borehole data, groundwater-related geophysical data, geologic models, as well as a national groundwater-surface water model have been established and integrated to support water management. This has enhanced the benefits of using groundwater models. Based on insight gained from this Danish experience, a scientifically realistic scenario for the use of groundwater modeling in 2020 has been developed, in which groundwater models will be a part of sophisticated databases and modeling systems. The databases and numerical models will be seamlessly integrated, and the tasks of monitoring and modeling will be merged. Numerical models for atmospheric, surface water, and groundwater processes will be coupled in one integrated modeling system that can operate at a wide range of spatial scales. Furthermore, the management systems will be constructed with a focus on building credibility of model and data use among all stakeholders and on facilitating a learning process whereby data and models, as well as stakeholders' understanding of the system, are updated to currently available information. The key scientific challenges for achieving this are (1) developing new methodologies for integration of statistical and qualitative uncertainty; (2) mapping geological heterogeneity and developing scaling methodologies; (3) developing coupled model codes; and (4) developing integrated information systems, including quality assurance and uncertainty information that facilitate active stakeholder involvement and learning.

A Global Measure for Depth of Investigation

Abstract: Depth of investigation (DOI) is a commonly requested parameter in geophysical surveys. For diffusive methods, such as groundbased or airborne EM, there is no specific depth below which there is no information on the resistivity structure, but the question is to what depth the model is most reliable. We present a new robust concept for the calculation of DOI that is valid for any 1D EM geophysical model. The method is based on the actual model output from the inversion and includes the full system response, contrary to assuming e.g. planar waves over a homogeneous halfspace. Equally important, the data noise and the number of data points is integrated in our calculation. Our methodology is based on a recalculated sensitivity (Jacobian) matrix of the final model and it can thus be used on any model type for which a sensitivity matrix can be calculated. Contrary to other sensitivity matrix methods we define a global and absolute threshold value contrary to defining a relative, say 5%, sensitivity limit. The threshold limit will apply to all 1D inverted data and will thus produce comparable numbers of DOI.

The ecology of Pediastrum (Chlorophyceae) in subarctic lakes and their potential as paleobioindicators

Abstract: Subarctic and arctic lakes are the focus of many paleolimnological studies, as they are still among the least impacted lakes by humans. Hence they provide an excellent setting for studies on long-term climatic variability without the overriding effects of direct anthropogenic perturbation. On the other hand, these ecosystems are highly vulnerable to even moderate anthropogenic influence like long-distance airborne transport of nutrients and pollutants. The paleolimnological studies conducted in these areas usually include a multitude of different proxies, but so far only few have used the green algal group of Pediastrum Meyen. These algae, however, preserve well in sediments and can be identified to species level, which lends them potential as a paleo-proxy. In this study we analysed the present Pediastrum assemblages from surface-sediments of 16 subarctic lakes in Finnish Lapland as well as bottom samples from the same sediment cores, which are “spot” samples from the recent past. We found a total of 14 Pediastrum taxa, five of which occurred at moderate to high relative abundances. The majority of the taxa showed distinct relationships to environmental variables measured. Of these, pH and dissolved organic carbon (DOC) explained most of the variance in the distribution of Pediastrum and generally summarised the main environmental gradients in our data set well. Five of the studied lakes lacked Pediastrum taxa altogether, and Pediastrum occurred at low abundances in four additional lakes. All of these nine lakes have extremely low nutrient concentrations and generally lowest pH and DOC in the data set and were defined by barren catchment areas and scarce lake macrophyte growth. According to a top–bottom analysis of sediment cores, the Pediastrum assemblages of the study lakes have changed moderately, suggesting changed environmental conditions in the lakes. Although these changes appear to be climate-related, more studies are needed to confirm this hypothesis.

Structural and geochronological evidence for Paleogene thrusting in the western Rhodopes, SW Bulgaria: Elements for a new tectonic model of the Rhodope Metamorphic Province

Abstract: [1] The Rhodope Metamorphic Province in the area around the Mesta Graben (SW Bulgaria) exposes a structurally lower complex, the Pangaion-Pirin Complex of Variscan continental crust and its cover (mostly orthogneiss and marble), and a higher complex, the Rhodope Terrane of mixed oceanic and continental origin with metamorphosed Jurassic arc magmatites. The boundary between the two is the top-to-the-southwest Nestos Shear Zone. The regional top-to-the-southwest shearing of the two basement complexes is related to the emplacement of the Rhodope Terrane over the Pangaion-Pirin Complex along this shear zone. Syntectonic and posttectonic Alpine intrusions within the basement can provide age limits for the thrusting. Zircons from the posttectonic Teshovo (south Pirin) Granitoid Pluton in the Pangaion-Pirin Complex yielded crystallization ages of 32 ± 0.2 Ma (LA-SF-ICP-MS U-Pb method). Zircons from two syntectonic granite plutons in the Rhodope Terrane (Dolno Dryanovo and Spanchevo) have circa 143 to 145 Ma old inherited magmatic cores and circa 55 to 56 Ma old magmatic rims. These ages, especially the presence of the Upper Jurassic/Lower Cretaceous cores in the plutons from the Rhodope Terrane, and the structural relations indicate that the southwestward thrusting of the Rhodope Terrane over the Pangaion-Pirin Complex took place in the Paleogene. A model is proposed in which the Pangaion-Pirin Complex represents the margin of Apulia and the structure of the Rhodopes is explained by a switch of subduction polarity from SW dipping in the Jurassic and Early Cretaceous to NE dipping in the Late Cretaceous and Paleogene.

Perfluorinated compounds (PFCs) in groundwater and aqueous soil extracts: using inline SPE-LC-MS/MS for screening and sorption characterisation of perfluorooctane sulphonate and related compounds

Abstract: Perfluorinated compounds (PFCs) have been recognised as emerging pollutants of global relevance. A fully automated method with inline solid-phase extraction coupled to electrospray ionisation liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) is presented and used for characterisation of soil adsorption and desorption for six PFCs: perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorobutane sulphonate (PFBS), and perfluorooctane sulphonate (PFOS). The method reduces sample turnaround time and solvent consumption and is suitable for low volume sampling. The only sample preparation necessary for water samples was sedimentation by centrifugation. The method has a total runtime of 21 min including inline sample cleanup (2 min for injection and SPE, 14 min for the chromatographic separation, 5 min for reconditioning). Negative AP-ESI with selective reaction monitoring (SRM) was used and the method was documented for quantification of the six environmentally important PFCs in subsoil matrix and related aqueous matrixes (groundwater and drainage water). Linearity was demonstrated in the range 5 to 2,500 ng/l and the LOD was between 2 and 8 ng/l in groundwater. Adsorption was characterised by linear Freundlich isotherms for all six compounds in two agricultural top soils (A horizon, sandy and clayey soil).Variability in sorption characteristics for soil types as well as compound properties were found, and correlation between the organic carbon normalised sorption coefficient (K OC) and PFC molecular weight was demonstrated. The K d values were in the range 0.1 to 33 (l/kg), and 0.3 to 65 (l/kg) for sorption and desorption respectively.

C, N, and H isotope fractionation of the herbicide isoproturon reflects different microbial transformation pathways.

Abstract: The fate of pesticides in the subsurface is of great interest to the public, industry, and regulatory authorities. Compound-specific isotope analysis (CSIA) is a promising tool complementary to existing methods for elucidating pesticide degradation reactions. Here, we address three different initial biotransformation reactions of the phenylurea herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) in pure culture experiments with bacterial and fungal strains. When analyzing isotopic changes in different parts of the isoproturon molecule, hydroxylation of the isopropyl group by fungi was found to be associated with C and H isotope fractionation. In contrast, hydrolysis by Arthrobacter globiformis D47 caused strong C and N isotope fractionation, albeit in a different manner than abiotic hydrolysis so that isotope measurements can distinguish between both modes of transformation. No significant isotope fractionation was observed during N-demethylation by Sphingomonas sp. SRS2. The observed isotope fractionation patterns were in agreement with the type of reactions and elements involved. Moreover, their substantially different nature suggests that isotope changes in natural samples may be uniquely attributed to either pathway, allowing even to distinguish the abiotic versus biotic nature of hydrolysis. Our investigations show how characteristic isotope patterns may significantly add to the present understanding of the environmental fate of pesticides.