Integrative Monitoring Analysis Aiming at the Detection of Spatial and Temporal Trends of Metal Accumulation in Mosses

Goal and Scope. The UNECE heavy metals in Mosses Surveys provide data on the accumulation of metals in naturally growing mosses throughout Europe. Using Germany as an example, this article concentrates on the elaboration and application of methods of data analysis that are necessary for a comprehensive interpretation of spatial and temporal trends in metal accumulation.Methods and Results. The sampling of mosses, and the chemical analysis of Cr, Cu, Fe, Ni, Pb, Ti, V and Zn in 1990, 1995 and 2000 are summarized briefly. The variogram analyses detect distinct autocorrelation structures in the sample data which may consequently be estimated for all sites in Germany without monitoring metal accumulation by means of ordinary kriging. A procedure for the geostatistical detection of spatial outliers was developed and applied and, after the elimination of the spatial outliers, several measurements were seen to indicate an adequate quality of the geostatistical estimations. The cluster analyses of the z-transformed estimation data result in a nominal multi-element index that indicates regional metal accumulation types over time. Percentile statistics serve for computation of an ordinal, scaled, multi-element accumulation index which is spatially differentiated over time in terms of multivariate, statistically defined ecoregions. The integrative statistical analysis reveals, from 1990 to 2000, that the metal accumulation declines up to 80% in some of the ecoregions. Hot spots of metal accumulation are mapped and interpreted by means of metadata analysis.Conclusions. Dot maps depict the spatial structure of the metal accumulation without spatial bias. This information, detailed with respect to metal species and space, should be generalized for better supporting the interpretation. The combination of geostatistical analysis and estimation, percentile and multivariate statistics is suitable for the calculation of indices that serve for a comprehensive mapping of metal accumulation in the ecoregions over time, for quantifying the bias of the surface estimation, and for mapping spatial outliers and hot spots of metal accumulation.     

Iodine Chemistry and its Role in Halogen Activation and Ozone Loss in the Marine Boundary Layer: A Model Study

A detailed set of reactions treating the gas and aqueous phase chemistry of the most important iodine species in the marine boundary layer (MBL) has been added to a box model which describes Br and Cl chemistry in the MBL. While Br and Cl originate from seasalt, the I compounds are largely derived photochemically from several biogenic alkyl iodides, in particular CH2I2, CH2ClI, C2H5I, C3H7I, or CH3I which are released from the sea. Their photodissociation produces some inorganic iodine gases which can rapidly react in the gas and aqueous phase with other halogen compounds. Scavenging of the iodine species HI, HOI, INO2, and IONO2 by aerosol particles is not a permanent sink as assumed in previous modeling studies. Aqueous-phase chemical reactions can produce the compounds IBr, ICl, and I2, which will be released back into the gas phase due to their low solubility. Our study, although highly theoretical, suggests that almost all particulate iodine is in the chemical form of IO-3. Other aqueous-phase species are only temporary reservoirs and can be re-activated to yield gas phase iodine. Assuming release rates of the organic iodine compounds which yield atmospheric concentrations similar to some measurements, we calculate significant concentrations of reactive halogen gases. The addition of iodine chemistry to our reaction scheme has the effect of accelerating photochemical Br and Cl release from the seasalt. This causes an enhancement in ozone destruction rates in the MBL over that arising from the well established reactions O(1D) + H2O 2OH, HO2 + O3 OH + 2O2, and OH + O3 HO2 + O2. The given reaction scheme accounts for the formation of particulate iodine which is preferably accumulated in the smaller sulfate aerosol particles.     

Skill assessment of three earth system models with common marine biogeochemistry

We have assessed the ability of a common ocean biogeochemical model, PISCES, to match relevant modern data fields across a range of ocean circulation fields from three distinct Earth system models: IPSL-CM4-LOOP, IPSL-CM5A-LR and CNRM-CM5.1. The first of these Earth system models has contributed to the IPCC 4th assessment report, while the latter two are contributing to the ongoing IPCC 5th assessment report. These models differ with respect to their atmospheric component, ocean subgrid-scale physics and resolution. The simulated vertical distribution of biogeochemical tracers suffer from biases in ocean circulation and a poor representation of the sinking fluxes of matter. Nevertheless, differences between upper and deep ocean model skills significantly point to changes in the underlying model representations of ocean circulation. IPSL-CM5A-LR and CNRM-CM5.1 poorly represent deep-ocean circulation compared to IPSL-CM4-LOOP degrading the vertical distribution of biogeochemical tracers. However, their representations of surface wind, wind stress, mixed-layer depth and geostrophic circulations (e.g., Antarctic Circumpolar Current) have been improved compared to IPSL-CM4-LOOP. These improvements result in a better representation of large-scale structure of biogeochemical fields in the upper ocean. In particular, a deepening of 20–40 m of the summer mixed-layer depth allows to capture the 0–0.5 μgChl L^?1 concentrations class of surface chlorophyll in the Southern Ocean. Further improvements in the representation of the ocean mixed-layer and deep-ocean ventilation are needed for the next generations of models development to better simulate marine biogeochemistry. In order to better constrain ocean dynamics, we suggest that biogeochemical or passive tracer modules should be used routinely for both model development and model intercomparisons.     

Practical visualization of rock structure

The conventionally applied method for visualizing the structure of a rock mass is limited to plotting the orientation of individual discontinuities by using the Schmidt stereographic net. Their spacing is not illustrated and other structural features, such as undulation and twisting, cannot be interpreted from such sterographic views. A new mode of visual presentation of rock structural features of one or several different types in rock volumes of any size that makes all this possible is proposed in the present report. The primary purpose is to quantify, for all elements of a rock mass where the structure has been evaluated by borehole investigations or mapping in the course of underground excavation, the orientation and average spacing of defined discontinuities like hydraulically and mechanically active fractures. These local structural patterns, which are plotted on three of the six faces of cubical boxes with defined edge length and with one edge oriented N−S can be combined by applying the mathematical tool for connecting faces with which certain visualization codes like Alias Sketch are equipped. This combines different local rock structures to form regional patterns that can reveal undulation and twisting and important variations in spacing of major discrete discontinuities. Visualization can be given in true perspective or orthographic form and larger discontinuities that have been identified in the field, such as fracture zones, can be introduced in the model for correlation with smaller features. Furthermore, the stress situation at all sites where rock stress measurements have been made can be visualized in the model in the form of principal planes. The proposed models can be visualized from any “camera angle” and also shown in Quick Time VR form, i.e. as being slowly rotated around any predetermined axis. This facilitates definition and selection of the rock structure, local or regional, for numerical calculations.     

Age structure and recharge conditions of a coastal aquifer (northern Germany) investigated with 39Ar, 14C, 3H, He isotopes and Ne

A tide-influenced two-layer aquifer system in northern Germany was investigated using environmental dating tracers (³H, ³⁹Ar, ¹⁴C), the noble gas isotopes ³He, ⁴He and Ne. The study area is a marshland at the River Ems estuary, exposed to regular flooding until?AD 1000. The construction of dykes, artificial land drainage and groundwater abstraction define the hydraulic gradient. The aquifer depicts a pronounced age stratification with depth. Tritium concentrations above 0.03 TU are found only in the top 30?m. Two tritium-free samples between 20 and 30?m depth show ³⁹Ar ages of 130 and 250?years. Below a clay layer?Cabout 50?m below surface level (mbsl)?Call analysed samples are ³⁹Ar free and, thus, older than 900?years. The initial ¹⁴C activities were about 70 pmC. Resulting ¹⁴C ages increase with depth and increase up to 9,000?years, in agreement with minimal ³⁹Ar ages. Concentrations of radiogenic ⁴He correlate with ¹⁴C ages. Samples in a mid-depth range (20?C70 mbsl) show significant gas loss. The gas loss is assigned to recharge in a methane producing environment. Deduced ⁴He ages were used to assign this water to a infiltration period of about AD 1000.     

Sources and transport of carbon and nitrogen in the River Sava watershed, a major tributary of the River Danube

Carbon and nitrogen dynamics were examined throughout the River Sava watershed, a major tributary of the River Danube, in 2005 and 2006. The River Sava exported 2.1 × 10¹¹ mol C/yr as dissolved inorganic carbon (DIC), and emitted 2.5 × 10¹⁰ mol C/yr as CO₂ to the atmosphere. Stable carbon isotope ratios indicate that up to 42% of DIC originated from carbonate weathering and 23% from degradation of organic matter. Loads of dissolved and particulate organic carbon increased with discharge and export rates were calculated to be 2.1 × 10¹⁰ mol C/yr and up to 4.1 × 10⁹ mol C/yr, respectively. Isotopic compositions (δ¹³C and δ¹⁵N) and C/N ratios indicated that soil organic matter was the dominant source of particulate organic matter for 59% of the samples. Eighteen percent of the samples were dominated by plankton, 12% by periodic inputs of fresh terrestrial plant detritus with C/N > 15, and about 11% of the samples were dominated by the contribution of aquatic vascular plants. Nitrate inputs were controlled by land use in the River Sava watershed. δ¹⁵N_NO3 values <6‰ were found in predominantly forested watersheds, while values >6‰ typically represented watersheds with a higher percentage of agricultural and/or urban land use. Elevated δ¹⁵N_NO3 values (up to +25.5‰) at some sites were probably due to the combined effects of low-flow and inputs from sewage and/or animal waste.     

Vertical Column Abundances of COF2 Above the Jungfraujoch Station, Derived from Ground-Based Infrared Solar Observations

Total vertical column abundances of carbonyl fluoride (COF₂) have been derived from observations made at the International Scientific Station of the Jungfraujoch (ISSJ; altitude 3.58 km, latitude 46.5°N, longitude 8.0°E), Switzerland. A systematic analysis of two microwindows containing lines of the ₁ band was performed, based on a large set of high resolution infrared solar absorption spectra recorded with Fourier transform spectrometers, from 1985 to 1995. Examination of the whole available database indicates a significant increase of the burden of COF₂ during the 1988–1995 period. The average exponential rate and the average linear rate referenced to 1992, calculated from daily mean measurements, are both equal to (4.0 ± 0.5)% yr^-1 (one error). The results are also evaluated and discussed within the context of seasonal variability and correlation between carbonyl fluoride and hydrogen fluoride (HF) columns above the ISSJ.     

The Budget of Turbulent Kinetic Energy in the Urban Roughness Sublayer

Full-scale observations from two urban sites in Basel, Switzerland were analysed to identify the magnitude of different processes that create, relocate, and dissipate turbulent kinetic energy (TKE) in the urban atmosphere. Two towers equipped with a profile of six ultrasonic anemometers each sampled the flow in the urban roughness sublayer, i.e. from street canyon base up to roughly 2.5 times the mean building height. This observational study suggests a conceptual division of the urban roughness sublayer into three layers: (1) the layer above the highest roofs, where local buoyancy production and local shear production of TKE are counterbalanced by local viscous dissipation rate and scaled turbulence statistics are close to to surface-layer values; (2) the layer around mean building height with a distinct inflexional mean wind profile, a strong shear and wake production of TKE, a more efficient turbulent exchange of momentum, and a notable export of TKE by transport processes; (3) the lower street canyon with imported TKE by transport processes and negligible local production. Averaged integral velocity variances vary significantly with height in the urban roughness sublayer and reflect the driving processes that create or relocate TKE at a particular height. The observed profiles of the terms of the TKE budget and the velocity variances show many similarities to observations within and above vegetation canopies.     

Zero velocity hypersurfaces for the general three-dimensional three-body problem

The equation of zero velocity surfaces for the general three-body problem can be derived from Sundman's inequality. The geometry of those surfaces was studied by Bozis in the planar case and by Marchal and Saari in the three-dimensional case. More recently, Saari, using a geometrical approach, has found an inequality stronger than Sundman's. Using Bozis' algebraic method, and a rotating frame which does not take into account entirely the rotation of the three-body system, we also find an inequality stronger than Sundman's. The comparison with Saari's inequality is more difficult. However, our result can be expressed in four-dimensional space and the regions where motion is allowed can be seen (numerically) to lie inside those obtained by the use of Sundman's inequality.Agrégé de Faculté.