激光剥蚀-等离子体质谱技术及其在地球化学宇宙化学和环境研究中的应用

激光剥蚀-等离子体质谱(LA-ICPMS)已成为地球化学、宇宙化学和环境研究领域元素和同位素原位分析最重要的技术之一。文章介绍了多种类型的质谱仪及其使用的激光器。用途最广的LA-ICPMS仪器之一是单接收器扇形磁场质谱仪,配有Nd:YAG激光剥蚀系统(激光波长分为193 nm和213 nm两种),MPI Mainz实验室使用的就是这套系统,文章对此作一详细介绍。文中阐述了数据优化技术及其多种校正过程;介绍LA-ICPMS在痕量元素和同位素分析领域的一些应用,包括参考物质的研制,Hawaiian玄武岩、Martian陨石、生物骨针和珊瑚虫中痕量元素分析及熔融包裹体和富钙-铝碳质球粒陨石中的铅和锶同位素测量。     

Net Ecosystem Metabolism and Nonconservative Fluxes of Organic Matter in a Tropical Mangrove Estuary, Piauí River (NE of Brazil)

Net ecosystem metabolism (NEM) was measured in the Piauí River estuary, NE Brazil. A mass balance of C, N, and P was used to infer its sources and sinks. Dissolved inorganic carbon (DIC) concentrations and fluxes were measured over a year along this mangrove dominated estuary. DIC concentrations were high in all estuarine sections, particularly at the fluvial end member at the beginning of the rainy season. Carbon dioxide concentrations in the entire estuary were supersaturated throughout the year and highest in the upper estuarine compartment and freshwater, particularly at the rainy season, due to washout effects of carbonaceous soils and different organic anthropogenic effluents. The estuary served as a source of DIC to the atmosphere with an estimated flux of 13 mol CO₂ m^?2 year^?1. Input from the river was 46 mol CO₂ m^?2 year^?1. The metabolism of the system was heterotrophic, but short periods of autotrophy occurred in the lower more marine portions of the estuary. The pelagic system was more or less balanced between auto- and heterotrophy, whereas the benthic and intertidal mangrove region was heterotrophic. Estimated annual NEM yielded a total DIC production in the order of 18 mol CO₂ m^?2 year^?1. The anthropogenic inputs of particulate C, N, and P, dissolved inorganic P (DIP), and DIC were significant. The fluvial loading of particulate organic carbon and dissolved inorganic nitrogen (DIN) was largely retained in two flow regulation and hydroelectric reservoirs, promoting a reduction of C:N and C:P particulate ratios in the estuary. The net nonconservative fluxes obtained by a mass balance approach revealed that the estuary acts as a source of DIP, DIN, and DIC, the latter one being almost equivalent to the losses to the atmosphere. Mangrove forests and tidal mudflats were responsible for most of NEM rates and are the main sites of organic decomposition to sustain net heterotrophy. The main sources for this organic matter are the fluvial and anthropogenic inputs. The mangrove areas are the highest estuarine sources of DIP, DIC, and DIN.     

Fluorescence as a Tool for Tracing the Organic Contamination from Pulp Mill Effluents in Surface Waters

Three‐dimensional fluorescence spectra of water samples from an eucalyptus bleached kraft pulp mill and from a river, upstream and downstream of the discharge of the effluent, revealed the existence of a peak at δ_exc = 280 nm and δ_em = 340 nm Δδ = 60 nm), characteristic of effluentπs organic matter. Humic substances were isolated from the effluent by sequential adsorption onto resins XAD‐8 and XAD‐4 in series. Their synchronous fluorescence spectra with Δδ = 60 nm do also exhibit an intense signal at δ_exc = 280 nm (≈ 300 nm in the humic acid fraction). The peak is absent in the spectra of humic substances isolated from a non‐polluted site of the river, but it is clearly seen in the spectra of the humic substances from a site downstream of the discharge of the effluent. Synchronous fluorescence spectra (Δδ = 60 nm) of water samples from the river and its lagoon were recorded and revealed to be an easy and fast way of tracing the organic contamination from the effluent.     

Relative equilibria of the restricted three-body problem in curved spaces

We use a formulation of the N-body problem in spaces of constant Gaussian curvature, \({\kappa }\in \mathbb {R}\), as widely used by A. Borisov, F. Diacu and their coworkers. We consider the restricted three-body problem in \(\mathbb {S}^2\) with arbitrary \({\kappa }>0\) (resp. \(\mathbb {H}^2\) with arbitrary \({\kappa }<0\)) in a formulation also valid for the case \({\kappa }=0\). For concreteness when \({\kappa }>0\) we restrict the study to the case of the three bodies at the upper hemisphere, to be denoted as \(\mathbb {S}^2_+\). The main goal is to obtain the totality of relative equilibria as depending on the parameters \({\kappa }\) and the mass ratio \(\mu \). Several general results concerning relative equilibria and its stability properties are proved analytically. The study is completed numerically using continuation from the \({\kappa }=0\) case and from other limit cases. In particular both bifurcations and spectral stability are also studied. The \(\mathbb {H}^2\) case is similar, in some sense, to the planar one, but in the \(\mathbb {S}^2_+\) case many differences have been found. Some surprising phenomena, like the coexistence of many triangular-like solutions for some values \(({\kappa },\mu )\) and many stability changes will be discussed.     

Hydrochemical and isotopic characteristics of groundwater in the Ndop plain,northwest Cameroon: resilience to seasonal climatic changes

Shallow groundwater (>30 mbgl) is an essential source of drinking water to rural communities in the Ndop plain, northwest Cameroon. As a contribution to water management, the effect of seasonal variation on the groundwater chemistry, hydrochemical controls, drinking quality and recharge were investigated during the peaks of the dry (January) and rainy (September) seasons. Field measurements of physical parameters were preceded by sampling 58 groundwater samples during both seasons for major ions and stable isotope analyses. The groundwater, which was barely acidic (mean pH of 6) and less mineralised (TDS < 272 mg/l), showed no significant seasonal variation in temperature, pH and TDS during the two seasons. The order of cation abundance (meq/l) was Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ in the dry and rainy seasons, respectively, but that of anions ( \( {\text{HCO}}_{3}^{ - } \)  >  \( {\text{NO}}_{3}^{ - } \)  > Cl^? >  \( {\text{SO}}_{4}^{2 - } \)  > F^?) was similar in both seasons. This suggests a negligible effect of seasonal variations on groundwater chemistry. The groundwater, which was CaMgHCO₃ and NaHCO₃, is chemically evolved rainfall (CaMgSO₄Cl) in the area. Silicate mineral dissolution and cation-exchange were the main controls on groundwater chemistry while there was little anthropogenic influence. The major ions and TDS concentrations classified the water as suitable for human consumption as per WHO guidelines. The narrow cluster of δ¹⁸O and δD of same groundwater from both seasons between the δ¹⁸O and δD values of May–June precipitation along the Ndop Meteoric Water Line indicates meteoric origin, rapid recharge (after precipitation) and timing of recharge between May and June rainfall. Diffuse groundwater recharge mainly occurs at low altitudes (<1,400 m asl) within the plain. Besides major ions and TDS, the similar δ¹⁸O and δD of groundwater from both seasons indicate a consistent groundwater recharge and flow pattern throughout the year and resilience to present day short-term seasonal climatic variations. However, controlled groundwater abstraction is recommended given the increasing demand.     

Understanding Causes of Conflict Over Common Village Pastures – A Comparative Analysis of Property Rights in Azerbaijan and Georgia

Abstract

Conflicts in the management of renewable natural resources are situations in which actors have diverging opinions on issues of natural resource use. In the literature, among the causal factors for conflicts discussed are resource wealth or scarcity and the role of governance. The evidence, however, is contradictory. In order to analyze the role of governance in more detail, we propose a combined analysis of property rights and conflicts. In this way, an improved understanding of the causes of local conflicts over renewable natural resources can be achieved. We use comparative case study data from pasture management in the Caucasus region, first, to classify conflicts according to the bundle of property rights approach and, second, to explore how the causal factors resource scarcity and current governance contribute to those conflicts.     

Synchronous Scan and Excitation-Emission Matrix Fluorescence Spectroscopy of Water-Soluble Organic Compounds in Atmospheric Aerosols

Three-dimensional excitation–emission matrix (EEM) fluorescence spectra of water-soluble organic compounds (WSOC) from aerosol samples were measured and compared with those reported in the literature for natural dissolved organic matter. The EEM profiles of the WSOC presented three characteristic excitation/emission (_Exc/_Em) peaks: 240/405 nm, 310/405 nm and 280/340 nm. The fluorescence intensities at _Exc/_Em240/405 nm and _Exc/_Em310/405 nm are located at wavelengths shorter than those reported for aquatic humic substances, indicating a smaller content of both aromatic structures and condensed unsaturated bond systems in the WSOC fraction. The EEM profiles of fractions obtained by the isolation procedure of the WSOC by the XAD resins showed that a fractionation has occurred and the XAD-8 eluate is highly representative of the total WSOC of collected aerosol. Synchronous scan spectra were more detailed than conventional fluorescence emission spectra, appearing more suitable for studying multicomponent samples such as the WSOC from atmospheric aerosols.     

Families of double symmetric “Schubart-like” periodic orbits

We consider a class of Hamiltonian systems with two degrees of freedom with singularities. This class includes several symmetric subproblems of the $n$ -body problem where the singularities are due to collisions involving two or more bodies. “Schubart-like” periodic orbits having two collisions in one period, are present in most of these subproblems. The purpose of this paper is to study the existence of families of such a periodic orbits in a general setting. The blow up techniques of total collision and infinity are applied to our class of Hamiltonian system. This allows us to derive sufficient conditions to ensure the existence of families of double symmetric “Schubart-like” periodic orbits having many singularities. The orbits in the family can be parametrized by the number of singularities in one period. The results are applied to some subproblems of the gravitational $n$ -body problem.     

Unravelling the moisture sources of the Alpine glaciers using tunnel valleys as constraints

A lack of archives has impeded reconstructions of moisture pathways for past glaciations in the European Alps. Here, we focus on the confluence area of two palaeoglaciers in the Swiss Plateau that were sourced on the northern (Aare glacier) and southern sides (Valais glacier) of the European Alps. We mapped tunnel valleys in the region using a drilling database, based on which we inferred the relative extent of each glacier c. 270 ka ago when the valleys were formed. We then compared this situation with that of the LGM. We found that, while the Valais glacier expanded farther into the foreland than the Aare glacier during the LGM, the opposite was the case c. 270 ka ago. We also found that LGM glaciers were non‐erosive in the distal foreland. These contrasts in extents and erosional efficiencies imply differences in moisture pathways between the LGM and the time when the tunnel valleys were formed.     

Assessing streams in Germany with benthic invertebrates: selection of candidate metrics

The process of selecting invertebrate-based candidate metrics for the German stream assessment system is described. The aim was to identify metrics indicating degradation types other than organic pollution and acidification (“general degradation”). For 18 out of 24 German stream types a data base of roughly 2,000 benthic invertebrate samples was generated; for each sample 79 metrics were calculated. Data on land use in the catchment were compiled for all sampling sites, together with data on hydromorphology for many sampling sites. Hydromorphological and land use parameters, which describe a clear gradient in the data sets were identified by Non-metric Multidimensional Scaling (NMS). Correlation analyses between land use/hydromorphological parameters and metric results were calculated separately for the individual stream types. Among those metrics best indicating catchment- and hydromorphological degradation in the majority of stream types are: proportion of Ephemeroptera, Plecoptera and Trichoptera; proportion of Plecoptera (mainly suited for mountain streams); number of Plecoptera taxa; proportion of xenosaprobic taxa; proportion of epirhithral preferring taxa. Differences of metric correlations between stream types and between degradation types are discussed, leading to a list of candidate metrics for assessing German streams.