Degradation Pathway of the Photochemical Oxidation of Ethylenediaminetetraacetate (EDTA) in the UV/H2O2-process

The degradation pathway for the oxidation of EDTA in the UV/H₂O₂-process was investigated. In absence of iron ions, the mineralization of EDTA is dominated by the reaction of the HO-radicals generated by the photolysis of H₂O₂. The organic degradation products iminodiacetate (IMDA), glycinate, oxamate, glyoxylate, oxalate and formate, and the inorganic degradation products carbon dioxide, ammonia, nitrate, nitrite, and cyanate were found. In the presence of iron ions, photolytic decarboxylation processes inside the complex get an important role during degradation, and the organic degradation products ethylenediaminetriacetate (ED3A), ethylenediaminediacetate (EDDA), ethylenediaminemonoacetate (EDMA) were also found. By combining product studies with balances of carbon and nitrogen, the degradation pathway in the UV/H₂O₂-process could be elucidated. The degradation of EDTA was fast (k_deg = 0.012 s^–1), and no toxic degradation products were identified. Therefore, the process is well suited for the elimination of EDTA in water treatment.     

Anwendung einer enzymatischen Methode zur Charakterisierung von Huminstoffen Enzymatic Characterization of Humic Substances

A method is described for the specific hydrolysis of amino acids from humic substances by using the proteolytic enzyme “Pronase E”. The amino acids are analyzed by a fluorescence detector after precolumn derivatization and HPLC-separation. The pattern and the concentration of amino acids after the enzymatic hydrolysis are set up for humic substances of different origin. Due to the results the enzymatic hydrolysis is suitable for the characterization of humic substances with a nitrogen content higher than 3%. As shown in a kinetic study of the hydrolysis of a fulvic acid the influence of humic substances on the enzyme activity increases in case of lower nitrogen content. Due to the specificity of the proteolytic enzyme the operationally defined method is limited as shown by a protein of a known amino acid content. The amino acids leucine, valine, tyrosine and histidine are released to the highest extent. The determined total extent for the hydrolysis of Insulin B is 26.34% and for Casein 38.37%. By comparison of the enzymatic hydrolysis with the classic acid hydrolysis the advantages of the biochemical method are the simple experimental handling and the mild reaction conditions. Amino acids which are very unstable like glutamine and asparagine can only be analyzed by the enzymatic hydrolysis.     

Beeinflussung der Enzymaktivität einer Protease durch Huminstoffe Influence of Humic Substances on the Activity of a Protease

This paper deals with the influence of different humic substances (HS) on the enzyme activity (EA) of the proteolytic enzyme pronase E. The EA was determined by analyzing the concentration of the amino acid valine hydrolyzed from caseine. For amino acid analysis, a flourescence detector was used after precolumn derivatization and HPLC-separation of the hydrolysis products. The data show that the presence of HS has no adverse effects on amino acid analysis. Based on this result, a decrease of EA was observed in the presence of HS acting as enzyme inhibitors. Clear inhibition effects could be seen for different fulvic acids (HO3 FA, FBR FA and FBR 1.0 FA) at concentrations of 150 mg/L. In case of FBI-2 FA, higher concentrations were necessary to decrease the EA significantly. At an inhibitor concentration of 1500 mg/L the EA was mostly found to be less than 50%. The standard deviations of the results don't allow a differentiation between the HS of different origin and treatment. Specifying HS according to their influence on EA has to remain uncertain. As shown in a kinetic study of the hydrolysis of L-Leucine-2-naphthylamide-hydrochloride, the inhibitor HO3 FA decreases the maximum velocity of the reaction but has no effect on the Michaelis constant. These results indicate that this HS acts as a noncompetitive inhibitor.     

The role of evaporites in the genesis of base metal sulphide mineralisation in the Northern Platform of the Pan-African Damara Belt, Namibia: geochemical and fluid inclusion evidence from carbonate wall rock alteration

The Otavi Mountain Land is a base metal sulphide ore province in northern Namibia where deposits are hosted by platform carbonates of the Otavi Group in a foreland fold-and-thrust belt on the northern edge of the Pan-African Damara Belt. Deposits have been classified as the Berg Aukas- or Tsumeb-types, based on differences in ore association, stratigraphic position and geochemistry of ores and gangue carbonates. Mineralisation at these deposits is accompanied by carbonate alteration in the form of dolomite and calcite veins, carbonate recrystallisation, calcitisation and carbonate silicification. Based on cathodoluminescence imaging, trace and rare earth element (REE), O and C isotope, and fluid inclusion data, a series of carbonate generations, constituting wall rock alteration around the Tsumeb and Kombat (Tsumeb-type) and Berg Aukas (Berg Aukas-type) deposits, was established. Similar data obtained on the recently discovered Khusib Springs deposit indicate a strong affinity to Tsumeb-type deposits. Tsumeb-type deposits are distinguished from Berg Aukas-type deposits by having trace element and REE concentrations that are significantly higher in the alteration products compared to the carbonate host rocks. Only around Tsumeb-type deposits a relative enrichment in light REE is noted for the hydrothermal carbonate generations that are cogenetic with the main stage of mineralisation. Microthermometric results from fluid inclusions in carbonate alteration phases and associated quartz indicate relatively high salinity (17–23 wt% NaCl equivalent) for the main mineralising and subsequent sulphide remobilisation stages at the deposits investigated. Estimated mineralisation temperatures are significantly higher for Tsumeb-type deposits (370–405 °C) with early sulphide remobilisation in Tsumeb at 275 °C, whereas they are lower at Berg Aukas (up to 255 °C). Fluid inclusion leachate analysis suggests that most of the observed salinity can be ascribed to dissolved, predominantly Ca- and Mg-carbonates and chlorides with subordinate NaCl. Na-Cl-Br leachate systematics indicate a derivation of the fluid salinity from the interaction with evaporitic rocks en route. Tsumeb-type mineralisation is interpreted to be derived from fluids expelled during Pan-African orogeny in the more intensely deformed internal zones of the Damara Belt further south. When the high salinity fluids reached the carbonate platform after having scavenged high concentrations of base metals, base metal sulphide precipitation occurred in zones of high porosity, provided by karst features in the carbonate sequence. Results obtained for the Berg Aukas-type deposits emphasise their derivation from basinal brines, similar to Mississippi Valley-type deposits, and confirm that mineralisation of the Berg Aukas- and Tsumeb-types are both spatially and temporally distinct. Received: 5 May 1999 / Accepted: 10 November 1999     

小秦岭金矿中黄铁矿微量元素原位LA-ICPMS分析及其对矿床成因的指示意义

位于河南和陕西交界的小秦岭金矿集区是我国仅次于胶东金矿的第二大黄金产地,大地构造位置上位于华北地台的南部边缘,属于秦岭造山带的边缘组成部分,近东西向展布.该地区金矿类型主要是石英脉型,少量蚀变岩型.     

Challenges of an integrated water resource management for the Distrito Federal, Western Central Brazil: climate, land-use and water resources

Land-use/cover change (LUCC) and climate change are major controlling factors for water resources in the Distrito Federal in Western Central Brazil. Dynamic LUCC in the region has severe impacts on water resources, while climate changes during the last three decades is thought to have only moderate effects. LUCC affects water quantity mostly during base flow conditions. River basins with substantial expansion of agriculture since the end 1970s show a dramatic decrease of base flow discharge by 40?C70%, presumably due to irrigation. In contrast, the effects of urbanization on runoff are less distinct, since factors controlling runoff generation might be more variable. For water quality, we found urban areas to have a strong influence on the parameters CSB, NH₄ ⁺, and suspended solids. In addition, we assume emerging pollutants, e.g. organic (micro)pollutants, might play a major role in the future. The project IWAS-áGUA DF focuses on creating the scientific base to face these problems in frame of an IWRM concept for the region. Results of our study will be a contribution to an IRWM concept for the Distrito Federal and will help to maintain high standards in water supply for the region.     

Geochronology,stratigraphy and geochemistry of Cambro-Ordovician,Silurian and Devonian volcanic rocks of the Saxothuringian Zone in NE Bavaria (Germany)—new constraints for Gondwana break up and ocean–island magmatism

International Journal of Earth Sciences - Stratigraphically well-defined volcanic rocks in Palaeozoic volcano-sedimentary units of the Frankenwald area (Saxothuringian Zone, Variscan Orogen) were...     

Metamorphic evolution of the Maud Belt: P–T–t path for high-grade gneisses in Gjelsvikfjella, Dronning Maud Land, East Antarctica

A metamorphic petrological study, in conjunction with recent precise geochronometric data, revealed a complex P–T–t path for high-grade gneisses in a hitherto poorly understood sector of the Mesoproterozoic Maud Belt in East Antarctica. The Maud Belt is an extensive high-grade, polydeformed, metamorphic belt, which records two significant tectono-thermal episodes, once towards the end of the Mesoproterozoic and again towards the late Neoproterozoic/Cambrian. In contrast to previous models, most of the metamorphic mineral assemblages are related to a Pan-African tectono-thermal overprint, with only very few relics of late Mesoproterozoic granulite-facies mineral assemblages (M₁) left in strain-protected domains. Petrological and mineral chemical evidence indicates a clockwise P–T–t path for the Pan-African orogeny. Peak metamorphic (M_2b) conditions recorded by most rocks in the area (T = 709–785 °C and P = 7.0–9.5 kbar) during the Pan-African orogeny were attained subsequent to decompression from probably eclogite-facies metamorphic conditions (M_2a).The new data acquired in this study, together with recent geochronological and geochemical data, permit the development of a geodynamic model for the Maud Belt that involves volcanic arc formation during the late Mesoproterozoic followed by extension at 1100 Ma and subsequent high-grade tectono-thermal reworking once during continent–continent collision at the end of the Mesoproterozoic (M₁; 1090–1030 Ma) and again during the Pan-African orogeny (M_2a, M_2b) between 565 and 530 Ma. Post-peak metamorphic K-metasomatism under amphibolite-facies conditions (M_2c) followed and is ascribed to post-orogenic bimodal magmatism between 500 and 480 Ma.     

An evaporitic facies in Neoproterozoic post-glacial carbonates: The Gifberg Group, South Africa

A geological study of the hitherto poorly described Neoproterozoic Gifberg Group, with emphasis on lithogeochemistry and O, C and Sr isotopic composition of the carbonate-dominated Widouw Formation (Vredendal Outlier, westernmost South Africa) revealed that the entire group is an equivalent of the relatively well constrained Port Nolloth Group in the external, paraautochthonous part of the Pan-African Gariep Belt further north. Thus, the Vredendal Outlier can be regarded as the southern extension of the Port Nolloth Zone. Two diamictite units are recognised in the Vredendal Outlier, which can be correlated respectively with the c. 750 Ma Kaigas Formation diamictite and the 583 Ma, syn-Gaskiers Numees Formation diamictite in the Gariep Belt proper. The dominating carbonate unit in the studied area is post-glacial with respect to the older of the two diamictite units. The combined textural, structural and geochemical evidence suggests that parts of the variably dolomitised limestone succession represent former evaporite beds. Sedimentation in a restricted, very shallow and proximal basin led to a wide range in C isotope ratios (δ¹³C_PDB from − 4.2 to + 4.8‰), very high Sr concentrations (derived from original anhydrite) and initial ⁸⁷Sr/⁸⁶Sr ratios that are significantly higher (0.70785) than those of coeval seawater. As C and Sr isotopes are commonly used for chemostratigraphic correlation, and high Sr concentrations in Neoproterozic carbonates are often interpreted as evidence of former aragonite, the findings of this study should be used as warning against uncritical use of geochemical and isotopic parameters for describing ancient seawater composition. Thus C and Sr isotope ratios alone in Neoproterozoic carbonates may be less powerful proxies of ancient seawater composition, and high Sr contents are not necessarily indicative of an “aragonite sea”, as previously inferred.