Considering water as the primary resource necessary for social life, agriculture, industry, and wealth, the importance of groundwater investigation is clear. Apart from many other pollutants, this work focusses on geogenic uranium (U) and radium (Ra), which both stand for natural radionuclides (NORM) that need to be considered frame of groundwater exploration and monitoring programmes due to their specific mobility and chemo-/radiotoxicity. As investigation of U and – to a lesser extent - Ra is done by an increasing number of scientific working groups, the global dataset is improving continuously. In order to give a summarized overview on available and recent literature, scientific papers, reports, and governmental documents have been reviewed for U-238 mass concentrations and Ra-226 and Ra-228 activity concentrations and collected in tables and global maps. Further natural isotopes of U and Ra have been rarely subject of investigation. The collected data were evaluated and interpreted in frame of an associated scientific publication (see citation). From the available data it can be concluded that high geogenic U occur mainly under oxidizing conditions and carbonate rich groundwater, which might be seen as indicator for elevated U concentrations. Certain geological formations, as for example sedimentary, granitic, and volcanic host rocks, promote high U concentrations in groundwater. For geogenic Ra, the search for definite indications proved difficult, since less clear correlation is given for any observed factor. In a global perspective, the most promising evidence for elevated Ra are highly reducing redox conditions, as well as the occurrence of Fe/Mn mineral phases. Furthermore, barite represents a sink for Ra due to its ability to incorporate Ra isotopes. Dissolution of those mineral phases eventually results in co-dissolution of Ra, when Ra is found in host rocks of investigated aquifers, or downstream of such groundwater reservoirs. Furthermore, cation exchange might enhance Ra mobility process, especially in case of sedimentary aquifers with low sorption capacity and/or aquifers with high salinity. Given those chemical requirements for the occurrence of U and Ra, a negative correlation between mother and daughter nuclide can be established. When knowledge on present geological and geochemical constraints is available, elevated U and Ra concentrations might be predictable, as long as anthropogenic influence is excluded.
Considering water as the primary resource necessary for social life, agriculture, industry, and wealth, the importance of groundwater investigation is clear. Apart from many other pollutants, this work focusses on geogenic uranium (U) and radium (Ra), which both stand for natural radionuclides (NORM) that need to be considered frame of groundwater exploration and monitoring programmes due to their specific mobility and chemo-/radiotoxicity. As investigation of U and – to a lesser extent - Ra is done by an increasing number of scientific working groups, the global dataset is improving continuously. In order to give a summarized overview on available and recent literature, scientific papers, reports, and governmental documents have been reviewed for U-238 mass concentrations and Ra-226 and Ra-228 activity concentrations and collected in tables and global maps. Further natural isotopes of U and Ra have been rarely subject of investigation. The collected data were evaluated and interpreted in frame of an associated scientific publication (see citation). From the available data it can be concluded that high geogenic U occur mainly under oxidizing conditions and carbonate rich groundwater, which might be seen as indicator for elevated U concentrations. Certain geological formations, as for example sedimentary, granitic, and volcanic host rocks, promote high U concentrations in groundwater. For geogenic Ra, the search for definite indications proved difficult, since less clear correlation is given for any observed factor. In a global perspective, the most promising evidence for elevated Ra are highly reducing redox conditions, as well as the occurrence of Fe/Mn mineral phases. Furthermore, barite represents a sink for Ra due to its ability to incorporate Ra isotopes. Dissolution of those mineral phases eventually results in co-dissolution of Ra, when Ra is found in host rocks of investigated aquifers, or downstream of such groundwater reservoirs. Furthermore, cation exchange might enhance Ra mobility process, especially in case of sedimentary aquifers with low sorption capacity and/or aquifers with high salinity. Given those chemical requirements for the occurrence of U and Ra, a negative correlation between mother and daughter nuclide can be established. When knowledge on present geological and geochemical constraints is available, elevated U and Ra concentrations might be predictable, as long as anthropogenic influence is excluded.
The report describes the scientific background and motivation to develop an OECD Guidance Document on the determination on dissolution and dispersion stability of nanomaterials in the environment. It presents the process and approach to develop the GD and summarizes its relevance for risk assessment and regulation of nanomaterials. The “OECD Guidance Document No. 318 for the testing of dissolution and dispersion stability of nanomaterials, and the use of the data for further environmental testing and assessment strategies" is available at the webpages of the OECD Test Guideline Programme. Veröffentlicht in Texte | 176/2020.
For an adequate and valid interpretation of data regarding the environmental fate and behavior of nanomaterials it is essential to describe parameters like dissolution (rate), dispersibility and dispersion stability. Aim of the project was the development of a standardized test method to determine dispersibility and dispersion stability of nanomaterials in simulated environmental media as new OECD Test Guideline. For this objective, both conceptual and experimental work was conducted and an international round robin was initiated and executed to validate the proposed test setup regarding reliability and reproducibility. Two comprehensive expert commenting rounds of the OECD Test Guideline program supported the refinement of the draft within this project. The test method developed in this project was submitted to the OECD Test Guideline program by UBA and published by OECD in October 2017 as new “Test Guideline on dispersion stability of nanomaterials in simulated environmental media (OECD No. 318)”. The presented final report summarizes the experimental work performed to develop the OECD Test Guideline. Veröffentlicht in Texte | 108/2017.
technologyComment of chromium production (RoW): Metallic chromium is produced by aluminothermic process (75%) and electroylsis of dissolved ferrochromium (25%) technologyComment of chromium production (RER): Metallic chromium is produced by aluminothermic process (75%) and electroylsis of dissolved ferrochromium (25%) ALUMINOTHERMIC PROCESS The thermic process uses aluminium as a reducing agent for chromium hydroxide. The charge is weighed and loaded into a bin, which is taken to an enclosed room to mix the contents. The firing pot is prepared by ramming refractory sand mixed with water around a central former. After ramming the firing pot, the inner surface is coated with a weak binder solution and dried under a gas fired hood before being transferred to the firing station. The raw material mix is automatically fed at a controlled rate into the firing pot, where the exothermic reaction takes place. When the metal has solidified following the reaction, the firing pot is removed and transferred by crane to a cooling conveyor. On removal from the cooling conveyor (by crane), the firing pot is placed on a stripping bogie for transferral to a stripping booth. Inside the closed booth, the pot casing is hoisted off the solidified metal/slag. The slag is separated from the Chromium metal “button” and sent to a despatch storage area. Water is used to reduce button temperature to below 100 ºC. After cooling the metal button is transferred to other departments on site for cleaning, breaking, crushing and grinding to achieve the desired product size. ELECTROLYTIC PROCESS In the electrolytic process normally high carbon ferrochrome is used as the feed material which is then converted into chromium alum by dissolution with sulphuric acid at temperatures at about 200 ºC. After several process steps using crystallisation filtration ageing, a second filtration and a clarifying operation the alum becomes the electrolyte for a diaphragm cell. Chromium is plated onto stainless steel cathodes until it attains a thickness of ca. 3 mm. The process is very sensitive. The additional de-gassing (heating at 420 °C) stage is necessary because the carbon content of the electrolytic chromium is sometimes too high for further industrial applications. The cooled chromium metal is fragmented with a breaker prior to crushing and drumming. The generated slag can be reused as refractory lining or sold as abrasive or refractory material. Overall emissions and waste: Emissions to air consist of dust and fume emissions from smelting, hard metal and carbide production; other emissions to air are ammonia (NH3), acid fume (HCl), hydrogen fluoride (HF), VOC’s and heavy metals. Emissions to water are overflow water from wet scrubbing systems, wastewater from slag and metal granulation, and blow down from cooling water cycles. Solid waste is composed of dust, fume and sludge, and slag. References: IPPC (2001) Integrated Pollution Prevention and Control (IPPC); Reference Document on Best Available Techniques in the Non Ferrous Metals Industries. European Commission. Retrieved from http://www.jrc.es/pub/english.cgi/ 0/733169
technologyComment of rare earth oxides production, from rare earth oxide concentrate, 70% REO (CN-SC): This dataset refers to the separation (hydrochloric acid leaching) and refining (metallothermic reduction) process used in order to produce high-purity rare earth oxides (REO) from REO concentrate, 70% beneficiated. ''The concentrate is calcined at temperatures up to 600ºC to oxidize carbonaceous material. Then HCl leaching, alkaline treatment, and second HCl leaching is performed to produce a relatively pure rare earth chloride (95% REO). Hydrochloric acid leaching in Sichuan is capable of separating and recovering the majority of cerium oxide (CeO) in a short process. For this dataset, the entire quantity of Ce (50% cerium dioxide [CeO2]/REO) is assumed to be produced here as CeO2 with a grade of 98% REO. Foreground carbon dioxide CO2 emissions were calculated from chemical reactions of calcining beneficiated ores. Then metallothermic reduction produces the purest rare earth metals (99.99%) and is most common for heavy rare earths. The metals volatilize, are collected, and then condensed at temperatures of 300 to 400°C (Chinese Ministryof Environmental Protection 2009).'' Source: Lee, J. C. K., & Wen, Z. (2017). Rare Earths from Mines to Metals: Comparing Environmental Impacts from China's Main Production Pathways. Journal of Industrial Ecology, 21(5), 1277-1290. doi:10.1111/jiec.12491 technologyComment of sodium chloride production, powder (RER, RoW): For the production of dry salt, three different types of sodium chloride production methods can be distinguished namely, underground mining of halite deposits, solution mining with mechanical evaporation and solar evaporation. Their respective products are rock salt, evaporated salt and solar salt: - Underground mining: The main characteristic of this technique is the fact that salt is not dissolved during the whole process. Instead underground halite deposits are mined with traditional techniques like undercutting, drilling and blasting or with huge mining machines with cutting heads. In a second step, the salt is crushed and screened to the desired size and then hoisted to the surface. - Solution mining and mechanical evaporation: In this case, water is injected in a salt deposit, usually in about 150 to 500 m depth. The dissolution of the halite or salt deposits forms a cavern filled with brine. This brine is then pumped from the cavern back to the surface and transported to either an evaporation plant for the production of evaporated salt or transported directly to a chemical processing plant, e.g. a chlor-alkali plant. - Solar evaporation: In this case salt is produced with the aid of the sun and wind out of seawater or natural brine in lakes. Within a chain of ponds, water is evaporated by sun until salt crystallizes on the floor of the ponds. Due to their natural process drivers, such plants must be located in areas with only small amounts of rain and high evaporation rates - e.g. in the Mediterranean area where the rate between evaporation and rainfall is 3:1, or in Australia, where even a ratio up to 15:1 can be found. There are some impurities due to the fact that seawater contains not only sodium chloride. That leads to impurities of calcium and magnesium sulfate as well as magnesium chloride. With the aid of clean brine from dissolved fine salt, these impurities are washed out. As a fourth form on the market, the so-called 'salt in brine' may be found, which is especially used for the production of different chemicals. In this case, the solution mining technique without an evaporation step afterwards is used. This dataset represents the production of dry sodium chloride by underground mining (51%) and by solution mining (49%) with modern solution mining technology (thermo compressing technology). References: Althaus H.-J., Chudacoff M., Hischier R., Jungbluth N., Osses M. and Primas A. (2007) Life Cycle Inventories of Chemicals. ecoinvent report No. 8, v2.0. EMPA Dübendorf, Swiss Centre for Life Cycle Inventories, Dübendorf, CH.
Dieser Bericht präsentiert den Hintergrund, Ablauf und die Inhalte zur Entwicklung eines OECD Leitfadens für die Untersuchung von Löslichkeit und Dispersionsstabilität von Nanomaterialien in der Umwelt und die Nutzung der dadurch gewonnenen Daten für weitere Umweltuntersuchungen und Umweltbewertungsstrategien. Die Löslichkeit(srate) und Dispersionsstabilität werden als die wichtigsten Treiber des Umweltverhaltens und â€Ìschicksals von Nanomaterialien in der Umwelt angesehen. Zur Bestimmung der Dispersionsstabilität von Nanomaterialien in der Umwelt liegt bereits die OECD Prüfrichtlinie (TG) 318 vor. Eine OECD Prüfrichtlinie zur Bestimmung der Löslichkeit(srate) von Nanomaterialien in der Umwelt befindet sich derzeit noch in der Entwicklung. Da noch keine solche OECD Prüfrichtlinie zur Bestimmung der Löslichkeit(-rate) für Nanomaterialien zur Verfügung steht, wurden in den Leitfaden solche Methoden aus Wissenschaft und vorliegenden OECD TG/GDs aufgenommen, die für Nanomaterialien als sinnvoll erachtet werden. Zur Unterstützung der Anwendung der OECD TG 318 sind zusätzliche Informationen zur Präsentation und Interpretation von Daten zur Dispersionsstabilität in den Leitfaden eingebracht worden. Darüber hinaus werden im Leitfaden vorläufige Anleitungen gegeben, wie Heteroagglomeration von Nanomaterialien in der Umwelt bestimmt werden kann. Der vorliegende Bericht stellt neben den Inhalten des Leitfadens und den Ablauf seiner Entwicklung auch seine Bedeutung für die Umweltbewertung von Nanomaterialien dar und gibt einen Ausblick, welche regulatorischen Tragweite dieser in der Zukunft haben kann. Der finale Leitfaden wurde im April 2020 von der OECD Arbeitsgruppe der Nationalen Koordinatoren des OECD Prüfrichtlinienprogramms (WNT) verabschiedet und ist nach Veröffentlichung auf den Internetseiten des OECD Prüfrichtlinienprogramms zu finden. Quelle: Forschungsbericht
Das Projekt "SP 1.1 A combined BaPS-13C stable isotope technique to study the interaction between C and N turnover in alkaline agricultural soils of the North China Plain" wird vom Umweltbundesamt gefördert und von Universität Hohenheim, Institut für Bodenkunde und Standortslehre, Fachgebiet Biogeophysik durchgeführt. In the intensively managed double-cropping production system of the North China Plain, the excessive use of nitrogen (N) fertilizer has resulted in adverse environmental impacts such as leaching of nitrate to shallow groundwater or gaseous losses of the greenhouse gas N2O. An understanding of N cycling in soil is essential for deriving sustainable fertilization strategies. Nitrogen transformations in soil are closely linked to the carbon (C) cycle. All heterotrophic decomposing micro organism simultaneously assimilate C and N during decomposing plant residues or soil organic matter. An understanding of this linkage is important, for example, for assessing the feedback of a changed N fertilization practice on the soil organic matter pool. To study and quantify the C and N fluxes in soil, we need a set of reliable and accurate methods. During the last decade a novel method, the Barometric Process Separation, has been used to measure gross nitrification rates in soil. Recently, it has been shown that the use of the BaPS method becomes problematic at soil pH greater than 6. At pH values above 6 the BaPS calculation is strongly affected by the CO2,aq term, i.e. the dissolution of gaseous CO2 during incubation. So far, no methods are available to accurately quantifying this term. In our study, we aim at developing a novel combined Barometric Process Separation (BaPS)-13C stable isotope technique, which allows an accurate quantification of the CO2,aq term. In parallel, we will study to which extent the incorporation of plant residues of different quality immobilises surplus soil nitrate and its potential to reduce nitrate leaching in soils with a nitrate-dominated mineral N pool. Moreover, we will study the mid- and short term interaction of C and N turnover at the process-level to get a better understanding on the feedback mechanism between both matter cycles.
Das Projekt "Study of sorption of the mobile forms of mercury by fly ash from thermal power plants with the aim of immobilising them in silts and soils" wird vom Umweltbundesamt gefördert und von GALAB durchgeführt. It is known that power station fly ash can act as a sorbent for mercury in aqueous solutions, and that it appears to bind strongly to mercury present in soil. Fly ash itself is a multi-component system, however, composed of a glass, amorphous, crystalline and carbon phases. In addition, mercury appears in many forms, varying significantly in their stability and the degree of threat posed to human health and the environment. The overall behaviour of the ash-mercury system is thus extremely complex, and may involve both physical and chemical bonding, precipitation and entrapment. For fly ash to be considered as a potential remediation material, detailed knowledge of the processes by which it removes mercury is needed. The project objectives are thus: - To determine kinetic characteristics of the sorption/desorption reactions, including those at high sorbate concentrations, of different mercury species with power station fly ash and its sub-components; - To add to the understanding of which components of power station fly ash are responsible for mercury immobilisation and the mechanisms through which this takes place; - To identify, characterise and quantify the different forms of mercury that result from its interaction with power station fly ash and its sub-components; - To assess the availability of mercury sorbed on power station fly ash to biological methylation; - To provide fundamental kinetic data for future use in the estimation of the suitability of power station fly ash for the stabilisation and remediation of mercury contaminated sites. The project will use two distinct ash types: the first with high alkalinity, the second type characteristic of coals with a low calcium content which form a lower alkalinity ash. As well as unmodified ash, the study will look at ash sorted to give fractions rich in the major constituents: glass cenospheres, isotropic and anisotropic coke, and intertinite. The sorption behaviour of the total ash and its fractions will be investigated with respect to the most important mercury species: inorganic (cationic, anionic in chloride complexes, oxidic), elementary (mercury vapour) and organic (CH3HgCl). Sorption and desorption characteristics and equilibrium constants will be established using isotherm techniques for mercury species in solution (and mercury vapour - at different partial pressures) exposed to ash and its components at their inherent pH which may range from 4 to 10.5. The rates of adsorption and desorption will be established, with time sequencing analysis of the sorbate solutions. The equilibrium and kinetic parameters of dissolution of elementary mercury and mercury oxides in weakly mineralised water (0.5 g/l) will be experimentally determined to establish the relationship with pH. Oxidation-reduction transformations of sorbed mercury will be carried out on ash samples containing various concentrations of inorganic or elementary mercury, with the help of weak redox reagents (oxygen from air, aldehy
Das Projekt "Sub project: Fault zone damage and chemical reactions at depth in the San Andreas Fault Zone: A study of SAFOD drill core samples" wird vom Umweltbundesamt gefördert und von Helmholtz-Zentrum Potsdam Deutsches GeoForschungsZentrum durchgeführt. The results of the first funding period, particularly the proof of several weakening and hardening mechanisms operating in the fault gouge of four SAFOD core samples (e.g. amorphous material, nano-scale pore spaces, dissolution-precipitation processes, intracrystalline plasticity) inspired a more detailed study of microstructures in order to specify the cause of mechanical weakness along the San Andreas Fault (SAF). Therefore we applied for and received four additional core samples from different depths and different distances to the fault contact. In particular, we will focus on: - The analysis of dominant microstructures in the new SAFOD samples. Based on our previous experience we will predominantly use the transmission electron microscopy (TEM). These studies have proven to be the most powerful tool for analyzing microstructures. The cutting of foils with the focused ion beam technique (FIB) allows identifying microstructures down to the nm scale without damage. - The observed microstructures will be interpreted in view of their implication for fault weakening mechanisms integrating previous results of the core samples from the first funding period. - The observed agglomeration of flocculated clay particles in previous samples calls for further detailed TEM investigations of clay minerals. - Some vein-calcites show evidence for intense intracrystalline plasticity (deformation twins and dislocation creep). We will measure dislocation and twin densities in calcite veins in the new sample set. The results will be used for stress estimations based on paleo-piezometric relationships. - First results of stable isotope analyses of vein calcites provide indications that the fluids were dominantly derived from deeper sources. We will further analyze stable isotopes with the aim to characterize the origin of fluids penetrating the fault gouge. - Mercury porosimetry and the BET gas adsorption methods will be used to measure the connected rock porosity pore volume and pore surface areas of our new samples. Porosity data will be used to roughly estimate permeability. - SAFOD microstructures will be compared to samples recently obtained from the Taiwan Chelungpu fault Drilling Project (TCDP).
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