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The article “Determination of organically bound fluorine sum parameters in river water samples - Comparison of combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS)” was originally published Online First without Open Access. After publication in volume 413, issue 1, page 103–115 of the journal “Analytical and bioanalytical chemistry”, the authors decided to opt for Open Choice and to make the article an Open Access publication. Therefore, the copyright of the article has been changed to © The Author(s) 2021 and the article is forthwith distributed under the terms of the Creative Commons Attribution 4.0 International License.
In this study, we compare combustion ion chromatography (CIC) and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) with respect to their applicability for determining organically Bound fluorine sum parameters. Extractable (EOF) and adsorbable (AOF) organically bound fluorine as well as total fluorine (TF) were measured in samples fromriver Spree in Berlin, Germany, to reveal the advantages and disadvantages of the two techniques used as well as the two established fluorine sum Parameters AOF and EOF. TF concentrations determined via HR-CS-GFMAS and CIC were comparable between 148 and 270 μg/L. On average, AOF concentrations were higher than EOF concentrations, with AOF making up 0.14–0.81% of TF (determined using CIC) and EOF 0.04–0.28% of TF (determined using HR-CSGFMAS).
The results obtained by the two independent methods were in good agreement. It turned out that HR-CS-GFMAS is a more sensitive and precise method for fluorine analysis compared to CIC. EOF and AOF are comparable tools in Risk evaluation for the emerging pollutants per- and polyfluorinated alkyl substances; however, EOF is much faster to conduct.
Permeable reactive barriers (PRBs) offer an alternative as opposed to more cost-intensive active methods for groundwater remediation, e.g. pump-and-treat. Long-term performance of PRBs, however, is crucial for the technology’s success. The paper summarises the results of long-term column experiments with elemental iron (Fe0) and hydroxyapatite (HAP) as reactive materials for the removal of uranium from groundwater. Good removal results have been achieved using elemental iron with possible reaction paths being reductive precipitation and adsorption on to corrosion products of Fe0.
Die Reduzierung von Schadstoffen im Grundwasser mit reaktiven Wänden ist eine neuartiges passives Sanierungsverfahren. Die am häufigsten angewandten Dekontaminierungsprozesse sind dabei chemische Reduktion, Oxidation, Ausfällung und Sorption, die im Bericht beispielhaft dargestellt sind. Blei, Chrom und insbesondere Uran werden unter den anorganischen Schadstoffen detailliert behandelt, da solche Grundwasserverunreinigung in vielen europäischen Ländern auftreten. Baumethoden für Dichtwände und reaktive Wände weisen gemeinsame Merkmale auf. Neben den gewöhnlichen Methoden werden Bohrverfahren, deep-soil-mixing, Strahltechnologien, Brunnengalerien, Injektionssysteme und Biobarrieren angewendet, um reaktive Wände zu errichten. Die Technik der reaktiven Wände besitzt ein großes Potential für die Sanierungstechnik der Zukunft.
Langzeitbeständigkeit von permeablen reaktiven Wänden zur Sanierung kontaminierter Grundwässer
(2003)
In Germany, about 60 million tons of demolition waste are generated annually. Approximately 70% of the demolition waste is currently recycled. Most recycling applications, for example in roadbed substructures, can be seen as a kind of downcycling. However, there are also some high-level applications for demolition waste. For instance, crushed and sieved concrete demolition waste can be used as concrete aggregate instead of natural materials. Depending on the crushing process, about a third of the broken concrete is currently concrete sand. At present, concrete sand fraction (0-4 mm) is rarely reused as a concrete aggregate. This is due to the fact that some important characteristics of crushed concrete sand are different from those of natural sand. As a result, it does not reach the standards required for aggregates. Concrete containing such aggregate is of lower quality than concrete made of natural aggregate. This paper describes an experimental investigation on the treatment of concrete sand gained from demolition waste by wet processing using a jig whereby the sand is separated by grain size and, more importantly, by density. Concrete produced with concrete sand which has been treated in this manner should have the same quality as concrete prepared with natural aggregate. Recycled sand used as aggregate substitutes natural resources and avoids disposal of waste. It has all the characteristics of an Ecomaterial. (author abst.)
The recycling of refractory materials in the chemical, metallurgical and glass industry has only had minor relevance until now because of the high performance required from these materials (stability against corrosion, inert when coming into contact with the glass melt, etc.). Refractory lifetimes are limited because of corrosion at higher temperatures. The best furnace lifetimes has been achieved with chromium oxide and chromium oxide corund refractories. Waste from the production and use of refractory material is generated in three main forms: as residues from cutting and grinding, as refractories which have limited or no contact with glass melts, and as refractories with infiltration of sublimation residues or condensates. The waste material is classified as hazardous waste due to its chromium content. In this study, arc furnace technology was used for thermal treatment of the waste materials to enable recycling of refractory materials. (author abst.)
This study was undertaken to investigate the long-term performance of hydroxyapatite (HAP) as reactive material for the removal of uranium in passive groundwater remediation systems. 237U used as a radioindicator enabled tracking the movement of the contamination front through a test column without taking samples or dismantling the apparatus. The stoichiometric ratio between uranium and HAP was found to be 1:(487±19). Uranium removal by HAP is of pseudo first-order kinetics and the rate constant was measured to be (1.1±0.1)×10-3 s-1. HAP can sorb more than 2900 mg/kg uranium. Possible reaction pathways of uranium and HAP are discussed. The data obtained enable the calculation of ideal lifetime for permeable reactive barriers (PRB) using HAP for uranium removal neglecting hydrological factors that may impair the function of PRBs.
Engineered capping systems are in most cases an indispensable and often the only efficient component required by the long-term safety concept for landfills, mine tailings tips and contaminated land. In Germany the composite liner is the main component of standard landfill cappings for municipal and hazardous waste landfills and the compacted clay liner (CCL) for landfills for inert or low-contamination waste. The composite liner is a technically highly effective but very expensive system. Research and experience has given rise to concern about the proper long-term performance of a conventional single CCL as a landfill capping. Therefore, alternative capping systems are discussed and applied for landfills and for the containment of contaminated sites. This paper gives an overview on various alternative engineered cappings and suitable systems for capping reflecting the state of the art and the expert view in Germany. According to the European Council Directive on the landfill of waste an impermeable mineral layer is recommended for the surface sealing of non-hazardous landfills and a composition of artificial sealing liner and impermeable mineral layer for hazardous landfills. In both cases a drainage layer thickness of at least 0.5 m is suggested. These recommendations should be interpreted flexibly and to some extent modified in the light of the experience and results presented in this paper.
This study was undertaken to investigate the long-term performance of elemental iron as reactive material for the removal of uranium in passive groundwater remediation systems. By using 237U as a radioindicator it was possible to track the movement of the contamination front through a test column without taking samples or dismantling the apparatus. The stoichiometric ratio between uranium and iron was found to be 1:(1390±62). The reaction between iron and uranium is of pseudo first-order kinetics and the rate constant was measured to be (1.1±0.09)×10-3 s-1. These data enable the calculation of ideal lifetime for permeable reactive barriers (PRB) using iron for uranium removal neglecting hydrological factors that may impair the function of PRBs.
Deponien im Jahr 2020
(2001)
Long-term performance of permeable reactive barriers has been investigated in laboratory experiments using elemental iron and hydroxyapatite as reactive materials and uranium as contaminant. Accelerated testing has been performed by applying elevated pollutant concentration and an increased flow velocity. The spatial distribution of uranium in the test columns has been investigated using a radioactive tracer. The results show that the migration pattern exhibits a linear behaviour.
Glossary Biomineralization A process by which living organisms produce minerals. - Chernobyl Ukrainian city site of the largest nuclear power plant accident in history. - Cut-off-wall Underground structure designed to prevent the flow of water. - DART Deep aquifer remediation tool. - Diffusion Movement of ions and molecules from places of higher concentration to places of lower concentration. - Electrochemical remediation Remediation technologies comprising electrochemical transport and transformation methods. - Electrokinetic screens Structures used to prevent radionuclides from diffusing from the polluted area into the environment. - Electromigration Transport of charged ions or ion complexes in solution. - Electroosmosis Movement of liquid relative to a charged stationary surface, - Electrophoresis Movement of charged particles relative to a stationary fluid. - Enhanced electrochemical remediation Use of pH control and additives to improve removal efficiency. - EURT East Urals Radioactive Trail area contaminated due to a nuclear accident. - Natural attenuation (NA) Remediation relying entirely on natural processes. - Permeable reactive barriers Passive in situ treatment zones of reactive material that degrades or immobilizes contaminants as groundwater flows through it. - Phytoremediation Soil remediation using living plants and their associated microorganisms. - Radionuclide or radioisotope An atom with an unstable nucleus whose excess energy is available to be imparted to a newly-created radiation particle within the nucleus or to an atomic electron. - Total material requirement (TMR) Sum of domestic and imported primary natural resources and their hidden flows.
Ressourcen aus Abfall
(2012)
Die Beseitigung unbehandelter Abfälle auf Deponien gehört der Vergangenheit an, nicht nur weil Verordnungen diese Praxis verbieten, sondern auch, weil wegen steigender Preise für Rohstoffe und sinkender Gehalte in Erzen auch in Abfällen nach Alternativen gesucht wird. In den Aschen aus Hausmüllverbrennungsanlagen können mit einfachen Verfahren Metalle zurückgewonnen werden. Mit dem Phosphor aus Klärschlammaschen können Düngemittel hergestellt und so natürliche Ressourcen geschont werden. In beiden Fällen ist die Anreicherung der Wertstoffe durch den Verbrennungsprozess vorteilhaft, da die Effizienz von Recyclingprozessen stark von der Konzentration im Ausgangsgut abhängig ist.--------------------------------------------------------------------------------------------------------------------------------
Disposal of untreated waste has come to end due to new legislation in this field. Furthermore as a response to increasing prices for primary raw materials and decreasing ore concentrations products from waste treatment display a source for secondary raw materials. Elemental metals can be easily separated from municipal solid waste incineration bottom ash. Fertilizers can be produced using phosphate from sewage sludge ashes thus preserving natural resources. In both cases the enrichment taking place in the incineration process facilitates the resource recovery, because the efficiency of recycling processes is dependent on the concentration of the input material.
Die Abfallwirtschaft in Deutschland behandelt eine Menge von 359 Mio. Tonnen. Den größten Anteil haben Bau- und Abbruchabfälle mit 54%. Die Behandlungsverfahren dafür unterscheiden sich stark von denen für Siedlungsabfälle. Gemäß Europäischer Abfallrichtlinie ist Recycling gegenüber einer energetischen Verwertung in der Hierarchie der Abfallbehandlungsverfahren höher bewertet. Bei der thermischen Behandlung entscheidet die Energieeffizienz des Verfahrens, ob eine Behandlung als Verwertung oder Beseitigung gilt. Nach dieser Richtlinie erfolgt die Berechnung der Energieeffizienz stark vereinfacht mit der sogenannten R1-Formel. Veröffentlichte Daten zu Wärme- und Stromproduktion verschiedener thermischer Abfallbehandlungsanlagen werden mit der R1-Formel und Daten aus der Literatur verglichen. Mengen und Entsorgungswege sowie Möglichkeiten zur Bewertung von Abfallbehandlungsverfahren werden diskutiert. ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Waste management in Germany covers an amount of 359 million tons. The largest fraction is construction and demolition waste (C&D waste) with some 54%. The treatment processes for C&D waste differ from those for municipal solid waste. According to the European Directive on Waste a waste hierarchy shall apply where recycling has a higher priority than energy recovery. A thermal treatment is regarded as recovery operation only if the energy efficiency is above a certain limit. Under the terms of the directive a simplified calculation of the energy efficiency is perfomed using the so-called R1 formula. Published data on heat and power production of several thermal waste treatment plants are compared to the R1 formula and data from literature. Amount and waste management options for different waste fractions and how to evaluate different waste management processes are discussed.
Kreislauf von Ressourcen
(2013)
Die Materialflüsse in Industriegesellschaften sind von enormer Größe. Im Jahr 2008 betrug der direkte Materialeinsatz (direct material input, DMI) (Czichos et al., 2008) in Deutschland 1687 Millionen Tonnen (Daten von destatis, 2010). Dazu gehören Energieträger (Kohle, Öl, Gas), Erze, Baumaterialien, Industrieminerale und Biomasse. Knapp 36 % davon (605 Millionen t) werden importiert. Mit zu berücksichtigen sind bei den Materialflüssen auch die nicht verwerteten Rohstoffentnahmen (z.B. Abraum im Bergbau, Bodenaushub, Bergematerial, Verbleib von Holzabfallen im Wald), die sich für die inländische Rohstoflentnahme auf 2229 Millionen Tonnen beliefen. Die nicht verwerteten Rohstoffentnahmen bei den Importen sind mehr als der Faktor 4 höher (2543 Millionen t) (Buyny et al., 2009).
Auf der Outputseite geht von diesen riesigen Mengen der größere Anteil in den Bestand (net addition to stock, 637 Millionen t), der nächst größere Anteil in den Export (388 Mt). Immerhin 256 Millionen Tonnen werden durch dissipative Nutzung in der Umwelt verteilt. Die Bilanz geht auf, wenn man Gase auf der Inputseite und Emissionen in die Atmosphäre auf der Outputseite (Verbrennung von fossilen Rohstoffen zu CO2 und Wasser) berücksichtigt. An diesen Zahlen erkennt man, dass Ressourcen nur in beschränkten Maß im Kreislauf geführt werden, sonst wäre der Zuwachs zum urbanen Lager nicht so groß.
Werkstoffe
(2012)
Municipal sewage sludge is a carrier of nutrients most important phosphorus (P) but also contains organic pollutants and heavy metals. A two steps thermal treatment is suggested based on 1. mono-incineration of sewage sludge under destruction of organic pollutants and 2. thermochemical treatment of the resulting ashes to remove heavy metals and increase P-bioavailability. The targeted products are marketable P-fertilisers. The thermochemical treatment was investigated in a gas tight lab-scale rotary furnace. Seven sewage sludge ashes of different origin and composition and one residue from gasification of sewage sludge were mixed with a chlorine donor (e.g. MgCl2) and thermochemically treated under systematic variation of operational parameters. The distributions of the heavy metals between solid and gas phase were determined. The heavy metals concentrations of the treated ashes met the legislative limits in most cases. The products from thermochemical treatment are suited raw materials for P-fertiliser production. Relevant process parameters such as temperature, type and concentration of Cl-donor and retention time were optimised for the thermochemical treatment step.
New horizons of the structural characterization of stainless steel slags by X-ray powder diffraction
(2007)
Analytik für Ersatzbaustoffe
(2008)
Elemental iron (Fe0) and hydroxyapatite (HAP) were evaluated as reactive materials in PRBs for uranium remediation. Laboratory experiments were carried out and a pilot-scale reactive barrier with Fe0 was installed in Pécs (Southern Hungary). Results of 2.5 years of operation are reported. The PRB has a considerable influence on groundwater composition: uranium concentrations decrease from 900 µg/l to <10 µg/l, TDS drop from 1,000 mg/l to 500 mg/l.
Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soilgroundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.