4 Material und Umwelt
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Dem Fachbeirat Bodenuntersuchungen des BMBF/UBA wurden die abschließenden Ergebnisse zum UFOPLAN-Forschungsvorhaben „Monitoring zur Verwertung von Bodenmaterial“ vorgestellt. Die potentielle Auswirkung der neuen Regularien in der geplanten Novelle der BBodSchV (4. Referentenentwurf der Mantelverordnung) auf die Erweiterung der Verwertungsmöglichkeiten von Bodenmaterialien wurden aufgezeigt.
The Brazilian sugarcane industry produced around 173 million tons (Mt) of bagasse in 2018. Bagasse is a by-product of juice extraction for ethanol and sugar production and is combusted in order to generate power, producing up to 10 Mt of ash per year. This ash contains various concentrations of plant nutrients, which allow the ash to be used as a crop fertilizer. However, the concentration and extractability of phosphorus (P), an essential plant nutrient, are low in bagasse ash. To increase the P content, we co-gasified and co-combusted bagasse with P-rich chicken manure. The resulting ash was thermochemically post-treated with alkali additives (Na2SO4 and K2SO4) to increase the availability of P to plants. We aimed to: (i) investigate the effect of thermochemical post-treatment of co-gasification residue and co-combustion ash on P availability to soybeans, (ii) explore the potential of chemical extraction methods (citric acid, neutral ammonium citrate, formic acid, and Mehlich-I) and diffusive gradients in thin films (DGT) to predict the availability of P to soybeans, and (iii) identify the responsible P-phases using X-ray diffraction . We evaluated P availability to soybeans growing in Brazilian Oxisol soil in two independent greenhouse pot experiments. The positive effect of thermochemical treatment on P availability from gasification residue was confirmed through the observation of increased P uptake and biomass in soybean plants. These findings were confirmed by chemical extraction methods and DGT. The gasification residue contained whitlockite as its main P-bearing phase. Thermochemical post-treatment converted whitlockite into highly soluble CaNaPO4. In contrast, co-combustion ash already contained highly soluble Ca(Na,K)PO4 as its main P-bearing phase, making thermochemical post-treatment unnecessary for increasing P availability. In conclusion, increased extractability and availability of P for soybeans were closely connected to the formation of calcium alkali phosphate. Our findings indicate that this combined methodology allows for the prediction of P-fertilization effects of ash.
Weltweit werden etwa 80–85 % aller abgebauten Rohphosphate für die Produktion von Düngemitteln verwendet. Bei noch steigendem Bedarf an Phosphor (P) geht man derzeit davon aus, dass die weltweiten P-Reserven noch über 200 Jahre ausreichen. Um den P-Vorrat langfristig abzusichern, sollte der in Reststoffen enthaltene Phosphor möglichst umfänglich genutzt werden. Dieser Forderung trägt das von der Bundesregierung 2012 erstmals beschlossene Deutsche Ressourceneffizienzprogramm ProgRess Rechnung. Rohphosphat wird auch seitens der Europäischen Kommission aufgrundseiner ökonomischen Bedeutung und des unsicheren Angebots als „kritischer Rohstoff“ eingestuft. Vor diesem Hintergrund hat die Bundesregierung in der Verordnung zur Neuordnung der Klärschlammverwertung vom 27. September 2017 in Deutschland eine verpflichtende technische Rückgewinnung von Phosphor für Abwasserbehandlungsanlagen ab einer Ausbaugröße von 100.000 Einwohnerwerten (12 Jahre nach Inkrafttreten der Verordnung) bzw. ab einer Ausbaugröße von über 50.000 Einwohnerwerten (15 Jahre nach Inkrafttreten der Verordnung) vorgeschrieben. Die Verordnung enthält keine Vorgaben hinsichtlich der anzuwendenden Technologie bei der Phosphorrückgewinnung. Ausgenommen von der Rückgewinnungspflicht sind Klärschlämme mit niedrigen Phosphorgehalten (weniger als 20 Gramm Phosphor je Kilogramm Klärschlamm-Trockenmasse). Auch die im Jahre 2017 verabschiedeten neuen Rechtsvorschriften für die Düngung verlangen zukünftig einen nachhaltigen und ressourceneffizienten Umgang mit Nährstoffen bei der landwirtschaftlichen Erzeugung und schränken die P-Zufuhr insbesondere auf hoch versorgten Böden ein (Düngeverordnung vom 26. Mai 2017). Dies wird zu einem mehr am Pflanzenbedarf orientierten und ggf. vermehrt überbetrieblichen Einsatz von wirtschaftseigenen Düngern führen. Um den politischen und gesetzlichen Anforderungen gerecht zu werden, müssen einerseits wirksame und kosteneffiziente technische Verfahren zum P-Recycling (weiter)entwickelt werden. Andererseits müssen die Recyclingprodukte die Anforderungen für eine direkte Verwendung in der Landwirtschaft oder als Rohstoff für die Herstellung von Düngemitteln erfüllen. In dem vorliegenden Standpunkt wird zunächst der potenzielle Beitrag von Reststoffen zur Deckung des P-Bedarfs in der deutschen Pflanzenproduktion geschätzt. Für die wichtigsten Reststoffe werden technische Verfahren zur P-Rückgewinnung bzw. Aufarbeitung skizziert. Auf Basis der Anforderungen der Landwirtschaft bzw. der Düngemittelindustrie
an die P-Recyclingprodukte werden deren Herstellungsverfahren bewertet. Schließlich wird der Regelungs- und Forschungsbedarf formuliert.
Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizers can also contain toxic pollutants such as chromium in its hexavalent state (Cr(VI)). This hazardous form of chromium is therefore regulated with low limit values for agricultural products even though the correct determination of Cr(VI) in these fertilizers may be hampered by redox processes, leading to false results. Thus, we applied the novel diffusive gradients in thin-films (DGT) technique for Cr(VI) in fertilizers and compared the results with the standard wet chemical extraction method (German norm DIN EN 15192) and Cr K-edge X-ray Absorption near-edge structure (XANES) spectroscopy. We determined an overall good correlation between the wet chemical extraction and the DGT method. DGT was very sensitive and for most tested materials selective for the analysis of Cr(VI) in P-fertilizers. However, hardly soluble Cr(VI) compounds cannot be detected with the DGT method since only mobile Cr(VI) is analyzed. Furthermore, Cr K-edge XANES spectroscopy showed that the DGT binding layer also adsorbs small amounts of mobile Cr(III) so that Cr(VI) values are overestimated. Since certain types of the P fertilizers contain mobile Cr(III) or partly immobile Cr(VI), it is necessary to optimize the DGT binding layers to avoid aforementioned over- or underestimation. Furthermore, our investigations showed that the Cr K-edge XANES spectroscopy technique is unsuitable to determine small amounts of Cr(VI) in fertilizers (below approx. 1% of Cr(VI) in relation to total Cr).
Phosphorus (P) resource availability is declining and the efficiency of applied nutrients in agricultural soils is becoming increasingly important. This is especially true for P fertilizers from recycled materials, which often have low plant availability. Specific co-fertilization with ammoniumcan enhance P plant availability in soils amended with these P fertilizers, and thus the yield of plants. To investigate this effect, we performed a pot experiment with maize in slightly acidic soil (pH 6.9) with one water-soluble (triple superphosphate [TSP]) and two water-insoluble (sewage sludge-based and hyperphosphate [Hyp]) P fertilizers and anammoniumsulfate nitrate with or without a nitrification inhibitor (NI). The dry matter yield of maize was significantly increased by the NI with the Hyp (from 14.7 to 21.5 g/pot) and TSP (from 40.0 to 45.4 g/pot) treatments. Furthermore, P uptake was slightly increased in all three P treatments with the NI, but not significantly. Olsen-P extraction and P K-edge micro-X-ray absorption near-edge structure (XANES) spectroscopy showed that apatite-P of the water insoluble P fertilizers mobilized during the plant growth period. In addition, novel nitrogen (N) K-edge micro-XANES spectroscopy and the Mogilevkina method showed that the application of an NI increased the fixation of ammonium in detectable hot spots in the soil. Thus, the delay in the nitrification process by the NI and the possible slow-release of temporarily fixed ammoniumin the soil resulted in a high amount of plant available Ammonium in the soil solution. This development probably decreases the rhizosphere pH due to release of H+ by plants during ammoniumuptake, whichmobilizes phosphorus in the amended soil and increases the dry matter yield of maize. This is especially important for water-insoluble apatite-based P fertilizers (conventional and recycled), which tend to have poor plant availability.
Es wird über aktuelle Arbeitsthemen und Entwicklungen im Fachbeirat berichtet. So wurde in einer Sondersitzung des Fachbeirats über die Entlassung aus der Nachsorgephase beim Einsatz von Geokunststoffprodukten in Böschungen diskutiert. Die Unterarbeitsgruppe Fremdüberwachung in der Produktion hat getagt. Darüber hinaus werden Änderungen in den Zulassungsrichtlinien für Kunststoffdichtungsbahnen, Kunststoff-Dränelemente und für die Fremdüberwachung kurz vorgestellt.
Es wird über aktuelle Arbeitsthemen und Entwicklungen im Fachbeirat berichtet. So wurde in einer Sondersitzung des Fachbeirats über die Entlassung aus der Nachsorgephase beim Einsatz von Geokunststoffprodukten in Böschungen diskutiert. Die Unterarbeitsgruppe Fremdüberwachung in der Produktion hat getagt. Darüber hinaus werden Änderungen in den Zulassungsrichtlinien für Kunststoffdichtungsbahnen, Kunststoff-Dränelemente und für die Fremdüberwachung kurz vorgestellt.
The suitability of common analytical methods for the determination of active substances from wood preservatives in aged wood samples was investigated during an interlaboratory study. Permethrin, propiconazole and tebuconazole were quantified in 1.5 and 8 year-old wood samples by gas chromatography and liquid chromatography. Generally, the applied Methods yielded reliable results for these samples. However, wood components can coelute with propiconazole and tebuconazole during liquid chromatography. Optimization of separation might be required if UV detection is applied.
Designing the performance of geogrids in reinforce soil constructions usually does not consider long-term behavior and possible failure modes of junctions between longitudinal and transverse ribs. How could behavior of junctions be included? To which extend is it necessary? On the conference Geo-Chicago 2016, Swan and Yuan presented an ultimate limit state equation for the short-term material resistance of junctions. We discuss limitations and suggest improvements to include long-term behavior of junctions. Nevertheless, the approach applies only to a specific mode of shear-tensile failure of junctions and only to strictly rigid geogrids. A new design concept presented in the same year by Jacobs on the conference GeoAmerica for the special case of the anchorage of geogrids, which reinforce capping system on long and steep slopes of landfills, tried to overcome these drawbacks. We discuss the aspects of this concept related to the long-term behavior
of junctions and the interplay between the load applied to junctions and the flexibility of longitudinal ribs. This interplay and the long-term junction strength determine the long-term behavior of geogrids.
Designing the performance of geogrids in reinforce soil constructions usually does not consider long-term behavior and possible failure modes of junctions between longitudinal and transverse ribs. How could behavior of junctions be included? To which extend is it necessary? On the conference Geo-Chicago 2016, Swan and Yuan presented an ultimate limit state equation for the short-term material resistance of junctions. We discuss limitations and suggest improvements to include long-term behavior of junctions. Nevertheless, the approach applies only to a specific mode of shear-tensile failure of junctions and only to strictly rigid geogrids. A new design concept presented in the same year by Jacobs on the conference GeoAmerica for the special case of the anchorage of geogrids, which reinforce capping system on long and steep slopes of landfills, tried to overcome these drawbacks. We discuss the aspects of this concept related to the long-term behavior of junctions and the interplay between the load applied to junctions and the flexibility of longitudinal ribs. This interplay and the long-term junction strength determine the long-term behavior of geogrids.
Mit der Novellierung der Bundes-Bodenschutz- und Altlastenverordnung (BBodSchV) (am 6.11.2020 im Bundesratsverfahren beschlossen) werden Regelungen zum Auf- und Einbringen von Bodenmaterial außerhalb der durchwurzelbaren Bodenschicht aufgenommen (sogenannte Verfüllungen). Ziel des Vorhabens war es, durch die Auswertung vorhandener und durchzuführender Untersuchungen eine Einstufung von Bodenmaterialien (jährlich fallen weit über 100 Mio. Tonnen davon an) für bestimmte Verwertungswege vornehmen zu können. Es sollte herausgefunden werden, ob Veränderungen hinsichtlich des Verwertungspotentials nachgewiesen werden können.
Basis für die Durchführung und Bewertung waren die neuen Regelungen (hier insbesondere die Untersuchung mit einem Wasser/Feststoffverhältnis von 2:1, neue nationale und europäische Elutions- und Untersuchungsverfahren) der novellierten BBodSchV. Der Fokus lag dabei auf den polyzyklischen aromatischen Kohlenwasserstoffen (PAK) sowie ausgewählte anorganische Stoffe (Schwermetalle und Anionen) unter der Berücksichtigung unterschiedlicher Bodenmaterialien zur Verwertung.
Dabei handelte es sich um:
- Böden aus urban geprägten Gebieten,
- Oberböden aus dem Straßenrandbereich in Form von Bankettschälgut,
- Baggergut aus Gewässern mit Verdacht auf eine Kontamination,
- Bergematerial (Mischung von Abraum- und Bodenmaterial),
- Auenböden mit vermuteten Verunreinigungen aus Industrie und Gewerbe.
Anhand der vorgelegten Ergebnisse kann nun eine Versachlichung der Diskussion um Ressorcenschutz vs. Schadlosigkeit der Verwertung erfolgen. Sie zeigen für die untersuchten Stoffe, dass bei einer Einführung der §§ 6-8 Novelle BBodSchV mit einer Erhöhung der Verwertungsquote für Bodenmaterial gerechnet werden kann. Eine Erhöhung des Deponievolumens ist somit nicht zu befürchten. Neben den ermittelten Daten konnten Grundlagen für die Überarbeitung verschiedener DIN-Normen für Bodenuntersuchungen erarbeitet werden.
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.
Municipal solid waste incineration (MSWI) is one of the leading technologies for municipal solid waste (MSW) treatment in Europe. Incineration bottom ash (IBA) is the main solid residue from MSWI, and its annual European production is about 20 million tons. The composition of IBA depends on the composition of the incinerated waste; therefore, it may contain significant amounts of ferrous and non-ferrous (NFe) metals as well as glass that can be recovered. Technologies for NFe metals recovery have emerged in IBA treatment since the 1990s and became common practice in many developed countries. Although the principles and used apparatus are nearly the same in all treatment trains, the differences in technological approaches to recovery of valuable components from IBA – with a special focus on NFe metals recovery – are summarized in this paper.
Over the past two decades, per- and polyfluoroalkyl substances (PFASs) have emerged as worldwide environmental contaminants, calling out for sophisticated treatment, decomposition and remediation strategies. In order to mineralize PFAS pollutants, the incineration of contaminated material is a state-of-the-art process, but more cost-effective and sustainable technologies are inevitable for the future. Within this review, various methods for the reductive defluorination of PFASs were inspected. In addition to this, the role of mechanochemistry is highlighted with regard to its major potential in reductive defluorination reactions and degradation of pollutants. In order to get a comprehensive understanding of the involved reactions, their mechanistic pathways are pointed out. Comparisons between existing PFAS decomposition reactions and reductive approaches are discussed in detail, regarding their applicability in possible remediation processes. This article provides a solid overview of the most recent research methods and offers guidelines for future research directions.
Almost 500 municipal solid waste incineration plants in the EU, Norway and Switzerland generate about 17.6 Mt/a of incinerator bottom ash (IBA). IBA contains minerals and metals. Metals are mostly separated and sold to the scrap market and minerals are either disposed of in landfills or utilised in the construction sector. Since there is no uniform regulation for IBA utilisation at EU level, countries developed own rules with varying requirements for utilisation. As a result from a cooperation network between European experts an up-to-date overview of documents regulating IBA utilisation is presented. Furthermore, this work highlights the different requirements that have to be considered. Overall, 51 different parameters for the total content and 36 different parameters for the emission by leaching are defined. An analysis of the defined parameter reveals that leaching parameters are significantly more to be considered compared to total content parameters. In order to assess the leaching behaviour nine different leaching tests, including batch tests, up-flow percolation tests and one diffusion test (monolithic materials) are in place.
A further discussion of leaching parameters showed that certain countries took over limit values initially defined for landfills for inert waste and adopted them for IBA utilisation. The overall utilisation rate of IBA in construction works is approximately 54 wt%. It is revealed that the rate of utilisation does not necessarily depend on how well regulated IBA utilisation is, but rather seems to be a result of political commitment for IBA recycling and economically interesting circumstances.
Potential use of incineration bottom ash in construction – Evaluation of the environmental impact
(2020)
Knowledge of the long-term leaching behavior of potentially harmful substances is crucial for the assessment of the environmental compatibility of reusing municipal solid-waste incineration bottom ash (MSWI BA) in construction, i.e., as a road base layer.
BA fractions obtained from wet-processing aiming at the improvement of environmental quality were used to investigate the mobility of relevant substances. Eluates from laboratory-scaled leaching procedures (column percolation and lysimeters) were analyzed to learn about the long-term release of substances. Unsaturated conditions and artificial rainwater (AR) were used in the lysimeter tests to simulate field conditions. In addition, batch test eluates were generated at usual liquid-to-solid ratios (L/S) for compliance testing purposes. A variety of cations and anions was measured in the eluates.
The wet treatment reduces the leaching of chloride and particularly sulfate by more than 60%. The release of typical contaminants for the treated MSWI BA such as the heavy metals Cu and Cr was well below 1% in the conducted leaching tests.
An increase in the Sb concentration observed in the lysimeter experiments starting at L/S 0.75 L/kg and in the column experiment at L/S 4 L/kg is assumed to be related to decreasing concentrations of Ca and thus to the dissolution of sparingly soluble calcium antimonate. The same leaching mechanism applies with V, but the concentration levels observed are less critical regarding relevant limit values. However, on the long term the behavior of Sb could be problematic for the application of MSWI BA in construction.