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Light concentration opens up the path to enhanced material efficiency of solar cells via increased conversion efficiency and decreased material requirement. For true material saving, a fabrication method allowing local growth of high quality absorber material is essential. We present two scalable fs-laser based approaches for bottom-up growth of Cu(In,Ga)Se2 micro islands utilizing either site-controlled assembly of In(,Ga) droplets on laser-patterned substrates during physical vapor deposition, or laser-induced forward transfer of (Cu,In,Ga) layers for local precursor arrangement. The Cu(In,Ga)Se2 absorbers formed after selenization can deliver working solar devices showing efficiency enhancement under light concentration.
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).
More sustainable waste management practices are an important element in the Transformation towards a circular economy (CE). Activities in this area should be dedicated to all groups of waste, including those generated in the water and sewage sector. This paper presents the characteristics of sewage sludge ash (SSA) coming from Polish municipal waste incineration plants. Due to the high content of nutrients such as phosphorus (8.01% P2O5), calcium (5.11% CaO) and magnesium (2.75% MgO), the analyzed SSA may constitute a valuable source of raw materials for the fertilizer industry.
Despite the good fertilizing properties of the SSA, in some cases the presence of heavy metals such as cadmium (0.74–1.4 mg/kg dry matter), lead (49.8–99 mg/kg dry matter), mercury (3.93 mg/kg dry matter) and arsenic (4.23–4.43 mg/kg dry matter) and poor bioavailability of P from SSA disqualifies this waste from direct use as a fertilizer. Therefore, it is necessary to look for methods that will allow the municipal SSA to be processed, for example, technologies for the extraction of phosphorus and the production of phosphate fertilizer. This way of SSA management is in the line with the CE assumptions, in which waste becomes a valuable source of secondary raw materials. Fertilizer produced from waste meeting quality, safety and labelling requirements and limits of organic, microbiological and physical contaminants will be able to be traded freely within the European Union (EU) and receive the CE marking. The idea of use of SSA for fertilizer purposes is consistent not only with the objectives of the CE but also with the Polish National Waste Management Plan 2022 and the Municipal Sewage Sludge Strategy 2019–2022, which emphasizes the necessity to maximize the use of biogenic substances contained in wastewater. Therefore, sustainable management of SSA, in particular its storage in a way enabling the recovery of phosphorus, should be promoted.
Uranium and thorium species in phosphate rock and sewage sludge ash based phosphorus fertilizers
(2020)
Phosphorus (P) is an essential element for all forms of life and is thus often applied as phosphate rock-based P-fertilizers in agriculture to enable continuous farming. However, these P-fertilizers contain also hazardous uranium (U) and thorium (Th), up to 660 and 220 mg/kg, respectively. On the contrary, novel P-fertilizers made from sewage sludge (ash) contain only low mass fractions of U and Th. In addition to the total amount of U and Th in P-fertilizers, their mobility and bioavailability is important, which depends to a large extent on their chemical state, especially oxidation state and chemical bonding. Thus, we analyzed their chemical state in various P-fertilizers by U and Th L3-edge HERFD-XANES spectroscopy. Phosphate rocks and sewage sludge-based P-fertilizers contain mainly U(IV) compounds which have only a low bioavailability. In contrast, acidic treatment of phosphate rock to produce super phosphates lead to an oxidation to U(VI) compounds (including formation of uranium phosphates) with a strongly increased bioavailability. On the contrary, all analyzed P-fertilizers contain Th in form of strongly insoluble phosphates and oxides with a low bioavailability. Additionally performed water extractions and Diffusive Gradients in Thin-films (DGT) experiments support these findings.
Many wooden artworks are contaminated by DDT (dichlorodiphenyltrichloroethane) as a result of a surface treatment by means of the liquid preservative Hylotox-59©. It was used until the end of the 1980s. DDT crystal structures are formed on the wood surfaces by the "blooming" of chlorine compounds. In addition to an aesthetic disturbance, it is assumed that DDT represents a health risk. Even decades after applying, the toxins in the wood preservatives are still detectable because they are of low volatility in many wood samples. Contaminated waste wood with natural biocide ageing, gilded and wood carved elements of an old picture frame and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen. Non-contact procedures using laser and plasma appear reasonable to remove the DDT crystals. During the experiments, health and safety issues for the operator have to be taken into account.
The removal of DDT was evaluated employing femtosecond and nanosecond laser radiation and cold atmospheric plasma techniques with different working gases (air, nitrogen, and argon). Before laser application, a chlorine measurement representing the DDT density on the wooden surface is done by X-ray fluorescence (XRF) analysis as reference. After laser processing, the XRF analysis is used again at the same surface position to determine the depletion rate. Additionally, a documentation and characterization of the sample surface is performed before and after laser and plasma treatment using optical microscopy (OM). For plasma processing with various systems a chlorine measurement is done by gas chromatographic-mass spectrometry (GCMS) analysis.