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- Phosphorus recovery (2)
- Sewage sludge ash (2)
- Antimony (1)
- Bioavailability (1)
- Field test (1)
- Heavy metal evaporation (1)
- Klärschlammasche (1)
- LIBS (1)
- Lead (1)
- Mercury (1)
Sewage sludge incineration is extensively practiced in some European countries such as the Netherlands, Switzerland, Austria and Germany. A survey of German sewage sludge ash showed that the recovery potential is high, approx. 19,000 t of phosphorus per year. However, the survey also discovered that the bioavailability of phosphorus in the sewage sludge ash is poor and that more than half of the ashes cannot be used as fertilizers due to high heavy metal content. A new thermochemical process for sewage sludge ash treatment was developed that transforms the ash into marketable fertilizer products. Sewage sludge ash was thermochemically treated with sodium and potassium additives under reducing conditions, whereby the phosphate-bearing mineral phases were transformed into plant available phosphates. High P-bioavailability was achieved with a molar Na/P ratio > 1.75 in the starting materials. Sodium sulfate, carbonate and hydroxide performed comparably as additives for this calcination process. Potassium carbonate and -hydroxide have to be added in a molar K/P ratio > 2.5 to achieve comparable P-solubility. The findings of the laboratory scale investigations were confirmed by an industrial demonstration trial for an ash treatment with sodium sulfate. Simultaneously, the volatile transition metal arsenic (61% removal) as well as volatile heavy metals such as cadmium (80%), mercury (68%), lead (39%) and zinc (9%) were removed via the off-gas treatment system. The product of the demonstration trial is characterized by high bioavailability and a toxic trace element mass fraction below the limit values of the German fertilizer ordinance, thus fulfilling the quality parameters for a P-fertilizer.
Es wurde ein Online-Analysenverfahren zur Bestimmung von Elementgehalten in Klär-schlammaschen und deren Produkten aus einem thermochemischen Verfahren entwickelt. Durch das thermochemische Verfahren können Wertstoffe aus den Aschen wieder für die Kreislaufwirtschaft nutzbar gemacht und Schadstoffe sicher entfernt werden. Das Analysensystem ist eine Methodenkombination von Online-Laser induzierter Plasma Spektroskopie (LIBS) und Online-Röntgenfluoreszenzanalyse (RFA). Robustheit und modulare Bauweise des Verfahrens sind wichtige Anforderungen um auch für andere Anwendungen nutzbar zu sein.
Small-arm shooting ranges often receive a significant input of lead (Pb), copper (Cu) and antimony (Sb) from ammunition. The goal of the present study was to investigate the mobility, distribution and speciation of Pb and Sb pollution under field conditions in both untreated and sorbent-amended shooting range soil. Elevated Sb (19–349 μg L⁻¹) and Pb (7–1495 μg Pb L⁻¹) concentrations in the porewater of untreated soil over the four-year test period indicated a long-term Sb and Pb source to the adjacent environment in the absence of remedial measures. Mixing ferric oxyhydroxide powder (CFH-12) (2%) together with limestone (1%) into the soil resulted in an average decrease of Sb and Pb porewater concentrations of 66% and 97%, respectively. A similar reduction was achieved by adding 2% zerovalent iron (Fe°) to the soil. The remediation effect was stable over the four-year experimental period indicating no remobilization. Water- and 1 M NH₄NO₃-extractable levels of Sb and Pb in field soil samples indicated significant immobilization by both treatments (89–90% for Sb and 89–99% for Pb). Results from sequential extraction analysis indicate fixation of Sb and Pb in less accessible fractions like amorphous iron oxides or even more crystalline and residual mineral phases, respectively. This work shows that amendment with Fe-based sorbents can be an effective method to reduce the mobility of metals both in cationic and anionic form in polluted shooting range soil.
Phosphorus-fertilizers from secondary resources such as sewage sludge ash (SSA) will become more important in the future as they could substitute conventional fertilizers based on the nonrenewable resource phosphate rock. Thermochemical approaches were developed which remove heavy metals from SSA prior to its fertilizer application on farmlands. We analyzed the chemical state of mercury and selenium in SSA before and after thermochemical treatment under different conditions for P-fertilizer production by X-ray absorption near edge structure (XANES) spectroscopy. In some incineration plants the mercury loaded carbon adsorber from off-gas cleaning was collected together with the SSA for waste disposal. SSAs from those plants contained mercury mainly bound to carbon/organic material. The other SSAs contained inorganic mercury compounds which are most probably stabilized in the SSA matrix and were thus not evaporated during incineration. During thermochemical treatment, carbon-bound mercury was removed quantitatively. In contrast, a certain immobile fraction of inorganic mercury compounds remained in thermochemically treated SSA, which were not clearly identified. HgSe might be one of the inorganic compounds, which is supported by results of Se K-edge XANES spectroscopy. Furthermore, the chemical state of selenium in the SSAs was very sensitive to the conditions of the thermochemical treatment.