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A set of 59 ancient magical artefacts, mainly made of lead, was selected from the collections of the Staatliche Museen zu Berlin in order to unravel their origins. All the selected artefacts have been studied for their Pb isotope compositions, which covered the whole range of the Mediterranean ore deposits. However, the majority (≈86%) were made of lead matching the small compositional range of the Laurion ore deposits. Only eight out of the 59 artefacts were made of recycled lead or lead from other ore deposits.
Additionally, all but two were approximately dated based on their inscriptions. The lead isotopic composition together with information obtained from the inscriptions, the resulting dating, the context of the find and the known history of each item allowed us to gain more detailed information about the origins of these magical artefacts. The Attic provenance of 36 curse tablets was confirmed, whereas for 11 curse tablets previously classified as non-Attic, the provenance was either confirmed and specified (six artefacts) or changed to Attic (five artefacts). Surprisingly, the majority (six out of eight) of the analysed curse tablets from the Egyptian collection showed a lead isotopic composition closely matching that of Laurion.
A Laurion-like lead isotopic composition was also observed for three of the four analysed oracular tablets from Dodona. Together with the dating information, this points to Laurion as the major and dominant lead source in the Aegean, at least during the fourth–third century B.C. The few curse tablets from earlier than the fourth–third century B.C. point to the use of multiple and thus isotopically more variable lead sources compared with the Roman times.
Stocks of high grade phosphate rock are becoming scarce, and there is growing concern about potentially harmful impurities in conventional phosphorus fertilizers. Sewage sludge ash is a promising secondary phosphorus source. However, to remove heavy metals and convert the phosphorus contained in sewage sludge ash into mineral phases available to plants, an after-treatment is required. Laboratory-scale calcination experiments of sewage sludge ash blended with sodium salts using dried sewage sludge as a reducing agent were carried out at 1000 °C. Thus, the Ca3(PO4)2 or whitlockite component of raw sewage sludge ash, which is not readily plant available, was converted to CaNaPO4 (buchwaldite). Consequently, nearly complete phosphorus solubility in ammonium citrate (a well-established indicator for plant availability) was achieved. Moreover, it was shown that Na2CO3 may be replaced by moderately priced Na2SO4. However, molar ratios of Na/P > 2 were required to achieve >80% phosphorus solubility. Such over-stoichiometric Na consumption is largely caused by side reactions with the SiO2 component of the sewage sludge ash – an explanation for which clear evidence is provided for the first time.
The present work shows that U can be effectively removed from groundwater using permeable reactive barriers with hydroxyapatite (HAP) as reactive material. The main factor influencing the removal processes is the composition of the groundwater, namely the concentration of Ca and carbonate. Sorption of U onto the HAP surface seems to be the dominant removal process with the possibility of remobilisation. Newly formed U-phosphate minerals were detected by ESEM/EDX and XRD in samples with high U content indicating either a dissolution-precipitation mechanism or sorption onto the apatite surface followed by alteration of the structure. The formed U-phosphate minerals are stable under common groundwater conditions and can be remobilised only at high pH-values and high carbonate concentrations.
Mikrostrukturelle und mineralogische Eigenschaften leichter Gesteinskörnungen aus Mauerwerkbruch
(2015)
Poröse RC-Leichtgranulate mit Rohdichten zwischen 600 kg/m³ und 1400 kg/m³ können nach einem mehrstufigen mechanischen Prozess durch thermische Erhärtung bei 1180 °C aus ziegelhaitigern Mauerwerkbruch hergestellt werden. Diese Granulate erfüllen die Anforderungen an leichte Gesteinskörnungen nach DIN EN 13055 und es lassen sich damit Leichtbetone nach DIN EN 206-1/DIN 1045-2 herstellen. Ihre Festigkeits- und Dauerhaftigkeitseigenschatten sind mit denen herkömmlicher Leichtbetone mit Blähtonkörnungen sehr gut vergleichbar. Das ist das Fazit aus dem in den letzten Jahren durchgeführten Verbundforschungsvorhaben "Aufbaukörnungen". Um jedoch die Granulatentstehung bzw. den Vorgang der Porosierung besser verstehen, den Herstellungsprozess optimieren und die Eigenschaften der Granulate maßschneidern zu können, wurden zusätzlich zu den makroskopischen Charakteristika, wie beispielsweise Porosität und Wasseraufnahme, die chemisch-mineralogischen und mikrostrukturellen Eigenschaften der Leichtgranulate untersucht. Dazu dienten Analysen mittels ICP-Emissionsspektrometrie, Röntgenpulverdiffraktometrie, Quecksilberporosimetrie und mikroskopischen Verfahren. Im Beitrag wird über die Ergebnisse der Gefüge- und Porenstrukturuntersuchungen an Leichtgranulaten im Vergleich zu herkömmlichem Blähton berichtet.
Most lightweight aggregates (LWA) are produced by thermal Treatment of natural raw materials such as clay and shale. In addition to the high energy costs thereby incurred, the availability of suitable raw materials is limited. Other LWA manufactured from industrial by-products and wastes do not always meet the quality criteria for use in high-Quality lightweight concrete. A real alternative is the use of novel lightweight aggregates (referred to as LWA, aggregates and granules) made from mineral construction and demolition waste. An appropriate manufacturing technology has recently been developed in the framework of a German research project /1, 2/. Masonry rubble of variable grain size containing different amounts of brick material (25 to 70 %) serves as raw material. The LWA are obtained in a multistage manufacturing process by a thermal or hydrothermal treatment, which causes the expansion and the hardening of the material. The novel LWA meet the acceptance criteria for conventional lightweight aggregates. They are suitable for the production of lightweight concrete /2-6/. However to create tailor-made LWA from masonry rubble, the novel expanded materials and the influence of manufacturing conditions have to be understood in more detail. This paper reports on ongoing investigations of the chemico-mineralogical composition and microstructure of the novel LWA and focuses on the results of Chemical analyses, XRD, ESEM, TG/DTA and fusibility tests.
The advantages and drawbacks of existing wet chemical phosphorus (P) recovery technologies, their applicability to different types of sewage sludge ash (SSA) and the role of the decay products of detergent zeolites as a source of reactive Al in SSA are analyzed. Since neither a purely acidic nor a purely alkaline treatment are able to provide satisfactory technical solutions a wet chemical phosphorus (P) recovery process for sewage sludge ashes (SSAs) is investigated in detail that is based on a sequential treatment of SSA with an acid and a base. As a result of an acidic pre-treatment, the P fraction of the raw SSA that was bound as – alkaline-insoluble – calcium phosphate (Ca–P) is converted into aluminum phosphate (Al–P). This newly formed Al–P can be easily dissolved via alkaline treatment and then easily separated from the alkaline leachate via precipitation of Ca–P. The Al-component can be reused as precipitant for P-removal in waste water treatment plants (WWTPs). The investigated process requires fewer chemicals than the direct acidic dissolution of all P-compounds contained in the SSA. This is due to the described rearrangement of the P component from Ca–P to Al–P. That such a rearrangement of P occurs indeed was confirmed through a combination of XRD, ICP and XRF analyses together with mass balance calculations. The present investigation proves that the process works for very different types of SSAs: For Al-rich SSAs that come from WWTPs where Al-salt is used for chemical P-removal the described sequential treatment process works best and yields P-recovery rates as high as 70–77%. But even for SSAs from WWTPs where only iron salt is used for chemical P-removal, a considerable amount of the reactive Al necessary for the described P-rearrangement is supplied by decay products of detergent zeolites, a hidden Al-source present in most SSAs produced in Europe.
The potential of a new wet chemical process for phosphorus and aluminium recovery from sewage sludge ash by sequential elution with acidic and alkaline solutions has been investigated: SESAL-Phos (sequential elution of sewage sludge ash for aluminium and phosphorus recovery). Its most innovative aspect is an acidic pre-treatment step in which calcium is leached from the sewage sludge ash. Thus the percentage of alkaline soluble aluminium phosphates is increased from 20 to 67%. This aluminium phosphate is then dissolved in alkali. Subsequently, the dissolved phosphorus is precipitated as calcium phosphate with low heavy metal content and recovered from the alkaline solution. Dissolved aluminium is recovered and may be reused as a precipitant in wastewater treatment plants.