Thermodynamic modeling of iron and zinc reduction from B2O3 ‒ CaO ‒ Fe2O3 ‒ ZnО melt by СО ‒ CO2 and H2 ‒ Н2О mixtures

The paper presents the thermodynamic modeling results of zinc and iron reduction from B2O3 ‒ CaO ‒ Fe2O3 ‒ ZnО melts by CO ‒ CO2 and H2 ‒ H2O mixtures containing 0 – 60 % CO2 (H2O) at 1273 – 1673 K using a technique describing the reduction of metals from an oxide melt by gas in bubbling processes, under conditions that provide an approximation to real systems. Its originality is equilibrium determination for each individual portion of gas supplied into the working fluid. The reducible metals oxides content in each calculation cycle is taken from the previous data. During the calculations, changes in the content of zinc (СZnO ) and iron (СFe2O3 , СFe3O4 and СFeO ) oxides in the melt and the degree of their reduction were estimated. When using CO or H2 as a reducing agent, this process proceeds in three stages. In the first stage, Fe2O3 is reduced to Fe3O4 and FeO. CFe2O3 values decrease to almost zero, while CFe3O4 and CFeO increase simultaneously. By the end of the stage, СFe3O4 reaches its maximum value. At the second stage, the Fe3O4 → FeO transition occurs, when СFeO values reach its maximum. At these stages, there is a slight increase in the CZnO . At the third stage, the values CFeO and CZnO decrease, and iron and zinc are reduced. An increase in temperature dramatically reduces the gas consumption for zinc reduction by 2 – 3 times, and the replacement of CO with H2 reduces it by less than 20 %. In the presence of oxidizing agents (CO or H2O), only zinc is reduced. The process ends when the final content of zinc oxide in the melt corresponds to the equilibrium with the initial gas composition. The higher the temperature, the less CZnO is. The obtained data are useful for the development of technologies for the selective recovery of metals.

PRELIMINARY RADIOCARBON DATING RESULTS OF BONE SAMPLES AT THE LAC-UFF, BRAZIL

ABSTRACT Collagen extraction depends on the state of bone preservation, and the acidity of Brazilian soils often prevents the use of this material for radiocarbon dating. When available, however, bone samples constitute very important chronological records for both archaeological sites and natural depositional sites of specific animals. The extraction of collagen was performed using two filters, the first aiming to remove insoluble contaminants, and the second, a vivaspin ultrafilter 30KD to retain large molecular weight materials. The collagen was liofilized and converted to CO2 by combustion in sealed quartz tubes with CuO and Ag. The graphite was produced by zinc reduction in independently sealed Pyrex™ tubes. In order to verify the accuracy of this protocol, we analyzed a modern bone and four previously dated fragments, including those from the Sixth International Radiocarbon Intercomparison (SIRI), and a fragment of human bone from the Amourins site, a Brazilian shellmound. The results for the known age material are in agreement with the expected and the studied sector of Amourins shellmound was dated 4100–3900 years cal BP from a chronological model performed with charcoal dating found in different stratigraphic layers. Samples were dated at the radiocarbon laboratory of Universidade Federal Fluminense (LAC-UFF) in Brazil.