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Formation of hexavalent chromium in Cr-containing steelmaking slag

Sato Y., Ijima K., Shibayama A., Inoue R.

Archives of Materials Science and Engineering

2018

Vol. 94, nr 1

5--10

Purpose: In present work, the mineral phases in chromium-containing slags were identified, and the formation mechanisms of Cr(VI) in Cr2O3-containing mineral phases were discussed. Design/methodology/approach: In steelmaking slag containing chromium, chromium is mainly present as spinel phases such as MgCr2O4 and (Mg,Fe)Cr2O4. When these Cr(III) oxides are oxidized to Cr(VI) oxide, the Cr(VI) is easily eluted from the slag due to its high solubility in water. Findings: The Cr (VI) adversely affects the human health and the environment. In this study, the influence of cooling rate, quenching temperature and oxidation/reduction condition during cooling on the Cr(VI) amount eluted from synthesized MgCr2O4, (Mg,Fe)Cr2O4 and CaCr2O4 were investigated. Research limitations/implications: The formation of Cr(VI) oxide in MgCr2O4 and CaCr2O4 compounds during heating under air was considered to be indispensable. The amounts of Cr(III) and Cr(VI) dissolved from MgCr2O4 were smaller than those from CaCr2O4. Since the formation of CrO3 in MgCr2O4 started at around 1400 K during cooling, slag should be cooled rapidly from the high temperature above 1400 K, or cooled in inert atmosphere in order to minimize Cr(VI) formation. FeO in (Mg,Fe)Cr2O4 solid solution suppressed Cr(VI), Cr(III) and Mg elution. Originality/value: The development of prevention method of Cr(VI) formation in the slags containing chromium is urgent in order to utilize the slags to land-fill and civil engineering works.

Temporal variability of sewage sludge heavy metal content from Greek wastewater treatment plants

Spanos T., Ene A., Patronidou C. S., Xatzixristou C.

Ecological Chemistry and Engineering. S

2016

Vol. 23, nr 2

271--283

The aim of this study was to evaluate the temporal variations of selected heavy metals level in anaerobic fermented and dewatered sewage sludge. Sewage sludge samples were collected in different seasons and years from three municipal wastewater treatment plants (WWTPs) located in Northern Greece, in Kavala (Kavala and Palio localities) and Drama (Drama locality) Prefectures. An investigation of the potential of sludge utilization in agriculture was performed, based on the comparison of average total heavy metal concentrations and of chromium species (hexavalent, trivalent) concentrations with the allowed values according to the Council Directive 86/278/EEC and Greek national legislation (Joint Cabinet Decision 80568/4225/91) guidelines. In this regard, all the investigated heavy metals (Cd, Cr, Cu, Ni, Pb, Zn, Hg) and chromium species Cr(VI) and Cr(III) have average concentrations (dry matter weight) well below the legislated thresholds for soil application, as following: 2.12 mg kg−1 Cd; 103.7 mg kg−1 Cr; 136.4 mg kg−1 Cu; < 0.2 mg kg−1 Hg; 29.1 mg kg−1 Ni; 62.0 mg kg−1 Pb; 1253.2 mg kg−1 Zn; 1.56 mg kg−1 Cr(VI) and 115.7 mg kg−1 Cr(III). Values of relative standard deviation (RSD) indicate a low or moderate temporal variability for domestic-related metals Zn (10.3-14.7%), Pb (27.9-44.5%) and Cu (33.5-34.2%), and high variability for the metals of mixed origin or predominantly resulted from commercial activities, such as Ni (42.4-50.7%), Cd (44.3-85.5%) and Cr (58.2-102.0%). For some elements the seasonal occurrence pattern is the same for Kavala and Palio sludge, as following: a) Cd and Cr: spring>summer>winter; b) Cu, Ni and Pb: winter>spring>summer. On average, in summer months (dry season) metal concentrations are lower than in spring and winter (wet seasons), with the exception of Zn. For Kavala and Palio the results demonstrate that the increased number of inhabitants (almost doubled) in summer time due to tourism does not influence the metal levels in sludge. Comparing the results obtained for similar spring-summer-winter sequences in 2007 and 2010/11 and for the spring season in 2007, 2008 and 2010, it can be noticed that, in general, the average heavy metal contents show an increasing tendency towards the last year. In all the measurement periods, the Palio sludge had the highest metal contents and Kavala sludge the lowest, leading to the conclusion that the WWTP operating process rather than population has a significant effect upon the heavy metal content of sludge. Cr(VI)/Cr(total) concentration ratios are higher for Kavala sludge in the majority of sampling campaigns, followed by Drama and Palio sludge. The metals which present moderate to strong positive correlation have common origin, which could be a domestic-commercial mixed source.