Post-measurement compressed calibration for ICP-MS-based metal quantification in mine residues bioleaching.

Bioleaching is an actual economical alternative to treat residues, which allows, depending on the chosen strategy, two possible outcomes: (1) a leachate enriched with target metals, or (2) a residue enriched in target metals through the leaching of interfering components (IC). This work aimed to study the metals released by bioprocessing the Panasqueira mine tailings, as a strategy to increase critical metals' relative concentration in residues. Biostimulation of the local microbiota was compared to a bioaugmentation approach using the autochthonous Diaphorobacter polyhydroxybutyrativorans strain B2A2W2. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was selected to study the metals released in the leachate through multi-element external standards. A new data treatment method was developed to use a preliminary sweep of intensities to quantify the non-initial target metals concentration in the leachate, based on preliminary ICP-MS intensity measurements. The results demonstrated that biostimulation was an efficient bioleaching strategy for the IC silicon, aluminium, magnesium, selenium, manganese, zinc, iron, and copper, by decreasing concentration, resulting in a relative increase in the gallium and yttrium (10x) levels in the treated residue. The strategy followed to quantify a large number of elements with ICP-MS using a reduced number of data points for calibration proved valid and speeded up the analytical process.

Full-scale accelerated carbonation of waste incinerator bottom ash under continuous-feed conditions.

Bottom ash (BA) is the dominant residue derived from the incineration of municipal solid waste or refuse-derived fuel (RDF). Costs for the disposal of the material chiefly depend on the leachability of salts and trace metals which may be cut by ageing the BA for several months to promote carbonation via uptake of carbon dioxide (CO2). Enhanced exposure to CO2 sources has been referred to as accelerated carbonation. Here we report on the successful implementation of the accelerated carbonation of BA in a continuously fed full-scale rotating drum reactor. The reactor was operated with the fine fraction (< 20 mm) of BA from an RDF incinerator and the exhaust of a combined heat and power unit was used as the reactant gas. The system was tested in 15 experiments and the process efficiency was addressed by maximizing the reactor loading and minimizing the BA residence time. Results confirmed that the reactor loading depended on the rotation-normalized mass flow rate of BA where the slope and intercept of the characteristic varied with the design of the reactor discharge and the use of mixing tools. According to leaching test results, BA residence times as low as 60 min were sufficient to render the carbonated BA a non-hazardous waste and convert it to a material suited for geotechnical applications. This outperforms previous laboratory findings and opens new perspectives for implementing the accelerated carbonation at incinerator sites.

Leaching of hexavalent chromium from young chromite ore processing residue.

Chromite ore processing residue (COPR) is a waste derived from the chromate extraction from roasted ores and is deposited in some countries in landfills. The objective of this study was to investigate the leaching characteristics of hexavalent Cr [Cr(VI)] from two COPR samples obtained from unlined landfills in the Kanpur area of northern India. Column experiments were conducted under water-saturated conditions to simulate Cr release from the wastes caused by tropical heavy-rain events. Leached Cr(VI) decreased from 1,800 to 300 mg L-1 (Rania site) and 1,200 to 163 mg L-1 (Chhiwali site) during exchange of 12 pore volumes, which approximately corresponds to 2 yr of monsoon precipitation. Flow interruptions for 10, 100, and 1,000 h had little effect on Cr(VI) concentrations in the leachate, suggesting that Cr(VI) leaching was not limited by slow release kinetics. Calcium aluminum chromium oxide hydrates (CAC), and highly soluble phases such as Na2 CrO4 may play a role in controlling Cr(VI) concentration in the leachates. The amount of Cr(VI) leached from the columns accounted for 16% of the total Cr(VI) present in both COPR samples. A decrease in the solid-phase Cr(VI)/Crtotal ratio along the column was identified by X-ray absorption near edge structure (XANES) spectroscopy. Consistently, the smallest Cr(VI)/Crtotal ratios were found in the lower column section closest to the inflow. Our results suggest that Cr(VI) leaching from the unlined COPR landfills will continue for centuries, highlighting the urgent need to remediate these dumpsites.

Towards optimized drum composting: evaluation of the radial mixing performance of a model substrate on the laboratory scale.

The rotating drum composter (RDC) is one of the most widespread reactor systems for biowaste treatment, worldwide. Nevertheless, knowledge on optimum operating conditions including, e.g. fill level, turning frequency, and mixing tool configuration is sparse. This study investigated the effect of static mixing tools (SMTs) on mixing in a rotating drum at high fill levels (60-80%). The methodological approach encompassed mixing experiments in a laboratory RDC using soaked wheat grains as a model material. The temporal course of material blending was quantified in terms of the entropy of mixing using digital image analysis. Experiments without SMTs showed the evolution of unmixed cores. With a single SMT, mixing was superior even at fill levels >70% while peripheral unmixed zones persisted when overly long SMTs were used. The results of this study may help to derive optimal process conditions for RDCs operated at high fill levels.

Continuous-feed carbonation of waste incinerator bottom ash in a rotating drum reactor.

Carbonation is a key process in the aging of waste incinerator bottom ash (BA). The reaction with CO2 decreases the BA alkalinity and lowers the leachability of amphoteric trace metals. Passive ageing over several months is usually performed in intermittently mixed BA heaps. Here we aimed at accelerating the process in a rotating drum reactor continuously fed with the BA and the reactant gas (10 vol-% CO2, volumetric flow rate 60 L/min). In one test, the gas was heated and humidified. Since carbonation depends on the specific CO2-supply, experiments were conducted at varied BA residence time (60, 80, and 100 min). Residence time was calculated by mass balancing and confirmed by the breakthrough time of two tracers. Leachates and solid phase properties of the treated BA served to evaluate the carbonation performance. The residence time of BA could be adequately controlled by the reactor loading and feed rate. A residence time of 80 min was sufficient to reduce the BA leachability such as to comply with the German regulatory standards for non-hazardous waste, whereas the untreated BA was hazardous waste. Decreased alkalinity was indicated by lower leachate pH and Ca(OH)2 contents of the BA as compared to the input. Leachate concentrations of amphoteric trace metals (Pb, Zn, Cu) decreased by at least one order of magnitude while oxyanions became slightly more mobile upon carbonation. In view of relatively short residence times and stable process performance, the rotating drum reactor seems promising for a full-scale implementation of BA carbonation.

A fast and simple method to monitor carbonation of MSWI bottom ash under static and dynamic conditions.

Accelerated carbonation may be employed to improve the leaching behaviour and the geotechnical properties of MSWI bottom ash (BA). Here we report on a novel method to monitor and evaluate the progress of carbonation in both static and dynamic reactor systems. The method is based on following the pressure drop in the gas phase induced by the CO2-uptake of BA and was benchmarked against carbonate contents as measured by thermogravimetry. Laboratory results demonstrated the serviceability and reproducibility of the method. Complementary logging of relative humidity and temperature showed constant moisture conditions and self-heating induced by the exothermal carbonation reaction, respectively. Under dynamic conditions BA carbonation was higher than in the static reactor. Consistently, the self-heating was more pronounced. After a reaction time of 120 min the pressure records indicated a CO2-uptake of 1.5 g CO2/100 g BA (static tests) and of 2.6 g CO2/100 g BA (dynamic tests). The proposed method is suited to study carbonation processes at minimum analytical expense and integrates over the small-scale heterogeneity of BA.

Trace metal stabilisation in a shooting range soil: mobility and phytotoxicity.

Due to impact and abrasion of projectiles firing berms of shooting ranges frequently exhibit increased levels of bullet-borne contaminants. Stabilisation of backstop soils may be a promising pre- and post-use treatment to minimise leaching and bioavailability. This study focused on mobility and phytotoxicity of antimony, copper, and lead in stabilised berm material compared to an untreated control. Ferric (goethite, deferrisation sludge) and phosphatic amendments (diammonium phosphate, calcium dihydrogen phosphate) were used. Batch and column experiments demonstrated effective stabilisation of the contaminants by ferric amendments. Sequential extractions showed an increase of contaminant fractions associated with iron (hydr)oxides. Stabilisation was accompanied by a detoxification of seepage water compared to the control soil as shown by Duckweed growth inhibition. Contrasting the ferric additives, phosphatic amendments effectively stabilised lead but mobilised copper and antimony possibly due to a competitive displacement process. Thereby, benefits of lead stabilisation were completely overridden; this was underlined by increased phytotoxicity relative to the untreated soil. Overall, understanding stabilised soil as a multicomponent system is a prerequisite for the choice of appropriate amendments. This requires the synopsis of results from complementary test methods and a screening for a wide range of substances.

Environmental status of groundwater affected by chromite ore processing residue (COPR) dumpsites during pre-monsoon and monsoon seasons.

Chromite ore processing residue (COPR) is generated by the roasting of chromite ores for the extraction of chromium. Leaching of carcinogenic hexavalent chromium (Cr(VI)) from COPR dumpsites and contamination of groundwater is a key environmental risk. The objective of the study was to evaluate Cr(VI) contamination in groundwater in the vicinity of three COPR disposal sites in Uttar Pradesh, India, in the pre-monsoon and monsoon seasons. Groundwater samples (n = 57 pre-monsoon, n = 70 monsoon) were taken in 2014 and analyzed for Cr(VI) and relevant hydrochemical parameters. The site-specific ranges of Cr(VI) concentrations in groundwater were <0.005 to 34.8 mg L-1 (Rania), <0.005 to 115 mg L-1 (Chhiwali), and <0.005 to 2.0 mg L-1 (Godhrauli). Maximum levels of Cr(VI) were found close to the COPR dumpsites and significantly exceeded safe drinking water limits (0.05 mg L-1). No significant dependence of Cr(VI) concentration on monsoons was observed.

Interfacial Processes and Influence of Composite Cathode Microstructure Controlling the Performance of All-Solid-State Lithium Batteries.

All-solid-state lithium-ion batteries have the potential to become an important class of next-generation electrochemical energy storage devices. However, for achieving competitive performance, a better understanding of the interfacial processes at the electrodes is necessary for optimized electrode compositions to be developed. In this work, the interfacial processes between the solid electrolyte (Li10GeP2S12) and the electrode materials (In/InLi and LixCoO2) are monitored using impedance spectroscopy and galvanostatic cycling, showing a large resistance contribution and kinetic hindrance at the metal anode. The effect of different fractions of the solid electrolyte in the composite cathodes on the rate performance is tested. The results demonstrate the necessity of a carefully designed composite microstructure depending on the desired applications of an all-solid-state battery. While a relatively low mass fraction of solid electrolyte is sufficient for high energy density, a higher fraction of solid electrolyte is required for high power density.

RecoPhos: full-scale fertilizer production from sewage sludge ash.

The substitution potential of sewage sludge for German primary phosphate imports has been estimated as 40%. Yet, a marketable option for the full scale recovery has been lacking. This study focuses on a full-scale process for the manufacture of a P-fertilizer from sewage sludge ash (SSA) adapted from the production of Triple Superphosphate. Given (i) conformity of the input with phosphate ores mined from sedimentary deposits, (ii) comparability of the product with a commercially available P-fertilizer regarding contaminant levels, P-fractionation and yield effects, and (iii) compliance of the output with the German Fertilizer Ordinance the RecoPhos P 38 fertilizer was discharged from the waste legislation regime. The fertilizer is currently being produced at a rate of 1000 tonnes per month and sold at a competitive price.