Selective formation of copper nanoparticles from acid mine drainage using nanoscale zerovalent iron particles

Nanoscale zerovalent iron (nZVI) has been investigated for the selective formation of Cu nanoparticles from acid mine drainage (AMD) taken from a legacy mine site in the UK. Batch experiments were conducted containing unbuffered (pH 2.67 at t=0) and pH buffered (pH 99.9% removal of all metals within 1 h when nZVI ≥1.0 g/L) from unbuffered AMD despite the coexistent of numerous other metals in the AMD, namely: Na, Ca, Mg, K, Mn and Zn. An acidic pH buffer enabled similarly high Cu removal but maximum removal of only <1.5% and <0.5% Cd and Al respectively. HRTEM-EDS confirmed the formation of discrete spherical nanoparticles comprised of up to 68% wt. Cu, with a relatively narrow size distribution (typically 20-100 nm diameter). XPS confirmed such nanoparticles as containing Cu0 , with the Cu removal mechanism therefore likely via cementation with Fe0 . Overall the results demonstrate nZVI as effective for the one-pot and selective formation of Cu0 -bearing nanoparticles from acidic wastewater, with the technique therefore potentially highly useful for the selective upcycling of dissolved Cu in wastewater into high value nanomaterials

Sorption and fractionation of rare earth element ions onto nanoscale zerovalent iron particles

The removal behaviour of rare earth element (REE), (Sc, Y, La-Lu), ions onto nanoscale zerovalent iron (nZVI) particles has been investigated. Batch sorption isotherms were conducted using REE-bearing acid mine drainage (AMD) and a range of different synthetic REE solutions, which were exposed to nZVI at 0.1-4.0 g/L. Maximum adsorption capacity of Yb and La was 410 and 61 mg/g respectively (1000 mg/L LaCl3 and YbCl3 starting concentration, initial pH=4.5, T=294 K), the highest currently reported in the literature. Aqueous REE removal to ultratrace concentrations (99.9% removal) was also recorded after 30 min (the first sampling interval) exposure of ≥0.5 g/L nZVI to 10 mg/L aqueous REE solutions (nitrate counterion). Similar rapidity and near-total removal ability was recorded for the exposure of nZVI to the AMD, however, a greater nZVI concentration was required, with the removal of all REEs (with the exception of La, Ce, Nd and Gd) to <1 µg/L when exposed to nZVI at 4.0g/L for 30 mins. In all systems nZVI was selective for the removal of HREE ions in preference to LREE ions, with the mechanism determined using HRTEM-EDS and XPS analysis as via surface mediated precipitation. Overall the results demonstrate nZVI as exhibiting great promise as an effective and versatile agent for simultaneous REE ion recovery and fractionation

Trend and cycle in primary commodity prices: A neo-Schumpeterian interpretation

This paper adapts Schumpeter's theory of economic development and the business cycle for the purpose of analysing movements in prices of primary commodities in both the short and long run. Schumpeter focuses his analysis on movements in prices of finished consumer goods, but he clearly recognizes that prices of primary products are both directly and indirectly affected by the same mechanism that drives finished goods prices. We extend Schumpeter's analysis by directly examining features of primary commodity production and consumption that are weakly developed by Schumpeter. We find that the extended analysis fits nicely to data on commodity prices over the period 1650 to 2008

Towards 'Precision Mining' of wastewater: Selective recovery of Cu from acid mine drainage onto diatomite supported nanoscale zerovalent iron particles

This paper introduces the concept of ‘Precision Mining’ of metals which can be defined as a process for the selective in situ uptake of a metal from a material or media, with subsequent retrieval and recovery of the target metal. In order to demonstrate this concept nanoscale zerovalent iron (nZVI) was loaded onto diatomaceous earth (DE) and tested for the selective uptake of Cu from acid mine drainage (AMD) and subsequent release. Batch experiments were conducted using the AMD and nZVI-DE at 4.0–16.0 g/L. Results demonstrate nZVI-DE as highly selective for Cu removal with >99% uptake recorded after 0.25 h when using nZVI-DE concentrations ≥12.0 g/L, despite appreciable concentrations of numerous other metals in the AMD, namely: Co, Ni, Mn and Zn. Cu uptake was maintained in excess of 4 and 24 h when using nZVI-DE concentrations of 12.0 and 16.0 g/L respectively. Near-total Cu release from the nZVI-DE was then recorded and attributed to the depletion of the nZVI component and the subsequent Eh, DO and pH recovery. This novel Cu uptake and release mechanism, once appropriately engineered, holds great promise as a novel ‘Precision Mining’ process for the rapid and selective Cu recovery from acidic wastewater, process effluents and leach liquors

Iron-mineral accretion from acid mine drainage and its application in passive treatment

This study demonstrates substantial removal of iron (Fe) from acid mine drainage (pH ≈3) in a passive vertical flow reactor (VFR) with an equivalent footprint of 154 m2 per L/s mine water and residence times of >23 h. Average Fe removal rate was 67% with a high of 85% over the 10-month trial. The fraction of Fe passing a 0.22 µm filter (referred to here as Fe-filt) was seen to be removed in the VFR even when Fe(II) was absent, indicating that the contribution of microbial Fe(II) oxidation and precipitation was not the dominant removal mechanism in the VFR. Removal rates of Fe-filt in the VFR were up to 70% in residence times as low as 8 h compared with laboratory experiments where much smaller changes in Fe-filt were observed over 60 h. Centrifugation indicated that 80–90% of the influent Fe had particle sizes <35 nm. Together with analyses and geochemical modelling, this suggests that the Fe-filt fraction exists as either truly aqueous (but oversaturated) Fe(III) or nanoparticulate Fe(III) and that this metastability persists. When the water was contacted with VFR sludge, the Fe-filt fraction was destabilized, leading to an appreciably higher removal of this fraction. Heterogeneous precipitation and/or aggregation of nanoparticulate Fe(III) precipitates are considered predominant removal mechanisms. Microbial analyses of the mine water revealed the abundance of extracellular polymeric substance-generating Fe-oxidizing bacterium ‘Ferrovum myxofaciens’, which may aid the removal of iron and explain the unusual appearance and physical properties of the sludge

FRET-Based Quantum Dot Immunoassay for Rapid and Sensitive Detection of Aspergillus amstelodami

In this study, a fluorescence resonance energy transfer (FRET)-based quantum dot (QD) immunoassay for detection and identification of Aspergillus amstelodami was developed. Biosensors were formed by conjugating QDs to IgG antibodies and incubating with quencher-labeled analytes; QD energy was transferred to the quencher species through FRET, resulting in diminished fluorescence from the QD donor. During a detection event, quencher-labeled analytes are displaced by higher affinity target analytes, creating a detectable fluorescence signal increase from the QD donor. Conjugation and the resulting antibody:QD ratios were characterized with UV-Vis spectroscopy and QuantiT protein assay. The sensitivity of initial fluorescence experiments was compromised by inherent autofluorescence of mold spores, which produced low signal-to-noise and inconsistent readings. Therefore, excitation wavelength, QD, and quencher were adjusted to provide optimal signal-to-noise over spore background. Affinities of anti-Aspergillus antibody for different mold species were estimated with sandwich immunoassays, which identified A. fumigatus and A. amstelodami for use as quencher-labeled- and target-analytes, respectively. The optimized displacement immunoassay detected A. amstelodami concentrations as low as 103 spores/mL in five minutes or less. Additionally, baseline fluorescence was produced in the presence of 105 CFU/mL heat-killed E. coli O157:H7, demonstrating high specificity. This sensing modality may be useful for identification and detection of other biological threat agents, pending identification of suitable antibodies. Overall, these FRET-based QD-antibody biosensors represent a significant advancement in detection capabilities, offering sensitive and reliable detection of targets with applications in areas from biological terrorism defense to clinical analysis

Atmospheric carbon capture performance of legacy iron and steel waste

Legacy iron (Fe) and steel wastes have been identified as a significant source of silicate minerals, which can undergo carbonation reactions and thus sequester carbon dioxide (CO2). In reactor experiments, i.e., at elevated temperatures, pressures, or CO2 concentrations, these wastes have high silicate to carbonate conversion rates. However, what is less understood is whether a more “passive” approach to carbonation can work, i.e., whether a traditional slag emplacement method (heaped and then buried) promotes or hinders CO2 sequestration. In this paper, the results of characterization of material retrieved from a first of its kind drilling program on a historical blast furnace slag heap at Consett, U.K., are reported. The mineralogy of the slag material was near uniform, consisting mainly of melilite group minerals with only minor amounts of carbonate minerals detected. Further analysis established that total carbon levels were on average only 0.4% while average calcium (Ca) levels exceeded 30%. It was calculated that only ∼3% of the CO2 sequestration potential of the >30 Mt slag heap has been utilized. It is suggested that limited water and gas interaction and the mineralogy and particle size of the slag are the main factors that have hindered carbonation reactions in the slag heap

Ambulatory heart rate range predicts mode-specific mortality and hospitalisation in chronic heart failure

Objective: We aimed to define the prognostic value of the heart rate range during a 24 h period in patients with chronic heart failure (CHF). Methods: Prospective observational cohort study of 791 patients with CHF associated with left ventricular systolic dysfunction. Mode-specific mortality and hospitalisation were linked with ambulatory heart rate range (AHRR; calculated as maximum minus minimum heart rate using 24 h Holter monitor data, including paced and non-sinus complexes) in univariate and multivariate analyses. Findings were then corroborated in a validation cohort of 408 patients with CHF with preserved or reduced left ventricular ejection fraction. Results: After a mean 4.1 years of follow-up, increasing AHRR was associated with reduced risk of all-cause, sudden, non-cardiovascular and progressive heart failure death in univariate analyses. After accounting for characteristics that differed between groups above and below median AHRR using multivariate analysis, AHRR remained strongly associated with all-cause mortality (HR 0.991/bpm increase in AHRR (95% CI 0.999 to 0.982); p=0.046). AHRR was not associated with the risk of any non-elective hospitalisation, but was associated with heart-failure-related hospitalisation. AHRR was modestly associated with the SD of normal-to-normal beats (R2=0.2; p<0.001) and with peak exercise-test heart rate (R2=0.33; p<0.001). Analysis of the validation cohort revealed AHRR to be associated with all-cause and mode-specific death as described in the derivation cohort. Conclusions: AHRR is a novel and readily available prognosticator in patients with CHF, which may reflect autonomic tone and exercise capacity

Male Imprisoned Firesetters Have Different Characteristics than Other Imprisoned Offenders and Require Specialist Treatment

Objective: This study investigated whether a group of firesetters (n = 68) could be distinguished, psychologically, from a matched group of non-firesetting offenders (n = 68). Method: Participants completed measures examining psychological variables relating to fire, emotional/ self-regulation, social competency, self-concept, boredom proneness, and impression management. Official prison records were also examined to record offending history and other offense-related variables. A series of MANOVAs were conducted with conceptually related measures identified as the dependent variables. Follow up discriminant function and clinical cut-off score analyses were also conducted to examine the best discriminating variables for firesetters. Results: Firesetters were clearly distinguishable, statistically, from non-firesetters on three groups of conceptually related measures relating to: fire, emotional/self-regulation, and self-concept. The most successful variables for the discrimination of firesetters determined via statistical and clinical significance testing were higher levels of anger-related cognition, interest in serious fires, and identification with fire and lower levels of perceived fire safety awareness, general self-esteem, and external locus of control. Conclusions: Firesetters appear to be a specialist group of offenders who hold unique psychological characteristics. Firesetters are likely to require specialist treatment to target these psychological needs as opposed to generic offending behavior programs

International trials of vertical flow reactors for coal mine water treatment

Vertical flow reactors (VFRs) were tested at coal mine sites in New Zealand, South Korea, and the USA. The objective was to evaluate the iron removal efficiency and iron removal mechanisms during field trials at low pH and circumneutral pH, and to evaluate the potential use of VFRs as stand-alone systems or in combination with other passive treatment technologies. Total iron and manganese removal efficiencies at circumneutral pH (6–8) often exceeded 90%, with effluent concentrations less than 1 mg/L. This is attributed to both homogeneous and heterogenous Fe(II) oxidation and filtration of the precipitated ferrihydrite. Iron removal efficiencies at moderately acidic conditions (pH 3–4.5) averaged close to 40%, with an average 71.0% removal in one of the trials after iron removal capacity was stabilized. Microbial Fe(II) oxidation and precipitation as schwertmannite together with aggregation of colloidal and nano-particulate Fe(III) are suspected to be the main removal mechanisms. Iron solubility limited removal under very acidic conditions (pH < 3). The reproducibility of the results with respect to previous research confirmed that VFRs can be used as stand-alone passive treatment systems for iron removal from mine waters with a footprint less than half of the area required by a conventional aerobic wetland. A VFR can also provide useful iron pretreatment for other passive treatment systems under circumneutral conditions, but would have to be combined with alkaline generating systems to achieve full iron removal from acidic mine waters