Settling selection of Chlamydomonas reinhardtii for samarium uptake.

Samarium (Sm) is a rare-earth element recently included in the list of critical elements due to its vital role in emerging new technologies. With an increasing demand for Sm, microbial bioremediation may provide a cost-effective and a more ecologically responsible alternative to remove and recover Sm. We capitalized on a previously selected Chlamydomonas reinhardtii strain tolerant to Sm (1.33 × 10-4 M) and acidic pH and carried out settling selection to increase the Sm uptake performance. We observed a rapid response to selection in terms of cellular phenotype. Cellular size decreased and circularity increased in a stepwise manner with every cycle of selection. After four cycles of selection, the derived CSm4 strain was significantly smaller and was capable of sequestrating 41% more Sm per cell (1.7 × 10-05 ± 1.7 × 10-06 ng) and twice as much Sm in terms of wet biomass (4.0 ± 0.4 mg Sm · g-1) compared to the ancestral candidate strain. The majority (~70%) of the Sm was bioaccumulated intracellularly, near acidocalcisomes or autophagic vacuoles as per TEM-EDX microanalyses. However, Sm analyses suggest a stronger response toward bioabsorption resulting from settling selection. Despite working with Sm and pH-tolerant strains, we observed an effect on fitness and photosynthesis inhibition when the strains were grown with Sm. Our results clearly show that phenotypic selection, such as settling selection, can significantly enhance Sm uptake. Laboratory selection of microalgae for rare-earth metal bioaccumulation and sorption can be a promising biotechnological approach.

Recovery technologies for indium, gallium, and germanium from end-of-life products (electronic waste) - A review.

Advanced high-tech applications for communication, renewable energy, and display, heavily rely on technology critical elements (TCEs) such as indium, gallium, and germanium. Ensuring their sustainable supply is a pressing concern due to their high economic value and supply risks in the European Union. Recovering these elements from end-of-life (EoL) products (electronic waste: e-waste) offers a potential solution to address TCEs shortages. The review highlights recent advances in pre-treatment and hydrometallurgical and biohydrometallurgical methods for indium, gallium, and germanium recovery from EoL products, including spent liquid crystal displays (LCDs), light emitting diodes (LEDs), photovoltaics (PVs), and optical fibers (OFs). Leaching methods, including strong mineral and organic acids, and bioleaching, achieve over 95% indium recovery from spent LCDs. Recovery methods emphasize solvent extraction, chemical precipitation, and cementation. However, challenges persist in separating indium from other non-target elements like Al, Fe, Zn, and Sn. Promising purification involves solid-phase extraction, electrochemical separation, and supercritical fluid extraction. Gallium recovery from spent GaN and GaAs LEDs achieves 99% yield via leaching with HCl after annealing and HNO3, respectively. Sustainable gallium purification techniques include solvent extraction, ionic liquid extraction, and nanofiltration. Indium and gallium recovery from spent CIGS PVs achieves over 90% extraction yields via H2SO4 with citric acid-H2O2 and alkali. Although bioleaching is slower than chemical leaching (several days versus several hours), indirect bioleaching shows potential, achieving 70% gallium extraction yield. Solvent extraction and electrolysis exhibit promise for pure gallium recovery. HF or alkali roasting leaches germanium with a high yield of 98% from spent OFs. Solvent extraction achieves over 90% germanium recovery with minimal silicon co-extraction. Solid-phase extraction offers selective germanium recovery. Advancements in optimizing and implementing these e-waste recovery protocols will enhance the circularity of these TCEs.

Bacterial leaching of critical metal values from Polish copper metallurgical slags using Acidithiobacillus thiooxidans.

Global economy faces an increasing problem of the supply risk of critical raw materials, therefore the search for secondary resources has become an urgent issue. Copper orebodies in Poland contain substantial amounts of metals deemed critical (e.g. Co, Mo, rare earth elements (REE) or V), which are not recovered during processing. The metals of interest are concentrated in metallurgical waste residues that should be classified as a secondary resource rather than as a waste. Bioleaching is a frontier technology promising for environment-friendly treatment of slags. Therefore, the objective of this work was to study the feasibility of metal (Co, Mo, REE, V) bioleaching from copper metallurgical wastes employing Acidithiobacillus thiooxidans bacterial strain as the leaching agent. The effect of particle size (fractions <0.25 mm and 0.25-0.5 mm) and pulp density (1%, 2%) was studied using three different slag samples (lead slag - LS, shaft furnace slag - SFS and granulated slag - GS). The bioleaching experiment was set up for 28 days under acidic conditions (pH t0 = 2.5). The results revealed that the microorganisms can catalyze metal extraction from slags as compared to leaching achieved under abiotic conditions. The optimal bioleaching yield was achieved under conditions at 0.25-0.5 mm particle size and 1% pulp density, regardless of used type of slag. After 28 days, the extracted amounts of metals were: 88% Co, 40% Mo, 83% REE and 55% V from LS, 100% Co, 44% Mo, 70% REE and 70% V from SFS and 95% Co, 70% Mo, 99% REE and 93% V from GS. All examined slags showed good potential for bioleaching of valuable elements. However, optimization of initial parameters is still needed for further efficiency improvement, especially in terms of the process duration.

The "Critical" Elements of Illness Management and Recovery: Comparing Methodological Approaches.

This study examined three methodological approaches to defining the critical elements of Illness Management and Recovery (IMR), a curriculum-based approach to recovery. Sixty-seven IMR experts rated the criticality of 16 IMR elements on three dimensions: defining, essential, and impactful. Three elements (Recovery Orientation, Goal Setting and Follow-up, and IMR Curriculum) met all criteria for essential and defining and all but the most stringent criteria for impactful. Practitioners should consider competence in these areas as preeminent. The remaining 13 elements met varying criteria for essential and impactful. Findings suggest that criticality is a multifaceted construct, necessitating judgments about model elements across different criticality dimensions.

From screens to seas: Tech contaminants in tiger sharks.

The potential negative impacts of Technology-Critical Elements (TCEs) on the environment and wildlife, despite increasingly recognized, remain largely overlooked. In this sense, this study aimed to investigate the concentrations of several TCEs, including rubidium (Rb), titanium (Ti) and various Rare Earth Elements (REEs), in different tissues of tiger sharks. Sharks incidentally caught by artisanal fleets in southern Brazil were opportunistically sampled and liver, gills, kidneys, heart, muscle, eyes, brain, skin, and teeth were analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Significant Rb concentration variations were observed across different tissues, with higher levels detected in kidneys and lower levels in the liver. Titanium concentrations also exhibited significant differences, with higher levels detected in teeth and lower levels in liver. Although no statistical differences were observed for the analyzed REEs, a trend of higher accumulation in the liver, gills, and skin was noted. Light Rare Earth Elements (LREEs) were found predominantly in all organs, with neodymium, lanthanum, and cerium as the most significant REEs detected. Several statistically significant correlations were identified between Rb and REEs, as well as between Ti and REEs, indicating systemic transport of these elements across different tissues. These findings indicate that the growing extraction and disposal of metallic elements, driven by technological advancements, may lead to their assimilation by marine fauna, particularly at higher trophic levels. The potential harmful effects on these organisms remain unknown and require urgent investigation. Additionally, as mining activities intensify globally, precise legislative measures are essential to address environmental concerns, species conservation, and human health considerations.

Low cost sample preparation method using ultrasound for the determination of environmentally critical elements in seaweed.

In this study, ultrasound (US) was evaluated for As, Cd, Pb, Mn, Sr and V extraction from seaweed samples. The following parameters of ultrasound-assisted extraction (UAE) using an US bath were: frequency (25 to 130 kHz), amplitude (30 to 100%), temperature (30 to 80 °C), sample mass (50 to 200 mg), extractant concentration (1 to 3 mol L-1 of HNO3) and treatment time (5 to 30 min). Acoustic density and power density distribution were calculated using the calorimetric method and mapping of the acoustic pressure distribution was also evaluated. The optimized UAE conditions were 200 mg of sample in 10 mL of 2 mol L-1 HNO3 and 30 min of sonication in a 25 kHz US bath (37.2 ± 4.0 W L-1) at 70% of amplitude and 70 °C. Analytes were quantified using inductively coupled plasma mass spectrometry and results were compared with values obtained using "silent" conditions (magnetic or mechanical stirring at 500 rpm, and without stirring), and a reference method based on microwave-assisted wet digestion (MAWD). The UAE method demonstrated the best extraction efficiency (higher than 95%) for all analytes, especially for As, Cd and V, with lower standard deviations (up to 5%) and lower blank values in comparison with the silent conditions. The proposed UAE method was more advantageous than the reference method, being faster, simpler, safer, more environmentally friendly, and with higher detectability (lower limits of quantification, from 0.0033 to 1.34 µg g-1). In addition, negligible blank values were obtained for UAE and no interference were observed in the determination step. Furthermore, the optimized UAE method was applied for Antarctic seaweed samples and comparison with results obtained by MAWD was satisfactory. In this sense, UAE is demonstrated to be a suitable option for sample preparation of seaweed samples and further determination of environmentally critical elements avoiding the use of concentrated reagents as in the MAWD reference method.

Soil low-density geochemical mapping of technology-critical elements (TCEs) and its environmental implications: The case of lithium in Portugal.

Increased use of technology-critical elements (TCEs) like lithium (Li), and their socio-environmental impacts, make it an issue of national and global importance. In Portugal, new Li exploration/exploitation projects are a very likely scenario. Thus, it is essential to establish geochemical backgrounds/thresholds for Li in soil, which can have several applications. Here, Li contents were determined and mapped from a previous low-density geochemical survey that covered the entire continental area of Portugal, following UNESCO's IGCP 259 project recommendations. The sampling sites were chosen in undisturbed/uncultivated land to ensure a reliable representation of "natural" soils. A total of 152 samples (0-20 cm; <2 mm) were taken for this study. Soil Li analysis was carried out by Flame Atomic Absorption Spectrometry (FAAS) after aqua regia (AR) extraction (geoavailable Li), while a subset of 55 samples underwent further digestion with a strong acid mixture to measure total Li (FAAS). This was done to ascertain the relationship between the two Li fractions and its environmental significance. Soil Li spatial distribution was produced with GIS software. Median values of 14 mg/kg for geoavailable Li and 60 mg/kg for total Li were estimated from these datasets. The first value is comparable to the median Li (11 mg/kg) from an AR-extraction for agricultural/grazing soils in Europe (GEMAS project). Based on spatial analysis, Cambisols overlying granitoids in northern/central Portugal contain the highest AR-extractable Li (40 mg/kg). Such areas are recognized for hard-rock Li mineralizations, mainly associated with aplite-pegmatites. Principal Component Analysis identified an important Li-Al relationship, linked to Cambisols and Leptosols overlying granitoids/metamorphic rocks. The geoavailable/total Li ratios revealed that >60 % of the samples have a relatively high proportion (>45 %) of Li that can be mobilized/dispersed in the surface environment. These findings are intended to support the management of potential concerns regarding Li mining in mainland Portugal.

Platinum Group Element distribution in water and marine biota from two impacted estuarine environments (Douro and Ave estuaries, Portugal).

Platinum Group Elements (PGEs) are contaminants of emerging environmental concern considering their continuous increasing use and subsequent release in the environment. While recent field studies provided PGE levels in seawater, scarce knowledge still exists regarding PGE contamination in marine organisms, especially for rhodium (Rh). Water, macroalgae and mussels were sampled along two representative urbanized estuarine systems and adjacent coastal areas (Douro and Ave estuaries, Portugal). Rhodium and platinum (Pt) concentrations were quantified through both stripping voltammetry and mass spectrometry in collected samples. Spatial mapping of PGE contamination was, to a certain extent, correlated with proxies of urban effluents. The use of Pt/Rh ratios reflected the dominant influence of PGE traffic emissions along the Douro and inputs from various sources (including industries) on the Ave Estuary. Macroalgae and mussels PGE concentrations reflected urban pressure, amplifying environmental signals, and supporting their relevant use as bioindicators of PGE contamination in estuarine/coastal systems.

Element distribution in electrochemically treated mine wastewater for efficient resource recovery and water treatment: A pilot study.

The feasibility of recovering major and critical elements from acid mine drainage using a pilot-scale electrochemical reactor (ECR) was investigated by assessing elements concentration and species distribution in the liquid and solid phase (sludge) in multistage tests. These were carried out at different electrical currents (18-22 amps) and thus, pH (8-12). The results showed that major metals Al, Cu and Fe were removed from the liquid phase at pH 5.9 while remaining the majority of Zn (57.2 ppm). On the other hand, at pH 7, the effluent was mainly composed of Mn (7.3 ppm). These results were confirmed by the simulation results using the PHREEQC model, which also identified the main chemical species in solution and the precipitates formed after the treatment (oxyhydroxides/sulfates/oxides). The ECR treatment led to sludges with targeted critical elements, some up to 20 times (Co, Be and Sb) higher than their earth's crustal abundance. At pH 10, rare earth elements in the sludge targeted Ce, followed by Nd and La. This study is one of the few studies carrying a detailed analysis of the behavioural distribution pattern of these elements at each pH, which opens the door for the potential of recovering these elements.

Investigation of potential metal emissions from galvanic anodes in offshore wind farms into North Sea sediments.

To evaluate potential metal emissions from offshore wind farms (OWFs), 215 surface sediment samples from different German North Sea OWFs taken between 2016 and 2022 were analyzed for their mass fractions of metals and their isotopic composition of Sr. For the first time, this study provides large-scale elemental data from OWFs of the previously proposed galvanic anode tracers Cd, Pb, Zn, Ga and In. Results show that mass fractions of the legacy pollutants Cd, Pb and Zn were mostly within the known variability of North Sea sediments. At the current stage the analyzed Ga and In mass fractions as well as Ga/In ratios do not point towards an accumulation in sediments caused by galvanic anodes used in OWFs. However, further investigations are advisable to evaluate long-term effects over the expected lifetime of OWFs, especially with regard to the current intensification of offshore wind energy development.

Future food contaminants: An assessment of the plant uptake of Technology-critical elements versus traditional metal contaminants.

Technology-critical elements (TCEs) include most rare earth elements (REEs), the platinum group elements (PGEs), and Ga, Ge, In, Nb, Ta, Te, and Tl. Despite increasing recognition of their prolific release into the environment, their soil to plant transfer remains largely unknown. This paper provides an approximation of the potential for plant uptake by calculating bioconcentration factors (BCFs), defined as the concentration in edible vegetable tissues relative to that in cultivation soil. Here data were obtained from an indoor cultivation experiment growing lettuce, chard, and carrot on 22 different European urban soils. Values of BCFs were determined from concentrations of TCEs in vegetable samples after digestion with concentrated HNO3, and from concentrations in soil determined after 1) Aqua Regia digestion and, 2) diluted (0.1 M) HNO3 leaching. For comparison, BCFs were also determined for 5 traditional metal contaminants (TMCs; As, Cd, Cu, Pb, and Zn). The main conclusions of the study were that: 1)BCF values for the REEs were consistently low in the studied vegetables;2)the BCFs for Ga and Nb were low as well;3) the BCFs for Tl were high relative to the other measured TCEs and the traditional metal contaminants; and 4) mean BCF values for the investigated TCEs were generally highest in chard and lowest in carrot. These findings provide initial evidence that there are likely to be real and present soil-plant transfer of TCEs, especially in the case of Tl. Improvements in analytical methods and detection limits will allow this to be further investigated in a wider variety of edible plants so that a risk profile may be developed.

Revealing the toxicity of monovalent and trivalent thallium to medaka fish in controlled exposure conditions.

Thallium (Tl) is a rare earth element increasingly being used in high-technology manufacturing. It is also an emerging pollutant with high exposure and toxicity risks to aquatic ecosystems. Tl exists in the environment in a monovalent [thallous, Tl(I)] or trivalent [thallic, Tl(III)] state. Currently, the stability of the two Tl species in natural water is uncertain and the toxicity in algae and daphnia are inconsistent due to lack of robust characterization of Tl species and matrix effects, while studies with fish are sparse. In this study, larvae of medaka fish (Oryzias latipes) were dosed with environmentally relevant concentrations of Tl(I) or Tl(III) spiked into synthetic and natural river water for 7 days to observe the toxic effects of two Tl species on fish. The transformation of Tl(I) and Tl(III) in water was analyzed by high performance liquid chromatography coupled with inductively coupled plasma and mass spectrometry. Analytical and toxicity results showed that Tl(I) is more stable presenting higher mortality and bioconcentration in medaka than Tl(III) in different water matrices. Tl(I)-induced LC50 and body burden in treated fish were highly correlated with its competitive ion, potassium (K), especially in waters containing medium K levels. This study provides reliable evidence regarding the stability and toxicity of Tl(I) and Tl(III) as well as the interaction of aqueous K versus Tl(I) in fish. Such information is useful for justifying water-quality guidelines and ecological risks of Tl pollution in natural water ecosystems.

Monitoring of ion release, bioavailability and ecotoxicity of thallium in contaminated paddy soils under rice cultivation conditions.

Paddy soils contaminated by thallium (Tl) have been frequently reported; however, their ecotoxicological impact in the paddy field is less known. We used a novel soil-fish exposure system with larvae of rice fish medaka (Oryzias latipes) to assess the bioavailability of Tl from soils to fish and causal toxicity under simulated conditions of rice cultivation. Two acidic soils [Pingzhen (Pc) and Sankengtzu (Sk)] spiked with monovalent Tl [Tl(I), 75-250 mg/kg] released higher Tl+ into pore or overlying waters than neutral soils [Sangkang (Su)], which resulted in higher mortality to exposed fish. The addition of K fertilizers into the system did not significantly reduce Tl release and fish mortality, but a drainage/re-flooding treatment worked effectively. The acidic Pc soil contaminated with low Tl(I) (2.5 and 15 mg/kg) caused higher sublethal toxicity in medaka than the neutral Su soil, including altered growth and swimming behavior with increased Tl body burden. These Tl-induced effects by low-Tl soils were significantly alleviated by K addition. The Tl/K ratios in aqueous phases were correlated with the mortality or Tl body burden in exposed fish. This study provides useful bio-analytical evidence that can help assess the ecological risks of Tl pollution in paddy field-related ecosystems.

Biomonitoring of metals in blood and urine of electronic waste (E-waste) recyclers at Agbogbloshie, Ghana.

There is growing evidence that e-waste recyclers may be exposed to potentially high levels of metals though associations between such exposures and specific work activities is not well established. In addition, studies have focused on metals traditionally biomonitored and there is no data on the exposure of recyclers to elements increasingly being used in new technologies. In the current study, levels of metals were measured in blood and urine of e-waste recyclers at Agbogbloshie (Ghana) and a control group. Blood and urine samples (from 100 e-waste recyclers and 51 controls) were analyzed for 17 elements (Ag, As, Ba, Cd, Ce, Cr, Eu, La, Mn, Nd, Ni, Pb, Rb, Sr, Tb, Tl, Y) using the ICP-MS. Most e-waste recyclers reported performing at least 4 different tasks in decreasing order as e-waste dismantling (54%), trading/selling of e-waste (45%), burning wires only (40%), and collecting wires after burning (34%). Mean levels of blood Pb, Sr, Tl, and urinary Pb, Eu, La, Tb, and Tl were significantly higher in recyclers versus controls. In general, the collectors and sorters tended to have higher elemental levels than other work groups. Blood Pb levels (mean 92.4 µg/L) exceeded the U.S. CDC reference level in 84% of the e-waste recyclers. Likewise, blood Cd, Mn, and urinary As levels in recyclers and controls were higher than in reference populations elsewhere. E-waste recyclers are exposed to metals traditionally studied (e.g., Pb, Cd, As) and several other technology-critical and rare earth elements which previously have not been characterized through human biomonitoring.

TCEs and environmental research: is the TCEs concept scientifically fruitful?

TCEs stands for technology-critical elements, a group of chemical elements for which imbalances between supply and demand exist or are deemed probable. This article challenges the scientific usefulness of such a classification when dealing with environmental and toxicological issues. Criticality is an economic conceptualization that is not well suited to guiding environmental chemistry research efforts. The classification is even counterproductive because it does not foster collaborative research with the countries directly touched by the environmental problems which are directly linked to the production of the elements.

Bourgeoning impact of the technology critical elements in the marine environment.

Contamination of the Technology Critical Elements (TCE) through e-wastes and beach plastic wastes are some of the attributes to the recent rise in marine pollution. A generalized study of pollutants in the marine waters showed no evidence of the effect of TCE. However, an in-depth study revealed the mean TCE concentrations in the sequence of gallium (Ga) > thallium (Tl) > niobium (Nb) > tellurium (Te) > tantalum (Ta) > germanium (Ge) > indium (In) in wastewater (0.38 ng.L-1) >sediment (0.3 ng g-1) e-wastes (0.29 ng g-1) > coastal water (0.26 ng.L-1) > plastic wastes (0.133 ng g-1) >fish (0.13 ng g-1). The mean site-wise analysis of all the samples showed high TCE during winter than in the summer seasons as well, in the sequence of Site-II>Site-I>Site-V>Site-IV>Site-III. The mean distribution coefficient (Kd) of TCE was high in the summer (1.95) than during the winter (1.60) seasons but, the reverse seasonal effects were observed with the bioavailability (%BA) and geo-accumulation index (Igeo). This index quantified TCE in e-wastes and plastic materials. Furthermore, these indicators labeled TCE as one among the sources for 'Fish Kill,' a futuristic threat to seafood consumers and a biomonitoring tool to marine pollution.

Municipal waste incineration fly ashes: from a multi-element approach to market potential evaluation.

BACKGROUND: Fly ashes from municipal solid waste incineration contain significant amounts of (technology critical) elements. Processes to recover Cu or Zn are already in practice, but it still remains difficult to evaluate the full secondary resource potential of the ashes. One reason is the absence of a worldwide comparable analytical basis for detailed market analyses. To encounter this, (i) an advice on how to analyse 65 elements after microwave-assisted digestion by ICP-OES and ICP-MS is delivered, (ii) the heterogeneity (hours to annual cycle) is evaluated for a incineration plant, (iii) leaching efficiency with three different eluents and (iv) the market potential of the elements as commodities are evaluated. RESULTS AND CONCLUSIONS: Aqua regia digestion was found to be sufficient to evaluated the recovery potential; except for the mass constituents Al, Si, Sn, Ti and the trace components Cr, Hf, Nb, U and W, for which HF-containing digestions delivered better recoveries. On different time scales, ashes were very homogenous and HCl- as well as H2SO4-supported leaching delivered, satisfying results within an hour (exceptions are, e.g., Bi and Sb). By applying characterisation factors of the life cycle assessment impact category "Resource depletion-minerals and metals" supplemented by the list of critical raw materials of the EU: Ag, Bi, Cd, Ga, In and Sb are most interesting elements to be recovered in future activities.

Mobility and retention of indium and gallium in saturated porous media.

Transport of indium and gallium is reported in laboratory column experiments using quartz sand as a model porous medium representative of a groundwater system. With increased use of indium and gallium in recent years, mainly in the semiconductor industry, concerns arise regarding their environmental effects. The transport and retention behavior of these two metals were quantified via batch and column experiments, and numerical modeling. The effect of natural organic matter on indium and gallium mobility was studied by addition of humic acid (HA). Measured breakthrough curves from column experiments demonstrated different binding capacities between indium and gallium, stronger for indium, with the presence of HA affecting retention dynamics. For indium, the binding capacity on quartz decreases significantly in the presence of HA, leading to enhanced mobility. In contrast, gallium exhibits slightly higher retention and lower mobility in the presence of HA. In all cases, the binding capacity of gallium to quartz is much weaker than that of indium. These results are consistent with the assumption that indium and gallium form different types of complexes with organic ligands, with gallium complexes appearing more stable than indium complexes. Quantitative modeling confirmed that metal retention is controlled by complex stability.

Recoveries of rare elements Ga, Ge, In and Sn from waste electric and electronic equipment through secondary copper smelting.

The recycling and recovery of valuable metals from waste materials is one of the key issues in maintaining the sustainability of base and rare metals. Especially WEEE (Waste Electric and Electronic Equipment) can be considered as a high potential resource for a number of valuable and critical metals like gallium, germanium and indium. During the mechanical processing of WEEE, these metals are primary separated into the non-ferrous scrap fractions, including copper fraction. As a consequence, the behavior of these valuable metals and the possibility of their recycling in secondary copper smelting are of great interest. This study experimentally investigates the distribution behavior of indium, gallium, germanium and tin between metallic copper and lime-free / lime-containing alumina iron silicate slags (LCu/s[Me] = [Me]Copper/(Me)Slag), as well as between solid Al-Fe spinel and slags (Lsp/s[Me] = {Me}spinel/(Me)slag). Moreover, the copper-slag-spinel equilibrium systems are examined. The experiments were executed simulating high alumina-bearing copper scrap smelting in typical black copper smelting conditions of pO2 = 10-10-10-5 atm (1 atm = 1.01325 × 105 Pa) and T = 1300 °C. The experimental technique employed utilized a highly advanced equilibration-rapid quenching method followed by Electron Probe Micro-Analysis (EPMA). The results show that tin and indium can be efficiently recovered into the copper phase in reducing process conditions (pO2 below 10-7 atm), whereas gallium dissolved preferentially into the solid spinel phase in all conditions examined. Gallium dissolution into slag and spinel was found to occur as GaO1.5, whereas indium in spinel was determined to be as InO1.5. In addition, germanium was seen to distribute preferentially into the copper phase with LCu/s[Ge] = 2-4, although its concentrations in all phases present were relatively low. Thus, the main route for germanium can be considered to be vaporization.

Fidelity to the Cognitive Processing Therapy Protocol: Evaluation of Critical Elements.

The contributions of individual therapy elements to the overall efficacy of evidence-based practices for the treatment of posttraumatic stress disorder (PTSD) are not well-understood. This study first examined the extent to which theoretically important treatment components of Cognitive Processing Therapy (CPT; i.e., skill in Socratic questioning; prioritizing assimilation; attention to practice assignments; emphasis on expression of natural affect) were successfully administered across the course of therapy for 68 PTSD-positive survivors of interpersonal trauma. Therapist fidelity in the administration of these four elements was evaluated in 533 taped CPT sessions of study participants included in one of two randomized controlled CPT treatment trials. Second, we examined therapist fidelity to these components as a predictor of session-to-session PTSD and depression symptom change. Third, follow-up analyses examined the influence of high therapist competence for these four components across an entire course of therapy on symptom change from pre- to posttreatment. Results showed consistently high adherence and more variable competence for these four treatment components. There were no significant effects of therapist fidelity on session-to-session symptom change. However, results showed that overall high therapist competence for "skill in Socratic questioning" and "prioritizing assimilation before overaccommodation" were related to greater client improvement in PTSD severity, but "attention to practice assignments" and "emphasis on expression of natural affect" were not. Overall competence ratings for the four components were not significantly associated with improvement in depressive symptoms. Findings contribute to increased understanding of the relationship between the key treatment components of CPT and symptom change.