Release Of Trace Elements Research Articles

Contaminants from a former Croatian coal sludge dictate the structure of microbiota in the estuarine (Raša Bay) sediment and soil.

Croatian superhigh-organic-sulfur Raša coal had been mined for nearly 400 years. The release of hazardous trace elements (HTEs) and toxic organic pollutants (TOPs) into the local environment by coal mining, preparation, and combustion activities has resulted in pollution. In this study, the diversity and composition of microbial communities in estuarine sediment and soil samples as well as community function responses to the pollutants were investigated. The results showed that PAH degradation does occur following 60 years of natural attenuation, the location is still heavily polluted by polycyclic aromatic hydrocarbons (PAHs) and HTEs. Microbial analyses have shown that high concentrations of PAHs have reduced the diversity and abundance of microbial communities. The pollution exerted an adverse, long-term impact on the microbial community structure and function in the brackish aquatic ecosystem. Microorganisms associated with the degradation of PAHs and sulfur-containing compounds have been enriched although the diversity and abundance of the microbial community have reduced. Fungi which are believed to be the main PAH degrader may play an important role initially, but the activity remains lower thereafter. It is the high concentrations of coal-derived PAHs, rather than HTEs, that have reduced the diversity and abundance of microbial communities and shaped the structure of the local microbiota. This study could provide a basis for the monitoring and restoration of ecosystems impacted by coal mining activities considering the expected decommission of a large number of coal plants on a global scale in the coming years due to growing global climate change concerns.

Transcriptomic, osmoregulatory and translocation changes modulates Ni toxicity in Theobroma cacao

Nickel is one of the most released trace elements in the environment and in the case of bioaccumulation in foods and beverages derived from cocoa beans can cause risk to human health. It is very important to understand how plants respond to toxic metals and which are the defense strategies they adopt to mitigate their effects. In the present study we used young plants of T. cacao, submitted to increasing Ni doses (0, 100, 200, 300, 400 and 500 mg Ni kg−1 soil) and evaluated them for a period of 30 days. Doses of Ni, from 300 mg of Ni kg−1 onwards in the soil, promoted changes in photosynthetic, antioxidant, osmoregulatory, transcriptomic and translocation levels, evidenced by the increase in the activity of antioxidant enzymes, proline, glycine betaine, upregulation of the metallothionein 2B gene (Mt2b), and lipid peroxidation of the cell membranes. Foliar gas exchange was severely affected at higher doses of Ni. In addition, reduced levels of stomatal conductivity and transpiration rate were observed from 300 mg Ni kg−1 dose onwards in the soil, which consequently affected CO2 assimilation. Phytostabilization and exclusion mechanisms control the translocation of Ni from the root to the shoot and reduce harmful effects on plant metabolism. Our results highlighted the toxicity of Ni, a trace element often underestimated in T. cacao. In particular, it was noted that doses of 100 and 200 Ni kg−1 soil, although high, do not induce toxicity in T. cacao plants. But Ni toxicity is observed from 300 mg Ni kg−1 soil onwards. This study contributed to the understanding of the harmful effects of higher doses of Ni in cacao plants and the biochemical processes the plant uses to mitigate the effects of this metal.

Geochemical and mineralogical characterization of phosphogypsum and leaching tests for the prediction of the mobility of trace elements.

Phosphoric acid manufacturing generates large amounts of phosphogypsum (PG); a by-product generally disposed in the surface or evacuated in the seawater without any pretreatment. Phosphogypsum may host non-negligible amounts of valuable elements such as rare earth elements (REEs), which are critical elements on the global market. Surface disposal of PG may be a sustainable option to allow further processing in order to recover valuable elements. However, surface disposal exposes PG to atmospheric conditions (e.g., water, oxygen) which may increase their reactivity and accelerate the release rate of chemical species. This study aims to evaluate the trace element release rate from PG at atmospheric conditions. The studied PG samples were collected from a Moroccan phosphate treatment plant. The samples were characterized for their (i) chemical composition using inductively coupled plasma optical emission spectrometry (ICP-OES) for major elements and inductively coupled plasma mass spectrometry (ICP-MS) for trace elements; (ii) mineralogical composition by X-ray diffraction (XRD), scanning electron microscope equipped with energy-dispersive spectrometer (SEM-EDS), laser-induced breakdown spectroscopy (LIBS), and the mineral chemical composition was analyzed by electron probe microanalyzer (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS); and (iii) chemical species release rate using leaching tests over 24h at 25 and 60°C. Chemically, the PG samples were mainly composed of Ca (23.03-23.35 wt.%), S (17.65-17.71 wt.%), and Si (0.75-0.82 wt.%), and non-negligible amounts of trace elements: REE (344-349ppm), Cd (3.5-7.4ppm), U (9.3-27.4ppm). Mineralogically, the PGs are mainly formed by gypsum (94.2-95.9 wt.%) and quartz (1.67-1.76 wt.%). In terms of chemical species release, the PGs showed a higher reactivity at 60°C compared to room temperature with a higher release rate at the beginning of the leaching tests. Quantitatively, the PG samples released 3.57-4.11µg/L/day of REE, 3.18-17.29µg/L/day of U, and 1.67-5.49µg/L/day of Cd. Based on the leaching results, we concluded that the trace elements (e.g., U, Cd, REE) are incorporated in PG crystal lattice, which may explain their low concentrations in the leachates. Consequently, total digestion of PG matrix is required to solubilize REE.

The distribution and behaviour of Fe, Al, Si, Mn, Cu and Ni in ombrotrophic tropical peat draining blackwater estuaries on Borneo Island

Tropical peat swamps are essential ecosystems, which provide numerous services, and also serve as a rich source of dissolved organic carbon (DOC), hydrogen ions and trace elements to peat draining rivers. However, not much is known about trace element export from tropical peat swamps. We investigated trace element dynamics in rivers and estuaries draining tropical peat swamps on Borneo, and examined the influence of estuarine processes as well as dissolved organic carbon (DOC) on the distribution and concentration of trace elements. Our results indicate acidic conditions (pH = 3.3) and high DOC concentration (3500 µmol L−1) at salinities<1. We observed an initial release of trace elements at low salinity (0.05<S< 0.5), followed by scavenging to particles at intermediate salinities (0.5<S<10) due to an increasing ionic strength and pH. Peak concentrations (µmol kg −1) of Al (24.9), Si (96.2), Mn (4.9), Cu (0.035) and Ni (0.047) were observed during the dry season (July), and Fe concentrations (43.2) were highest during the wet season (December). We used the NICA-Donnan model to investigate the combined impact of DOC and pH on the formation of solid iron hydroxide (Fe(OH)3(s)). The Maludam river was predicted to be supersaturated for Fe hydroxides and the results affirmed our model prediction. The output showed Fe and Cu had a strong affinity for DOC and to a lesser extent Al and Ni in the conditions prevailing at the study sites. Statistical analyses also indicated strong correlation between Cu and Ni (r2 = 0.97, 0.94 and 0.82) in Maludam, Sebuyau and Belait rivers and estuaries, respectively. The results obtained in this study are comparable to values published for southeast Asia and other continents for pristine peat draining rivers.

The role of plastics in the accumulation and release of trace elements in the environment

Abstract Plastics are an emerging class of environmental contaminants whose impacts are not yet fully understood. Trace elements, another class of environmental contaminant and commonly associated with plastics, have been widely researched and are known to be toxic to organisms. However, the combined impacts of these two contaminants on the environment remain unclear. Here, we reviewed the current knowledge of the types and concentrations of trace elements associated with plastics, the role of plastics in creating new exposure routes, the processes involved in the release of trace elements from plastics, and the transport of plastics through environmental compartments. Trace elements inherent in plastics, due to addition during manufacture for formation or functional properties, are typically present at higher concentrations than those that are acquired from the environment, and consequently are likely to have greater impacts. Trace elements are continuously released into environmental matrices from plastics but may be released at higher concentrations when exposed to rapid changes in environmental conditions (pH, ionic strength, redox potential, salinity, UV levels). Plastics potentially provide additional exposure routes for organisms to trace elements. For example, exposure to trace elements may occur when organisms ingest plastics, use them for shelter and nest building or as a surface to attach onto. Further research to improve our understanding of this complex contaminant should focus on environmentally relevant studies on trace element release and their effects.

Role of indigenous microorganisms and organics in the release of iron and trace elements from sediments impacted by iron mine tailings from failed Fundão dam

After Fundão Dam failure in 2015, most of Gualaxo do Norte River in Doce River Basin in Brazil became silted by iron mining tailings consisting mainly of fine-grained quartz, hematite, and goethite. Previous work pointed to the possibility of reductive dissolution of iron and manganese from tailings, leading to mobilization of iron, manganese and trace elements. Several microorganisms were shown to reduce Fe(III) to Fe(II) and Mn(III, IV) to Mn(II) “in vitro”, but their roles in mobilization of Fe and trace elements from freshwater sediments are poorly understood. In this work, bottom sediments and water collected in Gualaxo do Norte River were used to build anoxic microcosms amended with acetate, glucose or yeast extract, in order to access if heterotrophic microorganisms, either fermenters or dissimilatory Fe reducers, could reduce Fe(III) from minerals in the sediments to soluble Fe(II), releasing trace elements. The Fe(II) concentrations were measured over time, and trace elements concentrations were evaluated at the end of the experiment. In addition, minerals and biopolymers in bottom sediments were quantified. Results showed that organic substrates, notably glucose, fuelled microbial reduction of iron minerals and release of Fe(II), Mn, Ba, Al and/or Zn from sediments. In general, higher concentrations of organic substrates elicited mobilization of larger amounts of Fe(II) and trace elements from sediments. The results point to the possibility of mobilization of huge amounts of iron and trace elements from sediments to water if excess biodegradable organic matter is released in rivers affected by iron mine tailings.

Laboratory-Controlled Experiments Reveal Microbial Community Shifts during Sediment Resuspension Events.

In freshwater ecosystems, dynamic hydraulic events (floods or dam maintenance) lead to sediment resuspension and mixing with waters of different composition. Microbial communities living in the sediments play a major role in these leaching events, contributing to organic matter degradation and the release of trace elements. However, the dynamics of community diversity are seldom studied in the context of ecological studies. Therefore, we carried out laboratory-induced leaching experiments, using sediments from the Villerest dam reservoir (Villerest, France). To assess whole microbial community diversity, we sequenced the archaeal and bacterial 16S rRNA genes using Illumina MiSeq. Our results suggest that the degree of dissolved oxygen found in the water during these resuspension episodes influenced community dynamics, with anoxic waters leading to drastic shifts in sedimentary communities compared to oxic waters. Furthermore, the release of microbial cells from sediments to the water column were more favorable to water colonization when events were caused by oxic waters. Most of the bacteria found in the sediments were chemoorganotrophs and most of the archaea were methanogens. Methylotrophic, as well as archaeal, and bacterial chemoorganotrophs were detected in the leachate samples. These results also show that organic matter degradation occurred, likely participating in carbonate dissolution and the release of trace elements during freshwater resuspension events.

A new co-processing mode of organic anaerobic fermentation liquid and municipal solid waste incineration fly ash

A new co-processing mode of waste liquid from anaerobic fermentation of organic wastes and municipal solid waste incineration fly ash (MSWI-FA) dechlorination is reported in this paper. Taking acetic acid, the most common organic acid in anaerobic fermentation systems, as the representative of anaerobic fermentation organic acids, the improvement of the dechlorination effect and the mechanism of washing MSWI-FA with low concentrations of organic acid lotion were explored. The chlorine content of MSWI-FA was reduced to 0.82% after the optimal process washing pretreatment. Three anaerobic fermentation waste liquids (AFWLs) were used to verify that the chlorine content of MSWI-FA could be reduced to less than 1%, and the dechlorination effect of brewery wastewater, which reduced the chlorine content of MSWI-FA to 0.91%, was the best at this. The influence of the washing process on MSWI-FA pyrolysis was reflected in the whole process. The release of chloride decreased and the weight loss was mainly due to the release of CO2. The melting point of MSWI-FA, washed by the optimal process, was reduced by nearly 30 ℃, and only 0.06% chlorine remained after calcination at 1100 ℃, which was extremely beneficial in reducing the release of trace elements in MSWI-FA during heat treatment, and for the preparation of cement raw meal.

Trace elements released from dental implants with periimplantitis: a cohort study.

Pure titanium and Ti6Al4V alloy have been in use as dental implant contemporarily. Trace element release from implant bodies is a possible health problem. Well-healed and osseointegrated intrabony implants are only in contact with bone and blood, but in the case of periimplantitis, the possibility of corrosion and the release of trace elements from dental implant surfaces increases due to contact with external factors. The aim of this study is to evaluate the trace element levels in the blood serum and saliva of patients who have dental implants with periimplantitis compared with the control group. This study included 25 patients diagnosed with periimplantitis and 25 participants with healthy osseointegrated implants as the control group. The trace element levels in blood serum and saliva were measured by inductively coupled plasma-mass spectrometry (ICP-MS) and results were analyzed statistically. There is no statistically significant difference between groups for saliva samples except the aluminum (Al) levels of the study group are significantly lower than the control group (p < 0.05) and the mercury (Hg) levels of the study group are significantly higher than the control group (p < 0.05). On the other hand, there is a significant decrease in titanium (Ti), chromium (Cr), and iodine (I) in the blood serum samples of the study group (p < 0.05). There is no significant difference between the groups for other measured trace elements in the blood serum (p > 0.05). There is no statistically significant increase in titanium or aluminum levels in the study group compared with the control group.

Diagenesis of clastic ores of the Ishkininо Co-bearing massive sulfide deposit (Southern Urals): Mineralogical-geochemical data and thermodynamic modeling

Research subject. The transformed clastic ores (ore diagenites) of the Ishkinino Co-bearing massive sulfide deposit hosted by serpentinites of the Main Uralian Fault Zone.Materials and methods. The structures and textures of the ores were stu died. The trace element contents of sulfides and oxides were determined using LA ICP MS. The physical and chemical modeling of the diagenetic formation of accessory As minerals was conducted using the Selektor program package. Results. The clastic ores are transformed gravelites with angular and rounded clasts of serpentinites, sulfides and chromite in the psammitic matrix of the same mineral composition. No hydrothermal minerals remain in gravelites; they are replaced by crystalline pyrite-2, porous pyrite-3, anhedral pyrite-4, pyrrhotite, chalcopyrite and magnetite. Chalcopyrite and magnetite replace all sulfides, sulfarsenides, chromite and gangue minerals. Chromite occurs as fragmented crystals or inclusions into serpentinite clasts. The matrix hosts euhedral cobaltite crystals with nickeline, gersdorffite and native gold inclusions. Crystalline pyrite-2 is characterized by higher Mn, Co, Ni, Cu and Zn contents. Porous pyrite-3 exhibits higher Co, Cu and Se contents. Anhedral pyrite-4 is enriched in most trace element contents in comparison with other sulfides and pyrite generations. Chalcopyrite is characterized by higher contents of Zn and Se. Pyrrhotite contains the highest Ni and hi gher Co contents.Conclusions. The main trace elements in the ores of the deposit (Co and Ni), as well as Cu, Zn and Mn, are hosted not only in sulfides, but also in oxides. Thus, chromite contains Zn and Ni, while magnetite contains Mn and Cu. Selenium occurs in all sulfides in similar quantities. Tellurium is mostly concentrated in pyrite-4. A comparative analysis of our results with those reported on other massive sulfide deposits showed that the serpentinite-sulfide gravelites of the Ishkinino deposit had been intensely transformed during diagenesis, which resulted in low trace element contents in diagenetic sulfides. The diagenetic alteration of clastic ores led to the formation of authigenic cobaltite, gersdorffite, nickeline and native gold as a result of trace element release from primary hydrothermal minerals. Thermodynamic mode ling showed the possibility of formation of As-bearing minerals (in particular, nickeline) at temperatures of 200°C and below.

Distinct effects of transition metal (cobalt, manganese and nickel) ion substitutions on the abiotic oxidation of pyrite: In view of hydroxyl radical production

The abiotic oxidation of pyrite (FeS2) is a geochemically crucial reaction involved in acid mine drainage, the release of toxic trace elements and the generation of hydroxyl radicals (•OH) that can oxidize environmental substances. Studies on •OH generation from the abiotic oxidation of pyrite have drawn wide interest, but the effects of the common substitution of transition metal ions on •OH generation are still largely unknown, and worthy of comprehensive comparison. We therefore synthesized and comprehensively characterized micron-sized pyrites containing low concentrations of cobalt (Co), nickel (Ni), or manganese (Mn) ions, and tested the relative ability of these transition metal ion-substituted pyrites to generate •OH under abiotic oxidation. We found that transition metal ion substitutions inhibited the growth of pyrite crystals to various extents and increased Fe–S bond distances, leading to distinct alterations in surface chemical composition, conductivity, and the exposure of active faces. These differences resulted in an increase in •OH generation by the oxidation of transition metal ion-substituted pyrites, relative to pure pyrite, with the order of increase being Mn2+-substituted < Ni2+-substituted < Co2+-substituted pyrites. These substituent-dependent differences were explored by linking the crystal properties and physical chemistry of these pyrites to various reaction pathways that were possible in such contexts. For pure pyrite, the heterogeneous Fenton reaction was the chief generator of •OH. The substitution of pyrite with Co2+, which was redox-active, increased the conductivity of pyrite and accelerated the reduction of surface Fe3+ to Fe2+, resulting in a significant increase in H2O2 and •OH production. The substitution of pyrite with Mn2+, which was also redox-active, likewise increased the conductivity; however, the high oxidizing ability of surface Mn4+ inhibited the reduction of Fe3+ and thus decreased •OH generation. By contrast, the substitution of pyrite with Ni2+ did not affect electron transfer but led to absolute exposure of the (111) face of pyrite, which increased its activity toward O2 and H2O, slightly increasing H2O2 and •OH generation. These results highlight the vital role of transition metal ion-substituted pyrite in various geochemical processes.

Biomethane production from waste activated sludge promoted by sludge incineration bottom ash: The distinctive role of metal cations and inert fractions

Sludge incineration bottom ash (SA), a solid waste generated by incineration of waste activated sludge (WAS), has been demonstrated as an inexpensive additive to increase biomethane production from anaerobic digestion (AD) of WAS. However, how SA improved methanogenic performance of a WAS digester remains elusive. Here, we addressed this question by fractionating the SA into accessible leachate (SA-L) and inert residue (SA-R) and investigating their individual effects. The cumulative biomethane production was increased by 6.7%, 20.2% and 39.6% with addition of SA-L, SA-R and SA, respectively. Mechanistic study showed that release of organic-binding metals (Ca and Fe) from SA dissolution suppressed volatile fatty acids production by increasing the apparent activation energy (AAE) and decreasing the surface binding sites for hydrolytic/acidogenic enzymes during WAS hydrolysis-acidogenesis, while trace elements in SA-L promoted metabolism of methanogens (Methanothermobacter and Methanosarcina). In contrast, the gypsum/silicate-cored SA-R facilitated hydrolysis-acidogenesis with reduced AAE but drastically inhibited methanogenesis due to competition of sulfate-reducing bacteria Thermodesulfovibrio. The comparative analysis of KEGG-based functional genes indicated that the enhanced methane metabolism and reductive CO2 fixation pathways with SA addition could result from the release of trace elements to support key enzyme activities.

In situ disposal of crushed concrete waste as void fill material at UK nuclear sites: Leaching behavior and effect of pH on trace element release

The leaching behavior of stockpiled crushed concrete waste is important in determining its suitability for in situ disposal at UK nuclear sites. Sand sized particles from surface (0–0.1 m) and subsurface (2.5–2.7 m) samples were composed of silica and calcite grains in a matrix of calcium alumina-silicate hydrate (C-(A)-S-H) with Ca/Si ratios of 0.5 ±0.3 and 0.9 ±0.3 respectively. Calcite content was also higher in surface samples indicating a greater degree of weathering and carbonation. This resulted in lower leachate pH for the surface samples (pH 8–9.6) compared to subsurface samples (pH 10–11.3). The waste displayed a high acid buffering capacity but low alkaline buffering capacity. Element release as a function of pH was similar for surface and sub-surface samples and between different size fractions. Leaching of contaminant metals was close to minimum values at the pH values produced by the crushed concrete but increased by several orders of magnitude at pH <5 (for Al, Pb, Cr and V) and pH >12 (for Al and Pb). Weathering and carbonation during long-term stockpiling, therefore, has a positive impact by producing a waste with stable pH and low metal leaching potential suitable for in-situ disposal as a void fill material.

Environmental significance of trace elements in the Athabasca Bituminous Sands: facts and misconceptions.

The bituminous sands of Alberta, Canada, represent the second largest reserves of hydrocarbons on earth. Open pit bitumen mining and upgrading of the Athabasca Bituminous Sands (ABS), the largest of the deposits, began in 1967. Concerns about fugitive release of trace elements (TEs) to the environment began with studies of V, as this is the most abundant trace metal in bitumen. Recent studies, however, have extended to Ag, As, Be, Cd, Cr, Cu, Pb, Sb, and Tl, and this has led to considerable confusion about which TEs are relevant to ecosystem health. While V along with Ni, Mo, Se and Re are enriched in bitumen, Ag, As, Be, Cd, Cr, Cu, Pb, Sb and Tl are found almost exclusively in the mineral (i.e. sand) fraction of the ABS, with limited opportunity to become bioaccessible, much less bioavailable. Here, a summary is given of ten misunderstandings that have arisen regarding TEs in the environment of the ABS region. To help illustrate the significance of the misconceptions that have arisen regarding (a) air and (b) water resources, published and unpublished TE data obtained from the metal-free, ultraclean SWAMP lab is presented for: (a) snow, moss, and peat cores from bogs, and (b) the dissolved, particulate, and colloidal fractions of water from the Athabasca River (AR), as well as pristine groundwater. Natural enrichments of Ni in plants such as Rat Root (Acorus calamus) and pine (Pinus banksiana), Tl in fish (Percopsis omiscomaycus) and Cd in cranberries (Vaccinium oxycoccus), Labrador Tea (Rhododendron groenlandicum) and beaver (Castor canadensis), are also presented.

Dissolution behaviour of different rank coals in L‐glutamic acid N, N‐diacetic acid chelating agent: Implications to enhance coalbed methane recovery by acid stimulation

AbstractAcid stimulation is a promising method in improving coal seam permeability by demineralization in coal cleats. However, using conventional acids such as HCl and mud acid (12 wt.% HCl + 3 wt.% HF) may cause clay breakage, migration, and precipitation, leading to formation damage. In this study, we investigated the effect of L‐glutamic acid N, N‐diacetic acid (GLDA) chelating agent treatment on the dissolution behaviour of lignite (Coal L) and anthracite (Coal A), collected from Er′Lian Basin and Qinshui Basin, China. Characteristics of the raw and acid treated coal samples, including mercury intrusion porosimetry (MIP) results as well as metal elements distribution analysis of reacted leachates, micromorphology, mineral composition, and mass change were taken into consideration. It was found that high‐rank Coal A is more suitable for chemical stimulation. For both Coal L and Coal A, 5 wt.% GLDA solution is preferred to avoid sticking reaction products. Total porosities of Coal L and Coal A were increased by 3.9 and 1.1 times, respectively. Based on the water chemistry analysis of the reacted solutions, we found that acidic condition is beneficial for clay minerals and carbonates dissolution, while alkaline condition is favourable for the dissolution of quartz. Besides, the dissolution of minerals can trigger the release of trace elements, which is a potential environmental risk that needs to be taken into consideration before its in‐situ application in coal fields.

Spatial distribution of trace elements associated with organic carbon along the Beiyun River basin, Beijing, China

Pollution resulting from terrestrial and aquatic trace elements has become a severe problem across the world. Organic carbon (OC) content has a high affinity for metallic contaminants and it acts as a significant sink for trace elements. The decomposition of OC content directly influences the bioavailability of trace elements. The decomposition of OC content and OC distribution vary spatially, these processes affect the release of trace elements and need further research. In the current study, sediment samples from the surface sediment along Beiyun River (Section 1 to Section 4 from upper to lower reaches), which is situated in the rapidly urbanized Beijing metropolis, were measured for OC, moisture, hardness, and trace elements. The OC contents were found to have a substantial difference among all four river sections along the urbanized river gradient. Whereas the higher OC contents were found in Sections 2 (Urbanized uplands) and 3 (farmland) compared to those in Sections 1 (forest) and 4 (farmland and part of constructed areas). On the other hand, the highest value of the correlation coefficient was found among the different values of trace elements and OC content in the riverine zone of the Beiyun River basin. OC contents play a vital role in the transformation and origin of trace elements in the surface sediment of the Beiyun River basin. The One-way Analysis of Variance (ANOVA) was applied to compare the means of OC and trace elements at different sections indicating no significant difference. However, source identification of trace elements indicated that a geogenic source was responsible for higher contents of As and (69.95%). Simultaneously, the natural OC, agricultural activities, and industrial waste contributed about (21.10%) towards the Cd and Zn, and about 10% for Cr and Cu. The current study concludes that the absolute principle component analysis–multiple linear regression (APCA-MLR) method can be successfully used to investigate the trace elements (Zn, Ni, Pb, Mn, Cd, Cu, and As) interactions through OC content resulting in determination of the various sources of contamination to cause negative environmental impacts on the ecosystem and human health. So, the current study provides a baseline for a quantitative evaluation of trace elements under different sediment of OC contents.

Genesis of the sediment-hosted Haerdaban Zn-Pb deposit, Western Tianshan, NW China: Constraints from textural, compositional and sulfur isotope variations of sulfides

The sediment-hosted Haerdaban Zn-Pb deposit is a newly discovered Zn-Pb deposit in the Sailimu terrane, Western Tianshan (NW China), containing ca. 0.64 Mt of ore at 6.19 wt% Zn and 1.09 wt% Pb. The mineralization consists mainly of veins, breccias and semi-massive sulfide ores within the dolomitic limestone and calcareous slate. Using LA-ICP-MS, this study investigates trace element and sulfur isotope composition of sulfide to constrain the genesis of the deposit. Four pyrite types were identified by variations in texture and composition. Porous pyrite (Py1) shows a significant enrichment in Mn, Ag, Sb, Tl, Ba, Pb, Cu, and Zn, whereas the pyrite overgrowth (Py2) and euhedral pyrite (Py3) are enriched in Co and As, but depleted in all other trace elements. This compositional trend is attributed to the release of trace elements from pyrite during recrystallization from a porous to massive texture. Pyrite (Py4) associated with sphalerite is inclusion-rich, but exhibits a depletion in most trace elements, except Ni and Sb. The underlying carbonaceous sediments are interpreted as a source of Ni, Sb and other metals for the ore-forming fluids. Sphalerite displays a wide variety of colors from dark brown to pale yellow, primarily related to variations in Fe contents. The overall Fe contents (0.25 to 6.12 wt%), Cd contents (524 to 1875 ppm) and Zn/Cd ratios (320 to 1258) in sphalerite are compatible with those of SEDEX Zn-Pb deposit. The contents of other elements in sphalerite are generally low. Calculated temperatures using trace element contents in sphalerite (GGIMFis geothermometer) range from 163 °C to 309 °C, indicating progressive cooling of ore-forming fluid. Pyrite, sphalerite and galena display a wide range of δ34S values from +3.9 to +18.3‰. The association of lower positive δ34S values (+3.9 to +8.8‰) and epithermal suite elements (Ni, As, Sb, and Tl) enrichment in porous pyrite indicate that sulfur in early sulfides was derived from thermochemical sulfate reduction (TSR) with a possible magmatic input. The dominant population of heavier δ34S values (+13.8 to +18.3‰) of massive sulfide support TSR as the main source of sulfur. The intermediate δ34S values (+7.0 to +13.0‰) of vein sulfide are likely a mixing of TSR-derived sulfur with light sulfur leached from diagenetic pyrite. The current data support the classification of Haerdaban as a metamorphosed SEDEX Zn-Pb deposit, where the main mineralization was the product of remobilization and upgrading of early exhalative ores during hydrothermal events.

On leaching mechanisms of major and trace elements from concrete - Carbonation, exposure to deicing salt and external sulphates

Model simulations and tank leach tests are compared to investigate the surface release of major and trace elements from ordinary Portland cement concrete and how this is affected by carbonation, NaCl or Na2SO4 in the eluent. It is distinguished between surface dissolution processes and diffusion of species from inside the concrete. Whereas alkalis, Cr(VI) and Sr are mainly released by diffusion, Ca, SO42−, Al, V, Ba and Zn are primarily released by surface dissolution. Changes in the leaching of Cr(VI) and V from concrete exposed to carbonation, NaCl or Na2SO4 are explained by the solubility equilibria of ettringite in which SO42− is substituted by CrO42− or VO43−. Barite and strontianite control the release of Ba and Sr. It is likely that C–S–H with incorporated Zn controls the release of Zn.

Thermally Treated Waste Silt as Filler in Geopolymer Cement.

This study aims to investigate the feasibility of including silt, a by-product of limestone aggregate production, as a filler in geopolymer cement. Two separate phases were planned: The first phase aimed to determine the optimum calcination conditions of the waste silt obtained from Società Azionaria Prodotti Asfaltico Bituminosi Affini (S.A.P.A.B.A. s.r.l.). A Design of Experiment (DOE) was produced, and raw silt was calcined accordingly. Geopolymer cement mixtures were made with sodium or potassium alkali solutions and were tested for compressive strength and leaching. Higher calcination temperatures showed better compressive strength, regardless of liquid type. By considering the compressive strength, leaching, and X-ray diffraction (XRD) analysis, the optimum calcination temperature and time was selected as 750 °C for 2 h. The second phase focused on determining the optimum amount of silt (%) that could be used in a geopolymer cement mixture. The results suggested that the addition of about 55% of silt (total solid weight) as filler can improve the compressive strength of geopolymers made with Na or K liquid activators. Based on the leaching test, the cumulative concentrations of the released trace elements from the geopolymer specimens into the leachant were lower than the thresholds for European standards.

Zeolite addition to improve biohydrogen production from dark fermentation of C5/C6-sugars and Sargassum sp. biomass

Thermophilic biohydrogen production by dark fermentation from a mixture (1:1) of C5 (arabinose) and C6 (glucose) sugars, present in lignocellulosic hydrolysates, and from Sargassum sp. biomass, is studied in this work in batch assays and also in a continuous reactor experiment. Pursuing the interest of studying interactions between inorganic materials (adsorbents, conductive and others) and anaerobic bacteria, the biological processes were amended with variable amounts of a zeolite type-13X in the range of zeolite/inoculum (in VS) ratios (Z/I) of 0.065–0.26 g g−1. In the batch assays, the presence of the zeolite was beneficial to increase the hydrogen titer by 15–21% with C5 and C6-sugars as compared to the control, and an increase of 27% was observed in the batch fermentation of Sargassum sp. Hydrogen yields also increased by 10–26% with sugars in the presence of the zeolite. The rate of hydrogen production increased linearly with the Z/I ratios in the experiments with C5 and C6-sugars. In the batch assay with Sargassum sp., there was an optimum value of Z/I of 0.13 g g−1 where the H2 production rate observed was the highest, although all values were in a narrow range between 3.21 and 4.19 mmol L−1 day−1. The positive effect of the zeolite was also observed in a continuous high-rate reactor fed with C5 and C6-sugars. The increase of the organic loading rate (OLR) from 8.8 to 17.6 kg m−3 day−1 of COD led to lower hydrogen production rates but, upon zeolite addition (0.26 g g−1 VS inoculum), the hydrogen production increased significantly from 143 to 413 mL L−1 day−1. Interestingly, the presence of zeolite in the continuous operation had a remarkable impact in the microbial community and in the profile of fermentation products. The effect of zeolite could be related to several properties, including the porous structure and the associated surface area available for bacterial adhesion, potential release of trace elements, ion-exchanger capacity or ability to adsorb different compounds (i.e. protons). The observations opens novel perspectives and will stimulate further research not only in biohydrogen production, but broadly in the field of interactions between bacteria and inorganic materials.