Inorganic Fraction Research Articles

Air pollution induces pyroptosis of human monocytes through activation of inflammasomes and Caspase-3-dependent pathways

According to the World Health Organization (WHO), air pollution is one of the most serious threats for our planet. Despite a growing public awareness of the harmful effects of air pollution on human health, the specific influence of particulate matter (PM) on human immune cells remains poorly understood. In this study, we investigated the effect of PM on peripheral blood monocytes in vitro. Monocytes from healthy donors (HD) were exposed to two types of PM: NIST (SRM 1648a, standard urban particulate matter from the US National Institute for Standards and Technology) and LAP (SRM 1648a with the organic fraction removed). The exposure to PM-induced mitochondrial ROS production followed by the decrease of mitochondrial membrane potential and activation of apoptotic protease activating factor 1 (Apaf-1), Caspase-9, and Caspase-3, leading to the cleavage of Gasdermin E (GSDME), and initiation of pyroptosis. Further analysis showed a simultaneous PM-dependent activation of inflammasomes, including NLRP3 (nucleotide-binding oligomerization domain-like receptor pyrin domain containing 3) and Caspase-1, followed by cleavage of Gasdermin D (GSDMD) and secretion of IL-1β. These observations suggest that PM-treated monocytes die by pyroptosis activated by two parallel signaling pathways, related to the inorganic and organic PM components. The release of IL-1β and expression of danger-associated molecular patterns (DAMPs) by pyroptotic cells further activated the remnant viable monocytes to produce inflammatory cytokines (TNF-α, IL-6, IL-8) and protected them from death induced by the second challenge with PM.In summary, our report shows that PM exposure significantly impacts monocyte function and induces their death by pyroptosis. Our observations indicate that the composition of PM plays a crucial role in this process—the inorganic fraction of PM is responsible for the induction of the Caspase-3-dependent pyroptotic pathway. At the same time, the canonical inflammasome path is activated by the organic components of PM, including LPS (Lipopolysaccharide/endotoxin).Graphical PM-induced pyroptosis of human monocytes. Particulate matter (PM) treatment affects monocytes viability already after 15 min of their exposure to NIST or LAP in vitro. The remnant viable monocytes in response to danger-associated molecular patterns (DAMPs) release pro-inflammatory cytokines and activate Th1 and Th17 cells. The mechanism of PM-induced cell death includes the increase of reactive oxygen species (ROS) production followed by collapse of mitochondrial membrane potential (ΔΨm), activation of Apaf-1, Caspase-9 and Caspase-3, leading to activation of Caspase-3-dependent pyroptotic pathway, where Caspase-3 cleaves Gasdermin E (GSDME) to produce a N-terminal fragment responsible for the switch from apoptosis to pyroptosis. At the same time, PM activates the canonical inflammasome pathway, where activated Caspase-1 cleaves the cytosolic Gasdermin D (GSDMD) to produce N-terminal domain allowing IL-1β secretion. As a result, PM-treated monocytes die by pyroptosis activated by two parallel pathways—Caspase-3-dependent pathway related to the inorganic fraction of PM and the canonical inflammasome pathway dependent on the organic components of PM.

Stimuli-Responsive Surface Ligands for Direct Lithography of Functional Inorganic Nanomaterials.

ConspectusColloidal nanocrystals (NCs) have emerged as a diverse class of materials with tunable composition, size, shape, and surface chemistry. From their facile syntheses to unique optoelectronic properties, these solution-processed nanomaterials are a promising alternative to materials grown as bulk crystals or by vapor-phase methods. However, the integration of colloidal nanomaterials in real-world devices is held back by challenges in making patterned NC films with the resolution, throughput, and cost demanded by device components and applications. Therefore, suitable approaches to pattern NCs need to be established to aid the transition from individual proof-of-concept NC devices to integrated and multiplexed technological systems.In this Account, we discuss the development of stimuli-sensitive surface ligands that enable NCs to be patterned directly with good pattern fidelity while retaining desirable properties. We focus on rationally selected ligands that enable changes in the NC dispersibility by responding to light, electron beam, and/or heat. First, we summarize the fundamental forces between colloidal NCs and discuss the principles behind NC stabilization/destabilization. These principles are applied to understanding the mechanisms of the NC dispersibility change upon stimuli-induced ligand modifications. Six ligand-based patterning mechanisms are introduced: ligand cross-linking, ligand decomposition, ligand desorption, in situ ligand exchange, ion/ligand binding, and ligand-aided increase of ionic strength. We discuss examples of stimuli-sensitive ligands that fall under each mechanism, including their chemical transformations, and address how these ligands are used to pattern either sterically or electrostatically stabilized colloidal NCs. Following that, we explain the rationale behind the exploration of different types of stimuli, as well as the advantages and disadvantages of each stimulus.We then discuss relevant figures-of-merit that should be considered when choosing a particular ligand chemistry or stimulus for patterning NCs. These figures-of-merit pertain to either the pattern quality (e.g., resolution, edge and surface roughness, layer thickness), or to the NC material quality (e.g., photo/electro-luminescence, electrical conductivity, inorganic fraction). We outline the importance of these properties and provide insights on optimizing them. Both the pattern quality and NC quality impact the performance of patterned NC devices such as field-effect transistors, light-emitting diodes, color-conversion pixels, photodetectors, and diffractive optical elements. We also give examples of proof-of-concept patterned NC devices and evaluate their performance. Finally, we provide an outlook on further expanding the chemistry of stimuli-sensitive ligands, improving the NC pattern quality, progress toward 3D printing, and other potential research directions. Ultimately, we hope that the development of a patterning toolbox for NCs will expedite their implementation in a broad range of applications.

Microplastics in coastal farmed oyster (Crassostrea angulata) shells: Abundance, characteristics, and diversity

One of the most concerning emerging pollutants is microplastics (MPs), which can infiltrate soft tissues of organisms by ingestion, adhesion, and fusing and may even become embedded in biominerals. However, very little evidence is available about MPs in biominerals found in the wild. This study detected the abundance and characteristics of MPs in the shells of farmed oysters (Crassostrea angulata) off the coast of Taiwan and discussed the distribution, accumulation, and diversity in the oyster shells. The results showed that MPs were ubiquitous in oyster shells, with an average abundance of 0.70 ± 0.40 MPs/g. MPs abundance was significantly (p < 0.01) higher in small oyster shells (shell length < 6.5 cm, weight 5–10 g) and inorganic (CaCO3) fraction (HCl digestion) than in large oyster shells (>6.5 cm, 10–25 g) and an organic fraction (H2O2 digestion), respectively. However, there was no significant difference in MPs abundance between the top and bottom shells (p > 0.05). MPs with a size <2 mm accounted for 78.5 %, fibrous MPs for 93.7 %, and rayon for 89.5 %. The MPs diversity integrated index (MPDII) in oyster shells was low (0.27), and the small and fibrous MPs seemed more easily embedded in biominerals. The findings confirm the presence of MPs in oyster shells in coastal environments. In addition, oyster shells may contain higher amounts of MPs than soft tissues 4–5 times, which needs to be confirmed. Further revealing the distribution and accumulation of MPs in water/terrestrial biominerals will help to understand the fate of MPs in the environment.

In Situ IR Spectroscopy Studies of Atomic Layer-Deposited SnO2 on Formamidinium-Based Lead Halide Perovskite.

Perovskite photovoltaics has achieved conversion efficiencies of 26.0% by optimizing the optoelectronic properties of the absorber and its interfaces with charge transport layers (CTLs). However, commonly adopted organic CTLs can lead to parasitic absorption and device instability. Therefore, metal oxides like atomic layer-deposited (ALD) SnO2 in combination with fullerene-based electron transport layers have been introduced to enhance mechanical and thermal stability. Instead, when ALD SnO2 is directly processed on the absorber, i.e., without the fullerene layer, chemical modifications of the inorganic fraction of the perovskite occur, compromising the device performance. This study focuses on the organic fraction, particularly the formamidinium cation (FA+), in a CsFAPb(I,Br)3 perovskite. By employing in situ infrared spectroscopy, we investigate the impact of ALD processing on the perovskite, such as vacuum level, temperature, and exposure to half and full ALD cycles using tetrakis(dimethylamido)-Sn(IV) (TDMA-Sn) and H2O. We observe that exposing the absorber to vacuum conditions or water half-cycles has a negligible effect on the chemistry of the perovskite. However, prolonged exposure at 100 °C for 90 min results in a loss of 0.7% of the total formamidinium-related vibrational features compared to the pristine perovskite. Supported by density functional theory calculations, we speculate that FA+ deprotonates and that formamidine desorbs from the perovskite surface. Furthermore, the interaction between TDMA-Sn and FA+ induces more decomposition of the perovskite surface compared to vacuum, temperature, or H2O exposure. During the exposure to 10 ALD half-cycles of TDMA-Sn, 4% of the total FA+-related infrared features are lost compared to the pristine perovskite. Additionally, IR spectroscopy suggests the formation and trapping of sym-triazine, i.e., a decomposition product of FA+. These studies enable to decouple the effects occurring during direct ALD processing on the perovskite and highlight the crucial role of the Sn precursor in affecting the perovskite surface chemistry and compromising the device performance.

Impact of Long-Term Application of FYM and Fertilizer Nitrogen on Soil Aggregation and Aggregate Bound Nitrogen Fractions and Nitrogen Mineralization Pattern in Different Size Soil Aggregates: A Review

This review highlights the impact of long-term application of FYM and fertilizer nitrogen on soil aggregation and aggregate bound nitrogen fractions and nitrogen mineralization pattern in different size soil aggregates. Organic manures are an important factor to maintain the soil fertility level because soil organic matter is regarded as a key indicator when assessing soil quality. The integrated application of inorganic and organic amendments leads to increase in both the inorganic fractions (ammonical and nitrate nitrogen) as compare to their alone application. Organic manures and residues that are added to the soil increase the total nitrogen content of the soil by protecting it chemically and physically against microbial degradation. Through FYM and crop root biomass (rhizodeposition), organic matter and fertilizers have been added to the soil on a regular basis during the past 41 years, and the building of nitrogen shows that nitrogen is physically protected within macro aggregates.

Anammox-Mediated Hydroxyapatite Granules: Physicochemical Properties, 3D Hierarchy, and Biofilm Thickness.

Biomineralization inspired the development of simultaneous biological transformations and chemical precipitation for simultaneous nitrogen removal and phosphorus recovery from wastewater, which could compensate for the incapacity of phosphorus management in the new biological route of anaerobic ammonium oxidation (anammox). In this study, we strengthened anammox-mediated biomineralization by long-term feeding of concentrated N, P, and Ca substrates, and a self-assembled matrix of anammox bacteria and hydroxyapatite (HAP) was fabricated in a granular shape, defined as HAP-anammox granules. HAP was identified as the dominant mineral using elemental analysis, X-ray diffraction, and Raman spectroscopy. The intensive precipitation of HAP resulted in a higher inorganic fraction and substantially improved settleability of anammox biomass, which facilitated HAP precipitation by acting as nucleation and metabolically elevated pH. By using X-ray microcomputed tomography, we visually represented the hybrid texture of interwoven HAP pellets and biomass, the core-shell layered architecture of different-sized HAP-anammox granules, and their homogeneously regulated thickness of the outer biofilm (from 118 to 635 μm). This unique architecture endows HAP-anammox granules with outstanding settleability, active biofilm, and tightly bonded biofilm with the carrier, which may explain the excellent performance of these HAP-anammox granules under various challenging operational conditions in previous studies.

Selective Quantification of Organic and Inorganic Arsenic in Kelp Thalli and Kelp-Based Products

Kelp can accumulate large quantities of arsenic compounds even in the absence of considerable environmental pollution. A substantial difference in toxicity between organic and inorganic arsenic compounds makes the form of arsenic relevant for the risk assessment of consuming kelp thalli and kelp-based products.The aim of the study was to develop an analytical procedure for the selective quantification of organic and inorganic arsenic in kelp thalli by inductively coupled plasma mass spectrometry and solid-phase extraction without scheduled precursors.Materials and methods. The authors studied samples of Laminaria saccharina and Laminaria japonica, spiking mixtures of chemical compounds containing arsenic in different oxidation states, and bioactive dietary supplements based on kelp thalli. Solid-phase extraction was performed using Maxi-Clean SAX cartridges. The arsenic content was determined using an Agilent 7900 inductively coupled plasma mass spectrometer.Results. Microwave-assisted extraction with deionised water ensures 91% recovery of arsenic-containing compounds from kelp thalli, and the addition of hydrogen peroxide to the extractant provides complete extraction. Solid-phase extraction with an eluent based on 3% H2O2 can extract the organic fraction from a mixture of organic and inorganic arsenic compounds without washing the inorganic fraction off the cartridge.Conclusions. The authors offer an effective analytical procedure for the selective quantification of organic and inorganic arsenic in kelp thalli and kelp-based products. This procedure allows for the isolation of arsenic-containing compounds from the organic matrix of kelp with 3% hydrogen peroxide. Solid-phase extraction with this extractant can effectively separate organic and inorganic fractions without prior neutralisation of the test solution.

Interaction between P and Zn on the Changes in Different Inorganic Phosphorus Fractions under Waterlogged Soil Treated with and Without Organic Matter

Background: Phosphorus and zinc are two essential nutrients which are required for normal plant growth. These nutrients are mutually antagonistic in certain circumstances which can cause yield reductions in many crops due to either P or Zn deficiencies. Organic matter causes soil to clump and form soil aggregates, which improves soil structure. With better soil structure, permeability improves, in turn improving the soil’s ability to take up and hold water. The addition of organic manure may reduce the mobility of Zn in soil by forming stable chelates thereby may affect the formation of Zn-P complexes in soil. Thus, the present study was undertaken to find the interaction between P and Zn on the changes in different inorganic phosphorus fractions under waterlogged soil treated with and without organic matter. Methods: An incubation experiment has been conducted in the laboratory of Department of Agricultural Chemistry and Soil Science, University of Calcutta to find the interaction between P and Zn on the changes in different phosphorus fractions under waterlogged soil treated with and without organic matter. Treatments details: P0Zn0 - No Phosphorus + No Zn, P0Zn1 - No Phosphorus + Application of Zn at 2.5 mg/kg soil, P0Zn2 - No Phosphorus + Application of Zn at 5 mg/kg soil , P1Zn0 - Application of P at 10 mg/kg soil + No Zn, P1Zn1 - Application of P at 10 mg/kg soil + Application of Zn at 2.5 mg/kg soil,P1Zn2 - Application of P at 10 mg/kg soil + Application of Zn at 5 mg/kg soil, P2Zn0 - Application of P at 15 mg/kg soil + No Zn, P2Zn1 - Application of P at 15 mg/kg soil + Application of Zn at 2.5 mg/kg soil, P2Zn2 - Application of P at 15 mg/kg soil + Application of Zn at 5 mg/kg soil. The same treatment combination was studied with application of organic matter where organic matter was applied @1% by soil weight basis and another set of treatment combination were conducted in absence of organic matter. After application of all treatments, maintaining waterlogged condition, the soils were allowed to incubate at room temperature (30±2)°C for a period of 10, 20, 30, 40, 50 days interval and analyzed for different fractions of P. Result: The amount of Soluble and Loosely bound P fractions has been recorded highest (47.50 mg kg-1) in the treatment P2OM2 at 30 days of incubation in presence of organic matter. As regards to the interaction effect between P and organic matter it was observed that the amount of Al-P was recorded enhanced, being highest with their highest level of application. The individual application of P increased the amount of Fe-P content, being highest (56.96 mg kg-1) at 30 days of incubation with its highest level, while the application of organic matter at its highest level recorded highest amount of Fe-P (55.30 mg kg-1) content. The absolute amount of Reductant soluble P was recorded a lower value than Fe-P. The results suggest that Ca-P fraction was the dominant inorganic P fraction among other fractions and there is a synergistic effect was found between P and organic matter where there is an antagonistic effect found between P and Zn.

Adsorption of azithromycin in agricultural soils of the Bogotá savanna, Colombia

Azithromycin is one of the most widely used macrolide antibiotics in medical treatment. However, there is little information on studies of the ecotoxicity, persistence and mobility of this type of compounds in the environment, although their presence in surfaces and wastewater has already been detected (Hernández et al., 2015). Based on this approach, the present research performs an analysis of the behavior of the adsorption process of azithromycin in soils of different textural classes, with the intention of establishing a first approach to assess the destination and transport of such substances in the biosphere. From the results of the evaluation of the conditions of adsorption of azithromycin, it is established that the Langmuir model has a better fit for clay soils with correlation coefficients R2 between 0.998 and 0.961. In contrast, the Freundlich model fits the soil with higher sand fraction with a higher correlation, R2 of 0.9892. Finally, based on a correlation analysis between the clay content, the percentage of organic matter and the adsorption coefficient K, it was evident that the adsorption of azithromycin is mainly related to the inorganic fraction of the soil.

Chemical Fertilization Alters Soil Carbon in Paddy Soil through the Interaction of Labile Organic Carbon and Phosphorus Fractions

The influence of long-term chemical fertilization in paddy soils is based on the interaction between labile carbon and phosphorus fractions and the manner in which this influences soil organic carbon (SOC). Four soil depths (0–30 cm) were analyzed in this study. Easily oxidized organic carbon components, such as permanganate oxidized carbon (POXC) and dissolved organic carbon (DOC), and other physicochemical soil factors were evaluated. The correlation and principal component analyses were used to examine the relationship between soil depth and the parameter dataset. The results showed that Fe-P concentrations were greater in the 0–5 cm soil layer. DOC, inorganic phosphate fraction, and other soil physiochemical characteristics interacted more strongly with SOC in the 0–5 cm soil layer, compared to interactions in the 10–15 cm layer, influencing soil acidity. An increase in DOC in the 0–5 cm soil layer had a considerable effect on lowering SOC, consistent with P being positively correlated with POXC, but negatively with SOC and water-soluble carbon (WSC). The changes in SOC could be attributed to the relationship between DOC and inorganic phosphate fractions (such as Fe-P) under specific soil pH conditions. An increase in soil DOC could be caused by changes in the P fraction and pH. The DOC:Avai. P ratio could serve as a compromise for the C and P dynamic indicators. The soil depth interval is a critical element that influences these interactions. Agricultural policy and decision-making may be influenced by the P from chemical fertilization practices, considering the yields and environmental effects.

Compositional boundaries for functional dental composites containing calcium orthophosphate particles

ObjectivesTo investigate the interrelationships among handling, degree of conversion (DC), mechanical behavior and Ca2+ release of composites containing dicalcium phosphate dihydrate (DCPD, CaHPO4.2H2O), as a function of total inorganic content and DCPD: glass ratio. MethodsTwenty-one formulations (1 BisGMA: 1 TEGDMA, in mols) with inorganic fractions ranging from zero to 50 vol% and different DCPD: glass ratios were evaluated for viscosity (parallel plate rheometer, n = 3), DC (near-FTIR spectroscopy, n = 3), fracture toughness/K1C (single-edge notched beam, n = 7–11) and 14-day Ca2+ release (inductively coupled plasma optical emission spectroscopy, n = 3). Data were analyzed by ANOVA/Tukey test (except viscosity, where Kruskal-Wallis/Dunn tests were used, α: 0.05). ResultsViscosity and DC increased with DCPD: glass ratio among composites with the same inorganic content (p < 0.001). At inorganic fractions of 40 vol% and 50 vol%, keeping DCPD content at a maximum of 30 vol% did not compromise K1C. Ca2+ release showed an exponential relationship with DCPD mass fraction in the formulation (R2 = 0.986). After 14 days, a maximum of 3.8% of the Ca2+ mass in the specimen was released. ConclusionFormulations containing 30 vol% DCPD and 10–20 vol% glass represent the best compromise between viscosity, K1C and Ca2+ release. Materials with 40 vol% DCPD should not be disregarded, bearing in mind that Ca2+ release will be maximized at the expense of K1C.

Synergy of Organic and Inorganic Sites in 2D Perovskite for Fast Neutron and X‐Ray Imaging

AbstractFast neutron and X‐ray imaging are considered complementary nondestructive detection technologies. However, due to their opposite cross‐sections, development of a scintillator that is sensitive to both fast neutrons and X‐rays within a single‐material framework remains challenging. Herein, an organic–inorganic hybrid perovskite (C4H9NH3)2PbBr4 (BPB) is demonstrated as a scintillator that fully meets the requirements for both fast neutron and X‐ray detection. The hydrogen‐rich organic component acts as a fast neutron converter and produces detectable recoil protons. The heavy atom‐rich inorganic fraction efficiently deposits the energy of charged recoil protons and directly provides a large X‐ray cross‐section. Due to the synergy of these organic and inorganic components, the BPB scintillator exhibits high light yields (86% of the brightness of a commercial ZnS (Ag)/6LiF scintillator for fast neutrons; 22 000 photons per MeV for X‐rays) and fast response times (τdecay = 10.3 ns). More importantly, energy‐selective fast neutron and X‐ray imaging are also demonstrated, with high resolutions of ≈1 lp mm−1 for fast neutrons and 17.3 lp mm−1 for X‐rays; these are among the highest resolution levels for 2D perovskite scintillators. This study highlights the potential of 2D perovskite materials for use in combined fast neutron and X‐ray imaging applications.

Three Semiconductive 1D Naphthalene Diimide/Iodoplumbate Perovskites with High Moisture Tolerance and Long-Lived Charge Separation States.

Low-dimensional inorganic-organic hybrid perovskites with high moisture tolerance and long-lived charge separation states have captured significant attention in the field of optoelectronic devices. To further achieve the relationship between crystal structures and stability, as well as charge separation behaviors, three one-dimensional hybrid perovskites containing electron-deficient naphthalene diimide ammonium (NDIEA) and electron-rich iodoplumbate chains, [(H2NDIEA)Pb2I6]·2DMF (1), [(H2NDIEA)2Pb5I14·(DMF)2]·4DMF (2), and [(HNDIEA)2Pb2I6]·3H2O (3), were synthesized. Crystal structure determinations revealed various synthesis conditions leading to different stacking modes, especially the inorganic lead iodide fraction, which resulted in different water resistances and charge-separated behaviors. The comprehensive analysis found that strong intermolecular interactions (anion-π interactions and π-π interactions), and matching energy levels between protonated NDIEA and iodoplumbate chains, can facilitate the generation of long-lived charge separation states and extraordinary moisture stability, even in the water environment. In addition, the conductivity behavior of 3 was also explored in detail.

Changes in Soil Sulphur Fractions as Influenced by Nutrient Management Practices in Mulberry

Sulphur (S) plays a vital role in improving the quality of mulberry leaves because of its involvement in protein synthesis. The knowledge of different pools of S in soils and its bioavailability for mulberry nutrition is thus, required for optimizing S fertilization. Hence, the present study was designed to ascertain the influence of chemical fertilizer and farmyard manure (both are S sources) on S fractions and its bioavailability in soils. In this regard, four nutrient management practices viz., control (without any chemical fertilizers and organic manures), recommended doses of N, P and K fertilizers (100% RDF), 80% RDF, 60% RDF with four mulberry varieties viz., V-1, G-4, AGB-8 and MSG-2 besides a fallow were considered for the study. Furthermore, the bioavailability of S in soils was tested using four commonly used chemical extractants viz., CaCl2, NaHCO3, AB-DTPA and Mehlich-3 (with different modes and chemistry of extraction). Organic S was the dominant fraction in the experimental soils accounting for 94.7% of total soil S while the inorganic fraction constituted only 5.3% that includes water soluble, sorbed and carbonate occluded S. Lowest amount of organic S content in soils of unmanured control (579.6 mg kg−1) was observed while the 100% RDF treatment (673.2 mg kg−1) maintained a higher content of soil organic S. High amount of sorbed and occluded S was observed in control plot compared to other fertilizer treatments (100% RDF, 80% RDF and 60% RDF). There was a gradual decline in soil S fractions when the fertilizer inputs were reduced to 60% suggesting that recommended doses of fertilizer inputs could maintain the soil S fractions. In addition, the extractable fractions of S were influenced by the fertilizer application rates and the extractability of all four extractants decreased with the reduction in fertilizer inputs. The amount of S extracted by all four chemical extractants followed the order of NaHCO3 &gt; Mehlich-3 &gt; AB-DTPA &gt; CaCl2 across the tested soils. Dynamic relationships among the extractants indicated that they could extract the S from the same pools in soil. Of the four extractants tested for evaluating plant available S, Mehlich-3 showed a higher degree of correlations with plant tissue S concentration and applied S through chemical fertilizers and farmyard manure. Furthermore, it could maintain strong correlations with water soluble and organic S fractions which were found to contribute significantly to plant S concentration. Thus, Mehlich-3 can be recommended for the assessment of bioavailable S for the nutrition of mulberry.

Changes in soil phosphorus (P) fractions and P bioavailability after 10 years of continuous P fertilization

Phosphorus fertilization modify soil P fractions differing in availability, but little is known about bioavailability of these pools for the crops when increasing P fertilizer rates in the medium term. Our objectives were to evaluate: i) changes in Bray-1 P content (extracted with 0,03 M NH4F and 0,1 M HCl) and soil P fractions as estimated by physical (Cambardella and Elliot method, POM-P) and chemical fractionation (Hedley method), ii) the relationship between these fractions and P bioavailability quantified in a test crop, and iii) the interaction with sulfur (S) fertilization after 10 years of continuous P and S fertilization. Soil samples were taken after 10 years in an experiment that followed a maize - full season-soybean - double-cropped wheat /soybean sequence that received P and S fertilization when cereals were sown. Treatments consisted of a factorial combination of three P rates (0, 20, and 40 kg P ha−1) and four S rates (0, 12, 24, and 36 kg S ha−1) applied to cereals from 2000 to 2010. After that, a maize used as a test crop was sown and P uptake was considered as bioavailable P. Soil samples were taken before sowing the test crop, and P in soil was fractionated chemically by the Hedley method and physically by wet sieving. After 10 years, when P fertilizer was not applied, soil Bray-1 P decreased 50 % respect to the initial P values, and increased up to 2.3 times when evaluating the highest P fertilizer rate. P fertilization did not change in POM-P. P soil labile (NaHCO3-Pi) and moderately labile (NaOH- Pi and HCl 1 M- Pi) inorganic fractions increased 83 %, 50 %, and 22 % in response to P addition, representing an increase of 4.2, 4.9, and 4.5 mg kg−1 of these fractions per 100 kg of applied P. Likewise, these fractions were related with P uptake in the maize test crop with 1.6, 1.5, and 1 kg of P uptake ha−1 in mg kg−1 increase in each of these fractions, respectively. Then, these fractions may be responsible for the legacy-P after 10 years of continuous fertilization in a Luvic Phaeozem of the Pampas region.

Stable isotopes and a changing world.

The measurement of naturally occurring stable isotope ratios of the light elements (C, N, H, O, S) in animal tissues and associated organic and inorganic fractions of associated environments holds immense potential as a means of addressing effects of global change on animals. This paper provides a brief review of studies that have used the isotope approach to evaluate changes in diet, isotopic niche, contaminant burden, reproductive and nutritional investment, invasive species and shifts in migration origin or destination with clear links to evaluating effects of global change. This field has now reached a level of maturity that is impressive but generally underappreciated and involves technical as well as statistical advances and access to freely available R-based packages. There is a need for animal ecologists and conservationists to design tissue collection networks that will best answer current and anticipated questions related to the global change and the biodiversity crisis. These developments will move the field of stable isotope ecology toward a more hypothesis driven discipline related to rapidly changing global events.

Silurian black shales from Sousel-Barrancos Metallogenic Belt (Ossa-Morena Zone, Portugal): Characterization and interplay to Cu deposits

Black shales are commonly spatially associated with metal-rich deposits, wherein organic matter in these rocks may condition or influence the processes related with the concentration of metals and formation of ore deposits. In the Ossa-Morena Zone (South of Portugal), namely in the Sousel-Barrancos metallogenic belt, several Cu mineralized veins occurs, being generally hosted in Silurian metasedimentary units mainly composed of black and grey shales, with interbedded lyddites and black quartzites. This research aims to contribute to the study of the association between those Silurian black shales and the Cu ore deposition in the Sousel-Barrancos metallogenic belt. The petrographic, geochemical and mineralogical analysis of black shales was performed to characterize the organic and inorganic fractions, to investigate elements concentration and its mode of occurrence. The data allow to identify the spatial pattern of thermal maturation of these black shales related to the variability of metamorphic processes, and the studied samples collected in drill cores from Miguel Vacas deposit also allow to identify an irregular pattern of maturation associated to the pathway of hydrothermal fluids. A significant Cu enrichment in black shales in the supergene enrichment domains were identified and data seems to indicate that Cu concentration is not directly related with organic carbon content, probably indicating a distinct source for Cu content. The mobilization of hydrothermal fluids, possibly of magmatic source, contributed to the discrepant maturation of organic matter in black shales.

Emission characteristics of condensable particulate matter (CPM) from FCC flue gas

Particulate matter (PM) as a major air pollutant, generally includes filterable particulate matter (FPM) and condensable particulate matter (CPM). CPM has gradually attracted widespread attention recently, due to its increasing proportion in total PM emissions. Fluid catalytic cracking (FCC) units, the main emission source in refineries, mostly use wet flue gas desulfurization (WFGD), which will produce a large amount of CPM. However, CPM emission and composition of FCC units are actually unclear. In this work, we aimed to understand the emission characteristics of CPM in FCC flue gas and provide some potential control strategies. Here, the stack tests of three typical FCC units were conducted to monitor FPM and CPM, and the field monitoring FPM results are higher than the concentration provided by Continuous Emission Monitoring System (CEMS). The emission of CPM is at a high-level concentration from 28.88 to 86.17 mg/Nm3, divided into inorganic fraction and organic fraction. The inorganic fraction is mainly composed in CPM, where water-soluble ions including SO42−, Na+, NH4+, NO3−, CN−, Cl−, and F−, are the major contributors. Moreover, a variety of organic compounds are detected as qualitative analysis of organic fraction in CPM, which can be roughly classified into alkanes, esters, aromatics, and others. Finally, on the basis of the understanding of the characteristics of CPM, we have proposed two strategies for CPM control. This work is expected to advance CPM emission regulation and control in FCC units.

Investigating the Chemical Composition of Lanolin Waste to Improve the Production of Sustainable Natural Fibre Materials

e Natural Fibre Company process raw wool into natural fibre materials utilising several processing steps. During the manufacturing, intermittent difficulties downstream of the scouring process of raw wool were encountered. Critically, the formation of an unknown paste- like grease deposit - which lead to downstream complications. To characterise the unknown by- product, the chemical composition of different raw wool lanolin extracts routinely employed in the manufacture of fibres were compared against a sample of the unknown grease deposit using high-temperature gas chromatography coupled with mass spectrometry. Major components of the unknown grease were putatively identified as psi-cholesterol, pentadecenol, palmitic and oleic acid, and a homologous series with mass spectra consistent with glycol ethers. The identification of chemicals predominantly with high interfacial properties was indicative of a potential issue with the surfactants used in the scouring process. the high inorganic content could indicate the presence of potassium salts derived from the suint, warranting further investigation of the inorganic fraction using inductively coupled plasma-optical emission spectroscopy or mass spectrometry.

Modeling Strategies for Crude Oil-Induced Fouling in Heat Exchangers: A Review

Semi-empirical fouling models have proven more effective in predicting the fouling behavior of crude oils in heat exchangers. These models have aided refineries in optimizing operating conditions to minimize or eliminate fouling in preheat exchangers. Despite their complexity, the models continue to improve in approximating real behavior by taking into account previously neglected aspects. This paper summarizes these findings from various studies along with highlighting different factors which were considered to enhance the predictability of the models. A critical analysis is presented to emphasize that activation energy in the deposition term varies depending on the physical processes involved and may not conform to the precise definition of activation energy. Two primary modeling approaches for crude oil fouling have emerged, i.e., deterministic and threshold models. Threshold models have gained more attention due to their fewer adjustable parameters. The stability or compatibility of crude oils has a substantial impact on asphaltene deposition, which is a major contributor to fouling. However, incorporating this factor into fouling models has received little attention. The inclusion of parameters for inorganic fraction and ageing has increased predictability by accurately estimating the fouling thickness. The use of CFD to analyze fouling mechanisms is promising, particularly for complex geometries. The dynamic and moving boundary modeling approach has potential to broaden the applicability of fouling models.