Modes of Occurrence of Chromium and Their Thermal Stability in Low-Rank Coal Pyrolysis

Chromium (Cr) and the emission of its compounds into the environment have caused long-term environmental contamination. In this study, the modes of occurrence of Cr in low-rank coal and their thermal stability in pyrolysis were investigated by sequential chemical extraction (SCE), single-component samples (SCS) pyrolysis, and thermochemical equilibrium simulation. The results showed that organic matter, aluminosilicate, and carbonate were the dominant modes of occurrence of Cr in low-rank coal. The modes of occurrence and chlorine (Cl) content affected the volatilization of Cr in coal. The characteristic release temperature range of Cr bounded to aluminosilicate was >600 °C and 400–600 °C for Cr bounded to a disulfide. Cr bounded to organic matter almost released completely before 600 °C. Cl enhanced the volatility of Cr and reduced its release temperature in Cr bounded to aluminosilicate. The simulation showed the content of gas products was very low, mainly chlorides. While the content of solid products, sulfides, and oxides, was much higher than gas products, showing their high thermal stability. The sulfides and oxides in chars were closely related to the carbonate and aluminosilicate bound form of Cr. The results of the equilibrium simulation were consistent with the experimental results.

Effect of biochar addition on legacy phosphorus availability in long-term cultivated arid soil

Background Continuous application of phosphorus (P) nutrient in association with its low recovery results in large amounts of P being accumulated in soil in different forms. Use of biochar can be a possible means to mobilize soil legacy P and increase its bioavailability. Therefore, the aim of this study was to identify the potential impact of a range of biochar types on P fractions in a long-term cultivated arid soil with high legacy P content. Methodology The soil was treated with biochar produced from four feedstock sources (BFS): sewage sludge (SSB), olive mill pomace (OPB), chicken manure (CMB), and date palm residues (DRB) pyrolyzed at 300, 500, or 700 °C in addition to an untreated control. The soil biochar mixture was incubated for 1 month followed by soil P fractionations using sequential chemical extraction to separate soil P into: labile (Resin-Pi, NaHCO3-Pi, NaHCO3-Po), moderately labile (NaOH-Pi, NaOH-Po), and non-labile (HCl-Pi and Residual-P) pools. Results Biochar addition clearly influenced most of the soil P fractions; however, the extent of this effect greatly varied depending on BFS and pyrolysis temperature (PT). The most evident biochar impact was observed with labile P pool, with the greatest increase being observed in NaHCO3-Pi fraction in most biochar treatments. Irrespective of PT, SSB and CMB were the most effective biochar type in increasing labile inorganic P; the SSB and CMB increased Resin-Pi by 77 and 206% and NaHCO3-Pi by 200 and 188%, respectively. In contrast, DRB made no changes in any P fraction. Differences in effects of biochar types on labile P is presumably related to the higher content of P in biowaste-based biochar compared to plant-based biochar which have much lower P content. The SSB, CMB, and OPB produced at low temperature reduced HCl-Pi content, indicating that these biochars may have stimulated organic matter decomposition and thereby dissolution of non-labile Ca-associated P to labile P forms. Conclusion Overall, biochar addition appeared to be an effective approach in enhancing legacy P availability in arid soil. However, further studies are necessary to verify these findings in the presence of plant and for a longer period. Graphic abstract

Distribution and modes of occurrence of uranium in coals of Eastern Yunnan, China

Uranium is an environmentally hazardous element, and is commonly present at trace levels (2.4 μg/g for world coals) in coal deposits. However, selected coal deposits could be highly enriched in uranium. In this study, 15 coal samples were collected from Eastern Yunnan coal deposits, China, aiming to characterize the distribution and the occurrence of uranium in those coals. In studied samples, uranium content varied from 0.36 to 8.28 μg/g, with an average value of 3.76 μg/g. Generally, uranium content in coals from northern coal mines (3.02 ± 2.44 μg/g, n = 5) were lower than it in southern coal mines (4.13 ± 2.30 μg/g, n = 10). Uranium in coal samples showed no obvious correlation with total sulfur, whereas was positively correlated with ash yield. The results of sequential chemical extraction procedure confirm that organic-bound is the dominant occurrence of uranium. The slight enrichment of uranium in studied coals was probably attributed to sedimentation processes, hydrological conditions and tectonic structure of the coal deposits.

A Preliminary Study on Dependence of Mercury Distribution on the Degree of Coalification in Ningwu Coalfield, Shanxi, China

Mercury (Hg) is a toxic trace element emitted from coal conversion and utilization. Samples with different coal ranks and gangue from Ningwu Coalfield are selected and investigated in this study. For understanding dependence of mercury distribution characteristics on coalification degree, Pearson regression analysis coupled with Spearman rank correlation is employed to explore the relationship between mercury and sulfur, mercury and ash in coal, and sequential chemical extraction method is adopted to recognize the Hg speciation in the samples of coal and gangue. The measured results show that Hg is positively related to total sulfur content in coal and the affinity of Hg to different sulfur forms varies with the coalification degree. Organic sulfur has the biggest impact on Hg in peat, which becomes weak with increasing the coalification degree from lignite to bituminous coal. Sulfate sulfur is only related to Hg in peat or lignite as little content in coal. However, the Pearson linear correlation coefficients of Hg and pyritic sulfur are relatively high with 0.479 for lignite, 0.709 for sub-bituminous coal and 0.887 for bituminous coal. Hg is also related to ash content in coal, whose Pearson linear correlation coefficients are 0.504, 0.774 and 0.827 respectively, in lignite, sub-bituminous coal and bituminous coal. Furthermore, Hg distribution is directly depended on own speciation in coal. The total proportion of F2 + F3 + F4 is increased from 41.5% in peat to 87.4% in bituminous coal, but the average proportion of F5 is decreased from 56.8% in peat to 12.4% in bituminous coal. The above findings imply that both Hg and sulfur enrich in coal largely due to the migration from organic state to inorganic state with the increase of coalification degree in Ningwu Coalfield.

Development of a Tellurium Speciation Study Using IC-ICP-MS on Soil Samples Taken from an Area Associated with the Storage, Processing, and Recovery of Electrowaste

The optimization and validation of a methodology for determining and extracting inorganic ionic Te(VI) and Te(IV) forms in easily-leached fractions of soil by Ion Chromatography-Inductively Coupled Plasma-Mass Spectrometry (IC-ICP-MS) were studied. In this paper, the total concentration of Te, pH, and red-ox potential were determined. Ions were successfully separated in 4 min on a Hamilton PRPX100 column with 0.002 mg/kg and 0.004 mg/kg limits of detection for Te(VI) and Te(IV), respectively. Soil samples were collected from areas subjected to the influence of an electrowaste processing and sorting plant. Sequential chemical extraction of soils showed that tellurium was bound mainly with sulphides, organic matter, and silicates. Optimization of soil extraction allowed 20% average extraction efficiency to be obtained, using 100 mM citric acid as the extractant. In the tested soil samples, both tellurium species were present. In most cases, the soils contained a reduced Te form, or the concentrations of both species were similar.

Mercury Speciation in Various Coals Based on Sequential Chemical Extraction and Thermal Analysis Methods

Coal combustion is an anthropogenic source of mercury (Hg) emissions to the atmosphere. The strong toxicity and bioaccumulation potential have prompted attention to the control of mercury emissions. Pyrolysis has been regarded as an efficient Hg removal technology before coal combustion and other utilization processes. In this work, the Hg speciation in coal and its thermal stability were investigated by combined sequential chemical extraction and temperature programmed decomposition methods; the effect of coal rank on Hg speciation distribution and Hg release characteristics were clarified based on the weight loss of coal; the amount of Hg released; and the emission of sulfur-containing gases during coal pyrolysis. Five species of mercury were determined in this study: exchangeable Hg (F1), carbonate + sulfate + oxide bound Hg (F2), silicate + aluminosilicate bound Hg (F3), sulfide bound Hg (F4), and residual Hg (F5), which are quite distinct in different rank coals. Generally, Hg enriched in carbonates, sulfates, and oxides might migrate to sulfides with the transformation of minerals during the coalification process. The order of thermal stability of different Hg speciation in coal is F1 < F5 < F2 < F4 < F3. Meanwhile, the release of Hg is accompanied with sulfur gases during coal pyrolysis, which is heavily dependent on the coal rank.

Polarity-Based Sequential Extraction as a Simple Tool to Reveal the Structural Complexity of Humic Acids

A sequential chemical extraction with a defined series of eluotropic organic solvents with an increasing polarity (trichloromethane < ethyl acetate < acetone < acetonitrile < n-propanol < methanol) was performed on peat-bog humic acid. Six organic fractions were obtained and subjected to a physicochemical characterization utilizing methods of structural and compositional analysis. Advanced spectroscopic techniques such as Attenuated Total Reflectance (ATR-FTIR), total luminescence, and liquid-state 13C NMR spectrometry were combined with elemental analysis of the organic fractions. In total, the procedure extracted about 57% (wt.) of the initial material; the individual fractions amounted from 1.1% to 19.7%. As expected, the apolar solvents preferentially released lipid-like components, while polar solvents provided organic fractions rich in oxygen-containing polar groups with structural parameters closer to the original humic material. The fraction extracted with acetonitrile shows distinct structural features with its lower aromaticity and high content of protein-like structural motifs. The last two—alcohol extracted—fractions show the higher content of carbohydrate residues and their specific (V-type) fluorescence suggests the presence of plant pigment residues. The extraction procedure is suggested for further studies as a simple but effective way to decrease the structural complexity of a humic material enabling its detail and more conclusive compositional characterization.

Use of hydroxyapatite to reduce Cd pollution in agriculture soils for Chenopodium quinoa cultivation

&lt;p&gt;Cadmium is a metal distributed in low concentrations in the environment without biological function, but it can be toxic at high concentration for plants, animals, and/or humans. This element is one of the major soil pollutant, with high mobility and availability under the conditions of many agricultural soils. The use of nanoremediation techniques can be an effective solution for the in situ recovery of contaminated soils with Cd, although the existing information about the consequences of using nanoparticles in soils is still very scarce. In this context. Hydroxyapatite nanoparticles can be an effective amendment for remediation of soils. Quinoa (&lt;em&gt;Chenopodium quinoa&lt;/em&gt; Will) is a seed-producing crop that has been cultivated in the Andes for several thousand years but with a good adaptation to different climatic conditions. Currently, quinoa is an emerging multipurpose crop in other parts of the world, due to its high nutritional potential for both human food and animal feedstock and a good alternative to cereals, leading to significant demand and, consequently, cultivation. In this study, we investigated the capacity of hydroxyapatite nanoparticles for recovering artificially contaminated soils with Cd where grown quinoa. For this, seeds of &lt;em&gt;C. quinoa&lt;/em&gt; were sown in two different soil (Arenosol and Anthrosol) artificially contaminated with Cd&lt;sup&gt;2+ &lt;/sup&gt;(0; 5, 25 and 50 mg kg&lt;sup&gt;-1&lt;/sup&gt;) and amended or not with 1% (w/w) of hydroxyapatite nanoparticles. The pot assay was carried out under controlled conditions and in a greenhouse for three months. Initial soils were characterized physicochemically and at the end of the assay multielemental concentrations were determined in soil (total and available fraction and plants (shoots). Germination rate, shoot height and dry biomass were measured, as well as pigments, glutathione, ascorbate and H&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;2&lt;/sub&gt; contents were analysed in plant shoots in order to evaluate plant development and their physiological status. In parallel, a sequential chemical extraction was carried out to determine the Cd distribution in the different geochemical soil phases. Preliminary results indicated that hydroxyapatite nanoparticles have a high capacity to retain Cd. These nanoparticles seem to favour &lt;em&gt;C. quinoa&lt;/em&gt; growth even with the highest concentration of Cd added. Therefore, this study will serve as a basis for further scientific research on the potential use of hydroxyapatite in agriculture soils with different characteristics and Cd problems for secure C. quinoa cultivation.&lt;/p&gt;&lt;p&gt;&lt;strong&gt;Acknowledgements&lt;/strong&gt;&lt;/p&gt;&lt;p&gt;This research and postdoc contract from Arenas-Lago D. was supported by the project ED481D 2019/007 (Xunta de Galicia), and Portuguese funds through Funda&amp;#231;&amp;#227;o para a Ci&amp;#234;ncia e Tecnologia within the scope of the project UID/AGR/04129/2020 (LEAF).&lt;/p&gt;