Arsenic sorption by red mud-modified biochar produced from rice straw

Red mud-modified biochar (RM-BC) has been produced to be utilized as a novel adsorbent to remove As because it can effectively combine the beneficial features of red mud (rich metal oxide composition and porous structure) and biochar (large surface area and porous structure properties). SEM-EDS and XRD analyses demonstrated that red mud had loaded successfully on the surface of biochar. With the increasing of pH in solution, arsenate (As(V)) adsorption on RM-BC decreased while arsenite (As(III)) increased. Arsenate adsorption kinetics process on RM-BC fitted the pseudo-second-order model, while that of As(III) favored the Elovich model. All sorption isotherms produced superior fits with the Langmuir model. RM-BC exhibited improved As removal capabilities, with a maximum adsorption capacity (Q_max) for As(V) of 5923 μg g^?1, approximately ten times greater than that of the untreated BC (552.0 μg g^?1). Furthermore, it has been indicated that the adsorption of As(V) on RM-BC may be strongly associated with iron oxides (hematite and magnetite) and aluminum oxides (gibbsite) by X-ray absorption near-edge spectroscopy (XANES), which was possibly because of surface complexation and electrostatic interactions. RM-BC may be used as a valuable adsorbent for removing As in the environment due to the waste materials being relatively abundant.     

Immobilization of lead and cadmium from aqueous solution and contaminated sediment using nano-hydroxyapatite

The effectiveness and mechanism of nano-hydroxyapatite particles (nHAp) in immobilizing Pb and Cd from aqueous solutions and contaminated sediment were investigated. The maximum sorption amount (Q_max) of Pb and Cd in aqueous solution was 1.17 and 0.57 mmol/g. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) surface and depth analysis indicated that dissolution-precipitation is the primary immobilization mechanism for Pb, while surface complexation and intraparticle diffusion account for Cd sequestration. Different amounts of nHAp (0-10% nHAp/dry weight) were added to the contaminated sediment. Sequential extraction showed that nHAp could effectively reduce the exchangeable fraction of Pb and Cd in the sediment and significantly reduce the concentration in porewater. The results in this study showed that nHAp can immobilize Pb and Cd in sediment effectively.     

Uranium and neptunium retention mechanisms in Gallionella ferruginea/ferrihydrite systems for remediation purposes

The ubiquitous β-Proteobacterium Gallionella ferruginea is known as stalk-forming, microaerophilic iron(II) oxidizer, which rapidly produces iron oxyhydroxide precipitates. Uranium and neptunium sorption on the resulting intermixes of G. ferruginea cells, stalks, extracellular exudates, and precipitated iron oxyhydroxides (BIOS) was compared to sorption to abiotically formed iron oxides and oxyhydroxides. The results show a high sorption capacity of BIOS towards radionuclides at circumneutral pH values with an apparent bulk distribution coefficient (K_d) of 1.23 × 10⁴ L kg^?1 for uranium and 3.07 × 10⁵ L kg^?1 for neptunium. The spectroscopic approach by X-ray absorption spectroscopy (XAS) and ATR FT-IR spectroscopy, which was applied on BIOS samples, showed the formation of inner-sphere complexes. The structural data obtained at the uranium L_III-edge and the neptunium L_III-edge indicate the formation of bidentate edge-sharing surface complexes, which are known as the main sorption species on abiotic ferrihydrite. Since the rate of iron precipitation in G. ferruginea-dominated systems is 60 times faster than in abiotic systems, more ferrihydrite will be available for immobilization processes of heavy metals and radionuclides in contaminated environments and even in the far-field of high-level nuclear waste repositories.

     

复合赤泥在高浓度含磷废水处理中的应用

赤泥与石灰粉（CaO和Ca（OH）₂）按不同比例混合制成复合赤泥,通过投加实验考察了复合赤泥的除磷效果。结果证明,对于磷酸盐浓度为45 000 mg/L左右（以P计）的酸性工业废水,复合赤泥（赤泥与Ca（OH）₂按质量比1：1混合）投加量为240 g/L,去除率为99.97%;对于10 mg/L左右的含磷废水,赤泥的最佳投加浓度为15 g/L,上清液磷浓度可降至0.30 mg/L,出水低于0.5 mg/L的排放标准。根据以上研究结果,提出了对高浓度酸性磷酸盐废水的处理宜采用复合赤泥再加原状赤泥的二级处理方法。     

不同纳米修复剂对污染土壤中胡萝卜吸收、转运Cd的影响

通过盆栽实验研究不同纳米修复剂(羟基磷灰石HAP、赤泥RM、Fe3O4、胡敏酸-Fe3O4)对2种不同污染土壤Cd吸收、转运的影响。结果表明,上述纳米修复剂均可显著增加胡萝卜植株生物量,显著提高植株Cd胁迫的耐受指数;不同土壤施用不同纳米修复剂均显著降低胡萝卜植株Cd的含量,并且随着修复剂施加浓度的增加而显著降低;与对照相比,植株茎叶Cd含量最大降低达78.8%,根中Cd的含量最大降低67.8%;添加不同修复剂能不同程度地降低了土壤中Cd的转运系数和富集系数,这可能与施用不同纳米修复剂促进了土壤中非残留态Cd向残留态Cd的转化有关,总体而言,不同纳米型修复剂对降低Cd的有效性顺序为:RM～HAP>胡敏酸-Fe3O4>Fe3O4。     

Elevated CO2 concentration increase the mobility of Cd and Zn in the rhizosphere of hyperaccumulator Sedum alfredii

The effects of elevated CO₂ on metal species and mobility in the rhizosphere of hyperaccumulator are not well understood. We report an experiment designed to compare the effects of elevated CO₂ on Cd/Zn speciation and mobility in the rhizosphere of hyperaccumulating ecotype (HE) and a non-hyperaccumulating ecotype (NHE) of Sedum alfredii grown under ambient (350 μl l^?1) or elevated (800 μl l^?1) CO₂ conditions. No difference in solution pH of NHE was observed between ambient and elevated CO₂ treatments. For HE, however, elevated CO₂ reduced soil solution pH by 0.22 unit, as compared to ambient CO₂ conditions. Elevated CO₂ increased dissolved organic carbon (DOC) and organic acid levels in soil solution of both ecotypes, but the increase in HE solution was much greater than in NHE solution. After the growth of HE, the concentrations of Cd and Zn in soil solution decreased significantly regardless of CO₂ level. The visual MINTEQ speciation model predicted that Cd/Zn–DOM complexes were the dominant species in soil solutions, followed by free Cd²⁺ and Zn²⁺ species for both ecotypes. However, Cd/Zn–DOM complexes fraction in soil solution of HE was increased by the elevated CO₂ treatment (by 8.01 % for Cd and 8.47 % for Zn, respectively). Resin equilibration experiment results indicated that DOM derived from the rhizosphere of HE under elevated CO₂ (HE-DOM-E) (90 % for Cd and 73 % for Zn, respectively) showed greater ability to form complexes with Cd and Zn than those under ambient CO₂ (HE-DOM-A) (82 % for Cd and 61 % for Zn, respectively) in the undiluted sample. HE-DOM-E showed greater ability to extract Cd and Zn from soil than HE-DOM-A. It was concluded that elevated CO₂ could increase the mobility of Cd and Zn due to the enhanced formation of DOM–metal complexes in the rhizosphere of HE S. alfredii.     

Speciation and distribution of copper in a mining soil using multiple synchrotron-based bulk and microscopic techniques

Molecular-level understanding of soil Cu speciation and distribution assists in management of Cu contamination in mining sites. In this study, one soil sample, collected from a mining site contaminated since 1950s, was characterized complementarily by multiple synchrotron-based bulk and spatially resolved techniques for the speciation and distribution of Cu as well as other related elements (Fe, Ca, Mn, K, Al, and Si). Bulk X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that soil Cu was predominantly associated with Fe oxides instead of soil organic matter. This agreed with the closest association of Cu to Fe by microscopic X-ray fluorescence (U-XRF) and scanning transmission X-ray microscopy (STXM) nanoanalysis, along with the non-occurrence of photoreduction of soil Cu(II) by quick Cu L_3,2-edge XANES spectroscopy (Q-XANES) which often occurs when Cu organic complexes are present. Furthermore, bulk-EXAFS and STXM-coupled Fe L_3,2-edge nano-XANES analysis revealed soil Cu adsorbed primarily to Fe(III) oxides by inner-sphere complexation. Additionally, Cu K-edge μ-XANES, L_3,2-edge bulk-XANES, and successive Q-XANES results identified the presence of Cu₂S rather than radiation-damage artifacts dominant in certain microsites of the mining soil. This study demonstrates the great benefits in use of multiple combined synchrotron-based techniques for comprehensive understanding of Cu speciation in heterogeneous soil matrix, which facilitates our prediction of Cu reactivity and environmental fate in the mining site.     

Equilibrium partitioning theory to predict the sediment toxicity of the anionic surfactant C(12)-2-LAS to Corophium volutator

The study of the effect of the sorption of linear alkylbenzene sulfonates (LAS) on the bioavailability to marine benthic organisms is essential to refine the environmental risk assessment of these compounds. According to the equilibrium partitioning theory (EqP), the effect concentration in water-only exposure will be similar to the effect concentration in the sediment pore water. In this work, sorption and desorption experiments with two marine sediments were carried out using the compound C₁₂-2-LAS. The effect of the sediment sorption on the toxicity of benthic organisms was studied in water-only and in sediment bioassays with the marine mud shrimp Corophium volutator. In addition, three common spiking methods were tested for its application in the toxicity tests, as well as the stability of the surfactant during the water-only and sediment-water test duration. LC50 values obtained from water-only exposure showed a good correspondence with the pore water concentrations calculated from the sorption and desorption isotherms in the spiked sediments.     

The influence of copper on tebuconazole sorption onto soils, humic substances, and ferrihydrite

The aim of this study is to investigate how the presence of Cu influences tebuconazole (Teb) sorption onto contrasting soil types and two important constituents of the soil sorption complex: hydrated Fe oxide and humic substances. Tebuconazole was used in commercial form and as an analytical-grade chemical at different Teb/Cu molar ratios (1:4, 1:1, 4:1, and Teb alone). Increased Cu concentrations had a positive effect on tebuconazole sorption onto most soils and humic substances, probably as a result of Cu?Teb tertiary complexes on the soil surfaces. Tebuconazole sorption increased in the following order of different Teb/Cu ratios 1:4?>?1:1?>?4:1?>?without Cu addition, with the only exception for the Leptosol and ferrihydrite. The highest K _f value was observed for humic substances followed by ferrihydrite, the Cambisol, the Arenosol, and the Leptosol. The sorption of analytical-grade tebuconazole onto all matrices was lower, but the addition of Cu supported again tebuconazole sorption. The Teb/Cu ratio with the highest Cu addition (1:4) exhibited the highest K _f values in all matrices with the exception of ferrihydrite. The differences in tebuconazole sorption can be attributed to the additives present in the commercial product. This work proved the importance of soil characteristics and composition of the commercially available pesticides together with the presence of Cu on the behavior of tebuconazole in soils.     

Sorption of As,Cd and Tl as influenced by industrial by-products applied to an acidic soil: Equilibrium and kinetic experiments

In situ stabilization of toxic elements in contaminated soils by the addition of amendments is being considered as an effective technique for remediation. In this paper, we performed both kinetics and equilibrium-based sorption experiments of three toxic elements (As, Cd and Tl) in soils amended with two by-products (phosphogypsum and sugar foam, rich in gypsum and calcium carbonate, respectively) to ascertain the feasibility of their application for improving the sorption capacity of As, Cd and Tl from the soil at 25, 35 and 50 °C. Kinetic studies indicated that the sorption follows a pseudo-second-order (PSO) kinetics and the sorption is a two-step diffusion process where both film and intraparticle diffusion played important roles in the sorption mechanisms of the elements. The Langmuir isotherms applied for sorption studies showed that the estimated maximum sorption capacity of the elements in control and amended soils decreased in the order of Cd > As > Tl. Using the thermodynamic equilibrium parameters obtained at different temperatures, the thermodynamic constants of sorption (ΔG, ΔH and ΔS) were also evaluated, indicating spontaneous and endothermic nature of the process, except Tl which was exothermic. An optimal scaling procedure was undertaken to determine the relationships between the kinetic and equilibrium sorption parameters. By means of statistical analysis it was seen that these inter-parametric relationships are dependent on the element nature.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Passive dosing: an approach to control mutagen exposure in the Ames fluctuation test

By using dialysis equilibrium experiments, the sorption of a branched nonylphenol isomer [4-(1-ethyl-1,3-dimethylpentyl)-phenol] (NP111) on various humic acids (HAs) isolated from river sediments and two reference HAs was studied. The HAs were characterized by solid-state ¹³C direct polarization/magic angle spinning nuclear magnetic resonance (¹³C DP/MAS NMR) spectroscopy. Sorption isotherms of NP111 on HAs were described by a linear model. The organic carbon-normalized sorption coefficient (K_OC) ranged from 2.3 × 10³ to 1.5 × 10⁴ L kg⁻¹. Interestingly, a clear correlation between K_OC value and alkyl C content was observed, indicating that the aliphaticity of HAs markedly dominates the sorption of NP111. These new mechanistic insights about the NP111 sorption indicate that the fate of nonylphenols in soil or sediment depends not only on the content of HA, but also on its structural composition.     

Removal of Cu, Zn, and Cd from aqueous solutions by the dairy manure-derived biochar

Purpose

Biochar derived from waste biomass is now gaining much attention for its function as a biosorbent for environmental remediation. The objective of this study was to determine the effectiveness of biochar as a sorbent in removing Cd, Cu, and Zn from aqueous solutions.

Methods

Biochar was produced from dairy manure (DM) at two temperatures: 200°C and 350°C, referred to as DM200 and DM350, respectively. The obtained biochars were then equilibrated with 0–5 mM Cu, Zn or Cd in 0.01 M NaNO₃ solution for 10 h. The changes in solution metal concentrations after sorption were evaluated for sorption capacity using isotherm modeling and chemical speciation Visual MINTEQ modeling, while the solid was collected for species characterization using infrared spectroscopy and X-ray elemental dot mapping techniques.

Results

The isotherms of Cu, Zn, and Cd sorption by DM200 were better fitted to Langmuir model, whereas Freundlich model well described the sorption of the three metals by DM350. The DM350 were more effective in sorbing all three metals than DM200 with both biochars had the highest affinity for Cu, followed by Zn and Cd. The maximum sorption capacities of Cu, Zn, and Cd by DM200 were 48.4, 31.6, and 31.9 mg g^?1, respectively, and those of Cu, Zn, and Cd by DM350 were 54.4, 32.8, and 51.4 mg g^?1, respectively. Sorption of the metals by the biochar was mainly attributed to their precipitation with PO ₄ ^3? or CO ₃ ^2? originating in biochar, with less to the surface complexation through –OH groups or delocalized π electrons. At the initial metal concentration of 5 mM, 80–100 % of Cu, Zn, and Cd retention by DM200 resulted from the precipitation, with less than 20 % from surface adsorption through phenonic –OH complexation. Among the precipitation, 20–30 % of the precipitation occurred as metal phosphate and 70–80 % as metal carbonate. For DM350, 75–100 % of Cu, Zn, and Cd retention were due to the precipitation, with less than 25 % to surface adsorption through complexation of heavy metal by phenonic –OH site or delocalized π electrons. Among the precipitation, only less than 10 % of the precipitation was present as metal phosphate and more than 90 % as metal carbonate.

Conclusions

Results indicated that dairy manure waste can be converted into value-added biochar as a sorbent for sorption of heavy metals, and the mineral components originated in the biochar play an important role in the biochar's high sorption capacity.     

Temperature-dependent sorption of polycyclic aromatic hydrocarbons on natural and treated sediments

In aqueous environment temperature is considered to play a significant role in the sorption process of polycyclic aromatic hydrocarbons (PAHs) and its influence on the sorption equilibrium is indicative of sorption energies and mechanisms. In this study, sorptions of five PAHs on three heterogeneous sorbents including one river sediment (YHR), one estuary sediment (YRD) and one treated sediment with organic matter removed (IM) were carried out at a range of temperature from 5 °C to 35 °C. Stronger sorptions were observed at lower temperatures, with the equilibrium sorption coefficient K_d increasing 2-5 times as the temperature decreases 30 °C. The increase of K_d value was attributed primarily to the change of PAH water solubility, which predicted 40-75% of the increase of K_d in the sorption process. To provide insight into the sorption mechanism, enthalpy change (ΔH_S) for the sorption process was calculated and the values were observed to be negative for all of the interactions, suggesting that the exothermal sorption of PAHs inversely dependents on temperature. Based on the values of ΔH_S, van der Waals forces were inferred as the main sorption mechanism for the PAHs, especially on the YHR sediment which contained more organic matter. For sorption of larger size PAHs on the sorbents with low organic matter, specific interactions were deduced to contribute to the overall sorption.     

Sorption comparison between phenanthrene and its degradation intermediates, 9,10-phenanthrenequinone and 9-phenanthrol in soils/sediments

The degradation intermediates of phenanthrene (PHE) may have increased health risks to organisms than PHE. Therefore, environmental fate and risk assessment studies should take into considerations of PHE degradation products. This study compared the sorption properties of PHE and its degradation intermediates, 9,10-phenanthrenequinone (PQN) and 9-phenanthrol (PTR) in soils, sediments and soil components. A relationship between organic carbon content (f_OC) and single-point sorption coefficient (log K_d) was observed for all three chemicals in 10 soils/sediments. The large intercept in the log f_OC − log K_d regression for PTR indicated that inorganic fractions control PTR sorption in soils/sediments. No relationship between specific surface area and K_d was observed. This result indicated that determination of surface area based on gas sorption could not identify surface properties for PHE, PQN, and PTR sorption and thus provide limit information on sorption mechanisms. The high sorption and strong nonlinearity (low n values) of PTR in comparison to PHE suggested that the mobility of PTR could be lower than PHE. Increased mobility of PQN compared with PHE may be expected in soils/sediments because of PQN lower sorption. The varied sorption properties of the three chemicals suggested that their environmental risks should be assessed differently.     

Characterization and Cu sorption properties of humic acid from the decomposition of rice straw

Humic acid (HA) derived from rice straw decomposed for 1 (HA-1), 3 (HA-3), 6 (HA-6) and 12 (HA-12) months was characterized by potentiometric titration and solid-state cross-polarization magic-angle spinning ¹³C nuclear magnetic resonance spectroscopy (CPMAS ¹³C NMR). The sorption of Cu on examined HA was investigated using a combination of batch sorption, isothermal titration calorimetry (ITC) and sequential desorption. Results showed that the functional group content and the humification degree of HA tended to increase with increasing decomposition time especially in the latter stage of examined decomposition period. Cu sorption on HA was a rapid process that occurred within the first 1 h and the sorption capacity increased from 245.4 mmol kg⁻¹ on HA-1 to 294.6 mmol kg⁻¹ on HA-12. The sorption of Cu was endothermic, spontaneous and the randomness was increased during Cu sorption. Sorbed Cu on examined HA can be hardly released by NH₄Ac but nearly fully released by EDTA. Forming inner-sphere complexes was the main mechanism of Cu sorption on examined HA. This study could provide valuable information for a better understanding on the environmental impacts of the decomposition of organic waste.

     

不同粒径泥沙理化特性对磷吸附过程的影响

以北京大兴南海子湖表层沉积物为研究对象,测试分析了0.147～0.246 mm(细砂)、0.074～0.147 mm(极细砂)、0.0385～0.0740 mm(粉粒)和<0.0385 mm(粉粒粘粒混合物)4种粒径泥沙对磷的吸附行为,并采用相关分析及逐步回归分析探讨不同粒径沉积物中有机质(OM)、Fe、Al、Ca、Mn和TP含量对磷吸附过程的影响。结果表明,二级动力学方程和Langmuir模型能较好地描述南海子不同粒径泥沙的吸附动力学及等温吸附过程(R2>0.90)。粒径对单位质量泥沙吸附磷量具有明显影响,粉粒粘粒混合物>粉粒>细砂>极细砂。总体上,泥沙有机质(OM)、TP、Fe、Al、Ca和Mn含量随粒径的减小而增大,且粘粒对其影响较大。不同粒径泥沙(OM)、Fe、Al、Ca和Mn含量之间存在极显著正相关关系(P<0.01),且均对单位质量泥沙最大吸附量(Xm)和饱和吸附量(Cse)具有正效应,其中Al含量对该参数的影响更为显著。这说明泥沙对磷的吸附行为可能受到粒径和化学成分的共同影响。     

Adsorption of hydrogen sulfide by biochars derived from pyrolysis of different agricultural/forestry wastes

The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on three different biochars derived from agricultural/forestry wastes through pyrolysis at various temperatures (100 to 500 ºC) were investigated. In this study, the H₂S breakthrough capacity was measured using a laboratory-characterized using pH and Fourier transform infrared spectroscopy analysis. The results obtained demonstrate that all biochars were effective in H₂S sorption. The sorption capacity of the biochar for H₂S removal is related to the pyrolysis temperature and pH of the surface. Certain threshold ranges of the pyrolysis temperature (from 100 to 500 ºC) and pH of the surface are presented. It also concluded that the sorption capacity (for removing H₂S) of rice hull-derived biochar is the largest in three biochars (camphor-derived biochar, rice hull-derived biochar, and bamboo-derived biochar). These observations will be helpful in designing biochar as engineered sorbents for the removal of H₂S.Implications: This paper focuses on the adsorption of hydrogen sulfide (H₂S) by biochars derived from wastes. The characteristics and mechanisms of hydrogen sulfide (H₂S) adsorption on three different boichars derived from agricultural/forestry wastes through pyrolysis at various temperatures were investigated. In this study, the H₂S breakthrough capacity was measured using laboratory characterization with pH and Fourier-transform infrared spectroscopy analysis. The results obtained demonstrate that all biochars were effective in H₂S sorption. The sorption capacity of the biochar for H₂S removal is related to the pyrolysis temperature and pH of the surface.