Chemically modified biochar produced from conocarpus waste increases NO<Subscript>3</Subscript> removal from aqueous solutions

Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO₃ removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO₃ sorption capacity of 45.36 mmol kg^?1 predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO₃ sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m² g^?1) and formation of strong ionic complexes with NO₃. At an initial pH of 2, more than 89 % NO₃ removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar.     

Efficacy of woody biomass and biochar for alleviating heavy metal bioavailability in serpentine soil

Crops grown in metal-rich serpentine soils are vulnerable to phytotoxicity. In this study, Gliricidia sepium (Jacq.) biomass and woody biochar were examined as amendments on heavy metal immobilization in a serpentine soil. Woody biochar was produced by slow pyrolysis of Gliricidia sepium (Jacq.) biomass at 300 and 500 °C. A pot experiment was conducted for 6 weeks with tomato (Lycopersicon esculentum L.) at biochar application rates of 0, 22, 55 and 110 t ha^?1. The CaCl₂ and sequential extractions were adopted to assess metal bioavailability and fractionation. Six weeks after germination, plants cultivated on the control could not survive, while all the plants were grown normally on the soils amended with biochars. The most effective treatment for metal immobilization was BC500-110 as indicated by the immobilization efficiencies for Ni, Mn and Cr that were 68, 92 and 42 %, respectively, compared to the control. Biochar produced at 500 °C and at high application rates immobilized heavy metals significantly. Improvements in plant growth in biochar-amended soil were related to decreasing in metal toxicity as a consequence of metal immobilization through strong sorption due to high surface area and functional groups.     

Biosolids application affects the competitive sorption and lability of cadmium,copper, nickel,lead, and zinc in fluvial and calcareous soils

The objective of this research was to investigate the effects of biosolids on the competitive sorption and lability of the sorbed Cd, Cu, Ni, Pb, and Zn in fluvial and calcareous soils. Competitive sorption isotherms were developed, and the lability of these metals was estimated by DTPA extraction following their sorption. Sorption of all metals was higher in the fluvial than in the calcareous soil. Sorption of Cu and Pb was stronger than that of Cd, Ni, and Zn in all soils. Biosolids application (2.5%) reduced the sorption of all metals especially Cu and Pb (28–43%) in both soils (especially the calcareous soil) at the lower added metal concentrations (50 and 100 mg L^?1). However, it increased the sorption of all metals especially Pb and Cu in both soils (especially the calcareous soil; 15.5-fold for Cu) at the higher added concentrations (250 and 300 mg L^?1). Nickel showed the highest lability followed by Cd, Zn, and Pb in both soils. Biosolids increased the lability of the sorbed Ni in the fluvial soils at all added concentrations and the lability of Cd, Pb, and Zn at 50 mg L^?1, but decreased the lability of Cd, Pb, and Zn at 250 and 300 mg L^?1 in both soils. We conclude that at low loading rate (e.g., 50 mg L^?1) biosolids treatment might increase the lability and environmental risk of Cd, Cu, Pb, and Zn. However, at high loading rate (e.g., 300 mg L^?1) biosolids may be used as an immobilizing agent for Cd, Cu, Pb, Zn and mobilizing agent for Ni.     

Impact of natural and calcined starfish (<Emphasis Type="Italic">Asterina pectinifera</Emphasis>) on the stabilization of Pb,Zn and As in contaminated agricultural soil

Metal stabilization using soil amendments is an extensively applied, economically viable and environmentally friendly remediation technique. The stabilization of Pb, Zn and As in contaminated soils was evaluated using natural starfish (NSF) and calcined starfish (CSF) wastes at different application rates (0, 2.5, 5.0 and 10.0 wt%). An incubation study was conducted over 14 months, and the efficiency of stabilization for Pb, Zn and As in soil was evaluated by the toxicity characteristic leaching procedure (TCLP) test. The TCLP-extractable Pb was reduced by 76.3–100 and 91.2–100 % in soil treated with NSF and CSF, respectively. The TCLP-extractable Zn was also reduced by 89.8–100 and 93.2–100 % in soil treated with NSF and CSF, respectively. These reductions could be associated with the increased metal adsorption and the formation of insoluble metal precipitates due to increased soil pH following application of the amendments. However, the TCLP-extractable As was increased in the soil treated with NSF, possibly due to the competitive adsorption of phosphorous. In contrast, the TCLP-extractable As in the 10 % CSF treatment was not detectable because insoluble Ca–As compounds might be formed at high pH values. Thermodynamic modeling by visual MINTEQ predicted the formation of ettringite (Ca₆Al₂(SO₄)₃(OH)₁₂·26H₂O) and portlandite (Ca(OH)₂) in the 10 % CSF-treated soil, while SEM–EDS analysis confirmed the needle-like structure of ettringite in which Pb was incorporated and stabilized in the 10 % CSF treatment.     

Trichoderma harzianum: a green sorbent for Pb(II) uptake from aqueous solutions

This investigation describes the use of specially cultivated, nonliving biomass of Trichoderma harzianum as a biosorbent for the batch removal of Pb(II) from a stirred system under different experimental conditions. The metal removal depended upon pH, sorbent particle size, initial Pb(II) concentration, shaking speed, and sorption time. The optimal experimental conditions for the removal of Pb(II) by T. harzianum with an initial metal concentration of 100 mg L^?1 were obtained at a particle size of 53 μm, a pH of 4.5, a shaking speed of 200 rpm, and a contact time of 720 min. The results were analyzed in terms of adsorption isotherms and kinetic models. The Freundlich isotherm model and pseudo second-order model fitted well in the data. T. harzianum proved to be a good biomaterial for accumulating Pb(II) from aqueous solutions (q = 460 mg g^?1).     

哌嗪氨基二硫代甲酸型螯合树脂的合成及其吸附性能

用哌嗪和二硫化碳反应合成氨基二硫代甲酸中间体，再与二卤代烃反应得到1，4-双(二硫代酯基)哌嗪聚合物，考察了中间体和螯合树脂对Ag^ ，Cu^2 ，Zn^2 ，Ni^2 ，CO^2 ，Pb^2 ，Pd^2 ，Cr^3 的静态吸附性能，结果表明，两者均可以吸附金属离子，缩聚后的螯合树脂具有更强的吸附能力。     

Quantitative analysis and sorption of cadmium in environmental samples with a functionalized synthetic polymer

Quantitative analysis of cadmium in environmental samples was achieved with a polymeric sorbent synthesized by copolymerization of N,N-dimethylacrylamide and allyl glycidyl ether/iminodiacetic acid as chelating monomers with N,N′-methylenebisacrylamide as cross-linker. The polymer was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and scanning electron microscopy. The sorption capacity of the functionalized sorbent was 70 mg g^?1. The equilibrium sorption data of Cd(II) on polymeric sorbent were analyzed using Langmuir, Freundlich, Temkin, and Redlich–Peterson models. Based on equilibrium adsorption data, the constants at pH 4.2 and 20 °C were determined for the first three as 0.33 (L mg^?1), 17.5 (mg g^?1) (L mg^?1)^1/n, and 12.9 (J mol^?1). Recovery of 94% of the metal ion was obtained with 0.5 mol L^?1 nitric acid as an eluting agent.     

Optimisation of bisphenol A removal from water using chemically modified pine bark and almond shell

The ability of pine bark and almond shells to remove bisphenol A (BPA) from aqueous solutions was evaluated. Samples of these traditional agro-forestry by-products were milled, sieved into different particle size fractions (0.10–0.15 and 1.5–2.0 mm) and submitted to two different types of treatment. Sorption experiments were conducted in a batch system at room temperature and natural pH. Sorption equilibrium was attained after 48 h for all systems under study. Bisphenol A was adsorbed more effectively on the smaller particles of the sorbents. Pine bark and almond shell pretreated with formaldehyde presented higher sorption efficiency (95%), followed by almond shell (87%) and pine bark (82%) washed with hot water. All the sorption isotherms were found to fit a Freundlich equation, with correlation coefficients (R ²) between 0.823 and 0.989. The sorption coefficient (K _F) ranged from 0.06 to 0.74 (mg^1?1/n ·L ^1/n ·g ^?1). These results indicate that utilisation of both materials as an alternative sorbent for the removal of bisphenol A from contaminated waters is promising because they are available in large amounts and have an acceptable cost–efficiency ratio when compared with traditional adsorbents.     

Assessment of heavy metals contamination in soils surrounding a gold mine: comparison of two digestion methods

This study investigated two digestion methods (USEPA 3051: microwave, HNO₃ or Hossner: hot plate, HF–H₂SO₄–HClO₄) for heavy metals analysis in contaminated soil surrounding Mahad AD'Dahab mine, Saudi Arabia. Moreover, contamination metal levels were estimated. The Hossner and USEPA 3051 methods showed, respectively, average total contents of 17.2 and 18.1 mg kg^?1 for Cd, 11.6 and 10.6 mg kg^?1 for Co, 45.7 and 34.7 mg kg^?1 for Cr, 1030 and 1100 mg kg^?1 for Cu, 33,300 and 27,400 mg kg^?1 for Fe, 963 and 872 mg kg^?1 for Mn, 33.2 and 22.8 mg kg^?1 for Ni, 791 and 782 mg kg^?1for Pb, and 6320 and 2870 mg kg^?1 for Zn. A lack of significant differences and a high correlation coefficient (>90%) for Cd, Pb and Cu between the two digestion methods suggest that the total-recoverable method (USEPA 3051) may be equivalent to the total-total digestion method (Hossner) for determining these metals in the studied soil. However, significantly higher concentrations of Cr, Fe, Ni and Zn were found by the Hossner method comapred with the USEPA 3051 method. The soil samples have very or extremely high levels of Zn, Cu, Cd and Pb contamination, indicating very high potential ecological risk.     

Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces

This study examines the adsorption isotherms, kinetics and mechanisms of Pb²⁺ sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb²⁺ in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb²⁺ with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca²⁺ and PO₄ ^3? concentrations during the metal sorption processes. The Pb²⁺ sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb⁺. The sorption isotherm results indicated that Pb²⁺ sorption onto the Langmuir and Freundlich constant q _max and K _F is 9.52 and 8.18 mg g^?1, respectively. Sorption kinetics results indicated that Pb²⁺ sorption onto WCBP was pseudo-second-order rate constants K ₂ was 1.12 g mg^?1 h^?1. The main mechanism is adsorption or surface complexation (≡POPb⁺: 61.6%), co-precipitation or ion exchange [Ca_3.93 Pb_1.07 (PO₄)₃ (OH): 21.4%] and other precipitation [Pb 50 mg L^?1 and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb²⁺ removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb²⁺ indicates its potential as another promising way to remediate Pb²⁺-contaminated media.     

Performance and mechanism for cadmium and lead adsorption from water and soil by corn straw biochar

Cadmium (Cd) and lead (Pb) in water and soil could be adsorbed by biochar produced from corn straw. Biochar pyrolyzed under 400°C for 2 h could reach the ideal removal efficiencies (99.24%and 98.62% for Cd and Pb, respectively) from water with the biochar dosage of 20 g·L^–1 and initial concentration of 20 mg·L^–1. The pH value of 4–7 was the optimal range for adsorption reaction. The adsorption mechanism was discussed on the basis of a range of characterizations, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Raman analysis; it was concluded as surface complexation with active sorption sites (-OH, -COO-), coordination with π electrons (C = C, C = O) and precipitation with inorganic anions (OH^-, CO₃ ^2–, SO₄ ^2–) for both Cd and Pb. The sorption isotherms fit Langmuir model better than Freundlich model, and the saturated sorption capacities for Cd and Pb were 38.91 mg·g^-1 and 28.99 mg·g^–1, respectively. When mixed with soil, biochar could effectively increase alkalinity and reduce bioavailability of heavy metals. Thus, biochar derived from corn straw would be a green material for both removal of heavy metals and amelioration of soil.

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Characteristics,sources and health risk assessment of toxic heavy metals in PM<Subscript>2.5</Subscript> at a megacity of southwest China

Twenty trace elements in fine particulate matters (i.e., PM_2.5) at urban Chengdu, a southwest megacity of China, were determined to study the characteristics, sources and human health risk of particulate toxic heavy metals. This work mainly focused on eight toxic heavy metal elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The average concentration of PM_2.5 was 165.1 ± 84.7 µg m^?3 during the study period, significantly exceeding the National Ambient Air Quality Standard (35 µg m^?3 in annual average). The particulate heavy metal pollution was very serious in which Cd and As concentrations in PM_2.5 significantly surpassed the WHO standard. The enrichment factor values of heavy metals were typically higher than 10, suggesting that they were mainly influenced by anthropogenic sources. More specifically, the Cr, Mn and Ni were slightly enriched, Cu was highly enriched, while As, Cd, Pb and Zn were severely enriched. The results of correlation analysis showed that Cd may come from metallurgy and mechanical manufacturing emissions, and the other metals were predominately influenced by traffic emissions and coal combustion. The results of health risk assessment indicated that As, Mn and Cd would pose a significant non-carcinogenic health risk to both children and adults, while Cr would cause carcinogenic risk. Other toxic heavy metals were within a safe level.     

Efficient uranium immobilization on red clay with phosphates

Uranium is a very toxic and radioactive element. Removal of uranium from wastewaters requires remediation technologies. Actual methods are costly and ineffective when uranium concentration is very low. Little is known about the enhancement of sorption of uranyl ions by phosphate ions on aluminosilicates. Here, we studied sorption of uranyl acetate on red clay in the presence of phosphates. The concentration of U(VI) ranged 0.0001–0.001 mol/L, whereas the concentration of PO₄ ^3? was constant at 0.0001 mol/L. We designed a new method for the analysis of ternary surface complexes. We observed for the first time a remarkable improvement of U(VI) sorption on red clay under the influence of phosphates. We also found that at least two different ternary surface complexes U(VI)–phosphate–clay are formed in the sorbent phase. The complexation of UO₂ ²⁺ cations by phosphate ligands in the sorbent phase was confirmed by the X-ray photoelectron spectra of U 4f electrons.     

Purification of contaminated paddy fields by clean water irrigation over two decades

Paddy fields near a mining site in north part of Guangdong Province, PR China, were severely contaminated by heavy metals as a result of wastewater irrigation from the tailing pond. The following clean water irrigation for 2 decades produced marked rinsing effect, especially on Pb and Zn. Paddy fields continuously irrigated with wastewater ever since mining started (50 years) had 1,050.0 mg kg^?1 of Pb and 810.3 mg kg^?1 of Zn for upper 20 cm soil, in comparison with 215.9 mg kg^?1 of Pb and 525.4 mg kg^?1 of Zn, respectively, with clean water irrigation for 20 years. Rinsing effect mainly occurred to a depth of upper 40 cm, of which the soil contained highest metals. Copper and Cd in the farmlands were also reduced due to clean water irrigation. Higher availability of Pb might partly account for more Pb transferred from the tailing pond to the farmland and also more Pb removal from the farmland as a result of clean water irrigation. Neither rice in the paddy field nor dense weeds in the uncultivated field largely took up the metals. However, they might contribute to activate metals differently, leading to a different purification extent. Rotation of rice and weed reduced metal retention in the farmland soil, in comparison with sole rice growth. Harvesting of rice grain (and partially rice stalk) only contributed small fraction of total amount of removed metal. In summary, heavy metal in paddy field resulted from irrigation of mining wastewater could be largely removed by clean water irrigation for sufficient time.     

The importance of different forms of Pb on diminishing biological activities in a calcareous soil

In this experimental study, we evaluated the effect of different lead (Pb) fractions on biological properties in soil spiked with 0, 600, 1200 and 1800 mg kg^?1 Pb, during a 90-day incubation period at 25?28°C. Different Pb fractions were measured by sequential extraction at days 1 and 90 after soil treatment. Diethylenetriaminepentaacetic acid (DTPA)-extractable Pb and soil biological properties at days 1, 5, 15, 45 and 90 were measured. The concentration of Pb in soluble and exchangeable fractions was very high at day 1, but it showed remarkable transfer into carbonate and residual fractions by day 90. Substrate-induced respiration, basal respiration, acid and alkaline phosphatases, microbial populations (bacterial, fungal and actinomycetes) and biomass carbon decreased significantly with soil contamination compared with the control. With Pb ageing, these biological properties increased. Metabolic quotient (qCO₂) increased significantly compared with the control with increasing Pb concentration. The toxicity of various forms of Pb for the biological status of the soil was in the following order: KNO₃ extractable>NaOH extractable>EDTA extractable>HNO ₃ extractable>total content Pb. Thus, the bioavailable fractions are better indicators of Pb pollution in soils.     

Ecological and human health risks from metal(loid)s in peri-urban soil in Nanjing,China

In order to investigate the ecological and human health risks of metal(loid)s (Cu, Pb, Zn, Ni, Cd, Mn, Cr, and As) in peri-urban soils, 43 surface soil samples were collected from the peri-urban area around Nanjing, a megacity in China. The average contents were 1.19, 67.8, 37.6, 105, 167, 44.6, 722, and 50.8 mg kg^?1 for Cd, Cr, Ni, Pb, Zn, Cu, Mn, and As, respectively. A significant positive correlation was found between Cu, Pb, Zn, Cd, Mn, and As (p < 0.01), and Cr had a significant positive correlation with Ni (p < 0.01). Geoaccumulation indices indicate the presence of Cd and As contamination in all of the peri-urban soil samples. Potential ecological risk indices show that the metal(loid)s in the soil could result in higher ecological risks. Cd is the main contributor to the risk, followed by As. The levels of Cu, Pb, Zn, Cd, Mn, and As in stomach and intestinal phases show a positive linear correlation with their total contents. Mn, Zn, Ni, Cd, and Pb in stomach phase showed higher bioaccessibility, while in intestinal phase, Cu, Cr, and As had the higher bioaccessibility. The carcinogenic risk in children and adults posed by As, Pb, and Cr via ingestion was deemed acceptable. The non-carcinogenic risks posed by these metal(loid)s via ingestion to children are higher than to adults and mainly result from As.     

Effects of paclobutrazol (PP333) on lead and zinc accumulations in Pseudostellaria maximowicziana

Paclobutrazol (PP333) can enhance the resistance capabilities of plants to stress conditions. In this study, PP333 were sprayed on the lead (Pb) and zinc (Zn) accumulator plant Pseudostellaria maximowicziana, which was planted in Pb–Zn contaminated soil, and the effects of PP333 on Pb and Zn accumulation levels in P. maximowicziana were studied. Spraying 10?mg/L PP333 increased, while 20, 30 and 50?mg/L PP333 decreased, the biomass of P. maximowicziana compared with the control. The 10?mg/L PP333 had no significant effects on the photosynthetic pigment contents of P. maximowicziana compared with the control, while the other doses increased the contents. The activities of antioxidant enzymes (superoxide dismutase, peroxidase and catalase) and the Pb and Zn concentrations in P. maximowicziana were increased by PP333 compared with the control. These items had the increase trend with the increase of PP333 concentrations. Only 10 and 20?mg/L PP333 increased the amount of Pb extracted by P. maximowicziana shoots, while all of the doses increased the amount of Zn extracted by P. maximowicziana shoots. Thus, low concentration of PP333 could promote the growth and heavy metal extraction ability of P. maximowicziana shoots, with the 10?mg/L being the best.     

Determination of sorbent point zero charge: usefulness in sorption studies

Potentiometric mass titration (PMT) technique has been adapted to determine the pH _pzc of four vegetable wastes: grape stalks, cork, yohimbe bark and olive stones wastes used for Cu(II) removal. The pH at the point zero charge (pH _pzc), determined by PMT, are compared with that obtained by two classical techniques: mass titration (MT) and immersion technique (IT). PMT has been found to be an easy and appropriate technique to determine pH _pzc of the studied materials. From the results, the knowledge of sorbents pH _pzc provides information about the possible attraction and repulsion between sorbent and sorbate but in any case enables to ensure that electrostatic force is one of the mechanisms that takes place in metal sorption.     

富磷污泥生物炭去除水中Pb(Ⅱ)的特性研究

以城市污水厂富磷剩余污泥为研究对象,考察高温热解制备生物炭吸附剂对水中Pb(Ⅱ)的去除效果.研究表明,随着热解温度升高,制备的生物炭对Pb(Ⅱ)的吸附能力增强;在相同热解温度下,生污泥生物炭对Pb(Ⅱ)的吸附能力比消化污泥生物炭大.采用700℃热解1 h制备生污泥生物炭以研究对Pb(Ⅱ)吸附的影响因素,结果显示:吸附180 min达到吸附平衡;富磷污泥生物炭对Pb(Ⅱ)的去除率随pH增加而升高;生物炭投加量增加,对Pb(Ⅱ)去除率上升,而单位吸附容量迅速减小.污泥生物炭对Pb(Ⅱ)的吸附符合准二级反应动力学,Langmuir模型比Freundlich模型能更好地拟合等温吸附线.在pH 5.0、吸附时间3 h、生物炭投加量20 g.L-1条件下,对Pb(Ⅱ)的最大吸附量为34.5 mg.g-1,表明富磷污泥生物炭可以作为一种廉价的吸附剂.     

Ecotoxicological risks of the abandoned F–Ba–Pb–Zn mining area of Osor (Spain)

Due to its potential toxic properties, metal mobilization is of major concern in areas surrounding Pb–Zn mines. In the present study, metal contents and toxicity of soils, aqueous extracts from soils and mine drainage waters from an abandoned F–Ba–Pb–Zn mining area in Osor (Girona, NE Spain) were evaluated through chemical extractions and ecotoxicity bioassays. Toxicity assessment in the terrestrial compartment included lethal and sublethal endpoints on earthworms Eisenia fetida, arthropods Folsomia candida and several plant species, whereas aquatic tests involved bacteria Vibrio fischeri, microalgae Raphidocelis subcapitata and crustaceans Daphnia magna. Total concentrations of Ba (250–5110 mg kg^?1), Pb (940 to >5000 mg kg^?1) and Zn (2370–11,300 mg kg^?1) in soils exceeded intervention values to protect human health. Risks for the aquatic compartment were identified in the release of drainage waters and in the potential leaching and runoff of metals from contaminated soils, with Cd (1.98–9.15 µg L^?1), Pb (2.11–326 µg L^?1) and Zn (280–2900 µg L^?1) concentrations in filtered water samples surpassing US EPA Water Quality Criteria (2016a, b). Terrestrial ecotoxicity tests were in accordance with metal quantifications and identified the most polluted soil as the most toxic. Avoidance and reproduction tests with earthworms showed the highest sensitivity to metal contamination. Aquatic bioassays performed in aqueous extracts from soils confirmed the results from terrestrial tests and also detected toxic effects caused by the mine drainage waters. Algal growth inhibition was the most sensitive aquatic endpoint. In view of the results, the application of a containment or remediative procedure in the area is encouraged.