Highly efficient P uptake by Fe3O4 loaded amorphous Zr-La (carbonate) oxides: Electrostatic attraction, inner-sphere complexation and oxygen vacancies acceleration effect

Bimetallic oxides composites have received an increasing attention as promising adsorbents for aqueous phosphate (P) removal in recent years. In this study, a novel magnetic composite MZLCO was prepared by hybridizing amorphous Zr-La (carbonate) oxides (ZLCO) with nano-Fe₃O₄ through a one-pot solvothermal method for efficient phosphate adsorption. Our optimum sample of MZLCO-45 exhibited a high Langmuir maximum adsorption capacity of 96.16 mg P/g and performed well even at low phosphate concentration. The phosphate adsorption kinetics by MZLCO-45 fitted well with the pseudo-second-order model, and the adsorption capacity could reach 79% of the ultimate value within the first 60 min. The phosphate adsorption process was highly pH-dependent, and MZLCO-45 performed well over a wide pH range of 2.0-8.0. Moreover, MZLCO-45 showed a strong selectivity to phosphate in the presence of competing ions (Cl⁻, NO₃⁻, SO₄²⁻, HCO₃⁻, Ca²⁺, and Mg²⁺) and a good reusability using the eluent of NaOH/NaCl mixture, then 64% adsorption capacity remained after ten recycles. The initial 2.0 mg P/L in municipal wastewater and surface water could be efficiently reduced to below 0.1mg P/L by 0.07 g/L MZLCO-45, and the phosphate removal efficiencies were 95.7% and 96.21%, respectively. Phosphate adsorption mechanisms by MZLCO-45 could be attributed to electrostatic attraction and the inner-sphere complexation via ligand exchange forming Zr/La-O-P, -OH and CO₃²⁻ groups on MZLCO-45 surface played important roles in the ligand exchange process. The existence of oxygen vacancies could accelerate the phosphate absorption rate of the MZLCO-45 composites.     

不同钝化剂对土壤有效态铅和镉含量的影响

通过向土壤中添加蚕沙、熟石灰和磷酸二氢钾,研究不同钝化处理对土壤有效态重金属含量、pH值及有机质含量的影响.结果表明:添加蚕沙和熟石灰都能使土壤中高植物有效挂的有效态Pb和有效态Cd大幅下降;其中以单施蚕沙处理效果最优,其对Pb和Cd的钝化效率分别达到36.5％和39.2％,而蚕沙+熟石灰处理钝化效果次之,分别为24.3％和26.9％.磷酸二氢钾的钝化作用不明显.添加熟石灰对土壤pH值影响最大,而蚕沙大幅增加了土壤中有机质含量.经统计分析,土壤pH值、有机质含量都与土壤有效态Pb、Cd含量之间呈负相关,说明通过提高土壤pH值及有机质含量,降低土壤重金属活性是土壤重金属钝化的主要机理.     

Remediation of copper-contaminated topsoils from a wood treatment facility using in situ stabilisation

Five organic matters, three phosphate compounds, zerovalent iron grit (ZVIG, 2% by soil weight), two alkaline compounds, and two commercial formulations were incorporated, singly and some combined with ZVIG, into a highly Cu-contaminated topsoil (Soil P7, 2600 mg Cu kg⁻¹) from a wood treatment facility. Formulations and two composts were also singly incorporated into a slightly Cu-contaminated topsoil (Soil P10, 118 mg Cu kg⁻¹) from the facility surrounding. This aimed to reduce the labile pool of Cu and its accumulation in beans cultivated on potted soils in a climatic chamber. Lowest Cu concentration in soil solution occurred in P7 soils amended with activated carbon (5%) and ZVIG, singly and combined. Basic slag (3.9%) and compost of sewage sludge (5%) combined with ZVIG promoted shoot production and limited foliar Cu accumulation. For amended P10 soils, no changes occurred in soil solution and foliar Cu concentrations, but one compost increased shoot production.     

不同磷处理对污染土壤中有效态铅及磷迁移的影响

为了研究不同含磷化合物对污染土壤中铅有效性的影响及其在土壤剖面中的迁移状况,对3种不同性质的含磷化合物按含量为2500、5000 mg·kg-1进行了土柱试验.结果表明,对铅污染土壤施入磷酸氢钙(SSP)、磷矿粉(PR)及羟基磷灰石(HA)能显著降低土壤表层CaCl2(0.01 mol·L-1)提取态铅的含量,且有效铅的含量随磷施入含量的增加而显著降低.在施磷270 d后,施入含量为5000 mg·kg-1的磷酸氢钙(SSP5)、磷矿粉(PR5)及羟基磷灰石(HA5)处理土壤有效铅的含量分别比对照降低了86.6%、81.1%和89.7%.对不同深度土壤有效磷和全磷含量分析表明,土壤中施入不同溶解性质的磷显著增加了土壤表层(0～10 cm)的有效磷(Olsen-p)及全磷的含量,土壤中有效磷及全磷的含量随着土柱深度的增加而显著降低.除了SSP5处理外,上述不同磷处理对于大于50 cm深度的土壤中的有效磷和全磷变化没有显著影响,而所有处理对于大于70 cm深度的土壤中有效磷和全磷含量没有显著影响.这表明在铅污染土壤中施入不同性质的磷能显著降低土壤中CaCl2(0.01 mol·L-1)提取态铅的含量,而土壤中施入的磷在土壤垂直剖面的迁移却很少,即使是易溶性的磷酸氢钙(SSP)也不会造成大于70cm深度的土壤剖面中磷含量的显著性差异,其原因可能与土壤胶体对磷的强力吸附有关.     

Phosphate-induced differences in stabilization efficiency for soils contaminated with lead,zinc, and cadmium

Phosphates can cost-effectively decrease the mobility of Pb in contaminated soils. However, Pb always coexists with other metals in soil, their competitive reactions with phosphates have not been tested. In this study, the abilities of KH₂PO₄, K₂HPO₄, and K₃PO₄ to stabilize Pb, Zn, and Cd in soils contaminated with a single metal or a ternary metal for different phosphorus/metal molar ratios were investigated. Results indicated that the stabilization efficiency of KH₂PO₄, K₂HPO₄, and K₃PO₄ for Pb, Zn, and Cd in single metal contaminated soil (P/M ratio 0.6) was 96.00%–98.74%, 33.76%–47.81%, and 9.50%–55.79%, respectively. Competitive stabilization occurred in the ternary system, Pb exhibited a strong competition, the stabilization efficiency of Zn and Cd reduced by 23.50%–31.64%, and 7.10%–39.26%, respectively. Pyromorphite and amorphous lead phosphate formed with excess KH₂PO₄ or K₂HPO₄ addition, while K₃PO₄ resulted in the formation of a hydroxypyromorphite precipitate. Amorphous Zn and Cd phosphates and hydroxides were the primary products. The immobilization rate of Zn and Cd depends on pH, and increased significantly in response to the excess phosphate application. This approach provides insight into phosphate-induced differences in stabilization efficiency in soils contaminated with multiple metals, which is of theoretical and engineering significance.

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Feasibility of phosphate fertilizer to immobilize cadmium in a field

To reduce effectively cadmium (Cd) phytoextractability by phosphate fertilizer in Cd contaminated soil, fused and superphosphate (FSP) was applied at the rate of 0, 33.5 (recommendation level), 167.5, and 335 kg P ha⁻¹ for radish (Raphanus sativa L.). Unlike from what we expected, soil Cd extractability and Cd concentration in radish increased with increasing FSP application in the field. To determine the effect of FSP on Cd immobilization, FSP was mixed with the selected soil at the rate of 0, 200, 400, 800, and 1600 mg P kg⁻¹ and then incubated for 8 weeks. As observed in the field study, NH₄OAc extractable Cd concentration increased slightly with FSP addition up to 400 mg P kg⁻¹ and thereafter dramatically decreased upon increasing its application rate. Soil pH and negative charge were decreased at low level of FSP application up to 400 mg P kg⁻¹, but thereafter continually increased with increasing application level. This could be indirect evidence that net soil negative charge was increased by the specific adsorption of phosphate at the high rate of FSP application over 400 mg P kg⁻¹. The labile Cd fraction (water soluble and exchangeable + acidic fraction) increased with increasing FSP application by 400 mg P kg⁻¹ and thereafter gradually decreased with corresponding increase in unlabile fraction (oxidizable and residual fraction). Based on these results, FSP might be applied with a very high rate over 800 mg P kg⁻¹ to decrease Cd extractability in the selected field. However, this level is equivalent to 1440 kg P ha⁻¹, which is about 43 times higher than the recommendation levels for radish production and resulted in a significant increase in water soluble P concentration creating a new environmental problem. Therefore, the feasibility of FSP to reduce Cd extractability in the field is very low.     

Adsorption of sulfamethoxazole on functionalized carbon nanotubes as affected by cations and anions

The environmental risks of antibiotics have attracted lots of research attention, but their environmental behavior is not clear yet. Functionalized carbon nanotubes (CNTs) were used as model adsorbents and sulfamethoxazole (SMX) was used as a model antibiotic to investigate the effect of both cations (Ca²⁺, Cs⁺) and anions (phosphate) on antibiotics adsorption. Various mechanisms (such as electrostatic interaction, hydrophobic interaction, π-π and hydrogen bonds) play roles in SMX adsorption. Cations and anions could “wedge into” these mechanisms and thus alter SMX adsorption. This study emphasized that both increased and decreased SMX adsorption could be observed with the addition of cations/anions, depending on environmental conditions (such as pH in this current study). The net effect is the balance between the increased and decreased effects. The contribution of different mechanisms to the overall antibiotic adsorption on solid particles should be identified to accurately predict the apparent effect by cations and anions.     

Evaluation of the effectiveness of phosphate treatment for the remediation of mine waste soils contaminated with Cd, Cu, Pb, and Zn

The effectiveness of phosphate treatment for Cd, Cu, Pb, and Zn immobilization in mine waste soils was examined using batch conditions. Application of synthetic hydroxyapatite (HA) and natural phosphate rock (FAP) effectively reduced the heavy metal water solubility generally by about 84-99%. The results showed that HA was slightly superior to FAP for immobilizing heavy metals. The possible mechanisms for heavy metal immobilization in the soil involve both surface complexation of the metal ions on the phosphate grains and partial dissolution of the phosphate amendments and precipitation of heavy metal-containing phosphates. HA and FAP could significantly reduce Cd, Cu, Pb, and Zn availability in terms of water solubility in contaminated soils while minimizing soil acidification and potential risk of eutrophication associated with the application of highly soluble phosphate sources.     

The radioactivity measurements in soils and fertilizers using gamma spectrometry technique

Because of their mineral content, soils are naturally radioactive and one of the sources of radioactivity other than those of natural origin is mainly due to the extensive use of fertilizers. The main aim of this paper is to evaluate the fluxes of natural radionuclides in local production of phosphate fertilizers to determine the content of radioactivity in several commercial fertilizers produced in Algeria and to estimate their radiological impact in a cultivated soil even for the long-term exposure due to their application.For these purposes, virgin and fertilized soils were collected from outlying Setif region in Algeria and from phosphate fertilizers used in this area.Gamma spectrometry was exploited to determine activity concentration due to naturally occurring ²²⁶Ra, ²³²Th and ⁴⁰K in five types of samples (two different sorts of fertilizers, virgin and fertilized soils and well water used for irrigation) taken from Setif’s areas.The results show that these radionuclides were present in an average concentration of 134.7 ± 24.1, 131.8 ± 16.7, 11644 ± 550 Bq/kg for the first fertilizer NPK and 190.3 ± 30, 117.2 ± 10.3, 5312 ± 249 Bq/kg for the second fertilizer (NPKs). For the virgin and the fertilized soils, the corresponding values were respectively 47.01 ± 7.3, 33 ± 7, 329.4 ± 19.7 Bq/kg and 53.2 ± 10.6, 50.0 ± 7, 311.4 ± 18.7 Bq/kg. For well water, the values were 1.93 and 0.12 Bq/kg; however the third value was below the Minimum Detectable Activity (MDA).The radium equivalent activity (Raeq) and the representative level index I_γr for all samples were also calculated. The data were discussed and compared with those given in the literature.     

Phosphate removal using aerobic bacterial consortium and pure cultures isolated from activated sludge

In the present study, an attempt is made to evaluate the kinetics of biological phosphate removal using a bacterial consortium of activated sludge, as well as screening for dominant polyphosphates accumulating bacteria. The results showed an efficient phosphate uptake (P < 0.001) of the consortium, with rates related to the initial concentration of both phosphate and carbon sources. Short chain volatile fatty acids presented the suitable substrates for enhanced biological phosphorus removal, of which maximum yield reached 99.23% and 78.51% in basal salt medium supplemented with 0.5% of sodium acetate and lactate respectively. Fifteen phosphate-accumulating bacteria were isolated from the activated sludge and only four isolates were selected and characterized as Pseudomonas aeruginosa AS1, Moraxella lacunata AS2, Acinetobater junii AS3 and Alcaligenes denitrificans AS4. The highest efficiency of phosphate uptake using pure culture was achieved with Ac. junii AS3 (83.36) followed by P. aeruginosa AS1 (81.78%), Al. denitrificans AS4 (76.72%), and M. lacunata AS2 with 50.6%.