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.     

Internal eutrophication: How it works and what to do about it—a review

In the 1980s and 1990s, it became increasingly clear that changes in external nutrient loads alone could not entirely explain the severe eutrophication of surface waters in the Netherlands. Nowadays, 'internal eutrophication' has become a widely accepted term in Dutch water management practice to describe the eutrophication of an ecosystem without additional external input of nutrients (N, P, K). This review surveys the principal mechanisms involved in this process. It also discusses possible remedies to combat internal eutrophication.     

The influence of ClO− and acidity in the reaction between H2O2 and CuCl2

The potentially explosive reaction of hydrogen peroxide (H₂O₂) and copper chloride (CuCl₂) was investigated. Pressure tests revealed that the reaction was strongly temperature - dependent and can easily undergo runaway reaction. Nevertheless, there was only a slight pressure increase at the low temperatures studied or when using low concentrations of CuCl₂. Under the conditions generating the slight pressure increase, hypochlorite anions (ClO⁻) are generated and the acidity increases. As the reaction reaches completion, ClO⁻ disappears, and the acidity decreases. Interestingly, the addition of phosphate buffer to maintain the weakly acid conditions led to a runaway reaction, and the use of basic ClO⁻ promoted the exothermic reaction. Based on the results, acidity has a strong impact on the reaction behaviour.     

Effect of low-molecular weight organic acids on phosphorus release and phytoavailabilty of phosphorus in phosphate rocks added to soils

Phosphorus (P) is critically needed to improve soil fertility in many parts of the world. The use of water-soluble P fertilizers, e.g., single super-phosphate and triple super-phosphate in developing countries to improve crop production has been limited primarily by their high cost. The presence of indigenous phosphate deposits in some countries provides an incentive for direct application or local chemical treatment at low cost to improve the solubility of low reactive phosphate rocks (PRs). The use of naturally occurring low-molecular weight organic acids (LMWOAs) that are produced in soil as microbial metabolites or plant exudates from dead or living cells represents a new perspective in PR research. The LMWOAs contain various functional groups that may play a significant role in PR dissolution. Little information is available, however, about the potential of LMWOAs in releasing P from PRs. This study reports P release from 12 PRs, four each of low, medium, and high reactivity, obtained from various deposits (Kodjari, Tahoua, North Carolina, Gafsa, Khouribga, Tilemsi Valley, Central Florida, Sechura, Minjingu, North Florida, Hahotoe, and Parc W) using nine LMWOAs containing mono-, di-, and tri-carboxylic groups and a mineral acid (H₂SO₄). Laboratory studies showed that the organic acids are effective in releasing P from low and medium reactive PRs, but very ineffective in releasing P from high reactive PRs. The average amounts of P released by all the organic acids from the three types of PRs were 65.5 mmol kg⁻¹ PR from the low reactive PRs, 55.1 mmol kg⁻¹ from the medium, and 11.1 mmol kg⁻¹ from the high; those released from across all the PRs were 21.9 by the mono-carboxylic acid group, 54.2 by the di-carboxylic acid group, and 57.0 mmol P kg⁻¹ by the tri-carboxylic acid group. The P released was negatively correlated with the equilibrium pH, but positively correlated with Ca released from the PRs. Laboratory incubation studies on the release of P from PRs added to soils with or without organic acids and incubated at 25 °C for 15, 30, and 45 days showed that the percentage of plant-available P released varied considerably from 0.95 in the Kodjari PR to 40.1% in the North Carolina PR and was related to PR reactivity. A greenhouse study with corn (Zea mays L.) grown for 60 days on soils treated with PRs or with PRs mixed with organic acids showed that corn response to addition of oxalic or citric acid varied with P rates and PR sources, suggesting that organic acids have potential as amendments for increasing plant-available P in PR-treated soils.     

基于不同基质的强化生物除磷系统中生化反应机理研究进展

阐述了3种不同基质(乙酸盐、丙酸盐和葡萄糖)在强化生物除磷系统中的生化模型反应机理.重点介绍了聚磷菌(PAOs)、聚糖菌(GAOs)和产乳酸菌在厌氧/好氧条件下对能量及还原力(NADH2)的利用方式;聚-β-羟基链烷酸盐(PHA)的合成方式及存在形式,糖原、乳酸(L型)的代谢途径等.虽然控制基质条件可以实现稳定的强化生物除磷效果,但目前的生化模型并不能完全解释所有的代谢过程,今后要在分离纯种的PAOs及相关生化代谢过程中酶的活动等方面进行深入研究.     

Investigation on mechanism of phosphate removal on carbonized sludge adsorbent

For the removal of phosphate (PO₄^3 -) from water, an adsorbent was prepared via carbonization of sewage sludge from a wastewater treatment plant: carbonized sludge adsorbent (CSA). The mechanism of phosphate removal was determined after studying the structure and chemical properties of the CSA and its influence on phosphate removal. The results demonstrate that phosphate adsorption by the CSA can be fitted with the pseudo second-order kinetics and Langmuir isotherm models, indicating that the adsorption is single molecular layer adsorption dominated by chemical reaction. The active sites binding phosphate on the surface are composed of mineral particles containing Si/Ca/Al/Fe. The mineral containing Ca, calcite, is the main factor responsible for phosphate removal. The phosphate removal mechanism is a complex process including crystallization via the interaction between Ca^2 + and PO₄^3 -; formation of precipitates of Ca^2 +, Al^3 +, and PO₄^3 -; and adsorption of PO₄^3 - on some recalcitrant oxides composed of Si/Al/Fe.     

城市污水脱氮除磷中的化学问题

简述了污水中氮磷的来源、存在形式及危害,城市污水生物脱氮除磷基本原理。围绕生物脱氮除磷的化学原理,针对生物脱氮除磷工艺对pH值要求、污泥龄控制、碳源投加及脱氮新工艺进行了探讨。     

总磷排放标准的讨论

总磷是评价水质的重要指标,磷以多种形式存在,随着污水排放标准的不断更新．总磷标准的尺度不相一致。根据国家相关标准和规范,给出了能让已有标准内在联系更加完整和协调的建议．期待环境行政管理部门对废水中总磷排放标准作出更加明确合理的相关规定．     

Nutrient pathways and their susceptibility to past and future change in the Eurasian Arctic Ocean

Climate change is altering nutrient cycling within the Arctic Ocean, having knock-on effects to Arctic ecosystems. Primary production in the Arctic is principally nitrogen-limited, particularly in the western Pacific-dominated regions where denitrification exacerbates nitrogen loss. The nutrient status of the eastern Eurasian Arctic remains under debate. In the Barents Sea, primary production has increased by 88% since 1998. To support this rapid increase in productivity, either the standing stock of nutrients has been depleted, or the external nutrient supply has increased. Atlantic water inflow, enhanced mixing, benthic nitrogen cycling, and land–ocean interaction have the potential to alter the nutrient supply through addition, dilution or removal. Here we use new datasets from the Changing Arctic Ocean program alongside historical datasets to assess how nitrate and phosphate concentrations may be changing in response to these processes. We highlight how nutrient dynamics may continue to change, why this is important for regional and international policy-making and suggest relevant research priorities for the future.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-021-01673-0.     

Arsenic strongly associates with ferrihydrite colloids formed in a soil effluent

Arsenic mobility may increase in liquid phase due to association with colloidal Fe oxides. We studied the association of As with Fe oxide colloids in the effluent from water-saturated soil columns run under anoxic conditions. Upon exfiltration, the solutions, which contained Fe²⁺, were re-aerated and ferrihydrite colloids precipitated. The entire amount of effluent As was associated with the ferrihydrite colloids, although PO₄³⁻, SiO₄⁴⁻, CO₃²⁻ and dissolved organic matter were present in the effluent during ferrihydrite colloid formation. Furthermore, no subsequent release of As from the ferrihydrite colloids was observed despite the presence of these (in)organic species known to compete with As for adsorption on Fe oxides. Arsenic was bound via inner-sphere complexation on the ferrihydrite surface. FTIR spectroscopy also revealed adsorption of PO₄³⁻ and polymerized silica. However, these species could not impede the quantitative association of As with colloidal ferrihydrite in the soil effluents.