铁铝盐基离子对土壤中水溶性氟环境效应的影响

氧化物或粘土矿物可吸附氟离子,但磷酸根离子与氟离子存在竞争吸附效应,造成氟的环境存在量、存在形态及生物效应更加复杂,影响了环境中氟污染的治理.试验选用典型贵州黄壤和石灰土,通过向模拟高氟污染土壤中添加铁铝盐基离子和磷酸盐,采用两因素最优设计,研究外源物质对土壤中水溶性氟的影响.结果表明,FeCl3·6H2O或AlCl3·6H2O都能降低土壤中水溶性氟,而KH2PO4使土壤中水溶性氟增加,对黄壤和石灰土中水溶性氟影响效果大小依次为FeCl3·6H2O(AlCl3·6H2O)、KH2PO4.同时表明,采用铁铝盐基离子改变黄壤性质,达到降氟效果仍有很大潜力,而石灰土环境在高添加铁铝盐基离子水平下继续添加FeCl3·6H2O或AlCl3·6H2O降低土壤中水溶性氟的作用较弱.从土壤pH看,黄壤水溶性氟受试验因子影响复杂,土壤pH低水溶性氟不一定低,pH在4～6时,氟元素的形态及有效性尤其复杂,而石灰土中水溶性氟基本随pH降低而降低.     

Extrapolating phosphorus production to estimate resource reserves

Various indicators of resource scarcity and methods for extrapolating resource availability are examined for phosphorus. These include resource lifetime, and trends in resource price, ore grade and discovery rates, and Hubbert curve extrapolation. Several of these indicate increasing scarcity of phosphate resources. Calculated resource lifetime is subject to a number of caveats such as unanticipated future changes in resource discovery, mining and beneficiation technology, population growth or per-capita demand. Thus it should be used only as a rough planning index or as a relative indicator of potential scarcity. This paper examines the uncertainty in one method for estimating available resources from historical production data. The confidence intervals for the parameters and predictions of the Hubbert curves are computed as they relate to the amount of information available. These show that Hubbert-type extrapolations are not robust for predicting the ultimately recoverable reserves or year of peak production of phosphate rock. Previous successes of the Hubbert curve are for cases in which there exist alternative resources, which is not the situation for phosphate. It is suggested that data other than historical production, such as population growth, identified resources and economic factors, should be included in making such forecasts.     

Effect of fungicides on plant growth promoting activities of phosphate solubilizing Pseudomonasputida isolated from mustard (Brassica compestris) rhizosphere

This study was navigated to examine the effects of fungicide-stress on the activities of plant-growth-promoting rhizobacterium Pseudomonasputida with inherent phosphate solubilizing activity. The fungicide-tolerant and phosphate solubilizing P.putida strain PS9 was isolated from the mustard rhizosphere and tentatively identified following standard morphological, physiological and biochemical tests. To further consolidate the identity of the strain PS9, the 16S rDNA sequence analysis was performed. Following the BLAST program, the strain PS9 was identified as P.putida. In the presence of the varying concentrations (0-3200 μg mL⁻¹; at a two fold dilution interval) of four fungicides of different chemical families (tebuconazole, hexaconazole, metalaxyl and kitazin) amended in minimal salt agar medium, the P.putida strain PS9 showed a variable tolerance levels (1400-3200 μg mL⁻¹) against the tested fungicides. The strain PS9 produced plant-growth-promoting (PGP) substances in significant amount in the absence of fungicides. In general, fungicides applied at the recommended, two and three times of the recommended rates, decreased the PGP attributes of P.putida the strain PS9 and affected the PGP activities in concentration-dependent manner. Fungicides at the recommended dose had minor reducing effect while the doses higher than the recommended dose significantly reduced the PGP activities (phosphate solubilization, salicylic acid, 2,3-dihydroxy benzoic acid, and indole-3-acetic acid production except exo-polysaccharides, hydrogen cyanate and ammonia production). Of the four fungicides, tebuconazole generally, showed maximum toxicity to the PGP activities of the strain PS9. This study inferred that fungicides must be examined in vitro for their possible adverse effects on soil micro flora before their application in agricultural fields. Moreover, the results also suggested the prerequisite of application of fungicide-tolerant PGPR strains as bioinoculants so that their PGP activities may not be suppressed under fungicide stress.     

Concomitant rock phosphate dissolution and lead immobilization by phosphate solubilizing bacteria (Enterobacter sp.)

This paper examines the potential value of phosphate solubilizing bacteria (Enterobacter cloacae) in the dissolution of rock phosphate (RP) and subsequent immobilization of lead (Pb) in both bacterial growth medium and soils. Enterobacter sp. showed resistance to Pb and the bacterium solubilized 17.5% of RP in the growth medium. Enterobacter sp. did not enhance Pb immobilization in solution because of acidification of bacterial medium, thereby inhibiting the formation of P-induced Pb precipitation. However, in the case of soil, Enterobacter sp. increased Pb immobilization by 6.98, 25.6 and 32.0% with the RP level of 200, 800 and 1600 mg P/kg, respectively. The immobilization of Pb in Pb-spiked soils was attributed to pyromorphite formation as indicated by XRD analysis. Inoculation of phosphate solubilizing bacteria with RP in soil can be used as an alternative technique to soluble P compounds which can cause eutrophication of surface water.     

Release characteristics and control of nitrogen,phosphate, organic matter from spent mushroom compost amended soil in a column experiment

Spent mushroom compost (SMC) is a co-product of edible mushroom which contains abundant nutrients including organics, nitrogen (N) and phosphorous (P). This study is related to the release potential of nitrogen, phosphate and organic matter from SMC amended soil in column-based experiments. Results showed that due to SMC application, NH₄⁺–N and NO₃⁻–N concentrations in leachate decreased by 92.5% and 76.3%, respectively, while EC and COD_Cr concentrations increased by 84.2% and 481.9%, respectively, as compared to chemical fertilizers. Moreover, a minor loss of TN_cum (65%) and TP_cum (almost equal value) exhibited good nutrient retention capacity. Leaching test results demonstrated that the mixed application of SMC and chemical fertilizers could alleviate excessive COD_Cr level in SMC leachate. The release process of nutrients in SMC amended soil could be described by first/first order mixed model, indicating that nutrients leached from SMC follow a two-stage pattern.     

High phosphate removal using La(OH)3 loaded chitosan based composites and mechanistic study

Our present study was to prepare a biomass-supported adsorbents with high adsorptive capacity and high selectivity to prevent the accelerated eutrophication in water body. To this end, different metal hydroxide (La, Zr and Fe) first was successfully loaded on chitosan microspheres. Then the quaternary ammonium group with different content was introduced into the adsorbent by polymerization. By comparison of adsorption properties, chitosan-La(OH)₃-quaternary ammonium-20% (CS-La-N-20%) has strong adsorption to phosphate (160 mg/g) by immobilizing nano-sized La(OH)₃ within a quaternary-aminated chitosan and it maintain high adsorption in the presence of salt ions. The pH results indicated that the CS-La-N-20% would effectively sequestrate phosphate over a wide pH range between 3 and 7 without significant La³⁺ leaching. What's more, adsorption capacity on the introduce of positively charged quanternary-aminated groups was significantly higher than that of the unmodified adsorbents at alkaline conditions. The column adsorption capacity reached 1300 bed volumes (BV) when phosphate concentration decreased until 0.5 mg/L at 6 BV/hr. The column adsorption/desorption reveals that no significant capacity loss is observed, indicating excellent stability and repeated use property. Characterizations revealed that phosphate adsorption on CS-La-N-20% through ligand exchange (impregnated nano-La(OH)₃) and electrostatic attraction (positively charged quanternary-aminated groups). All the results suggested that CS-La-N-20% can serve as a promising adsorbent for preferable phosphate removal in realistic application.     

Agronomic application of olive mill wastewaters with phosphate rock in a semi-arid Mediterranean soil modifies the soil properties and decreases the extractable soil phosphorus

Olive mill wastewater (OMW), a by-product of the olive-mill industry, is produced in large amounts in Mediterranean countries. The presence of indigenous phosphate deposits in some countries like Tunisia 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 present in OMW represents a new perspective in PR research and a possible solution for the recycling of the OMW. The present work was aimed at evaluating, under natural situations (field of olive trees), the effects of agronomic application of OMW (amounts applied: 30, 60 m(3) ha(-1)) with PR (amounts applied: 150 kg ha(-1)) on olive trees soil properties. We measured organic C, nitrogen (N), extractable phosphorus (P), exchangeable calcium (Ca), and exchangeable potassium (K), as well as other properties (pH and electrical conductivity). Our data provide evidence that agronomic application of OMW with PR has important effects on soil properties. Increases in organic C, total N, extractable P and exchangeable potassium (K) were found after the first agronomic application of OMW and PR. These increases were only temporary, following the second agronomic application of OMW and PR, significant reductions were detected in the extractable soil P (19.67 mg kg(-1) in the control soil vs. 8.99 mg kg(-1) in the amended soil). Changes in the extractable soil P could alter plant productivity and plant community structure because shifts in nutriment availability can affect the balance between limiting and non-limiting nutrients.     

Adsorption and recovery of phosphate from water by amine fiber, effects of co-existing ions and column filtration

A weak-base adsorption fiber, acrylic amine fiber (AAF), was prepared for removal and recovery of phosphate from water. The adsorption properties of the AAF for phosphate and effects of co-existing ions were investigated using batch and column filtration experiments, scanning electron microscope, and Fourier transform infrared techniques. Experimental results showed that AAF had a high phosphate adsorption capacity of 119?mg/g at pH?7.0. The effects of calcium, sulfate, carbonate, nitrate, and fluoride showed that sulfate and calcium inhibited phosphate adsorption. However, AAF showed higher binding affinity toward phosphate than sulfate. Column filtration results showed that AAF could filter 1420 bed volumes of tap water containing 1.0?mg-P/L of phosphate. The saturated AAF could be regenerated using 0.5?mol/L hydrochloric acid solution and reused. After desorption, phosphate was recovered through precipitation of hydroxyapatite (Ca₅(PO₄)₃OH). The easy of regeneration, good adsorption performance, and the fiber morphology of AAF make it an attractive alternative for phosphate recovery from multiple water sources.     

Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC–Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC–Zr was 83.6 mg P/g. Furthermore, the QC–Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl^?, NO₃^?, ${\text{SO}}_4^{2?}$, ${\text{SO}}_4^{\mathrm{4}?}$) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC–Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both –N⁺(CH₃)₃ groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between –N⁺(CH₃)₃ and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO₄)x). The ³¹P nuclear magnetic resonance (NMR) study implied that P surface–precipitated and inner–sphere complexed with zirconium hydroxide at a ratio of 3:1.     

磷肥工业含氟废液钾盐转化法生产氢氟酸的研究

用氨中磷肥工业产生的氟硅酸溶液得到氟化铵溶液,再将氟化铵溶液与氟化钾在一定的条件下反应得到氟化氢钾并挥发出氨,氟化氢钾的分解温度为400℃,将其加热分解得氟化氢气体和氟化钾,氟化氢气体可以产氢氟酸,氟化钾和氨循环使用,同时副产二氧化硅,钾盐及产物闭路循环,整个处理过程无废物排放,处理成本低。