离子交换分离法与偶氮氯膦Ⅲ指示剂联用微量测定含金属及磷有机物中硫

近年来,有机物中硫的微量测定采用Schoneger氧瓶燃烧,过氧化氢吸收为前处理产生的SO42-与原子吸收法或与电分析法等联用已有报道,但多为间接测定,且金属离子的干扰未作更详细研究。而上述前处理生成的SO42-在非水介质中以钡盐直接滴定的方法,不需专门仪器、方法简便、准确度符合要求,目前国内外仍广泛应用。但常遇到金属、磷的干扰及终点不敏锐等三个困难。许多金属指示剂如钍啉及许多变色酸双偶氮衍生物如二甲基偶氮磺Ⅲ、偶氮砷Ⅲ等已被用作钡盐滴定的指示剂。

适应高盐循环水处理的复合水处理剂RP－92的研制与工业应用

以新型磷羧酸共聚物ＲＰ－９２（Ａ）为主剂的复合水稳剂ＲＰ－９２处理高盐水质的循环冷却水，实验室动态模拟试验结果为碳钢试管的腐蚀速率小于０．０１５ｍｍ／ａ，结垢粘附速率小于３．６ｍｇ／（ｃｍ２·月）。经现场８０００ｈ连续运行，现场监测换热器碳钢试管的平均腐蚀速率小于０．０６１ｍｍ／ａ，结垢粘附速率小于１１．０ｍｇ／（ｃｍ２·月），且无孔蚀现象，处理效果优于传统无机聚磷配方，水中总磷含量也有较大幅度下降。ＲＰ－９２经毒性评价，属低毒，对环境基本无影响。

膨润土市场前景喜人

随着城市工业化进程的加快,水污染日益严重。今年的特大水灾直接危及着人们的饮水安全,氯、磷有机物的不断汇集导致水质发生了一系列物理、生物、化学的复杂水质变化,使得水的可饮性降低。保护水质已提到环保的重要议事日程上。目前,净化污水的最有效途径是应用膨润土作吸附剂,而且价格低廉,被认为是一种可取代活性炭的除臭材料,在社会上的用途极其广泛。世界上生产膨润土的国家有50多个、公司100多家,美国是世界上最大的膨润土生产国,其产量占全世界产量1200万吨的32％。其次是德国、希腊和意大利,产量占世界总产量的22％。而美国膨润土出口量约占世界贸易额的40％,其中12％～15％市场在欧洲。

Phosphate-Solubilizing and -Mineralizing Abilities of Bacteria Isolated from Soils

Microorganisms capable of solubilizing and mineralizing phosphorus （P） pools in soils are considered vital in promoting P bioavallability. The study was conducted to screen and isolate inorganic P-solubilizing bacteria （IPSB） and organic P-mineralizing bacteria （OPMB） in soils taken from subtropical flooded and temperate non-flooded soils, and to compare inorganic P-solubilizing and organic P-solubilizing abilities between IPSB and OPMB. Ten OPMB strains were isolated and identified as Bacillus cereus and Bacillus megaterium, and five IPSB strains as B. megaterium, Burkholderia caryophyUi, Pseudomonas cichorii, and Pseudomonas syringae. P-solubilizing and -mineralizing abilities of the strains were measured using the methods taking cellular P into account. The IPSB strains exhibited inorganic P-solubilizing abilities ranging between 25.4-41.7 μg P mL^-1 and organic P-mineralizing abilities between 8.2-17.8μg P mL^-1. Each of the OPMB strains also exhibited both solubilizing and mineralizing abilities varying from 4.4 to 26.5 μg P mL^-1 and from 13.8 to 62.8 μg P mL^-1, respectively. For both IPSB and OPMB strains, most of the P mineralized from the organic P source was incorporated into the bacterial cells as cellular P. A significantly negative linear correlation （P 〈 0.05） was found between culture pH and P solubilized from inorganic P by OPMB strains. The results suggested that P solubilization and mineralization could coexist in the same bacterial strain.

White organic light-emitting devices based on fac tris(2-phenylpyridine) iridium sensitized 5,6,11,12-tetraphenylnap-hthacene

We have fabricated the white organic light-emitting devices （WOLEDs） based on 4,4＇ -bis（2,2 -diphenyl vinyl）-1,1＇ - biphenyl （DPVBi） and phosphorescence sensitized 5,6,11,12,-tetraphenylnaphthacene （rubrene）. The device structure is ITO/2T-NATA （20 nm）/NPBX （20 nm）/CBP： x%Ir（ppy）3：0.5% rubrene （8 nm）/NPBX （5 nm）/DPVBi （30 nm）/Alq（30 nm）/LiF（0.5 nm）/A1. In the devices, DPVBi acts as a blue light-emitting layer, the rubrene is sensitized by a phosphorescent material, fac tris （2-phenylpyridine） iridium [Ir（ppy）3], acts as a yellow light-emitting layer, and N,N＇ -bis- （1-naphthyl）- N,N＇ -diphenyl -1, 1＇ -biphenyl-4,4＇ -diamine （NPBX） acts as a hole transporting and exciton blocker layer, respectively. When the concentration of Ir （PPY）3 is 6wt%, the maximum luminance is 24960 cd/m^2 at an applied voltage of 15 V, and the maximum luminous efficiency is 5.17 cd/A at an applied voltage of 8 V.

人工湿地法处理农业非点源污染的研究

简述了人工湿地法去除氮、磷、有机物的主要机理、人工湿地内植物的作用及其它一些问题,从而说明了人工湿地是一种造价低、运行简单及管理方便的农业非点源污染控制系统。并详细论述了人工湿地环境效应和经济效应,为人工湿地处理农业非点源污染技术的应用提供了参考。

高排放标准下污水处理厂深度处理工艺分析

依托3座市政污水处理厂开展了混凝沉淀-深床滤池-消毒深度处理工艺的效果分析。生物二级处理出水中需要关注SCOD、NO_(3)^(-)-N、颗粒性磷和PO_(4)^(3-)-P的去除效果,这些组分占COD、TN和TP的平均比例分别为71%、87%和75%以上。深度处理对COD、TN和TP的平均去除率分别为25.4%、15.5%和47.6%,ΔCOD/ΔPAC与ΔTP/ΔPAC(平均质量比)分别为1.4和0.07。深度处理显著提升了出厂水水质,对COD、TN、TP、SS和色度稳定达标起到了保障作用。

Behavior of different phosphorus species in suspended particulate matter in the Changjiang estuary

Suspended particulate matter （SPM） collected in the Changjiang （Yangtze River） estuary in June 2006 was separated into five fractions via water elutriation： clay-very fme silt （〈8 μm）, fine silt （8-16 μm）, medium silt （16--32 μm）, coarse silt （32~53 μm） and sand （〉63 μm）. The SPM and fractionated particles were sequentially analyzed by a modified SEDEX sequential extraction method to obtain six species of phosphorus： exchangeable or loosely-sorbed P, organic P, Fe-bound P, authigenic P, detrital P and refractory P. The results indicated that all particulate phosphorus species except for detrital P were negatively correlated to particle size; a high detrital P content was found in coarse silt and very coarse silt. From the inside of the river mouth to the gate of the fiver mouth, organic P, Fe-bound P and refractory P in the suspended particles decreased and a higher amount of exchangeable P appeared around the gate of the fiver mouth. From the gate of the river mouth to the sea, exchangeable P and organic P in suspended panicles increased distinctly. The total particulate P flux into the estuary from the Changjiang River was about 45.45×10^8μmol/s during sampling. Of this, about 8.27×10^8μmol/s was associated with the ＂truly suspended＂ fraction. The bio-available particulate P flux was about 13.58×10^8μmol/s. Of this, about 4.24 ×10^8μmol/s w as transported by ＂truly suspended＂ particles.

Simultaneous Determination of PIP and POP in Seawater

A method for simultaneous determination of particulate inorganic phosphorus (PIP) and particulate organic phosphorus (POP) in seawater was improved. After using cellulose acetate membrane to filter the seawater samples and washing the membrane with 1mol/L hydrochloric acid, PIP was extracted into hydrochloric acid phase and POP was left on the membrane. POP was oxygenated at 120℃, 0.12MPa with potassium persulphate. Phosphomolybdate blue spectrophotometry was used in the determination. The proper volume of seawater sample for simultaneously determining PIP and POP was 100-150ml, containing PIP≥0.27μg, POP≥0.69μg. Relative Standard Deviation (RSD) of the determination of PIP and POP was 5.8% and 4.3% respectively. This method was used to determine POP and PIP in the surface water of Huiquan Bay, Qingdao, China. PIP content there averaged at 69.0μg/L and POP at 3.3μg/L. PIP is the main form (>93%) of particulate phosphorus (PP). Maximum PIP coincided with flood tide, indicating that PIP mainly originated from disturbance of surface sediments. At the offshore area, maximum of PIP appeared at flood tide and minimum of PIP appeared at ebb-tide. The maximum of POP presented at about 10:00am, which suggests that POP is closely related to biological metabolism. The control factor of POP in seawater was concluded to be biological metabolization.

Synthesis and Crystal Structure of 2-(Diphenylphosphine oxide)-3-(diphenylphosphine oxide ethynyl) spiro [bicyclo[2.2.1]hepta-2,5-diene-7,1'-cyclopropane]

The Diels-Alder reaction of bis(diphenylphosphine oxide)butadiyne (BDPPOB) with spiro[2.4]hepta-4,6-diene affords the title compound, 2-(diphenylphosphine oxide)-3-(diphen- ylphosphine oxide ethynyl)spiro[bicyclo[2.2.1] hepta-2,5-diene-7,1-cyclopropane] (DDSHC, C35H28O2P2, Mr = 542). Its crystal structure belongs to monoclinic system, space group P21/n with a =12.708(3), b = 14.666(4), c = 15.048(4) ? = 93.903(5) ? V = 2798.1(13) ?, Z = 4, Dc = 1.288g/cm3, F(000)=1136, (MoK? = 0.187mm-1, final R = 0.0626 and wR= 0.1422 for 4685 independent reflections with I > 2(I). Structural analyses reveal that the title compound is nonplanar and the dihedral angles between two phenyl rings around each phosphorus atom are 71.7(2) and 70.7(3)? respectively.

Oxidation of Elemental Sulfur in Selected Soils of China

An incubation experiment was carried out in laboratory to study the effect of temperature, moisture, phosphorus, organic matter, cropping and previous elemental sulfur application on elemental sulfur oxidation in four selected soils, fluvo-aquic soil, black soil, yellow-brown soil and red soil. In all the soils tested, sulfur oxidation rate was influenced by temperature and the temperature coefficient (Q10) values at the range from 10 to 30 ℃ were 4.41, 4.05, 6.19 and 3.71 for the four soils, respectively. The rate of sulfur oxidation was parabolically related to soil Water content. The optimum moisture content for the maximum oxidation rate was different among soils. Phosphorus increased the oxidation rate of elemental sulfur by 57.7%, 33.1%, 21.7% and 26.4% for the above four soils, respectively, compared with the control (no phosphorus applied). Organic material of corn straw which was ground and passed through a 0.5-mm sieve also increased the oxidation rate of elemental sulfur in the four soils by 59.8%, 7.8%, 39.2% and 540.4%, respectively. Elemental sulfur which was applied previously to soils significantly enhanced the oxidation of elemental sulfur subsequently added and increased sulfur-oxidizing populations such as autotrophic elemental sulfur oxidizers with pH optimum 6.8, autotrophic thiosulfate oxidizers with pH optimum 6.8, heterotrophic thiosulfate oxidizers and heterotrophic sulfate producers. Cropping had little effect on elemental sulfur-oxidizing potentiality of soils.

Isolation and Characterization of Novel Chlorpyrifos Degrading Fungus Isaria Farinosa

Chlorpyrifos is a well known organophosphorus pesticide used worldwide. Microorganisms including bacteria, fungi and actinomycetes have been reported to be efficient degraders of chlorpyrifos. The present study was successful in isolating a novel fungus that could degrade chlorpyrifos effectively upto 800 ppm concentration. Morphological and molecular characterization studies revealed the identity of the fungus as Isariafarinosa.

Synthesis and Crystal Structure of O,O-Dimethyl-N-(β-triphenylgermanyl)propionyl-α- aminobenzylphosphonates

The title compound (C30H32NO4PGe), O,O-dimethyl-N-(β-triphenylgermanyl) propionyl-α-aminobenzylphosphonates was synthesized by a convenient method, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal is triclinic, space group P-1 with parameters: a=9.7753(5), b=11.5773(5), c=13.5059(6) ?, α=104.185(1),β= 95.971(1), γ =96.727(1)°, V=1457.63(12) ?3, Z=2, Mr=574.13, Dc=1.308 g/cm3, λ=0.71073 ?, μ = 1.139mm-1, and F(000)=596. The structure was solved by direct methods. The structure was refined to R=0.0257, wR=0.0705 for 5080 observed reflections with I >2σ(I).The result of structure analysis indicates that atom Ge is sp3 hydridized because the arrangement of the four carbon atoms bonded to it is a distorted tetrahedron. The geometry of the three phenyl groups linking with the Ge atom looks like a propeller form.

In situ doping brushite on zinc manganese oxide toward enhanced water oxidation performance: Mimicry of an oxygen‐evolving complex

We report in situ doping of brushite on zinc manganese oxide（ZMO）, fabricated by calcining a Mn（II） oxalate‐impregnated metal‐organic framework. The doping process was conducted in com‐bination with the photocatalytic water oxidation reaction which was catalyzed by ZMO in neutral phosphate‐buffered aqueous solution containing [Ru（bpy）3]^2＋‐Na2S2O8 and calcium（II） triflate salt, exhibiting greatly enhanced water oxidation performance with optimized turnover frequency of 0.18 mmol（O2） mol（Mn）^（–1） s^（–1）. Different analytical techniques indicated that photodeposited calci‐um‐phosphate（CaP） acted as a co‐catalyst to promote the O2 evolution activity of ZMO. This system involved the use of manganese oxide and calcium ion, and the operation was conducted under am‐bient temperature and neutral conditions, thus, it efficiently mimicked the oxygen‐evolving complex in photosystem II.

Characterizing Constituents of Sediment Phosphorus Fractionation in a Freshwater Shallow Lake System

This study aimed to characterize constituents of phosphorus （P） fractionation as wel as reciprocities among factors in sediments of a freshwater shal ow lake. [Method] Surface sediment was discretely sampled at 24 sites through Van Veen grabs. Based on a modified sequential extraction scheme, P fractionation was determined as Fe/Al bound P （Fe/Al-P）, Ca bound P （Ca-P）, solute and re-ductive P （S/R-P） and organic P （OP）. Curve estimation and Pearson product-mo-ment correlation were employed for statistical analysis. [Result] Total P （TP） content ranged from 443 to 774 mg/kg. Inorganic P （IP） was the major component of TP, of which Ca-P was dominated with an average of 51%±9.7%. Average contents of P fractionation were in the fol owing order： Ca-P（51%） 〉 OP（29%） 〉 S/R-P（8%） 〉Fe/Al-P（7%）. The molar ratio of Fe to P was 11 - 20, close to the threshold value of P leaching. [Conclusion] In freshwater shal ow lakes, IP and Ca-P were prone to be relatively high, whereas Fe/Al-P was low compared with deep lakes. Occurrence of spatial y monotonic gradient indicated the primary causation of anthropogenic sources. Imminent sediment P liberation was also expected. Close associations a-mong TP, Fe/Al-P and Ca-P, implying that anthropogenic P was mainly bound to metals in particulates. Significant correlations of TOC and P fractionation highlighted endogenous mechanism and authigenic origin in sediments.

Design,synthesis and biological evaluation of amino organophosphorus imidazoles as a new type of potential antimicrobial agents

A series of amino organophosphorus imidazoles were designed and synthesized as a novel structural type of antimicrobial agents.Bioactive evaluation in vitro showed that compound 3f exhibited equipotent or superior anti-methicillin-resistant Staphylococcus aureus(anti-MRSA) and anti-S. cerevisiae efficiencies(minimal inhibitory concentration(MIC)=2 μg/mL) to clinical drugs,and the combinations with antibacterial or antifungal drugs enhanced the antimicrobial efficiency. Highly active molecule 3f showed low propensity for bacteria to develop resistance, and the preliminary action mechanism studies demonstrated that 3f was membrane-active, but had no significant intercalation towards MRSA DNA. The computational study on 3f reasonably explained its high antimicrobial activity. Experimental data revealed that ground-state 3f-HSA complexes were formed mainly through hydrophobic interactions and hydrogen bonds with a spontaneous process, and the non-radioactive energy transfer from HSA to 3f occurred beyond F鰎ster resonance energy transfer theory. The participation of metal ions in 3f-HSA supramolucular system could increase the concentration of free compound 3f, and shorten its storage time and half-life in the blood to improve the maximum antimicrobial efficacy.

Biocompatible metal-free organic phosphorescent nanoparticles for efficiently multidrug-resistant bacteria eradication

Organic phosphorescence materials with longlived triplet excitons that can highly generate active singlet oxygen(1O2) through the energy transfer with the molecular oxygen under photoexcitation, serve as highly efficient antibacterial agent. Herein, we report bright red-emissive organic phosphorescent nanoparticles(PNPs) based on a metal-free organic phosphor encapsulated with biocompatible block copolymers. The obtained PNPs with an ultra-small particle size of around 5 nm and a long emission lifetime of up to 167 μs showed effective 1O2 generation ability under visible light(410 nm) excitation in aqueous media, which can efficiently eradicate multi-drug resistant bacteria both in vitro and in vivo. This is the first demonstration of metal-free organic PNPs for photodynamic antimicrobial therapy, expanding the application scope of metal-free organic room temperature phosphorescent materials.

Influence of Long-Term Fertilization on Selenium Accumulation in Soil and Uptake by Crops

Continuous applications of organic and inorganic fertilizers can affect soil and food quality with respect to selenium （Se） concen- trations. A long-term （over 20 years） experimental field study, started in 1989, was conducted to investigate the changes in soil Se fractions and its uptake by crops, as affected by different fertilizer practices, in the North China Plain with an annual crop rotation of winter wheat and summer maize. The long-term experiment was arranged in a complete randomized block design consisting of 4 replications with 7 fertilizer treatments： 1） organic compost （OC）, 2） half organic compost plus half N-P-K chemical fertilizers （OC ＋ NPK）, 3） N-P-K fertilizers （NPK）, 4） N-P fertilizers （NP）, 5） P-K fertilizers （PK）, 6） N-K fertilizers （NK）, and 7） an un-amended control. Soil samples from the surface （20 cm） were collected in 1989, 1994, 1999, 2004 and 2009 to characterize Se and other soil properties. In 2009, the average soil Se concentrations in the treatments （149 ± 8 beg kg-1） were higher than those in the soil samples collected in 1989 at the beginning of the experiment （112 4- 4 beg kg-1）, and decreased in the order of OC 〉 OC ＋ NPK 〉 NPK NP 〉 PK NK 〉 control. Sequential extraction showed the oxidizable fraction （50.06%± 3.94%） was the dominant form of Se in the soil, followed by the residual fraction （24.12% ± 2.89%）, exchangeable fraction （15.09% ± 4.34%） and Fe-Mn oxides fraction （10.73%±4.04%）. With an increase of soil K, the exchangeable Se concentrations in the soil increased. The Se concentrations in the soil tillage layer （0-20 cm） were mainly related to soil organic carbon （SOC）, although different contributions came from atmospheric deposition, irrigation and fertilizers. With the accumulation of SOC, the uptakes of soil Se by two crops were inhibited. For the OC and OC ＋ NPK treatments, Se concentrations in wheat grains were lower than the critical standard of Se in stable food （100 μg kg·1]. Additionallv. Se concentrations in grains were also decreased by the deficiencies of major soil nutrients, especially P.

Biochar and Compost Increase Crop Yields but the Effect is Short Term on Sandplain Soils of Western Australia

Sandplain soils on the south coast of Western Australia have low inherent fertility, which is mainly due to poor nutrient retention caused by insufficient clay and organic colloidal material. Previous research has shown the benefits in nutrient levels and retention from adding clay to sandplain soils; however, there is almost no information on the addition of organic amendments. A field experiment was established at the Esperance Downs Research Station, Western Australian, in May 2010, to assess the effects of wheat straw(WS) and chicken manure(CM) biochars and compost with and without phosphorus(P) addition on soil properties and crop production over five growing seasons. The five seasons alternated between winter and summer crops. The CM and WS biochar and compost treatments significantly increased crop yields and P uptake in 3, 2 and 1 of the five seasons, respectively. The yield increases(P < 0.05) were no more than 8%. By the end of the third season, no differences in crop yields were found that could be attributed to the organic amendments. The addition of P increased crop yields in each winter cropping season. Phosphorus addition explained more than 30%of the variation in crop yields. Despite marginal P levels and summer drought conditions, arbuscular mycorrhizal root colonisation was not affected by the organic amendments. There were no significant interactions between the organic amendments and P addition in terms of crop yields, P uptake or P uptake efficiency. We conclude that much of the effect of the organic amendments was due to direct nutrient addition which dissipated over time.