取代芳烃对酵母菌毒性的定量结构－活性相关研究

定量测定了苯胺类、苯甲酸类、卤代苯类、苯腈类、硝基苯类、苯酚类等６类化合物对酵母菌的生长抑制毒性，结果表明化合物的最小产生清晰抑菌圈浓度Ｃ＿（ｍｉｚ）与辛醇－水分配系数及一阶分子连接性价指数有如下关系：ｌｏｇ（１／Ｃ＿（ｍｉｚ））＝０．３８ｌｏｇＫ＿（ｏｗ）＋０．３３￣１Ｘ￣ｖ－０．３８ｒ＝０．９２ｓ＝０．２２ｎ＝７７．在上述６类取代苯类化合物中，它们与酵母菌的反应性大小有如下顺序：卤代苯类≈苯甲酸类＜苯胺类＜苯腈类＜苯酚类＜硝基苯类化合物；用Ｆｒｅｅ－Ｗｉｌｓｏｎ法研究各基团对酵母菌毒性的贡献大小，其顺序为：—Ｂｒ（０．８４）＞—Ｃｌ（０．５４）＞—ＣＨ＿３（０．３９）＞—ＮＯ＿２（０．３５）＞—ＣＯＯＨ（０．１９）≈—ＯＨ（０．１７）≈—ＣＨＯ（０．１７）≈—ＣＮ（０．１４）＞—Ｆ（—０．０３）＞—ＮＨ＿２（—０．０８）．苯胺类、苯腈类、苯酚类、硝基苯类化合物对酵母菌的毒性与化合物的分子连接性指数３Ｘｖ、４Ｘ、３Ｘ有良好的相关性．     

HPLC法测定废水中苯胺类化合物

用乙醚为提取有机相，提取前先经碱化，提取后加酸使苯胺成盐，吹去乙醚，用ＨＰＬＣ法测定苯胺类化合物。方法适用于测定废水中苯胺类化合物。检出限：苯胺３．０ｎｇ，邻硝基苯胺０．５ｎｇ，对硝基苯胺１．０ｎｇ。线性范围：苯胺０．８１７－１３．０７２μｇ／ｍｌ，邻硝基苯胺０．１４６４－２．３４２４μｇ／ｍｌ，对硝基苯胺０．２５３－４．０４８μｇ／ｍｌ。精密度（ＣＶ）：苯胺２．３８％，邻硝基苯胺１．０９％，对硝     

4种农药在稻田水中的残留降解

对乐果、杀虫单、丁草胺和氰戊菊酯４种 经，在稻田水中的残留降解情况，进行了及比较。结果表明，４种农药在稻田水中的残留降解符合Ｃ－Ｃｏ．３＾ｋｔ或Ｃ＝Ａ．ｅ＾－１６＋Ｂ．３＾βｉ的数学式，据此可计算其平均降解半衰期（ｔ０．５）分别为：１．８６、１．３５、０．８８和０．３８ｄ，其中丁草胺和氰戊菊酯的降解前快后慢，氰戊菊酯的降解愉丁乐果，土壤吸附氰戊菊酯是其降解快的重要原因，脂溶性农药对水环境的污染要轻     

苯酚及苯酚类催化氧化的色谱电化学法测定及研究

研究了１：１２磷钼杂多酸（ＰＭｏ１２）修饰电极对苯酚及苯二酚类（对苯二酚、间苯二酚）的催化氧化作用，以及苯酚和苯酚类在涂敷十二烷基磺酸钠（ＳＤＳ）的Ｃ１８键合固定相上的分离方法，采用修饰电极色谱电化学法对其进行分离检测。对苯二酚、邻苯二酚、间苯二酚及苯酚的线性范围依次为４．０×１０＾１１ｍｏ１／１－２．０×１０＾－８ｍｏ１／１，４．０×１０＾１１ｍｏ１／１－２．０×１０＾－８ｍｏ１／１，８．０×１     

滇池,洱海水及沉积物中重金属元素的行为

洱海水中重金属元素的含量不同，平均值以１０＾－９计算：Ｃｕ１．６，Ｐｂ０．５９，Ｚｎ９．８，Ｃｄ０．００９，Ｃｒ０．２４，水质较好；沉积物中每一样品同一元素的含量一般均趋于平均值，以１０＾－６计算：Ｃｕ１１１，Ｐｂ６０，Ｚｎ１２７，Ｃｄ０．５９１，Ｃｒ１３０。因此，洱海至今仍是一个较清洁的湖泊。滇池水质较差，内草海段水中重金属元素含量明显上升，以１０＾－９计算：Ｃｕ５．８，Ｐｂ０．５５，Ｚｎ３２，     

水系沉积物中铅含量的快速荧光测定方法的研究

建立了简单、快速测定Ｐｂ＾２＋的荧光测定方法。在ｐＨ＜６．８的酸度条件下,Ｐｂ＾２＋与浓度为１．４－２．０ｍｏｌ／Ｌ的Ｃｌ＾－形成的铅氯配合物在２６２．５ｎｍ的紫外光激光下发射出４８５．０ｎｍ可用于痕量铅离子测定的荧光,在选定激发单色器通带１０．０ｎｍ,发射单色器通带２０．０ｎｍ的仪器条件下,荧光强度与１．０×１０＾－７－１．０×１０＾－５ｍｏｌ／Ｌ范围的Ｐｂ＾２＋的线性关系可用△Ｆ＝１．０１×１     

2,4—二氯苯基荧光酮与铬显色反应的研究与其应用

研究了铬（Ⅳ）－２，４－二氯苯基荧光酮（ＤＣＩＰＥ）－溴化十六烷基三甲胺（ＣＴＭＡＢ）体系的显色条件，试验结果表明，在ｐＨ５．２～７．０范围内，铬与ＤＣＩＰＦ及ＣＴＭＡＢ形成红色三元胶束配合物，其最大吸收波长为５７８ｎｍ，表现摩尔吸光系数为１．４０×１０＾５Ｉ．ｍｏｌ＾－１．ｃｍ＾－１，铬（Ⅵ）含量在０～９．０μｇ／２５ｍｌ范围内符合比耳定律，配合物的组成为Ｃｒ（Ⅵ）：ＤＣＩＰＦ＝１：２，拟定方法     

用二氧化氯降解废水中的苯胺类化合物（1）COD去除规律的研究

用二氧化氯氧化降解８种苯胺类化合物，测定了ＣＯＤ去除率与时间及ＣＯＤ去除率与ＣｌＯ２用量之间的关系；结果表明最终的ＣＯＤ去除率多数都在７０％以上，羟基类苯胺化合物可达９０％以上．反应符合ｌｎＣＯＤ＝Ｋ１ＷＣｌＯ２＋Ａ１及ｌｎＣＯＤｔ＝Ｋ２ｔ＋Ａ关系式．ＣＯＤ去除率还与ｐＨ值的大小有一定的相关性．     

诱导动力学-停流流动注射光度法测定水中铁的价态分布

依据Ｆｅ（Ⅱ）－Ｃｒ（Ⅵ）－Ⅰ＾－氧化还原反应的诱导作用,提出了诱导动力学－停流光度法测定Ｆｅ（Ⅱ）的方法并建立了测定条件：〔Ｃｒ（Ⅵ）〕＝１．８×１０＾－３ｍｌｌ·Ｌ＾－１,〔Ⅰ〕＝２．０×１０＾－２ｍｏｌ·Ｌ＾－１,ｐＨ＝１．９,５９０ｎｍ;在此条件下,线性范围为０－２．２μｇ·ｍＬ＾－１,检测限为０．００９μｇ·ｍＬ＾－１Ｆｅ（Ⅱ）;２５倍的Ｆｅ（Ⅲ）对测定无干扰。测定Ｆｅ（Ⅲ）后,将Ｆｅ（     

藻类－卤虫－对虾系统深度处理含盐含汞化工废水的模拟试验研究

利用藻类－卤虫－对虾系统深度处理含盐含汞化工废水的模拟试验研究表明，该系统对ＢＯＤ５和ＣＯＤ去除率分别达９５．５％和８０．０％，对ＰＯ４＾２－和Ｈｇ＾２＋去除率都在９８％以上。在卤虫密度５２．１个／Ｌ和３６．０个／Ｌ，藻类密度２５７２５．８万个／Ｌ和２０９２４．９万个／Ｌ，水中汞能被不同营养等级的生物累积，在水中汞浓度１．０×１０＾２－７．８×１０＾３和２．１０×１０＾２－１．０４×１０＾４；卤虫     

颗粒物微界面吸附模型的分形修正--朗格缪尔(Langmuir)、弗伦德利希(Freundlich)和表面络合模型

运用分形理论修正了颗粒物微界面吸附模型,建立了朗格缪尔(Langmuir)、弗伦德利希(Freundlich)和表面络合模型的分形吸附等温线方程式．其中,朗格缪尔(Langmuir)吸附等温线的分形表达式为：Γ=ΓmCc^1/m／(b^m Cc^1/m),指数m与颗粒物表面分维Ds的关系如下：m∝ac^D/2-1∝ro^Do-2;表面络合模型的分形表达式为：Γ=ΓmCs^(n/x)/(b^(n/x) Cs^(n/x)),而且lgb=lg(ks／kb) pH,指数x／n与颗粒物表面分维Ds的关系如下：x／n∝0^D/2-1∝r0^D-2;相应的弗伦德利希(Freundlich)吸附等温线的分形形式分别为：Γ=(Γm／bm)Cs^1/n,Γ=(Γm／b^(x/n))Cr^(n/x),通过对献中的数据的模拟初步讨论了分形模型的适用性,结果表明,它们具有更接近于实际的描述微界面吸附过程的能力,通过lg(x／n)=lgk’ (Dn-2)lgro计算出土壤颗粒和尾矿砂颗粒的表面分形维数分别为2．42和2．72。     

烟雾箱与数值模拟研究苯和乙苯的臭氧生成潜势

结合光化学烟雾箱实验与数值模拟研究了苯和乙苯在NO x存在条件下的光氧化臭氧生成潜势.重复实验表明,在乙苯-NO x反应体系中,反应物初始浓度、温度、湿度和光照强度接近的条件下,整个反应过程中臭氧的最大偏差仅为4%,证明了烟雾箱的可重复性较高.在烟雾箱实验的基础上,使用MCM(master chemical mechanism)模拟了苯和乙苯的光氧化O3生成,并将其结果与实验数据进行了比对分析.干燥(≤5%)时MCM对苯和乙苯的模拟结果与实验结果较接近,如在苯-NO x反应体系中,MCM模拟的O3峰值比实验值偏大20%;在湿度为5%~70%时,MCM模拟的乙苯光氧化O3峰值与实验值偏高约(10%~25%).用MCM模拟了太阳光照条件下苯和乙苯的臭氧生成等值线,得到在它们浓度为(10~50)×10-9,NO x在(10~100)×10-9时,苯和乙苯的6 h臭氧贡献值分别为(3.1~33)×10-9和(2.6~122)×10-9,臭氧峰值范围分别是(3.5~54)×10-9和(3.8~164)×10-9.此外,模拟得到苯和乙苯的最大增量反应活性(maximum incremental reactivity,MIR)值分别为0.25/C和0.97/C(每单位碳).该结果与Carter通过SAPRC机制得到的MIR值趋势一致.模拟得到苯和乙苯的最大臭氧反应活性(maximum ozone reactivity,MOR)分别为0.73/C和1.03/C.苯的MOR值远高于Carter使用SAPRC得到的结果,说明根据Carter得到的苯MOR会低估苯的O3潜势.     

Particulate matter assessment of a wetland in Beijing

To increase the knowledge on the particulate matter of a wetland in Beijing, an experimental study on the concentration and composition of PM₁₀ and PM_2.5 was implemented in Beijing Olympic Forest Park from 2013 to 2014. This study analyzed the meteorological factors and deposition fluxes at different heights and in different periods in the wetlands. The results showed that the mean mass concentrations of PM₁₀ and PM_2.5 were the highest at 06:00–09:00 and the lowest at 15:00–18:00. And the annual concentration of PM₁₀ and PM_2.5 in the wetland followed the order of dry period (winter) > normal water period (spring and autumn) > wet period (summer), with the concentration in the dry period significantly higher than that in the normal water and wet periods. The chemical composition of PM_2.5 in the wetlands included NH₄⁺, K⁺, Na⁺, Mg^2 +, SO₄^2 −, NO₃⁻, and Cl⁻, which respectively accounted for 12.7%, 1.0%, 0.8%, 0.7%, 46.6%, 33.2%, and 5.1% of the average annual composition. The concentration of PM₁₀ and PM_2.5 in the wetlands had a significant positive correlation with relative humidity, a negative correlation with wind speed, and an insignificant negative correlation with temperature and radiation. The daily average dry deposition amount of PM₁₀ in the different periods followed the order of dry period > normal water period > wet period, and the daily average dry deposition amount of PM_2.5 in the different periods was dry period > wet period > normal water period.     

Controls on the phosphorus content of fine stream bed sediments in agricultural headwater catchments at the landscape-scale

There have been no landscape-scale assessments which quantify the relative importance of the organic and mineral properties of BS (bed sediment) and associated catchment characteristics (geology, land cover and mean topsoil phosphorus (P) content) for BSP concentration. Mid infra red diffuse reflectance spectrometry was applied to estimate the quantities of organic matter, dithionite extractable aluminium- (Al_d) and iron (Fe_d), kaolinite, dioctahedral clay and mica (D&M) minerals in 1052 snapshot samples of fine (<150 μm) BS in small to medium-sized (5-55 km²) agricultural headwater catchments across a large area (15 400 km²) of central England. Analyses included estimates of BS specific surface area, cerium (Ce) concentrations (enriched in P-bearing apatite and P-fertilsers), and catchment average topsoil P content.Simple linear regression demonstrated that the proportion of variance in BSP explained by specific components of BS across all catchments declined in the following order: Al_d > Fe_d > topsoil P = kaolinite = residual iron> organic matter = Ce> D&M > mineral SSA. No single component accounted for more than 36% of the variance in BSP. Multiple regression - including a classification of bedrock lithology and proportions of arable and grassland by area - accounted for 61.9% of the variance in BSP. The proportion of arable and grassland by area in each catchment was also a statistically significant predictor of BSP. Across this large region - with widely differing geology and soils - Fe_d in BS is more strongly associated with kaolinite than D&M minerals because iron-oxyhydroxides and kaolinite form contemporaneously during pedogenesis. The SSA of fine bed sediments is largely determined by catchment area, fitted accurately using a power function.     

Urease inhibitor reduces N losses and improves plant-bioavailability of urea applied in fine particle and granular forms under field conditions

A field lysimeter/mini plot experiment was established in a silt loam soil near Lincoln, New Zealand, to investigate the effectiveness of urea fertilizer in fine particle application (FPA), with or without the urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT - “Agrotain”), in decreasing nitrogen (N) losses and improving N uptake efficiency. The five treatments were: control (no N) and ¹⁵N-labelled urea, with or without NBPT, applied to lysimeters or mini plots (unlabelled urea), either in granular form to the soil surface or in FPA form (through a spray) at a rate equivalent to 100 kg N ha⁻¹. Gaseous emissions of ammonia (NH₃) and nitrous oxide (N₂O), nitrate (NO₃⁻) leaching, herbage dry-matter (DM) production, N-response efficiency, total N uptake and total recovery of applied ¹⁵N in the plant and soil varied with urea application method and with addition of NBPT. Urea with NBPT, applied in granular or FPA form, was more effective than in application without NBPT: N₂O emissions were reduced by 7-12%, NH₃ emissions by 65-69% and NO₃⁻ leaching losses by 36-55% compared with granular urea. Urea alone and with NBPT, applied in FPA form increased herbage DM production by 27% and 38%, respectively. The N response efficiency increased from 10 kg DM kg⁻¹ of applied N with granular urea to 19 kg DM kg⁻¹ with FPA urea and to 23 kg DM kg⁻¹ with FPA urea plus NBPT. Urea applied in FPA form resulted in significantly (P < 0.05) higher ¹⁵N recovery in the shoots compared with granular treatments and this was improved further when urea in FPA form was applied with NBPT. These results suggest that applying urea with NBPT in FPA form has potential as a management tool in mitigating N losses, improving N-response efficiency and increasing herbage DM production in intensive grassland systems.     

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect

Batch experiments were conducted to evaluate fluoride removal by Al,Fe,and Ti-based coagulants and adsorbents,as well as the effects of coexisting ions and formation of aluminum–fluoride complexes on fluoride removal by co-precipitation with alum(Al_2(SO_4)_3·18H_2O).Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8.Nano-crystalline TiO_2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3–5.Coexisting anions in water decreased the removal of fluoride in the order:phosphate(2.5 mg/L) arsenate(0.1 mg/L) bicarbonate(200 mg/L) sulfate(100 mg/L) = nitrate(100 mg/L) silicate(10 mg/L) at a pH of 6.0.The effect of silicate became more significant at pH 7.0.Calcium and magnesium improved the removal of fluoride.Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)_3 precipitates from 8.9 to 8.4,indicating the chemical adsorption of fluoride at the surface.The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH 6.5.A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF~(2+),AlF~(+2),and AlF_3complexes.The AlF_x complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.     

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin(2,3,7,8-TCDD) is an efcient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2 O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus(RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and O3 is 4.80 × 10 20cm3/(mole·sec) at 298 K and 760 Torr. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.     

pH值对石灰(石灰石)湿法脱硫反应机理的影响

为了探讨ｐＨ值对石灰石湿法脱硫反应机理的影响,进行了用亚硫酸钙沉淀与水的混合液吸收ＳＯ２的实验,研究表明,溶液中离子化合物的型态与体系的ｐＨ值密切相关。体系ｐＨ值小于７时,硫阴离子主要以ＨＳＯ＾－３型态存在,脱硫反应以生成Ｃａ（ＨＳＯ３）２为主;体系ｐＨ值大于７时,硫阴离子主要以ＳＯ＾－２３型态存在,脱硫反应以生成ＣａＳＯ３．１／２Ｈ２Ｏ或ＣａＳＯ４．２Ｈ２Ｏ为主。     

Adsorption of fluoride on clay minerals and their mechanisms using X-ray photoelectron spectroscopy

This research investigates the adsorption mechanisms of fluoride (F) on four clay minerals (kaolinite, montmorillonite, chlorite, and illite) under different F⁻ concentrations and reaction times by probing their fluoride superficial layer binding energies and element compositions using X-ray photoelectron spectroscopy (XPS). At high F⁻ concentrations (C ₀ = 5–1000 mg·L⁻¹), the amount of F⁻ adsorbed (Q _F), amount of hydroxide released by clay minerals, solution F⁻ concentration, and the pH increase with increasing C ₀. The increases are remarkable at C ₀>50 mg·L⁻¹. The QF increases significantly by continuously modifying the pH level. At C ₀<5–100 mg·L⁻¹, clay minerals adsorb H⁺ to protonate aluminum-bound surface-active hydroxyl sites in the superficial layers and induce F⁻ binding. As the C ₀ increases, F⁻, along with other cations, is adsorbed to form a quasi-cryolite structure. At C ₀>100 mg·L⁻¹, new minerals precipitate and the product depends on the critical Al³⁺ concentration. At [Al³⁺]>10^−11.94 mol·L⁻¹, cryolite forms, while at [Al³⁺]<10^−11.94 mol·L⁻¹, AlF₃ is formed. At low C ₀ (0.3–1.5 mg·L⁻¹), proton transfer occurs, and the F⁻ adsorption capabilities of the clay minerals increase with time.