MB(A2/O)处理城市污水富磷上清液的化学除磷研究

为开发新型除磷脱氮工艺，研制了将MBR和A²/O工艺相结合的新型MB(A²/O)反应器。研究了MB(A²/O)反应器处理城市污水厌氧富磷上清液的化学除磷，并分析了过程机理及特性。结果表明：对于TP在30～45 mg/L的富磷上清液，采用含20% Ca(OH)₂的工业石灰与P的最佳投加质量比为22.5；纯Ca(OH)₂与P的最佳投加质量比为5.6（摩尔比为2.5）；FeSO₄·7H₂O与P的最佳投加质量比为10.7（Fe^2＋与P的摩尔比为1.3）；Al₂(SO₄)₃·12H₂O与P的最佳投加质量比为12（Al^3＋与P的摩尔比为1.3）时，均可使出水TP稳定在0.3 mg/L以下；以石灰、NaOH的联合投加方式可大幅减少石灰投加量。     

钛石膏改性胶结材干化湖泊污泥效果及机理

通过不同养护龄期下钛石膏改性胶结材和生石灰掺量对城市湖泊污泥干化效果影响的对比研究,揭示了钛石膏改性胶结材干化污泥的效果和机理。实验结果表明,随着养护龄期增长,干化污泥含水率减少量逐渐增大;同一养护龄期,掺20%钛石膏改性胶结材的干化污泥含水率减少量明显高于掺20%生石灰的干化污泥含水率减少量;干化污泥p H趋于8时,掺20%生石灰干化污泥所用时间是掺20%钛石膏改性胶结材所用时间的7.5倍。XRD和SEM分析表明,钛石膏改性胶结材水化生成难溶的水化硅酸钙凝胶和钙矾石晶体,将大量自由水转化为结晶水;同时,水化硅酸钙凝胶、钙矾石晶体和污泥中固体颗粒之间的互相搭接和紧密结合,彻底改变了原污泥松散团聚的结构体系,将干化污泥中各相牢固地粘结成一个整体,这是钛石膏改性胶结材干化效果好的关键。     

碳酸根对磷酸钙沉淀反应回收磷的影响简

以模拟的厌氧消化液为处理对象，通过小试实验，考察不同初始磷浓度C_P、Ca/P物质的量比、pH和温度下，碳酸根（CO₃^2-）对磷酸钙沉淀反应回收磷的影响；利用扫描电镜（SEM）、X射线衍射仪（XRD）和傅里叶变换红外光谱（FTIR）对沉淀产物进行表征。结果表明，高浓度的CO₃^2-对以磷酸钙沉淀反应去除和回收磷的效率影响较大；C_P相同时，CO₃^2-浓度（C_CO3^2-）越大，P的去除率越低，低C_P（20 mg/L）时尤为显著；当C_CO3^2-相同时，随着C_P的增大，反应速率加快，P的去除率逐渐升高，但升高幅度越来越小；增大Ca/P比和pH能提高P的去除率，降低CO₃^2-对磷酸钙沉淀反应的抑制作用，综合考虑实际效果，应选择Ca/P比为3.33，pH为9.0作为适宜的反应条件；升高温度对降低CO₃^2-对磷酸钙沉淀反应的抑制作用贡献不大。在C_P为60 mg/L，Ca/P比为1.67，pH为9.0，温度为20℃的条件下，当C _CO3^2-为0时，得到的沉淀产物主要为羟基磷灰石HAP；当C _CO3^2-为30 mmol/L时，得到的沉淀产物为磷酸钙和碳酸合磷灰石的混合物。     

天然矿物固硫剂及其对煤粉燃烧的影响

选取CaCO₃、Ca(OH)₂质量配比＝3∶2作为主固硫剂，用钙基固硫剂质量的2％的Na₂CO₃对其改性，利用蛭石作为固硫添加剂。在Ca/S＝2.25的情况下,通过固硫实验考察了主固硫剂以及添加剂的加入对固硫率的影响。实验结果表明，煤粉掺入该固硫剂在950℃下燃烧0.5 h，固硫率可以达到85％。还对添加不同固硫剂的煤粉进行热重实验，分析其对煤粉燃烧特性及动力学参数的影响。结果表明，固硫添加剂的加入不但能提高固硫率，还有利于煤的燃烧，减少灰渣的处理量。     

超细粉煤灰基成型吸附剂的动态吸附实验

以粉煤灰为原料制备成型吸附剂，对水溶液中亚甲基蓝和Cr⁶⁺进行动态吸附研究，绘制穿透曲线，利用Origin软件对实验数据分析处理，得出穿透曲线的通式C_t=A₁－A₂〖〗1+(t/t₀)^p+A₁。结果表明，初始浓度C₀=25 mg/L，填料高度不同时，达到穿透点的时间随填料高度的增加而增加；填料高度h=200 mm，初始浓度不同时，达到穿透点的时间随初始浓度的增加而减小；该吸附剂对有机染料和重金属离子均有较好的吸附性能；穿透曲线通式的回归线性相关系数表明，该通式可很好地反映超细粉煤灰成型吸附剂的动态吸附过程。     

纳米TiO2-xNx催化剂的制备及其活性研究

以钛酸丁酯为前驱物、无水乙醇作溶剂、二乙醇胺作为抑制剂,采用溶胶凝胶法制备TiO₂溶胶，在NN₃气流中直接进行热处理，制备一系列不同焙烧温度的淡黄色的掺氮纳米TiO₂粉体。经XRD、UV-Vis和FTIR分析表明，实验制得的TiO_2-xN_x在350、400、450、500和550℃热处理3 h后仍为锐钛型；450℃保温3 h掺氮样品具有最佳的紫外-可见光响应，其吸收边红移至720 nm左右。罗丹明B的可见光降解实验及产物分析表明，掺氮样品具有良好的可见光催化活性。     

燃油锅炉燃烧过程SO2的生成与排放特征

燃料燃烧过程是大气污染物的重要来源之一，对人体健康、空气质量和气候变化产生非常重要的影响。以62台燃油锅炉（≤10.5 MW）的燃料特性分析数据和SO₂排放实测数据为基础，通过统计分析方法，研究了燃油燃烧过程中燃油硫含量S和过量空气系数α对硫的转化率、SO₂排放因子和排放浓度的影响，获得了基于燃料消耗量、燃料发热量的SO₂排放因子EF_C、EF_H以及SO₂标态折算浓度C′_SO2与硫含量S间的关联式。结果表明，在过量空气系数α＞1的燃油燃烧过程中，EF_C、EF_H、C′_SO2与燃油硫含量S呈现出显著的线性正相关性，而与过量空气系数α无关，其关系式分别为：EF_C=18.86602×S，EF_H=443.78751×S ，C′_SO2＝1 509.28337×S；硫转化率η和基于燃料硫含量的SO₂排放因子EF_S则与燃油硫含量S和过量空气系数α无关，其平均值分别为96.3％和1.93 kg/kg。     

超重力-磷酸钠法脱除低浓度SO2

为开发脱硫率高、成本低、可回收SO₂的脱硫技术,以旋转填料床为吸收设备,磷酸钠溶液为吸收剂,系统开展了液气比L/G、转速N、气体中SO₂浓度CSO₂,in、吸收剂磷酸浓度CL和初始pH等工艺参数和溶液再生循环次数对脱硫率η影响的实验研究。结果表明,η随L/G、N、CL和初始pH的增加而增大,且它们的值越低时,η增加越明显;受G和CSO₂,in影响较小。在适宜操作条件下,脱硫率达99%以上,出口SO₂浓度低于100 mg/m³。磷酸钠溶液可再生循环使用,脱硫率稳定在99%以上。表明超重力-磷酸钠法脱硫技术在小的液气比下即可达到高的脱硫率,吸收剂循环使用,可实现低成本并达标治理SO₂废气,且适用范围宽,具有良好的工业应用前景。     

模拟医疗废物在管式电阻炉上的热解特性研究

在管式电阻炉上对由聚丙烯、面巾纸、纱布、医用脱脂棉、一次性口罩、医用乳胶手套等按一定比例组成的模拟医疗废物在氮气气氛进行了热解研究。重点探讨了10 K/min，20 K/min，30 K/min和40 K/min等不同升温速率对热解产物分布、产气特性和热解过程的影响。结果表明，随着温度升高，模拟废物的热解产生气体的主要成分逐渐由CO₂和CO转变为C₃H₆、CH₄、C₂H₆、C₂H₄和C₃H₈。同时，热解处理对模拟废物的减量化效果比较明显，固体残留率仅为5.61%～7.02%。而且，加热速率对模拟医疗废物热解过程的影响较大。     

SGA对垃圾焚烧飞灰中重金属的固化性能研究简

根据EPA 1311、HJ/T 299-2007、HJ/T 300-2007和HJ 557-2009等国内外不同标准，研究了深圳某垃圾焚烧发电厂垃圾焚烧飞灰的浸出毒性，探讨了六硫代胍基甲酸（sixthio guanidine acid，SGA）、二甲基二硫代氨基甲酸盐（sodium dimethyl dithio carbamate，SDD）和Ca（OH）₂浓度对垃圾焚烧飞灰中重金属的固定性能的影响。研究结果表明，随着浸提液pH的降低，该厂焚烧飞灰中大部分金属元素的浸出量增大，焚烧飞灰浸出液中的Cd、Ni、Pb和Zn浓度分别超过国家危险废物鉴别标准（GB5085.3-2007）规定值的4.75倍、1.47倍、6.72倍和2.20倍，属于危险废弃物，必须进行稳定化处理。当固化剂SGA加入量为0.1 mol/kg时，稳定化后的重金属浸出浓度已经低于危险废物鉴别标准，且对Cd、Cr、Cu和Pb的固化性能优于SDD和Ca（OH）₂；当固化剂SGA、SDD和Ca（OH）₂加入量为0.5 mol/kg时，稳定化后的焚烧飞灰重金属浸出浓度均低于国家危险废物鉴别标准（GB 5085.3-2007）中的规定值。与SDD和Ca（OH）₂相比，SGA对垃圾焚烧飞灰中重金属的固化处理更具有优势。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.