基于自碳黑的水化硅酸钙制备及其磷回收特性

以白碳黑、硅灰、硅藻土和硅胶筛选硅质原料,并与钙质原料电石渣制备了水化硅酸钙。借助XRF、BET、FT—IR等表征手段,通过多次重复除磷实验,研究了硅质原料特性对水化硅酸钙回收磷性能的影响。结果表明,白碳黑具有极高的反应活性,因此可作为制备具有磷回收特性的水化硅酸钙的硅质原料。结合XRD等表征发现,白碳黑的有效利用率是影响水化硅酸钙回收磷性能的关键,该利用率取决于白碳黑与电石渣的摩尔配比以及水热反应温度。当电石渣与白碳黑的摩尔比为1．6：1,反应温度为170℃时,白碳黑具有最佳的利用效率。该条件制备的水化硅酸钙可作为晶种,在其表面结晶形成羟基磷灰石,从而达到磷回收的目的,磷回收后固体物质中的磷含量为19．05％。     

粉煤灰、电石渣及其配合物碳酸化特性

为了促进粉煤灰和电石渣建材化高效利用和协同矿化CO_2减排,研究了粉煤灰、电石渣及其配合物的碳酸化特性。实验采用pH在线测试方法分别对粉煤灰、电石渣以及两者配合物的碳酸化过程的pH进行在线测试,并对原料和产物进行XRD、TGA和SEM表征。结果表明:相同条件下,粉煤灰碳酸化浆液pH降到7.0的平均速度约为电石渣的51倍;与等量电石渣单独碳酸化相比,粉煤灰与电石渣按照4:1(质量比)复配碳酸化pH降低到7.0的速度较纯电石渣提高了近5.6倍,且在相同电石渣配量的条件下,粉煤灰-电石渣复配料比碳酸钙-电石渣复配料的碳酸化反应完成时间缩短了31.6%,说明电石渣与粉煤灰复配后进行碳酸化反应具有明显协同促进作用。TGA分析表明,纯粉煤灰和纯电石渣的固碳率分别约为2%和61.3%,粉煤灰与电石渣复配料的固碳率较等量单一电石渣和粉煤灰的固碳率之和的计算值提高了19.6%。SEM分析表明,粉煤灰与电石渣复配料碳酸化产物碳酸钙颗粒在粉煤灰表面呈现异位分散附着形态,而单一电石渣碳酸化产物碳酸钙则在电石渣颗粒表面呈现原位聚集附着形态。这可能是复配料固碳率提高的主要原因。     

用电石渣、钢渣和煤矸石制备可控性低强度材料

可控性低强度材料(CLSM)是一种替代传统的回填材料,具有低强度、自流平、自我填充与自密实的特性,并在欧美地区得到广泛应用的一种材料。为了加强对可控低强度材料的研究,提出了以电石渣、钢渣、煤矸石为主要原料制备可控低强度材料,研究其不同温度、不同原料配比条件对其抗压强度的影响,通过X射线衍射分析了其物质发生的化学变化及变化规律。电石渣和钢渣的比例在1∶1附近时抗压强度达到最大,温度升高和氯化钙加入量的增加也有利于抗压强度的提高,氧化钙、二氧化硅等部分原料转变为复合硅酸盐晶体。     

浅析电石渣固硫

研究了用电石渣作为固硫剂,探讨了最佳固硫的燃烧温度、电石渣用量和粒径,并掺入适量的 Ｆｅ_２Ｏ_３对电石渣进行改性,发现用电石渣固硫与其他钙基因硫剂相当,具有良好的应用前景。     

锰磁活性炭的制备及其性能表征

以酶解提制烟碱后的烟渣和电解锰渣回收锰为原料,制备具备磁性和发达孔隙的活性炭。利用氮气吸附技术、红外光谱（FTIR）表征与分析了活性炭表面的孔隙结构和物化性质,考察了活性炭对亚甲基蓝的吸附性能和磁学性能。结果表明：以Mn／C基质废弃物为原料制得活性炭具有磁学性能;适量锰的添加有利于活性炭微孔的形成和发育;采用一步焙烧法有助于磁化物和活性炭基体相互作用形成化学键合,提高饱和磁化强度,实现废弃资源的充分利用。     

磷石膏基胶结材固结磷尾矿性能及浸出特征

以磷石膏基材料代替水泥作为磷尾矿充填胶结材,研究了磷尾矿固结浆体和硬化体性能、浸出液污染特性和固结机理。结果表明,在同样条件下,磷石膏基材料固结磷尾矿浆体比水泥泌水量要小、浆体流动性能更优;磷石膏基材料胶结磷尾矿硬化体除3 d抗压强度略低外,其他龄期的强度是水泥的1.21~1.95倍。3 d之后,磷石膏基材料和水泥胶结尾矿硬化体浸出液总磷含量基本相近,但pH明显远低于水泥,总磷也低于污水综合排放标准限值,对环境危害低。硬化体SEM和XRD分析发现,磷石膏基材料水化生成的水化硅酸钙凝胶、针状钙矾石晶体和磷尾矿中白云石、含磷矿物生成的透钙磷石等,是整个磷尾矿固结硬化体具有较高强度、较低总磷含量和pH值主要原因。该研究表明,磷石膏基材料固化磷尾矿比水泥更有应用前景。     

改良型湿法制备活性白土清洁生产及末端治理实验研究

传统湿法制备活性白土工艺中存在水耗、酸耗大等清洁水平较低的问题,本研究提出了在生产工艺流程中循环使用硫酸酸性废液、并从循环3次的硫酸废液中回收铝盐制备无铁硫酸铝的一种改良型湿法制备活性白土工艺,对末端治理采用电石渣替代石灰作为中和剂进行了探索性实验研究。实验结果表明,改良型湿法制备活性白土工艺对活性白土产品的理化性质无明显影响,产品质量符合行业标准,且酸的利用率从20%提高到约90%,水耗减少量为原工艺的1/3,无铁硫酸铝主要参数符合相关产品技术标准(HG/T2225-2001)。用电石渣作为中和剂处理酸性废液能够实现出水水质稳定达标,处理成本从255万元降低至210万元。本研究的实施使得活性白土的生产工艺清洁生产水平有较大提高。     

电石渣固硫性能的研究

研究采用电石渣作为固硫剂，探讨了最佳固硫的燃烧温度，电石渣用量和粒径，并掺入适量的Ｆｅ２Ｏ３对电石渣进行改性，发现用电石渣固硫能与其它钙基固硫剂人有很的应用前景。     

利用白云石回收污泥厌氧消化液中的磷

为经济有效地从污泥厌氧消化液中回收磷,构建了以白云石提供钙镁源的磷回收方法,探讨了磷回收的工艺条件与效果。通过盐酸酸化厌氧消化液以降低其碳酸盐含量,同时利用白云石溶于冷稀盐酸的特性使其钙镁缓慢释放到酸化的厌氧消化液中形成第一步磷回收体系,考察体系酸化pH、白云石与厌氧消化液的固液比以及反应pH对白云石的钙镁释放和磷回收效果的影响;第一步磷回收后的上清液为第二步厌氧消化液磷回收提供钙镁源,研究投加钙磷摩尔比对磷回收效果的影响。实验结果表明,当固液比为5.0时,在酸化pH为4.0～4.5且酸化溶出时间为10 h以及反应pH为9.0的条件下,第一步磷回收产物以磷酸钙盐沉淀为主,厌氧消化液磷回收率及回收产物含磷率（以P2O5计）分别达到99.43%和38.49%;第一步磷回收后的上清液按一定的钙磷摩尔比投加到酸化后的厌氧消化液中进行第二步磷回收,当投加钙磷摩尔比为0.20时,在反应pH为9.0的条件下,回收产物同时含有磷酸钙盐和磷酸铵镁,厌氧消化液中氮、磷回收率分别达到13.19%和90.90%,回收产物氮、磷含量（以P2O5计）分别为0.26%和39.58%;经XRD、XRF、ICP及SEM等分析表征,2步磷回收的产物以磷酸钙盐和磷酸铵镁为主要成分,杂质少。研究表明,利用白云石为钙镁源,通过分别构建不同的磷回收体系可以分步从污泥厌氧消化液中经济有效地回收磷,且磷回收率和回收产物含磷率高。     

改性腐植酸盐-丙烯酰胺-丙烯酸复合吸水树脂制备及性能研究

以改性腐植酸盐、丙烯酰胺、丙烯酸为原料,采用水溶液聚合法制备了复合高吸水性树脂PAAH,考察了交联剂用量、引发剂用量、单体配比和反应温度对产品性能的影响,得到了最佳反应条件:交联剂和引发剂分别占单体总质量分数的0.6%和0.9%;丙烯酸与丙烯酰胺摩尔比为9;反应温度60℃。在此条件下制备的高吸水性树脂具有良好的耐温耐盐性,对纯水吸收倍率为1 298.22 g/g,盐水吸收倍率为261.53 g/g。     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

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.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

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.     

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.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.