不同Ca/P比下碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟污水处理厂污泥厌氧消化液为处理对象,进行磷酸钙沉淀除磷小试实验,考察了不同Ca/P物质的量比下碳酸根(CO2-3)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,磷酸钙沉淀反应是一个快速过程,CO2-3的存在并未改变这一显著特征。磷酸钙沉淀反应过程中,CO2-3的存在降低了磷的去除率,改变了沉淀物形貌、结构和组分;实验设定范围内,磷酸钙的过饱和度越高,越难形成晶体态羟基磷灰石((Ca5(PO4)3OH,HAP);当pH值为9.0,Ca/P比为1.67时,CO2-3取代HAP晶格中的PO3-4,形成碳磷灰石(CHAP);当pH值为9.0,Ca/P比为3.33和5.01时,CO2-3和PO3-4之间竞争,形成碳酸钙(CaCO3);增大Ca/P能有效提高磷的去除率,降低CO2-3对磷酸钙沉淀反应的抑制作用,但综合考虑实际效果,选择Ca/P比为3.33作为适宜的反应条件。     

有机膨润土负载纳米零价铁还原-类芬顿氧化降解2,4-二氯苯酚

目前,虽然有很多关于纳米零价铁(NZVI)通过吸附、还原和氧化作用去除各种污染物的报道,但关于如何联合这些方法来提高污染物的去除率仍然不是很清楚。本实验研究了联合有机膨润土DK1(十六烷基三甲基铵盐改性,d(001)=2.2 nm)吸附、NZVI还原、类芬顿氧化作用来去除溶液中2,4-二氯苯酚(2,4-DCP)的方法。在反应前30分钟,有机膨润土DK1负载NZVI(NZVI/DK1)通过吸附还原作用去除溶液中2,4-DCP,2,4-DCP和COD的去除率分别为16.1%和7.8%,说明了吸附还原作用对2,4-DCP的去除效果是有限的。接着向溶液中滴加适量的H2O2,在5 min内2,4-DCP的去除率由16.1%提高到了99%以上,COD的去除率达到了64.1%,这可能是由于NZVI腐蚀形成铁的氧化物缓慢释放出Fe2+和Fe3+,增强了芬顿反应对2,4-DCP和降解产物的氧化去除效果。通过SEM,EDS,UV-Vis和GC-MS等分析方法佐证了上面的结果。最后提出了联合吸附、还原和Fenton氧化去除2,4-DCP的机制。     

曝气吹脱法用于牛场沼液污染物的去除

氨吹脱是一种有效的污水脱氮处理技术,其中曝气吹脱法又简单易行。为了探究曝气吹脱法用于牛场沼液污染物去除的最优条件,实验研究了温度、曝气量、初始p H等参数对氨氮去除效果的影响,并探讨了投加Ca(OH)2及曝气吹脱对COD、TP的去除作用。结果显示:温度、曝气量是影响氨氮去除效果的关键因素,30℃、4 000曝气量条件下氨氮去除率最高;由于沼液本身p H会受吹脱影响升高,因此,调节初始p H在8~9.5范围内对氨氮去除效果无显著影响;Ca(OH)_2能去除少量COD及TP,吹脱也能对COD去除有一定影响,投加7.7 g/L Ca(OH)_2吹脱后,沼液COD、TP去除率分别为9.7%、14.8%。最优条件30℃、4 000曝气量下,不加Ca(OH)2吹脱能得到70%以上的的氨氮去除率。一般情况下建议不加Ca(OH)_2进行沼液氨吹脱。     

强酸性高浓度含砷废水处理方法与经济性评价

研究了硫化物沉淀和中和沉淀工艺对强酸性体系下As(Ⅲ)和As(Ⅴ)处理效果,考察了沉淀剂种类与投量、酸度(或平衡pH)等因素对除砷效果的影响,结合共沉淀产物的元素组成与价态分析探讨了2种工艺的除砷机理。研究表明,硫化物沉淀对As(Ⅲ)去除效果优于As(Ⅴ),且As(Ⅴ)去除过程中存在As(Ⅴ)转化为As(Ⅲ)的还原过程;中和沉淀对As(Ⅲ)和As(Ⅴ)去除率均可达到98%以上,但不存在砷形态转化过程。进一步以云南某硫精制酸化工厂实际含砷废水为对象,研究了硫化物沉淀(以Na2S为硫源)、中和共沉淀(Fe(Ⅲ)-Ca(OH)2,Fe(Ⅲ)-NaOH,单独Ca(OH)2和Ca(OH)2-Fe(Ⅱ)等)除砷效果和处理成本,发现上述几种工艺砷去除率均可达到99.0%左右;Na2S共沉淀法处理成本最高,单独Ca(OH)2成本最低但废渣产生量大;Ca(OH)2-Fe(Ⅱ)可在不大幅提高成本的基础上确保处理效果并降低废渣产生量。在工程中应综合原水水质特点、处理水质目标、可接受的处理成本以及含砷废渣处置要求等,确定最佳的处理技术方案。     

垃圾焚烧发电厂渗滤液生化出水的催化臭氧氧化处理

垃圾焚烧发电厂渗滤液生化出水是一种高盐,且含腐殖酸类和水溶性小分子有机物的复杂废水.本研究提出了采用Ca(OH)2预处理,并催化臭氧氧化处理的新工艺路线,对工艺参数和催化过程机理进行了分析.结果表明,Ca(OH)2可以有效地预处理去除生化出水中的腐殖酸类大分子有机物,当其用量为12 g/L时,可使COD的去除率达到70％～75％.Ca(OH)2可强化催化臭氧氧化处理预处理废水中剩余的难降解小分子有机物,其机理可能是及时去除了反应体系中生成的碳酸根离子,其适宜用量为2 g/L废水.当搅拌转速小于600 r/min,进口气相中臭氧浓度小于66.24 mg/L时,增大反应体系搅拌强度和进口臭氧浓度可以强化废水COD的去除速率.该工艺在深度处理垃圾渗滤液生化出水中难降解有机物领域具有较大的应用前景.     

水铁矿吸附磷酸根的影响因素

为了修复水体富营养化,选取了人工合成的水铁矿作为除磷吸附剂。通过批量实验研究了震荡速度、吸附时间、吸附剂投加量、溶液初始p H、含磷初始浓度、反应温度和共存离子等因素对吸附作用的影响。结果表明:水铁矿的吸附具有快速吸附,缓慢平衡的特点;随着投加量的增加,溶液中磷酸根的去除率逐渐增加;溶液初始p H在酸性条件下,溶液中磷酸根的去除率最好;在室温25℃下,水铁矿对不同浓度的磷酸根溶液均具有很好的吸附效果;溶液共存离子的存在对磷酸根去除率有一定影响,HCO_3~-的影响最大。     

碳酸根型镁铝水滑石对铬酸根和磷酸根离子的吸附性能

为研究水滑石类材料对水体中铬酸根和磷酸根离子的同时吸附去除性能,采用共沉淀法合成碳酸根型镁铝水滑石(Mg-Al-CO3LDHs),利用傅立叶转换红外光谱、X射线晶体衍射、表面积、X光吸收近边结构等手段对合成材料进行表征,并研究Mg-Al-CO3LDHs在不同初始浓度、p H、吸附时间、阴离子干扰条件下同时去除铬酸根和磷酸根离子的性能。结果表明,Mg-Al-CO3LDHs对铬酸根和磷酸根离子最大吸附量分别为0.042 mmol/g和0.146 mmol/g。吸附动力学实验数据的拟合结果以Elovich为最佳。竞争实验表明,溶液中含有少量磷酸根离子即可抑制铬酸根离子的吸附,但铬酸根离子对磷酸根离子的吸附影响不大。X光吸收近边结构结果表明,铬与构造中心的铝产生键结而吸附。     

某城市污水处理厂废水化学除磷沉淀特性及影响因素

通过对西安市某污水处理厂进水、厌氧池上清液、二沉池出水、污泥浓缩水、污泥脱水进行Fe CI_3·6H_2O、PAC除磷实验,并以Fe CI_3·6H_2O为沉淀剂对厌氧池上清液从p H、Fe/P摩尔比、腐殖酸、挥发性脂肪酸(VFA)等因素进行批次实验分析磷去除状况。实验显示,三氯化铁、PAC对进水除磷效果不佳,厌氧池上清液用Fe CI_3·6H_2O为沉淀剂时磷去除率较低,二沉池出水、污泥浓缩水以及污泥脱水用Fe CI_3·6H_2O、PAC时其正磷去除率均可达到80%左右。通过对比不同p H值、Fe/P摩尔比、腐殖酸和VFA浓度对厌氧池上清液除磷效果的影响,结果表明,在p H=4~5,Fe/P=1.3时磷的去除效果达到78%以上,腐殖酸浓度对磷去除率影响不大,VFA在低于10 mg/L和高于60 mg/L时对磷去除率影响较大。     

改性硅藻土/纳米零价铁复合材料去除水中Cu~(2+)的研究

应用改性硅藻土(CDt)/纳米零价铁(NZVI)复合材料对水溶液中的重金属Cu~(2+)进行去除研究。结果表明,CDt/NZVI能高效去除水中Cu~(2+),在CDt/NZVI投加量为0.075g、pH=5、Cu~(2+)初始质量浓度为20mg/L、溶液体积为100mL时,Cu~(2+)去除效果最好,去除率达到98.52%。CDt/NZVI对Cu~(2+)的去除机理包括吸附和还原,吸附过程符合Langmuir方程,最大吸附量为74.29mg/g;还原产物主要为Cu_2O和Cu~0。CDt/NZVI具有良好的循环利用性,循环3次后Cu~(2+)去除率仍能保持在65%以上。     

有机配体对纳米零价铁还原硝基苯的影响与机理

通过FeSO4·7H2O与NaBH4反应,采用液相还原法制备纳米级零价铁(NZVI),并用XRD,SEM对其性能进行表征。研究了纳米零价铁还原硝基苯(NB)的动力学规律及柠檬酸、草酸、柠檬酸钠、草酸钠、乙二胺四乙酸二钠(EDTA二钠盐)几种有机小分子对其还原效率的影响,并对其机理进行了初步探讨。结果表明,纳米零价铁去除硝基苯反应符合准一级动力学方程,并且当硝基苯浓度一定时,增加NZVI投加量,去除率会显著增大;当NZVI浓度一定时,硝基苯浓度越低,去除率越高;柠檬酸和EDTA二钠盐在较低浓度时抑制还原反应进行,而在3 mmol/L左右时,具有促进还原反应进行的作用,而草酸、柠檬酸钠和草酸钠则为抑制作用。     

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.