磷酸钙盐结晶除磷工艺性能研究

研究了主要工艺条件pH和Ca/P对磷酸钙盐结晶除磷工艺性能的影响。通过分批实验,建立了磷去除率与pH之间的指数函数关系以及磷去除率与Ca/P之间的对数函数关系。连续运试表明,在pH=9.0、Ca/P=2的条件下,磷酸钙盐结晶除磷反应器的容积负荷为1.10 kg P/(m3.d),磷去除率为51%。灵敏度分析表明,pH对磷去除率的影响大于Ca/P,将Ca/P提高至6,容积负荷提高至1.60 kg P/(m3.d),磷去除率提高至74.3%;将pH提高至10.0,容积负荷提高至1.80 kg P/(m3.d),磷去除率提高至83.5%。工艺操作上可选pH作为优先控制对象。     

水解酸化-磷酸铵镁法-EGSB组合工艺处理大豆蛋白废水

采用水解酸化-磷酸铵镁(MAP)法-EGSB组合工艺对大豆蛋白废水进行处理,考察了水解酸化系统运行效果,并对其运行参数进行优化;提出MAP法对高浓度氨氮废水的处理方法,并评选其处理高浓度氨氮废水的适宜条件。结果表明,水解酸化系统运行稳定,最适pH为7.0,最佳水力停留时间为12h,氨氮转化率高达95.8%;MAP法处理高浓度氨氮废水的优选条件为n(Mg):n(N):n(P)=1:1:0.8,此条件下氨氮去除率为88.3%,磷酸去除率为76.7%;EGSB反应器经过三个月的启动后可稳定运行,有机负荷高达到9.88 kg·(m~3·d)~(-1),COD去除率达到90.0%左右。水解酸化-MAPEGSB组合工艺在处理大豆蛋白废水时可获得连续稳定的处理效果,为大豆蛋白废水处理的工程化提供了基础依据。     

基于响应面法优化MAP法处理垃圾渗滤液工艺的研究

利用单因素实验以及响应面法(response surface methodology,RSM),对磷酸铵镁法(magnesium ammonium phosphate,MAP)去除垃圾渗滤液氨氮的影响因素进行了分析和探讨。考察了pH值为8.0～11.0、n(Mg)∶n(N)摩尔比为0.8～1.6、n(P)∶n(N)摩尔比为0.8～1.3条件下,分析氨氮去除率的变化,用Design-Expert软件处理实验数据,得到了二次响应曲面模型以及优化的水平值。基于经济和操作简便性的考虑,pH值由优化水平的8.3调整为9.5,n(Mg)∶n(N)、n(P)∶n(N)摩尔比取优化水平分别为1.40、1.19,氨氮去除率平均值为92.2%,虽然该条件比最佳条件下的氨氮去除率降低了2个百分点,但从操作的难易程度以及经济性方面,体现了其优势。通过X衍射与电镜扫描分析沉淀物质的成分与晶形,表明大部分沉淀物质为磷酸铵镁。     

几种常见离子对粉煤灰合成沸石除磷效果影响研究

研究了几种常见无机离子(SO2-4、HCO-3、NO-3、SiO2-3、Ca2 、Mg2 )对3种阳离子饱和的粉煤灰合成沸石(Ca沸石、Al沸石和Fe沸石)除磷效果的影响.结果表明,与纯水比较,NO-3和SO2-4的存在能提高沸石的磷去除率;HCO-3对沸石除磷起抑制作用;高浓度的SiO2-3显著提高溶液pH,从而促进Ca沸石的除磷,但抑制Al沸石和Fe沸石的除磷作用;Ca2 的存在能够显著提高沸石的磷去除率;Mg2 能促进Al沸石和Fe沸石除磷,但对Ca沸石除磷有一定抑制作用.     

MAP法处理饲料级磷酸氢钙母液的研究

运用 MAP(磷酸铵镁)法处理高浓度饲料级磷酸氢钙母液,研究了处理的最优反应条件并分析了最优条件下所得产物成分.结果表明,母液处理的最优反应条件为pH=9.5,n(NH4 ):n(PO43-)=1:1,反应时间 10 min,反应温度40℃以下.该条件下,当温度为40℃时,PO43-、Mg2 和Ca2 的去除率分别达到 98.46%、92.54%和98.48%,残留浓度分别为 15.91、70.25 和2.94 me/L.生成的沉淀产物中 P2O5、NH4 -N、CaO 和MgO 所占重量百分比分别为29.08%、6.07%、2.83%和 15.91%,所含 MAP 可作为肥料回收利用.     

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。     

纳米零价铁颗粒除磷反应机理

从溶液化学与固相表征两方面对纳米零价铁(NZVI)去除水中磷酸根(PO3-4)的机理进行初步探究。分别研究不同初始p H值、溶解氧(DO)对NZVI除磷效果的影响,结果表明,酸性环境(p H为3.0~7.0)有利于NZVI除磷,且初始p H值越低,磷去除率越高;好氧环境较厌氧环境更利于磷的去除,DO8.0 mg/L时对磷酸根的去除率是厌氧条件(DO0.1 mg/L)下的2倍。采用Na OH对反应后含磷NZVI进行解析,发现磷解析率不到30%,说明吸附并非NZVI除磷惟一作用机理。微米铁、NZVI和Ca(OH)2等7种不同去除材料中以Ca(OH)2的共沉淀作用去除率最大(99.9%),NZVI次之(87.2%),表明NZVI除磷机理中还存在共沉淀作用。采用多种固相表征手段对NZVI除磷前后进行分析:扫描电子显微镜(SEM)显示反应后出现不规则颗粒;X射线衍射(XRD)表明Fe3(PO4)2是主要反应产物;X射线光电子能谱(XPS)分析未发现磷被还原成低价态。研究表明,NZVI可有效去除水中磷酸根,主要去除机理包括:NZVI对磷酸根的吸附作用、NZVI在水中腐蚀产生的Fe2+离子对磷酸根的化学沉淀作用及铁氢氧化物与磷酸根的共沉淀作用。     

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。     

利用白云石石灰去除与回收污泥厌氧消化液中氮和磷

以白云石石灰为实验材料去除与回收污泥厌氧消化液中的氮磷,通过小试实验研究不同投药固液比S/L、初始pH值、反应温度、搅拌速度及反应时间对去除与回收氮磷效果的影响。实验结果表明,在最佳投药固液比S/L为300mg/L,最佳初始pH值范围为8.5~9.5,反应温度为25.0℃,搅拌速度为150 r/min,反应时间为24 h条件下,氨氮(NH+4-N)和磷(PO3-4-P)的去除率分别为37.26%和89.60%。利用X射线衍射仪(XRD)、扫描电镜(SEM)对沉淀产物进行了表征,通过分析可知沉淀产物中含有磷酸铵镁(MAP),可实现废水中氮磷经济有效的回收。     

剩余污泥水解酸化液中营养元素与有机质的回收

为回收剩余污泥水解酸化液中的营养元素与有机质,构建了白云石-水解酸化液钙镁溶出体系,获得富含钙镁的溶出液,控制溶出液反应pH和反应时间进行第1阶段回收,以回收后的上清液进一步作为钙镁源从水解酸化液中进行第2阶段回收。结果表明,钙镁溶出的适宜条件为酸化pH 4.0~4.5、白云石颗粒50~80目、固液比3∶100(每100mL水解酸化液中投加3g筛分后白云石)、溶出时间10h;第1阶段回收适宜的反应pH为8.5,氮(以氨氮计)回收率、磷(以可溶性正磷酸盐(以P计)计)回收率分别为10.24%和95.89%;第2阶段回收适宜的镁磷摩尔比为0.60、反应pH为9.0,此时氮、磷回收率分别为14.60%和83.91%;傅立叶红外变换(FTIR)和电感耦合等离子直读光谱(ICP)分析表明,回收产物主要由无机养分和有机质组成,重金属含量极少。利用白云石提供钙镁源能经济有效地回收剩余污泥水解酸化液中的氮、磷等营养元素,同时回收有机质,回收产物品质符合《有机-无机复混肥料》(GB 18877—2009)中Ⅰ型肥料要求。     

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.     

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.     

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.     

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.