羟基磷灰石除氟滤料的吸附平衡及动力学

羟基磷灰石(HAP)是一种高容量、环保型饮用水除氟材料。以氢氧化钙和磷酸为原料采用沉淀法合成了羟基磷灰石,并用红外光谱和XRD图谱进行了表征。研究了接触时间、pH值和温度等因素对羟基磷灰石吸附氟性能的影响。通过对吸附过程中的热力学动力学参数的计算来判断吸附的实质过程。研究结果表明,60 min以内吸附速率较快,在约70 min时吸附过程趋于平衡;酸性环境中的吸附效果要比在碱性环境中要好;升高温度有利于吸附的进行。吸附过程更符合Langmuir吸附模型,说明化学吸附占主导地位;吸附过程是一个自发的吸热过程,其中ΔGo<0,ΔHo为13.10 kJ/mol,Ea为15.24 kJ/mol,ΔSo为31.42 J/(mol.K);吸附过程符合拟二级动力学模型。     

方解石基羟基磷灰石的制备及其对水中氟化物的去除效能研究

采用方解石基羟基磷灰石材料去除水溶液中的氟化物。研究吸附剂用量、反应时间、F-初始浓度、共存阴离子分别对吸附量的影响,以及吸附过程中材料渗透率的变化。结果表明:反应在100min达到平衡,饱和吸附量为10.98mg/g;吸附量随着吸附剂用量、F-初始浓度的提高以及反应时间的延长而增大,当反应达到平衡时不再发生变化;除HCO-3外,其他共存阴离子(NO-3、SO2-4和Cl-)对吸附量影响不大;材料渗透率随反应时间的延长而下降,但大大高于传统羟基磷灰石材料的渗透率;方解石基羟基磷灰石材料对水溶液中氟化物的吸附符合Langmuir等温吸附方程以及Psuedo-二级动力学吸附模型,符合单层吸附反应。同时,采用扫描电子显微镜(SEM)、X射线衍射(XRD)对方解石基羟基磷灰石材料及其反应产物进行表征,探讨方解石基羟基磷灰石材料的除氟机制。     

羟基磷灰石的制备及除氟性能研究

采用化学沉淀法，使用不同原料制备羟基磷灰石；研究羟基磷灰石的除氟性能及除氟机理。静态吸附试验结果表明，样品对氟离子的吸附性能良好，吸附平衡时间一般在3 h左右；随着溶液氟离子浓度的增加，平衡吸附容量不断增加，两者都没有极限值，属于弗兰德里希（Freundlich）吸附。     

焙烧态锂铝水滑石对水中氟离子吸附性能研究

采用尿素水热法合成了不同摩尔比的锂铝水滑石(Li/Al LDHs),经480℃煅烧后制备出焙烧态锂铝水滑石(Li/AlLDOs)。研究了Li/Al LDOs对水中氟离子的吸附性能,分别考察了吸附时间、吸附温度和pH等因素对吸附效果的影响,并对吸附机制进行了探讨。结果表明,Li/Al LDOs吸附水中氟离子的行为符合准二级动力学方程,吸附等温数据符合Freundlich吸附等温方程,pH对吸附效果影响较大。X射线衍射分析表明,水滑石样品经历了物相转变及重构过程,Li/Al LDOs可有效去除水体中的氟离子。     

掺铁碳羟基磷灰石复合物对铅离子废水的吸附

采用废弃蛋壳和自制纳米Fe3O4为原材料,采用水热法制备Fe3O4/碳羟基磷灰石复合物(简称掺铁碳羟基磷灰石复合物,Fe-CHAP),将其用于吸附含Pb2+废水。通过BET比表面积、FTIR和XRD等表征手段对样品进行测试,分别探讨了影响吸附性能的主要因素,如pH、吸附剂用量、吸附时间、Pb2+初始浓度以及反应温度等。研究结果表明,在p H=5.0、0.03 g Fe-CHAP、150 mg/L Pb2+初始浓度、作用时间45 min和反应温度323 K等优化条件下,Fe-CHAP对Pb2+的去除率和吸附容量分别为98.59%和492.95mg/g。Langmuir等温模型较好地拟合了吸附实验数据,相关系数高达0.99,饱和吸附容量高达1 111.11 mg/g;准二级动力学模型较好地描述该吸附行为,相关系数高达0.999;热力学参数ΔG、ΔH和ΔS的计算值显示该吸附过程为自发吸热过程。     

介电泳增强吸附法去除饮用水中的氟离子

高氟水的危害引起了人们的广泛关注。为减少饮用水中含量过高的氟离子(F~-),基于介电泳技术建立了一种新的去除水体中F~-的方法,组装了介电泳装置,将介电泳技术和吸附法结合,增强了对F~-的去除效果。探讨了吸附剂种类、投加量和外加电压对于F~-去除效果的影响,并用SEM对电极进行表征。结果表明,羟基磷灰石对F~-具有最佳的吸附性能,其饱和吸附量为5.88 mg·g~(-1),Langmuir吸附等温方程能够很好地描述羟基磷灰石对F~-的吸附热力学行为,说明吸附满足单分子层吸附模型。在优化的实验条件下(羟基磷灰石投加量6 g·L~(-1),外加电压15 V),F~-去除率由单纯吸附法的67.02%提高到90.39%,达到了WHO饮用水水质标准,且无二次污染。SEM的表征结果表明,经过介电泳后,羟基磷灰石在电极上相互连接形成细长的线状结构。研究为减少高氟水中的氟离子提供了一种快速、高效的新方法。     

转炉渣诱导磷酸钙结晶法去除和回收废水中磷的研究

以转炉渣为晶种材料,利用批次结晶沉淀实验,研究不同的反应条件对诱导磷酸钙结晶法去除和回收废水中磷的影响。结果表明,最优反应条件为:pH=9.5,Ca/P摩尔比2∶1,转炉渣用量1.7 g/L,反应时间3 h,在此条件下,碳酸根对反应的影响甚小,对养猪场废水和污泥浓缩池上清液的处理,最高去除率分别达到95.36%和96.54%;转炉渣循环利用10次,回收磷的效果仍然很好。运用扫描电子显微镜(SEM)、X射线能谱仪(EDS)和X射线衍射仪(XRD)等测试手段对在最优工艺条件下重复使用10次的转炉渣进行了表征,证明回收的磷主要以羟基磷灰石(HAP)形态存在。     

活化赤泥的除氟性能

以成本低的铝工业废矿渣（赤泥）为原材料,通过高温煅烧和酸化处理对赤泥进行活化,制备了除氟吸附剂。研究了反应时间、投加量、初始氟浓度、溶液温度、共存阴离子和pH值对活化赤泥除氟效果的影响。结果表明,接触反应时间为18 h时,吸附接近平衡。活化赤泥对氟离子的吸附符合Lagergren二级吸附动力学方程。另外,初始浓度越高,吸附容量越大。与Freundlich相比,Langmuir吸附等温模型可以更好地描述氟离子的吸附特性,最大吸附量可达2.71 mg/g。SO24-、Cl-和NO3-存在时（〈1 000 mg/L）,对氟离子的吸附几乎没有影响,然而,HCO3-、PO34-和氟离子共存时,会对氟吸附造成不利影响。活化赤泥在pH值3.5～11.0时,具有较好的吸附稳定性。活化赤泥是一种吸附容量高、性能稳定的环境友好型除氟材料,具有应用潜力。     

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。     

季铵化改性木屑纤维素的制备及对氟离子的吸附研究

以3-氯-2-羟丙基三甲基氯化铵(CTA)为醚化剂,对木屑纤维素进行了季铵化改性.探讨了季铵化改性木屑纤维素用量、pH、吸附温度、氟离子初始浓度和吸附时间对氟离子静态吸附率的影响,以及流速对氟离子动态吸附率的影响.结果表明:(1)静态吸附最佳工艺条件:季铵化改性木屑纤维素用量为3.0 g/L,pH为4.0～6.0,吸附温度为25 ℃,吸附时间为120 min.在此最佳工艺条件下,季铵化改性木屑纤维素对100 mL 50.00 mg/L氟离子溶液的吸附率最高可达90.11%.(2)在pH为5.0、25 ℃的条件下,将50.00 mg/L氟离子溶液以5 mL/min的流速流经装有3.0 g/L季铵化改性木屑纤维素的吸附柱,吸附率可达97.95%.(3)季铵化改性木屑纤维素对溶液中氟离子的吸附过程为放热过程,在吸附过程中存在着化学吸附.(4)木屑来源丰富、价格价廉,季铵化改性木屑纤维素对溶液中氟离子的吸附效果好,且吸附工艺简单、易于实现工业化,具有良好的应用前景.     

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.     

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.     

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.     

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.     

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.