高浓度复合型聚铁硅絮凝剂PFSS和PSFS的形态分布研究

采用紫外分光光度法、逐时络合比色法和红外图谱从不同角度对高浓度聚合硫酸铁硅和聚合硅酸铁的形态分布及转化规律进行了探讨。紫外吸收表明，聚铁硅絮凝剂中主要以Fe（OH）2^＋、Fe2（OH）2^4＋等二聚体为主，而且还有三聚体或其他聚合形态的存在；逐时络合分析显示，复合型聚铁硅体系中硅形态以Si（c）为主，铁形态以Fe（a）和Fe（c）为主；红外图谱证实高浓度聚铁硅是以羟桥为主结构连接的高分子复合物，在1100cm^-1附近M-OH-M的振动证明有铁羟基及其聚合态存在，且其形态区别于PFS。     

聚铁硅型混凝剂的形态分析及性能研究

以水玻璃和聚合硫酸铁为原料制备不同碱化度(B)及不同Fe/Si摩尔比的系列聚合硫酸铁硅混凝剂(PFSS)并对其形态进行分析。采用FeFerron逐时络合比色法发现随熟化时间延长,Fe(a)和Fe(b)的含量逐渐减少,Fe(c)的含量逐渐增多,而碱化度越大,PFSS中铁越易从Fe(a)向Fe(c)转化。采用显微电泳实验发现PFSS随着投加量增加,Zeta电位升高。采用超滤法测定了制备的PFSS分子量的分布情况,并将其与PFS进行了比较,结果发现,PFSS的分子量明显比PFS的分子大。     

聚硅基复合氯化铁絮凝剂的制备及其在采油废水处理中的应用

采用硅酸钠制备聚硅酸,探讨了活化pH、活化剂、硅酸钠浓度(以SiO_2质量分数计)及聚合温度等因素对聚硅酸稳定性的影响.利用聚硅酸及氯化铁制备聚硅基复合氯化铁(PSiF),并通过正交试验分析了活化pH、Si/Fe(摩尔比)、OH/Fe(摩尔比)、制备时间对PSiF絮凝性能的影响.综合考虑絮凝性能、稳定性以及经济性等因素,确定PSiF适宜的制备条件为SiO_2质量分数2%～3%;活化pH为2～3;Si/Fe为0.50～0.75;OH/Fe为0.50～0.75;制备时间为0.5 h;聚合温度低于25℃.对比PSiF、PAC、FeCl_3对采油废水的处理效果,PSiF除浊、除COD效果以及经济性最好,是一种应用前景广阔的新型絮凝剂.     

聚铁硅型混凝剂的形态分析及性能研究

以水玻璃和聚合硫酸铁为原料制备不同碱化度(B)及不同Fe／Si摩尔比的系列聚合硫酸铁硅混凝剂(PFSS)并对其形态进行分析。采用Fe-Ferron逐时络合比色法发现随熟化时间延长，Fe(a)和Fe(b)的含量逐渐减少，Fe(c)的含量逐渐增多，而碱化度越大，PFSS中铁越易从Fe(a)向Fe(c)转化。采用显微电泳实验发现PFSS随着投加量增加，Zeta电位升高。采用超滤法测定了制备的PFSS分子量的分布情况，并将其与PFS进行了比较，结果发现，PFSS的分子量明显比PFS的分子大。     

天然有机物对零价铁去除水体中砷的影响研究

在研究零价铁对水体中砷去除动力学的基础上,着重探讨了天然有机物腐殖酸对零价铁除砷的影响.并对零价铁的腐蚀产物进行了分析.结果表明,水体中的砷可以通过在零价铁腐蚀产物上的吸附得到快速去除.腐殖酸显著降低了砷的去除率,这归因于腐殖酸与零价铁腐蚀产生的铁离子形成络合物,阻止了Fe(OH)3(或Fe(OH)2)沉淀的产生.腐殖酸浓度越高.砷的去除率越低.1.00 mg腐殖酸最多可以络合约0.75 mg铁离子.当铁离子与腐殖酸的络合达到饱和后,零价铁进一步腐蚀产生的铁离子可形成Fe(OH)3(或Fe(OH)2)沉淀,这些沉淀物可吸附水体中的腐殖酸和砷,从而加速砷的去除.冷冻干燥后的零价铁腐蚀产物的结构以无定型为主,含有少量的结晶化合物,包括γ-Fe2O3、γ-FeO(OH)和Fe3O4等.腐殖酸的存在可进一步增加腐蚀产物中的无定型成分.光电能谱(XPS)分析结果显示,吸附在腐蚀产物上的砷为5价,没有发现5价砷被还原成3价砷.在应用零价铁修复砷污染水体时,应考虑腐殖酸的影响.     

聚硅酸铁混凝剂净水效能及机理

采用共聚法制备聚硅酸铁(PSF)混凝剂,同时研究PSF的水解规律,并对比研究PSF与复合铝铁(PFA)的微观品质及对低温低浊水、屠宰废水及含磷模拟水的混凝性能,并初步探讨PSF除磷(或除有机物)的机理.结果表明,混凝剂混凝性能的优劣取决于其微观性质,而PSF独特的微观特征正是其具有优异混凝性能的根本原因.不同pH值对P(或有机物)与PSF之间的络合模式具有不同的影响,3种水解形态Fe(OH)2 、Fe3 及Fe(OH)3在宽泛的pH范围内(5＜pH＜9.5)稳定存在并基本均为定值,这些可能都是PSF在宽泛的近中性范围内及碱性范围内具有优异除磷、除有机物性能的重要原因.可以认为PSF的混凝机理是以电中和(配位)/脱稳为前提条件,以架桥为必要条件,以卷扫网捕为补充条件.     

工业聚合铝的形态分析方法研究

主要探讨了工业聚合铝 (PACl)的形态分析方法 ,即Al Ferron逐时络合比色法。重点研究了 2类Ferron比色液的稳定性及其对工业PACl形态分析的影响特征。     

工业聚合铝的形态分析方法研究

主要探讨了工业聚合铝(PACl)的形态分析方法，即Al-Ferron逐时络合比色法。重点研究了2类Ferron比色液的稳定性及其对工业PACl形态分析的影响特征。     

聚硅硫酸钛（PTSiS）的合成及形貌分析

以硅酸钠和硫酸钛为原料,用共聚法制备了不同硅钛比(硅钛摩尔比分别为3∶1、1∶1和1∶3)的新型绿色无机高分子絮凝剂——聚硅硫酸钛(PTSiS)。用紫外连续扫描光谱仪(UV/Vis)、红外光谱仪(IR)、X-射线衍射(XRD)、扫描电镜(SEM)和倒置生物显微镜对样品中钛硅的微观品貌进行了多方面物性分析。结果表明:当硅钛比为3∶1时,硅酸钠和硫酸钛反应完全。此时,聚硅酸的骨架硅(Si—O—Si)与钛元素发生同晶取代或与钛离子水解形成的表面羟基发生络合,形成的聚硅硫酸钛(PTSiS)是一种高分子的硅钛聚合物,而不是单纯的原料混配。另外,聚硅硫酸钛(PTSiS)具有枝杈长链的网络结构,其骨架主要由框架钛结构(Ti—O—Si)组成。     

铁碳材料还原NO络合吸收体系中Fe(Ⅲ)EDTA的性能

在湿法烟气脱硝中,Fe(Ⅱ)EDTA是一种常用的螯合剂,对NO有良好的络合吸收能力,但是Fe(Ⅱ)EDTA容易被O2氧化成对NO无络合能力的Fe(Ⅲ)EDTA。因此,选择合适的还原剂实现Fe(Ⅲ)EDTA的高效还原是络合脱硝的关键技术之一。比较了铁碳(Fe/AC)和铁粉(Fe)在不同搅拌速度下对Fe(Ⅲ)EDTA的还原,系统探讨了铁碳质量比、O2浓度、铁碳中Fe与Fe(Ⅲ)EDTA的摩尔比、pH值和Fe(Ⅲ)EDTA初始浓度对铁碳还原Fe(Ⅲ)EDTA的影响,考察了Fe/AC投加前后NO吸收效率的变化,同时通过BET、XRD表征技术对铁碳材料进行了分析。结果表明:Fe/AC能很好地再生Fe(Ⅱ)EDTA,从而提高NO吸收效率。提高搅拌速度、铁碳中Fe与Fe(Ⅲ)EDTA的摩尔比、Fe(Ⅲ)EDTA初始浓度,Fe(Ⅲ)EDTA的还原速率会相应增大;O2浓度及pH增大会降低Fe(Ⅲ)EDTA的还原速率。表征结果表明,铁碳表面形成的氢氧化物为γ-Fe OOH。     

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.     

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.     

A History of Dry Cleaners and Sources of Solvent Releases from Dry Cleaning Equipment

Approximately 25, 000-35, 000 dry cleaning facilities currently operate in the U.S. The release of perchloroethylene and other solvents from these establishments represents a major source of soil and groundwater contamination. The manner in which dry cleaning solvents escape from dry cleaning plants is, for all practical purposes, identical for chlorinated and petroleum hydrocarbon solvents and is related to one of the following events: the catastrophic failure of a component of the dry cleaning system, the improper installation, operation or maintenance of the dry cleaning equipment or a combination of all of these causes. Acceptable customs, codes and regulations can also dictate what is authorized for operation of a dry cleaning facility in a particular community, geographic area during a particular time frame. Environmental litigation dealing with the origin of a solvent release from dry cleaners tends to focus on the design and manufacture of dry cleaning industry machines such as washers, washer extractors, tumblers, solvent filters, water separators, stills and spotting boards. A thorough analysis of the daily operations of dry cleaners often reveals that poor maintenance, failure to follow the manufacturer's instructions and the actions of the operator are the most likely causes of soil and groundwater pollution. In order to forensically evaluate the most probable origins of a solvent release and to examine issues regarding liability, a thorough understanding of the history of dry cleaning and a detailed analysis of the operation and maintenance of the dry cleaning equipment are necessary. The discovery of solvent plumes in the vicinity of dry cleaning plants may suggest that the solvent source is the dry cleaning plant; however, the presence of these plumes does not necessarily indicate that the dry cleaning equipment was defectively designed or manufactured. A thorough review of the type of equipment used over the life of the dry cleaning plant and verifiable solvent mileage records frequently indicates that operators of the plant have disposed of solvent and contaminated solids into the municipal sewer or on ground surfaces.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Malathion-induced sublethal toxicity on the hematology of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on hematological parameters of the cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable hematological alterations were observed. The study on hematological parameters revealed a highly significant decrease (P < 0.01) in the total erythrocytes count in malathion-exposed animals from 24 hours to 96 hrs of exposure as compared to control. Significant decreases (P < 0.01) of hemoglobin and packed cell volume were also observed from 48 hrs to 240 hrs. A significant increase (P < 0.01) in leucocytes count was noted throughout the exposure period. Elevated numbers of lymphocytes and eosinophils as found in the present study revealed lymphocytosis as well as eosinophilia, suggesting that this was a result of direct stimulation of the immunological defense due to the presence of a toxic substance or may be associated with tissue damage. The cytomorphological and cytopathological study of erythrocytes and leucocytes in malathion-exposed frogs at 0.006 ppm concentration revealed various cytotoxic effects at different exposure times. It was noted that the size and the shape of the erythrocytes were subjected to variation in different blood disorders.