原位水解生成的羟基氧化铁凝聚吸附除磷效能与机制简

将不同摩尔比Fe³⁺与OH^-（[Fe³⁺]：[OH^-]=1：0、1：1、1：2和1：3）反应获得原位水解生成的羟基氧化铁（in situ FeO_xH_y），研究了具有不同水解程度的羟基氧化铁对凝聚吸附除磷效能与机制。研究显示，In situ FeO_xH_y对磷的去除率随铁投量增大而升高，且均在中性pH范围内具有最佳除磷效果；在相同铁投量条件下，磷去除率随着[OH^-]：[Fe³⁺]的升高而降低；当体系碱度较低时（pH<6），引入OH^-可促进Fe³⁺水解而提高除磷效果。4种羟基氧化铁均可在15 s内可快速吸附磷，且吸附过程符合准二级动力学模型；Freundlich模型均可很好地描述磷在4种羟基氧化铁表面的吸附行为。磷酸盐吸附后，In situ FeO_xH_y表面Zeta电位明显降低，且[Fe³⁺]：[OH^-]为1：0的羟基氧化铁降低最为显著。结合MINITEQ计算软件磷酸盐、铁盐形态分析结果显示，对于碱度较低的体系，通过投加一定量OH^-可促进Fe³⁺水解，进而使得其更易与水中H₂PO₄^-与HPO₄^2-结合，生成具有多核羟基的磷酸铁络合物，进而提高除磷效果。     

碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟的厌氧消化液为处理对象，通过小试实验，考察不同初始磷浓度Cp、Ca／P物质的量比、pH和温度下，碳酸根（CO3 2-）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（FT．IR）对沉淀产物进行表征。结果表明，高浓度的CO3 2-对以磷酸钙沉淀反应去除和回收磷的效率影响较大；Cp相同时，CO3 2-浓度（CCO3^2-）越大，P的去除率越低，低C，（20mg／L）时尤为显著；当CCO3^2-相同时，随着Cp的增大，反应速率加快，P的去除率逐渐升高，但升高幅度越来越小；增大Ca／P比和pH能提高P的去除率，降低CO3 2-对磷酸钙沉淀反应的抑制作用，综合考虑实际效果，应选择Ca／P比为3．33，pH为9．0作为适宜的反应条件；升高温度对降低CO3 2-对磷酸钙沉淀反应的抑制作用贡献不大。在Cp为60ITIg／L，Ca／P比为1．67，pH为9．0，温度为20℃的条件下，当CCO3^2-为0时，得到的沉淀产物主要为羟基磷灰石HAP；当CCO3^2-为30mmol／L时，得到的沉淀产物为磷酸钙和碳酸合磷灰石的混合物。     

水体中常见无机阴离子对TiO2薄膜光催化降解甲醛的影响

选择了5种水体中常见的阴离子(Cl^-，SO^2-₄，HPO^2-₄/HPO^2-₄，HCO^-₃/CO^2-₃和NO^-₃)，分别考查了其对TiO₂薄膜光催化降解模拟甲醛废水的反应速率的影响；从上述离子的光吸收，对·OH的捕获及其生成的相应的无机自由基的氧化作用以及与甲醛的竞争吸附3个方面讨论了上述离子影响TiO₂薄膜光催化降解模拟甲醛废水的反应速率的原因。结果表明，HCO^-₃/CO^2-₃对TiO₂薄膜光催化降解甲醛具有抑制作用，Cl^-和SO^2-₄的影响不大，H₂PO^-₄/HPO^2-₄和NO^-₃具有促进作用。造成上述结果的主要原因是HCO^-₃/CO^2-₃具有很强的·OH捕获作用；Cl^-，SO^2-₄对·OH捕获作用以及竞争吸附都较弱；H₂PO^-₄/HPO^2-₄在TiO₂表面具有较强的吸附能力，释放出的H⁺起到了酸催化剂的作用；NO^-₃在紫外光的照射下可以产生·OH，此外NO^-₃作为电子受体而降低了TiO₂表面光生电子和空穴的复合几率。     

几种阴阳离子对磷钨酸光催化降解甲基橙的影响

以磷钨酸为光催化剂，在紫外灯照射下，对甲基橙溶液进行光催化降解，考察了几种阴阳离子对磷钨酸光催化降解甲基橙溶液的影响。结果表明：Mg²⁺、Ca²⁺、NO^-₃、SO^2-₄和CO^2-₃均对催化活性有促进作用，其中Mg²⁺和Ca²⁺仅有微弱的促进作用；NO^-₃和SO^2-₄随着浓度的增加促进作用也有所增加；CO^2-₃则随着浓度的增加促进作用呈下降趋势；Mn²⁺、Al³⁺和Cl^-对光解反应存在较强的抑制作用，且Al³⁺和Cl^-随着其浓度的增加，抑制作用增强。     

黄菖蒲和狭叶香蒲根系对氮磷的吸收动力学

采用改进的常规耗竭法，研究了黄菖蒲（Iris pseudacorus L.）和狭叶香蒲（Typha angustifolia L.）根系对NH₄⁺、NO₃^-和H₂PO₄^-的吸收特征及差异。结果表明，这2种植物根系对NH₄⁺、NO₃^-和H₂PO₄^-的吸收动力学特征均可采用Michaelis-Menten方程描述。2种植物根系对NH₄⁺、NO₃^-和H₂PO₄^-的亲和力（Km）和最大吸收速率（Vmax）有显著差异。吸收H₂PO₄^-时，黄菖蒲根系具有较高的Vmax值和较低的Km值，说明黄菖蒲具有嗜磷特性，并能够适应广范围浓度的H₂PO₄^-环境，适宜用于污染水体磷的去除；吸收NO₃^-时，狭叶香蒲根系具有较高的Vmax值和较低的Km值，表明狭叶香蒲可用于广范围浓度NO₃^-污染的水体修复；吸收NH₄⁺时，黄菖蒲根系具有较低的Vmax值和Km值，而狭叶香蒲根系具有较高的Vmax值和Km值，说明黄菖蒲适宜用于NH₄⁺污染较轻水体的修复，而在NH₄⁺污染较重水体中宜选用狭叶香蒲作为先锋植物。     

低温条件下BAF+SPD组合工艺对滇池入湖河水的脱氮效果

为缓解湖泊富营养化问题，需进一步降低入湖河流氮的含量。针对滇池流域新运粮河的低C/N水质特征，研究了冬季低温条件下的微曝气生物滤池（BAF）及固相反硝化（SPD）组合异位脱氮工艺。结果表明，BAF+SPD组合工艺启动挂膜阶段，约3周后，NH₄⁺-N的去除率达80%以上，而反硝化细菌增殖相对缓慢，约5周后，NO₃^--N的去除率达80%以上；稳定运行的低温阶段，除降雨时间外，NH₄⁺-N平均去除率达80%，出水NH₄⁺-N浓度<1 mg/L；NO₃^--N平均去除率达到85%以上，出水NO₃^--N浓度<1 mg/L；TN平均去除率达80%以上，出水TN浓度<2 mg/L，主要水质指标达到国家地表水Ⅴ类标准。     

MB(A2/O)处理城市污水富磷上清液的化学除磷研究

为开发新型除磷脱氮工艺，研制了将MBR和A²/O工艺相结合的新型MB(A²/O)反应器。研究了MB(A²/O)反应器处理城市污水厌氧富磷上清液的化学除磷，并分析了过程机理及特性。结果表明：对于TP在30～45 mg/L的富磷上清液，采用含20% Ca(OH)₂的工业石灰与P的最佳投加质量比为22.5；纯Ca(OH)₂与P的最佳投加质量比为5.6（摩尔比为2.5）；FeSO₄·7H₂O与P的最佳投加质量比为10.7（Fe^2＋与P的摩尔比为1.3）；Al₂(SO₄)₃·12H₂O与P的最佳投加质量比为12（Al^3＋与P的摩尔比为1.3）时，均可使出水TP稳定在0.3 mg/L以下；以石灰、NaOH的联合投加方式可大幅减少石灰投加量。     

鸟粪石结晶法回收垃圾渗滤液氨氮研究

采用MgSO₄·7H₂O和Na₂HPO₄·12H₂O使NH₃-N生成MgNH₄PO₄·6H₂O（鸟粪石）结晶沉淀法回收渗滤液中NH₃-N。考察了pH值、反应时间、药剂配比对NH₃-N去除率的影响。结果表明，鸟粪石结晶回收NH₃-N反应的适宜pH值为9～9.5之间，过高的pH会破坏鸟粪石晶体结构，导致固定氨从MgNH₄PO₄中游离出来，不利于氨氮的去除。在pH值为9.5、反应时间为25 min、Mg²⁺∶NH⁺₄∶PO^3-₄=1.5∶1∶1.5的最佳条件下，渗滤液中NH₃-N浓度由初始3 500 mg/L,经结晶沉淀后降低至175 mg/L，去除率达95%。鸟粪石结晶沉淀过程中几乎不吸收重金属，同时回收了氨氮，其沉淀产物鸟粪石是一种优良的缓释肥原料。     

pH值控制MAP法脱氮进程的可行性研究

MAP沉淀法处理高NH₃-N废水，操作简便，处理效果好。本试验以NH₃-N浓度为1 000 mg/L的模拟废水为研究对象，研究结果表明，在Mg²⁺∶PO^3-₄∶NH⁺₄=1.2∶1.2∶1（摩尔比）、NaOH投加量为675 g/L的条件下NH₃-N去除率高达98%以上。试验选择出水pH作为控制反应进程的参数，并建立了出水pH与NH₃-N去除率之间的关系。通过调整NaOH投加量控制出水pH在7.5～8之间时，NH₃-N去除率最高，可达98%以上。X-衍射图谱及定量分析表明，沉淀物中MAP的纯度较高，具有一定的回收价值。     

TiO2光催化降解水中土霉素的动力学研究

环境中抗生素的出现及其引起的危害正受到越来越多的关注。以高压汞灯为光源，选用较为广泛的抗生素土霉素（OTC）为处理对象。考察了初始质量浓度、反应过程中光照、催化剂投加量、溶液起始pH、溶液中DOM和NO^-₃对光催化降解的影响，研究了其光降解动力学。结果表明，TiO₂光催化氧化法能够有效去除水中半微量的OTC，OTC的光降解过程符合一级反应动力学模型；UV/TiO₂联用工艺对TOC也有很好的去除效果，反应90 min，TOC去除率可达74%；OTC的初始浓度从30 mg/L增大到90 mg/L，反应速率从0.0619 min^-1降低到0.0130 min^-1；随着光催化剂投加量的增大，光降解速率常数先增大后减小；增加溶液的pH值，速率常数逐渐减小；溶液中的DOM和NO^-₃也可以影响光降解效率。     

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.     

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 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.     

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

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on intestinal parameters of cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable histopathological alterations were observed. The study on intestinal parameters revealed acute pathological conditions in the intestinal wall. The toxic effect became evident as the cytoplasm of the cells disintegrated and the cells became empty and vacuolated. The cell membranes were also ruptured. Degenerative changes of the absorptive surface (villi) of the intestine in the different periods of exposure were pronounced. Severe atrophic nature (necrotic mucosa) of the intestine began from 48 hrs onwards to 96 hrs of exposure.     

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.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

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.