Fenton试剂氧化苯酚的影响因素与过程研究

考察了H2O2与Fe^2＋剂量、反应时间、初始pH值、无机离子（Cl^-、SO4^2-）和进料方式对Fenton氧化降解苯酚效率的影响，测定了Fenton试剂氧化苯酚过程中的Fe^2＋和高锰酸钾消耗量。实验结果表明，在H2O2与Fe^2＋剂量分别为20和2mmol／L、初始pH为4．00、反应30min的条件下，酚去除率约为97％，COD去除率约为87％。并获得了在初始pH值为4．00时的COD去除率最高；Cl^-的存在将显著降低COD的去除率；SO4^2-对COD去除无显著影响；分批次加入药剂对COD去除效果明显优于一次性加入。在Fenton发生反应的第1min，Fe^2＋浓度可降低到初始浓度的65％左右，大约在20minFe^2＋浓度降到最小值（H2O2接近耗尽），然后随着反应的继续再增大，这说明了中间产物还原Fe^3＋作用的存在。     

电极-SBBR处理含铜有机污水

采用电极一SBBR系统去除Cu^2＋，考察了电流强度，IA竞争离子（阴离子SO4^2-、NO3^-、CL^-和阳离子Zn^2＋、Ph^2＋）、初始含Cu^2＋量及溶液pH值对除铜效除果的影响。结果表明，当电流强度为40mA时Cu^2＋去除率最高为98％。投加阴（SO4^2-、NO3^-、Cl^-）、阳（Zn^2＋、Pb^2＋）离子均会引起出水Cu^2＋浓度的增加，且Cl^-和Ph^2＋含量分别为45mg／L和30mg／L时对Cu^2＋去除的影响更为显著。进水Cu^2＋浓度为30mg／L时，Cu^2＋去除率最高为98．48％，当进水Cu^2＋≥70mg／L时，出水Cu^2＋浓度不能达标。酸性（pH4．0～4．5）与碱性（pH9．0～10．0）条件均不利于Cu^2＋的去除，且酸性条件的负面影响更显著．当pH为4．5～7．5时．Cu^2＋去除率最高为97．78％。     

不同硅铝比的ZSM-5型沸石分子筛吸附水中Cu2＋离子的研究

考察了3种不同硅铝比的ZSM-5沸石分子筛（25H、38H和50H，25、38和50为硅铝比）对水中Cu2＋的吸附过程及其影响因素。结果表明，3种材料均能有效吸附去除水中Cu2＋离子，动力学符合假二阶动力学模型，吸附等温线符合Langmuir吸附等温式。3种材料吸附速率及吸附容量顺序为：25H〉50H〉38H，其中，25H最大吸附容量达到12．83mg／g。投加量由0．8g／L增加至2．0g／L，材料对Cu2＋吸附去除率由87．0％增加至97．5％。考察水中常见阳离子对吸附的干扰作用，结果表明，干扰离子的影响顺序为：Pb2＋〉K＋〉Na＋〉Mg2＋；随着干扰离子浓度的增大，材料对Cu2＋的去除率显著下降。硅铝比及晶粒形貌均对沸石分子筛吸附Cu2＋有较大影响，小的孔径不利于Cu2＋的吸附，低硅铝比有利于Cu2＋在分子筛上的吸附。     

粉煤灰-H2O2催化氧化水中对氨基苯酚的试验研究

研究了利用电厂粉煤灰作为非均相催化剂，催化H2O2氧化对氨基苯酚（PAP），讨论了各种因素对PAP去除率的影响。结果表明，在30℃，pH=1．5，H2O2和PAP的起始浓度分别为0．50mol／L和0．10mol／L，反应时间为100min，粉煤灰用量为6.0％，搅拌速度为1000r／min的条件下，粉煤灰具有良好的催化活性，能有效地催化H2O2氧化PAP，PAP的去除率可达81％左右。该法可用于预处理含PAP的工业废水。     

潜流人工湿地-生物接触氧化处理低温低浓度生活污水

在低温低浓度生活污水的实验研究中，回流比和气水比是影响潜流人工湿地一生物接触氧化组合工艺污染物去除效果的重要因素，推荐回流比R=1．0，气水比为4：1，在该工况下，进水COD浓度在170．8～221．3mg／L时，平均去除率可达90％；进水NH3-N浓度在17．3～25．9mg／L，平均去除率45％～65％；进水TN浓度在25．1～38．49mg／L时，平均去除率45％～65％；进水TP浓度在2．2～3．1mg／L时，平均去除率65％～80％。污染物沿程浓度分析结果表明，该组合工艺可以在低温季节通过曝气促进氨氮硝化，大幅提高NH3-N和TN去除率，同时可以充分发挥复合潜流湿地功能。     

Cu^2＋、Zn^2＋对生物脱氮系统的影响

Cu^2＋和Zn^2＋是污水处理工艺中经常遇到的金属离子。在驯化好的活性污泥系统中，研究了金属离子Cu^2＋和Zn^2＋在0～100mg／L浓度下对活性污泥生物脱氮系统的影响。试验发现Cu^2＋＞5mg／L、Zn^2＋＞30mg／L时，对硝化过程具有明显的抑制作用，在同样浓度的试验条件下cu“对硝化过程的抑制作用比Zn^2＋大。Cu^2＋≤0．5mg／L时对反硝化过程具有一定的促进作用，有助于提高TN的去除效果；Cu^2＋＞0．5mg／L时，对反硝化产生抑制作用，随着浓度的增加，TN去除率逐渐下降。Zn^2＋不影响反硝化过程，仅在大于30mg／L时，对硝化过程产生抑制作用。重金属Cu^2＋对生物脱氮系统的影响明显强于Zn^2＋。     

电混凝处理电镀综合废水

采用电混凝法处理酸性电镀综合废水，首先研究了不同电流密度对总氰化物、重金属和化学需氧量（COD）去除率的影响。实验结果表明，电混凝可有效去除酸性电镀综合废水中的氰化物与重金属。随着电流密度的增大，总氰化物与重金属的去除率逐渐提高。当电流密度为10mA／cm2时，废水中残留的总氰化物、Cu2＋、Ni2＋、Cr6＋和Zn2＋ 的浓度分别为23．0、25．0、4．5、0．2和0．2mg／L。为了进一步提高去除率，在电化学体系中添加H2O2，随着H2O2投量的增大，总氰化物、重金属、COD去除率不断提高。当H2O2投量为3mL／L时，处理过废水中残留总氰化物、Cu2＋、Ni2＋、Cr6＋、Zn2＋和COD的浓度分别为0．2、2．0、3．0、1．5、0．1和220mg／L。     

饮用水源水无机金属污染的应急处理

根据密云水库供水现状，针对突发性无机金属污染事件，采用聚合氯化铝辅助化学沉淀法进行应急处理。选用Cu2＋、Fe2＋、Zn2＋和Cd2＋ 4种金属离子为目标污染物，首先通过小试实验确立了最佳混凝处理条件。结果表明，调节pH值为8．0左右，可使初始浓度为5mg／L和10mg／L的Cu2＋浓度降至0．96mg／L和0．67mg／L；初始浓度为1．5mg／L和3mg／L的Fe2＋浓度降至0．27mg／L和0．24mg／L；初始浓度为0．05mg／L和0．1mg／L的Cd2＋浓度降为0．0089mg／L和0．0078mg／L；调节pH值为9．0时，可使初始浓度为5mg／L和10mg／L的Zn2＋浓度降至0．57mg／L和0．48mg／L。4种污染物出水浓度均低于国家饮用水标准。在小试基础上，在北京第九水厂开展无机金属污染处理的中试实验，结果表明所选用的聚合氯化铝辅助化学沉淀法简便易行，可实现污染物快速、有效去除。     

Fe~(3+)催化过氧化钙体系降解水中三氯乙烯

采用Fe~(3+)催化过氧化钙(CP)处理水溶液中三氯乙烯(TCE),考察了CP和Fe~(3+)投加量、地下水中常见阴离子和腐殖酸对TCE降解效果的影响。结果表明,Fe~(3+)催化CP体系可以有效降解TCE,但相同药剂投加量下效率低于Fe~(3+)催化H_2O_2体系。在TCE初始摩尔浓度为0.15mmol/L,CP和Fe~(3+)投加量分别为3.00、6.00mmol/L时,180min时TCE去除率达到了96.1%。常见阴离子Cl~-、HCO_3~-和SO_4~(2-)对TCE的降解有抑制作用,NO_3~-对TCE降解几乎无影响,而腐殖酸对TCE降解有促进作用。自由基清除实验表明TCE降解的主导自由基为HO·,Cl~-的释放效果显示HO·的氧化作用可使降解的TCE完全矿化。因此,Fe~(3+)催化CP技术适用于污染场地地下水中TCE的修复治理。     

制备条件及水中常见离子对Pd-Cu／AC催化还原去除硝酸盐的影响

以浸渍法制备Pd—Cu／AC催化剂，以氢气为还原剂对催化还原硝酸盐进行研究，考察了制备条件及水中常见离子对催化还原的影响。结果表明，在200～500℃、30—240min焙烧条件下，适宜的焙烧温度为300℃，时间为2h；在100～300W，1～5min的微波条件下，微波功率引起的催化剂活性变化比微波照射时间显著，微波处理综合效应不利于催化性能的提高。活性炭经0．01～0．1mol／LEDTA处理后催化剂的活性随EDTA浓度增加，氨氮生成率没有明显变化。反应过程中氨氮的生成受No；的浓度影响明显，较高N2-浓度有利于选择性的提高。在初始NO3^-浓度100mg／L的条件下，Pd—Cu／AC催化还原硝酸盐的反应为一级反应。水中共存离子影响研究表明，CO3^2-、HCO／的存在不仅会硝酸盐的去除效率明显降低，同时导致氨氮生成率明显增加，S^2-存在使催化剂中毒，催化效率极低，Cl^-、SO4^2-的存在对硝酸盐的去除影响较小；水中阳离子存在时催化活性大小顺序为K＋〈Na＋〈Ca^2＋〈Mg^2＋〈Al^2＋，氨氮的生成率大小顺序为K^＋〉Na^＋〉Ca^2＋〉Mg^2＋〉Al^2＋。     

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.     

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 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.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.