H_2O_2/Fe~0、H_2O_2/Fe~(2+)、H_2O_2/Fe~(3+)3种体系处理印染废水

采用H2O2/Fe0、H2O2/Fe2+、H2O2/Fe3+3种体系分别对印染废水进行处理,研究pH值、H2O2投加量、不同价态铁元素的投加量及反应时间对印染废水的COD和色度处理效果的影响。实验最佳的处理条件:H2O2/Fe0体系在pH为3.0,Fe0投加量为3.0 mmol/L,H2O2投加量为9.0 m L/L,反应时间为40 min时,COD去除率达到95.99%,色度去除率达到100%;H2O2/Fe3+体系在pH为3.0,Fe3+投加量为5.0 mmol/L,H2O2投加量为12.5 m L/L,反应时间为100 min时,COD去除率达到95.89%,色度去除率达到100%;H2O2/Fe2+体系在pH为3.0,Fe2+投加量为6.0 mmol/L,H2O2投加量为12.0m L/L,反应时间为100 min时,COD去除率达到95.85%,色度去除率达到100%。对比分析3种体系在各因素下的处理结果,H2O2/Fe0体系和H2O2/Fe3+体系都要优于H2O2/Fe2+体系,其中H2O2/Fe0体系的处理效果最好。     

Fenton氧化/混凝沉淀协同处理腈纶聚合废水

采用Fenton法处理湿法腈纶聚合废水,考察了H2O2投加量、Fe2+投加量、p H和反应时间等因素对氧化和混凝作用去除废水污染物的影响,并分析了废水可生化性和特征污染物的变化。结果表明,Fenton法可以有效去除废水中有机污染物,在初始p H为3.0,Fe2+投加量为15.0 mmol/L,H2O2投加量为90.0 mmol/L的条件下,反应120 min后废水COD去除率可以达到56.8%,其中氧化和混凝作用对应的去除率分别为43.3%和13.5%;处理后废水的BOD5/COD由0.24升高至0.43;处理后废水中丙烯腈以及其他多数有机污染物能被有效去除。     

絮凝-Fenton试剂氧化处理印染废水

采用Fenton试剂对某染袜厂2种印染废水(印染红和印染蓝)进行处理。考察了硫酸亚铁投加量、双氧水投加量、反应时间及pH值对印染废水的色度及COD去除率的影响,通过正交实验确定了Fenton试剂处理该废水的最佳操作条件为:反应时间30 min、双氧水(30%)投加量4 mL/L、硫酸亚铁投加量300 mg/L、pH值为4左右。在最佳条件下,印染蓝废水经氧化处理后COD去除率大于80%,色度去除率95%以上;印染红废水需经絮凝预处理后再用Fenton试剂氧化处理,其脱色率达到了99.6%,COD去除率为91.2%,出水COD浓度为96 mg/L,可达标排放。     

生化-Fenton氧化联合工艺处理石化净化水的回用

净化水是经过一定预处理的石化废水,具有很高的回用价值,为此采用生化-Fenton联合工艺对净化水进行了处理,研究了初始pH、反应温度、H2O2与Fe2+的摩尔投加比、投加量和反应时间等因素对废水COD去除率的影响。结果表明,Fenton氧化反应可有效去除生化处理出水中的COD,在H2O2(30%)投加量为6.34 m L/L,H2O2与Fe2+的摩尔投加比为5∶1,pH值为4,温度30℃,反应时间2h条件下,废水COD的去除率可达79.7%。GC-MS分析结果表明,Fenton氧化反应对难降解有机污染物具有较好的去除效果,同时可有效提高废水的可生化性,B/C比最大可提升至0.58,氧化出水经生化处理后的剩余COD可降至77.9 mg/L,达到工业回用水标准。     

超声波/Fenton处理含酚废水的影响因素

实验研究主要影响因素对超声波/Fenton试剂处理苯酚废水效果的影响,确定工艺参数。以人工配制的模拟苯酚废水为实验水样,通过静态实验研究p H值、Fe SO4·7H2O投加量、H2O2投加量和超声时间对苯酚和COD去除率的影响。研究结果表明,对于苯酚浓度为200 mg/L,COD为476.6 mg/L苯酚废水,在实验用水量为1 000 m L,p H值为6,Fe SO4·7H2O投加量为800 mg/L,H2O2投加量为Qth,超声时间为30 min的条件下,苯酚去除率可达到92.27%,COD去除率可达到82.48%,处理后苯酚浓度为14.80 mg/L,COD为83.50 mg/L。p H值、Fe SO4·7H2O投加量、H2O2投加量和超声时间对超声/Fenton工艺处理苯酚废水均有较显著地影响,工程应用时应给予足够的重视。     

Fenton氧化法深度处理抗生素废水二级出水

采用Fenton氧化法对青霉素和土霉素混合废水二级处理出水进行深度处理,通过正交和单因素实验研究了废水初始反应pH值、H2O2投加量、Fe2+/H2O2摩尔比及反应时间等因素对废水处理效果的影响。实验结果表明,Fenton氧化法处理的最佳反应条件为:初始pH值4、H2O2(30%)投加量50 mL/L、Fe2+/H2O2摩尔比1/20和反应时间60 min,处理后出水COD小于120 mg/L,COD去除率在75%以上,急性毒性(HgCl2毒性当量)小于0.07 mg/L,满足《发酵类制药工业水污染物排放标准》(GB21903-2008)表2标准要求。     

零价铁Fenton技术处理含聚乙烯醇的印染退浆废水

采用零价铁Fenton技术处理含聚乙烯醇(PVA)的印染退浆废水。通过单因素实验和正交实验,考察了初始pH、H2O2投加量、铁屑粒径及投加量和反应时间对实验结果的影响。结果表明,初始pH和H2O2投加量对处理效果影响很大。最佳反应条件是初始pH=4.0,H2O2投加量为100mmol/L,铁屑(粒径为1~3mm)投加量为15g/L,反应时间为30min。在该条件下,出水PVA质量浓度为0.9mg/L,PVA去除率为99.9%,COD去除率为23.6%,BOD5/COD由0.12升高至0.34,可生化性明显提高。无论从处理效果考虑还是从成本考虑,零价铁Fenton技术都优于传统Fenton技术。     

CuO/C-Al_2O_3催化剂处理印染废水的试验研究

采用浸渍—焙烧法制备了CuO/C-Al2O3催化剂,以H2O2为氧化剂,考察催化剂投加量、氧化剂投加量、pH、温度和反应时间等因素对印染废水中色度和COD去除效果的影响。结果表明,利用CuO/C-Al2O3可有效提高H2O2对印染废水的处理效果,COD的去除率可达到82%,色度的去除率可达到98%;本试验装置最佳的处理条件为反应温度60℃、pH 4、H2O2投加量80 mL/L、催化剂投加量40g/L、反应时间60min。     

UV-Fenton体系预处理四氢呋喃废水实验研究

采用UV-Fenton体系预处理四氢呋喃废水,实验结果表明,pH值、反应时间、Fe2+和H2O2投加量等因素对处理效果有较大的影响。实验确定的最佳反应条件为:原水pH=5,Fe2+投加量2.5 mmol/L,H2O2投加量12 mmol/L,反应时间90 min,连续曝气,在此条件下,COD去除率可达85%左右。经UV-Fenton体系处理后,废水的B/C值由0.16增至0.47,可生化性提高,可满足后续生化处理的要求。     

高硬度富锶地下水的软化沉淀-超滤膜联用工艺

针对一种高硬度富锶地下水,分别采用石灰和石灰-碳酸钠两种方法,利用药剂软化/超滤膜工艺对其进行软化处理,同时考察了药剂投量对出水锶含量的影响。结果表明,采用石灰软化/超滤膜法,Ca(OH)2最佳投加量为270 mg/L时,出水总硬度(以CaCO3计)由287.12 mg/L降低到96.44 mg/L,硬度去除率为66.41%,出水锶含量也由原水中的0.37 mg/L下降为0.21 mg/L;而采用石灰-碳酸钠软化/超滤膜法,Ca(OH)2和Na2CO3最佳投加量分别为270 mg/L、160mg/L时,出水总硬度降低到60.34 mg/L,硬度去除率达78.98%,锶含量仅为0.02 mg/L。2种处理方法出水总硬度均达到预期目标,石灰软化/超滤膜法可使出水锶含量满足富锶水的要求,而石灰-碳酸钠软化/超滤膜法则造成了对人体有益微量元素锶的大量损失。     

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.     

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.     

Influence of crop residues on trifluralin mineralization in a silty clay loam soil

Trifluralin is typically applied onto crop residues (trash, stubble) at the soil surface, or onto the bare soil surface after the incorporation of crop residues into the soil. The objective of this study was to quantify the effect of the type and amount of crop residues in soil on trifluralin mineralization in a Wellwood silty clay loam soil. Leaves and stubble of Potato (Solanum tuberosum) (P); Canola (Brassica napus) (C), Wheat (Triticum aestivum) (W), Oats (Avena sativa), (O), and Alfalfa (Medicago sativa) (A) were added to soil microcosms at rates of 2%, 4%, 8% and 16% of the total soil weight (25 g). The type and amount of crop residues in soil had little influence on the trifluralin first-order mineralization rate constant, which ranged from 3.57E-03 day^?1 in soil with 16% A to 2.89E-02 day^?1 in soil with 8% W. The cumulative trifluralin mineralization at 113 days ranged from 1.15% in soil with 16% P to 3.21% in soil with 4% C, again demonstrating that the observed differences across the treatments are not of agronomic or environmental importance.     

Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.