螯合沉淀法处理电镀废水的工业实践

介绍了一个采用螯合沉淀法处理电镀废水的典型工业实例.在工业装置上,进行了氢氧化钠、硫化钠和DT-CR去除重金属离子效果的对比,讨论了DTCR的加入量与处理成本的关系和pH值对DTCR用量的影响.结果表明,将废水的pH值调至8.0～8.5后再加DTCR,可以使DTCR的使用量最少,处理成本最低;此法对重金属离子的去除效果远优于传统化学沉淀法.     

以改进的化学沉淀法处理硫酸铵废水

针对MAP化学沉淀法处理氨氮废水中存在的问题。如处理成本高、处理后的废水中磷浓度高，对化学沉淀法进行了改进研究，考察Mg^2＋以外的二价金属离子（Ni^2＋，Mn^2＋，Zn^2＋，Cu^2＋，Fe^2＋）在磷酸根作用下对氨氮的去除效果。针对废水中磷浓度高的问题，进行了MAP沉淀法的条件优化实验。结果表明。通过体系pH值和沉淀剂投加比例的合理控制，可以使在高浓度氨氮废水在出水氨氮浓度达标的同时，实现废水中的氮磷浓度同时控制；针对NaOH作pH调节剂成本过高，而以Ca（OH）2作pH调节剂时，钙离子严重影响MAP沉淀效果。对硫酸铵废水体系提出了CaSO4沉淀——MAP沉淀新工艺。结果表明，这一改进完全可以消除钙离子的影响。实现以石灰取代传统的NaOH调节剂。     

pH对中和沉淀法处理涂装废水效果影响及作用机理

采用中和沉淀法对涂装废水进行处理,研究了pH(4~12)对废水中总磷、COD、浊度、总铁、总镍、总锰等12种主要污染物去除率的影响,并结合絮体粒度分布、Zeta电位、絮体形貌和XRD图谱等表征方式对COD和重金属的去除机理进行了分析。研究结果表明,在综合考虑后续生化处理需要和处理成本的条件下,中和沉淀法处理涂装废水的适宜pH为8,废水经处理后所有重金属离子浓度和总磷浓度均达到《污水排入城镇下水道水质标准》(GB/T 31962-2015)B级标准,COD、浊度和氨氮的去除率分别为30.05%、46.51%和72.49%。无机污染物去除的主要途径包括磷酸盐沉淀形成、氢氧化物沉淀形成和吸附絮凝作用。COD的去除机制随着pH的变化而不同,在pH=2.18~8时,COD的去除主要由于不溶性金属络合物的形成、电性中和与卷扫网捕,在pH=10~12时,主要的作用机制为氢氧化物絮体对其的吸附作用和卷扫网捕。这对中和沉淀法工艺处理实际涂装废水有重要的指导意义。     

各种影响因子对电解法预处理医药废水的影响研究

探讨了电解法预处理医药废水时停留时间、电解电压、废水初始浓度、温度和废水pH值等影响因子对去除色度、COD和提高废水可生化性等处理效果的影响,并考察了其应用于工业实际废水处理的可行性.实验结果表明:电解法更适合高浓度医药废水的处理,色度的去除率可达到90%以上;电解时间宜控制在40～60 min;电解电压越高,废水COD和色度去除效果越好;在实验温度范围内,温度对色度和COD去除率的影响不大;废水pH值为7.5时电解效果最佳,工程运用宜控制在6～9之间.     

各种影响因子对电解法预处理医药废水的影响研究

探讨了电解法预处理医药废水时停留时间、电解电压、废水初始浓度、温度和废水pH值等影响因子对去除色度、COD和提高废水可生化性等处理效果的影响，并考察了其应用于工业实际废水处理的可行性。实验结果表明：电解法更适合高浓度医药废水的处理，色度的去除率可达到90％以上；电解时间宜控制在40-60min；电解电压越高，废水COD和色度去除效果越好；在实验温度范围内，温度对色度和COD去除率的影响不大；废水pH值为7．5时电解效果最佳，工程运用宜控制在6—9之间。     

腐殖质络合体系中水溶性铁的絮凝法去除

针对天然水体及一些废水中铁主要以腐殖质络合态存在,用常规化学碱沉淀法难以有效将其去除的问题,该文研究了以氯化铝为絮凝剂的絮凝沉淀法对含有富里酸络合态铁(FA-Fe)的模拟废水及垃圾渗滤液中水溶性铁的去除效果影响,初步探讨了铝盐对富里酸络合体系中水溶性铁的去除作用机理。结果表明:在处理模拟废水时,水溶性铁的去除率随氯化铝投加量的增加而增大,随废水中FA浓度的增加而减少,腐殖酸(HA)的加入仅对游离态Fe3+的去除有促进作用;在pH为8.0、氯化铝投加量为1.0 g·L~(-1)的条件下处理100 mg·L~(-1)FA和10 mg·L~(-1)Fe3+配成的模拟废水时,水溶性铁的去除率可达94.7%,比常规碱沉淀法提高了11.1%。在pH为8.0、氯化铝投加量为5.0 g·L~(-1)、适量投加HA的条件下处理垃圾渗滤液,水溶性铁的去除率最高可达95.1%。在絮凝过程中,铝盐主要通过形成不溶性聚合物吸附FA-Fe来提高水溶性铁的去除效率。     

UV/H_2O_2协同光降解处理酒石酸镍废水

含镍电镀废水中酒石酸的存在,使得废水中总镍无法通过化学沉淀法去除,无法满足达标排放要求。采用UV/H_2O_2光降解法处理酒石酸镍体系废水,考察了不同反应p H值、过氧化氢投加量、光照时间对酒石酸镍体系络合废水的处理效果。实验结果表明:UV/H_2O_2法对酒石酸镍体系废水有很好的协同处理效果,光降解过程呈拟一级动力学过程;优化的酒石酸镍废水处理工艺为反应p H值3.0,30%过氧化氢投加量2 m L·L~(-1),15 W功率紫外灯光照下反应120 min,在优化的工艺条件下,采用化学沉淀法去除水中镍,处理后电镀废水中总镍可满足《电镀污染物排放标准》(GB 21900-2008)中0.5 mg·L~(-1)要求。     

中和/沉淀法处理含氰电镀废水的问题

在电镀废水中常见的金属离子有 Zn、Cu、Ni、Cr 和 Cd 等几种。常用的去除方法有沉淀法、氧化还原法、离子交换法和萃取法。如果溶液中的铬是六价,则必须先把它还原成三价铬。含氰废水,应该先把氰去掉。这一点目前尚未充分引起人们注意。本文就沉淀法处理含氰电镀废水的问题进行讨论。沉淀法处理重金属废水,简易、投资省、可行性也好。所用沉淀法有:氢氧化物沉淀 pH 8—11碳酸盐沉淀投加白云石粉硫化物沉淀投加 Na_2S 或 H_2S中和沉淀法的原理是控制溶液的 pH 值,使金属离子形成氢氧化物沉淀。所需 pH 值,可从金属氢氧化物的溶度积求算。     

混凝沉淀法深度处理酒精废水

采用混凝沉淀法对酒精废水进行深度处理实验及放大应用研究。结果表明，混凝剂种类、投加量、pH值及沉降时间对处理效果都起着重要作用。通过正交实验确定最优化组合，即聚合硫酸铝投加量为60mg／L，pH为8．0左右，沉降时间为90min条件下，废水COD去除率达41．91％；浊度去除率达46．15％；NH3-N去除率达49．61％。混凝沉淀法处理酒精废水可有效减轻后续膜处理工艺负荷，有助于提高回用水质。     

钙型天然斜发沸石去除猪场废水中营养物的实验研究

以钙型天然斜发沸石为实验材料,研究反应时间、沸石投加量、pH值、有机物浓度等因素对去除实际猪场废水中氨氮、磷和COD效果的影响。研究表明,钙型天然斜发沸石对实际猪场废水的处理效果良好,在沸石投加量为250 g/L、pH值为8.0～9.0、反应时间为24 h的条件下,钙型天然斜发沸石对氨氮、磷和COD的去除率分别达到96%、97%和84%。pH值对钙型天然斜发沸石氨氮去除效果影响不大,但对磷和COD的去除效果影响较显著;当pH值由6.0升高至7.0时,磷的去除率由63%迅速升高至93%,pH值为8.0以上时,去除率接近95%;随pH值的升高,COD的去除率先升高后降低,在pH值为8.0时,去除率达到最大,为84%。废水COD浓度对氨氮去除率的影响基本可忽略,但对磷的去除有轻微的抑制作用。采用固定滤柱过滤时,水力负荷控制在375 mL/h以下,氨氮、磷和COD的去除效果较好。     

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.