次氯酸钠氧化—磷酸铵镁沉淀法处理草甘膦废水并回收磷

针对草甘膦废水处理与磷回收难题,研究了次氯酸钠氧化草甘膦与磷酸铵镁沉淀法回收磷工艺的可行性。实验结果表明,次氯酸钠氧化草甘膦的最佳工艺条件为:次氯酸钠加入量109 g/L,溶液pH为9.0,氧化时间20 min。次氯酸钠氧化草甘膦的主要降解途径为:C—N键断裂生成羟基乙酸和乙酸;C—P键断裂生成磷酸(主要反应)。正交实验得到的磷酸铵镁沉淀法回收磷的最佳工艺条件为溶液pH 9.0、镁磷摩尔比1.2、氮磷摩尔比1.4、反应时间15 min,在此条件下磷酸盐回收率达99.3%。XRD图谱证实所得固体主要成分为磷酸铵镁。     

Treatment of Perchlorate‐Contaminated Groundwater Using Highly Selective,Regenerable Ion‐Exchange Technology: A Pilot‐Scale Demonstration

Treatment of perchlorate‐contaminated groundwater using highly selective, regenerable ion‐exchange technology has been recently demonstrated at Edwards Air Force Base, California. At an influent concentration of about 450 μg/l ClO₄^?, the bifunctional anion‐exchange resin bed treated approximately 40,000 empty bed volumes of groundwater before a significant breakthrough of ClO₄^? occurred. The presence of relatively high concentrations of chloride and sulfate in site groundwater did not appear to affect the ability of the bifunctional resin to remove ClO₄^?. The spent resin bed was successfully regenerated using the FeCl₃^?HCl regeneration technique recently developed at the Oak Ridge National Laboratory, and nearly 100 percent of sorbed ClO₄^? was displaced or recovered after elution with as little as about two bed volumes of the regenerant solution. In addition, a new methodology was developed to completely destroy ClO₄^? in the FeCl₃^?HCl solution so that the disposal of perchlorate‐containing hazardous wastes could be eliminated. It is therefore anticipated that these treatment and regeneration technologies may offer an efficient and cost‐effective means to remove ClO₄^? from contaminated groundwater with significantly reduced generation of waste requiring disposal. © 2002 Wiley Periodicals, Inc.     

Factors affecting sodium hypochlorite extraction of CCA from treated wood

Significant amounts of chromated copper arsenate (CCA) treated wood products, such as utility poles and residential construction wood, remain in service. There is increasing public concern about environmental contamination from CCA-treated wood when it is removed from service for reuse or recycling, placed in landfills or burned in commercial incinerators. In this paper, we investigated the effects of time, temperature and sodium hypochlorite concentration on chromium oxidation and extraction of chromated copper arsenate from CCA-treated wood (Type C) removed from service. Of the conditions evaluated, reaction of milled wood with sodium hypochlorite for one hour at room temperature followed by heating at 75 °C for two hours gave the highest extraction efficiency. An average of 95% Cr, 99% Cu and 96% As could be removed from CCA-treated, milled wood by this process. Most of the extracted chromium was oxidized to the hexavalent state and could therefore be recycled in a CCA treating solution. Sodium hypochlorite extracting solutions could be reused several times to extract CCA components from additional treated wood samples.     

Surfactant‐Oxidant Co‐Application for Soil and Groundwater Remediation

In situ chemical oxidation (ISCO) typically delivers oxidant solutions into the subsurface for contaminant destruction. Contaminants available to the oxidants, however, are limited by the mass transfer of hydrophobic contaminants into the aqueous phase. ISCO treatments therefore often leave sites with temporarily clean groundwater which is subject to contaminant rebound when sorbed and free phase contaminants leach back into the aqueous phase. Surfactant Enhanced In situ Chemical Oxidation (S‐ISCO^®) uses a combined oxidant‐surfactant solution to provide optimized contaminant delivery to the oxidants for destruction via desorption and emulsification of the contaminants by the surfactants. This article provides an overview of S‐ISCO technology, followed by an implementation case study at a coal tar contaminated site in Queens, New York. Included are data points from the site which demonstrate how S‐ISCO delivers desorbed contaminants without uncontrolled contaminant mobilization, as desorbed and emulsified contaminants are immediately available to the simultaneously injected oxidant for reaction. ©2016 Wiley Periodicals, Inc.     

Treatment of MTBE‐Contaminated Waters with Fenton's Reagent

Methyl tertiary‐butyl ether (MTBE) is commonly used as a fuel additive because of its many favorable properties that allow it to improve fuel combustion and reduce resulting concentrations of carbon monoxide and unburnt hydrocarbons. Unfortunately, increased production and use have led to its introduction into the environment. Of particular concern is its introduction into drinking water supplies. Accordingly, research studies have been initiated to investigate the treatment of MTBE‐contaminated soil and groundwater. The summer 2000 issue of Remediation reported the results of an initial study conducted by the authors to evaluate the treatment of MTBE using Fenton's reagent. In this follow‐up study, experiments were conducted to further demonstrate the effectiveness of using Fenton's reagent (H₂O₂:Fe⁺²) to treat MTBE‐contaminated groundwater. The concentration of MTBE was reduced from an initial concentration of 1,300 μg/l (14.77 μ moles) to the regulatory level of 20 μg/l (0.23 μ moles) at a H₂O₂:Fe⁺² molar ratio of 1:1, with ten minutes of contact time and an optimum pH of 5. The by‐products, acetone and tertiary butyl alcohol, which are always present in MTBE in trace amounts, were not removed even after 60 minutes of reaction time. © 2002 Wiley Periodicals, Inc. *     

两级氧化法处理油田压裂返排液

采用两级氧化法处理油田压裂返排液。在次氯酸钠、次氯酸钙、过氧化氢、高锰酸钾4种氧化剂中,次氯酸钠的氧化效果最好。以次氯酸钠作为一级氧化剂,进行一级氧化处理;再分别采用次氯酸钙、过氧化氢、高锰酸钾进行二级氧化处理。在次氯酸钠加入量为40mL/L、一级氧化反应时间为30min、二级氧化反应时间为30min、初始废水COD为3976mg/L的条件下,二级氧化剂过氧化氢、次氯酸钙、高锰酸钾的最佳加入量分别为80,40,40mL/L,对应的COD去除率分别为82.60%,71.50%,83.50%。     

In situ chemical oxidation of residual LNAPL and dissolved‐phase fuel hydrocarbons and chlorinated alkenes in groundwater using activated persulfate

A treatablity study (TS) was conducted to evaluate the efficacy of in situ chemical oxidation (ISCO) using activated persulfate, alone and in combination with air sparging (AS), for treating a source area contaminated with residual light nonaqueous‐phase liquid (LNAPL), dissolved‐phase fuel hydrocarbons (HCs), and dissolved‐phase chlorinated alkenes at Edwards Air Force Base (AFB), California. The TS was implemented in two phases. Phase I included injecting a solution of sodium persulfate and sodium hydroxide (NaOH) into groundwater via an existing well where residual LNAPL and dissolved‐phase contaminants were present. Because the results of Phase I indicated a limited distribution of the activated persulfate, Phase II was performed to assess whether AS could enhance the distribution of the sodium persulfate. Each phase was followed by groundwater monitoring and sampling at the injection well and at three monitoring wells, located 20 to 44 feet from the injection well. Results from Phases I and II of the TS indicated that (1) alkaline‐activated persulfate was effective in promoting the dissolution of LNAPL and the degradation of dissolved‐phase contaminants, but only at the injection well; (2) the addition of AS was effective in enhancing the radius of persulfate distribution from less than 20 feet to greater than 44 feet, and (3) persulfate alone (i.e., not in an activated state) was effective in reducing the concentrations of dissolved‐phase fuel HC and chlorinated alkenes. © 2009 Wiley Periodicals, Inc.     

不同氧化法对模拟聚合物驱废水降黏效果的影响

分别采用UV-Fenton试剂氧化法、次氯酸钙氧化法和二氧化氯氧化法处理模拟聚合物驱废水,考察了各工艺条件对废水降黏效果的影响。实验结果表明:在初始废水pH为7、反应温度为50℃、反应时间为20 min的条件下,UV-Fenton试剂氧化法适宜的H2O2加入量为1 mmol/L,n(H2O2)∶n(Fe2+)=10,处理后废水降黏率达65.7%;次氯酸钙氧化法适宜的次氯酸钙加入量为500 mg/L,处理后废水降黏率达81.7%;二氧化氯氧化法适宜的二氧化氯加入量为100 mg/L,处理后废水降黏率为40.9%。3种氧化法对模拟聚合物驱废水的降黏率大小顺序为:次氯酸钙氧化法>UV-Fenton试剂氧化法>二氧化氯氧化法。     

Two-stage Sequential Electrochemical Treatment of Nitrate Brine Wastes

Nitrates in concentrated brines can be electrochemically reduced in the cathodic chamber of a split-cell electrochemical reactor with formation of ammonium (and small amounts of nitrite). Fortunately, ammonium may be electrochemically oxidized to nitrogen gas in the anodic reaction chamber if a coupled sequential process is used. The presence of chloride in the brine waste is an important consideration in oxidative electrochemical processes, however, because it cycles through oxidized and reduced states at the electrode surfaces and in the bulk solution. Electrochemical oxidation converts chloride ions to “active chlorine” species with additional oxidizing capability (chlorine, hypochlorous acid and hypochlorite – essentially bleach), as well as to chlorates, depending on the reaction conditions. The production of these active species improves treatment performance in the ammonium oxidation phase since oxidation is no longer limited to the electrode surface. However, the process must be engineered to minimize loss of process efficiency due to parasitic side reactions (chloramines and chlorate). In this study, two-stage batch electrolysis was conducted using a three-electrode (copper anode, platinum-coated titanium cathode, silver/silver chloride reference) electrochemical cell, with the anodic and cathodic chambers separated by a Nafion 117 membrane. Treatment of nitrate and ammonium was tested with and without the presence of chloride in the waste. No significant difference was observed in cathodic nitrate reduction with chloride present or absent. However, the presence of chloride in the solution favored overall soluble nitrogen elimination upon oxidation. Increasing applied current increased production of undesirable byproducts (especially chlorate).     

Decomposition of dichloromethane and in situ alkali absorption of resulting halogenated products by a packed-bed non-thermal plasma reactor

For an effective decomposition and removal of organic halogenated compounds, a packed-bed non-thermal plasma reactor with in situ absorption of the resulting halogenated products by alkaline sorbent incorporated was proposed. In the plasma reactor, α-Al₂O₃ particles of 1 and 3 mm (mean particle diameter) were packed as solid dielectric medium to enhance the plasma power density in the reactor. Further, alkaline sorbent of Ca(OH)₂ was doped onto the surface of α-Al₂O₃ particles, in order to remove halogenated products by in situ absorption with Ca(OH)₂. A high-voltage and high-frequency pulsed power of −15 to 15 kV and 1 kHz was applied to the wire electrode of the plasma reactor by means of a DC power source. In the present study, as the sample of an organic halogenated compound that is most popularly used, we selected dichloromethane (CH₂Cl₂), and 500 ppm of the initial concentration of CH₂Cl₂ was fed into the reactor accompanied by air at a fixed flow rate of 500 × 10⁻⁶ m³ min⁻¹ at room temperature. As a result, it was recognized that the amount of CH₂Cl₂ decomposed by non-thermal plasma in an α-Al₂O₃ particle bed increased with an increase in plasma input power. The ratio of decomposition of CH₂Cl₂ was almost 100% at 13 kV of electric power and 1 kHz frequency, and CO₂, CH₃Cl, COCl₂, HCl, and Cl₂ were observed as the major reaction products. On the other hand, when CH₂Cl₂ was introduced into the plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ were packed, the ratio of decomposition of CH₂Cl₂ became higher, compared to the case that α-Al₂O₃ particles were not doped with Ca(OH)₂. Moreover, there were no halogenated by-product gases detected in the outlet gas from the reactor. As the solid reaction products, CaClOH and Ca(ClO)₂·4H₂O were detected on Ca(OH)₂ by X-ray diffraction. From these findings, it was recognized that CH₂Cl₂ was decomposed more effectively without producing unwanted harmful halogenated by-products in the proposed non-thermal plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ sorbent were packed.     

次氯酸钠氧化预处理草甘膦生产废水

利用次氯酸钠对草甘膦生产废水进行预处理，废水ｐＨ对处理效果影响不大，可将次氯酸钠直接投入到原碱性废水中，在其用量相当理论量的４０％、氧化时间为４ｈ时，草甘膦的去除率为９８％。预处理后的废水对厌氧消化过程不再产生抑制作用。     

Impact of iron concentration and ph on zero‐valent iron dechlorination of DDT for brownfields

Soil contamination with persistent pesticides such as dichloro‐diphenyl‐trichloroethane (DDT) is a major issue at many brownfield sites. A technology that can be used to treat DDT‐contaminated soil using surfactants is to enhance the migration of the contaminants from the soil phase to the liquid phase, followed by the dechlorinating of the mobilized DDT in the liquid phase using zero‐valent iron (ZVI). The DDT degradation using ZVI occurs under anaerobic conditions via reductive reactions. The effect of the iron concentration on the dechlorination rate is assessed in the range of 1 to 40 percent (weight to volume) for remediation of a DDT‐contaminated site in Ontario, Canada. The optimum percentage of iron is found to be 20 percent at which the dechlorination rates of DDT and 1,1‐dichloro‐2,2‐bis(p‐chlorophenyl)ethane (DDD) were 4.5 and 0.6 mg/L/day, respectively. While mixing of the reaction solution is shown to be important in providing the iron surface available for the dechlorination reaction throughout the reaction solution, there is no significant difference between batch and fed‐batch mode of adding iron to the dechlorination process. Low pH values (pH = 3) increased the dechlorination rates of DDT and DDD to 6.03 and 0.75 mg/L/day, respectively at a 20 percent iron concentration, indicating increased dechlorination rates in acidic conditions. © 2010 Wiley Periodicals, Inc.     

Evaluation of a soil‐amendment process demonstration for reducing the bioavailability of lead

The U.S. Environmental Protection Agency (EPA) evaluated an in‐situ application of a soil‐amendment process at a residential site that was contaminated with lead. The goal of the evaluation was to determine if the soil‐amendment process resulted in lower concentrations of bioavailable lead in the contaminated soils. The relative bioavailability of lead (bioaccessible lead) was measured by an in vitro test procedure that uses a highly acidic extraction procedure to simulate human digestive processes. The soil‐amendment demonstration showed that the 11.2 percent mean reduction in bioavailable lead concentration between untreated and treated soils was not statistically different. © 2002 Wiley Periodicals, Inc.     

Preliminary Studies on Converting Agricultural Waste into Biodegradable Plastics—Part IV: Polysaccharide Containing Natural Materials

Corn distillers’ dry grain, corncob powder, hardwood powder, and sugar beet pulp were separately anionized by oxidation with sodium hypochlorite in aqueous solution. Solid reaction products instantly precipitated upon admixing each of the above-oxidized materials with soy protein isolate. Infrared spectra and differential scanning calorimetry supported the hypothesis that soy protein isolate complexed with all of the above-oxidized polysaccharides. Reaction products with either oxidized corn distillers’ dry grain or oxidized sugar beet pulp provided hard, brittle pellets with tensile strengths as high as 9.5 MPa, suggesting that these materials could be viable as biodegradable plastics.     

Removal of substituted phenols onto iron‐treated Nostoc sp. biomass

This study explored the possibility of removing 4‐nitrophenol (4‐NP) and 2,4‐dichlorophenol (2,4‐DCP) from water by using a dead blue‐green algae, Nostoc sp., dried and untreated and dried and treated with iron (Fe‐treated with 0.1 M ferric chloride solution for 1 day). The Nostoc sp. untreated and Fe‐treated biomass were used to study the sorption and desorption of 4‐NP and 2,4‐DCP. The effects of solute concentration, ionic strength, and temperature on sorption and desorption in the presence of untreated and treated Nostoc sp. biomass were investigated. The Fe‐treated Nostoc sp. biomass sorbed higher amounts of both 4‐NP and 2,4‐DCP than the untreated biomass. The percent cumulative desorption decreased from 6.41% to 0.28% and 1.84% to 0.19%, respectively, for 4‐NP and 2,4‐DCP for the Fe‐treated biomass. Biosorption of 4‐NP and 2,4‐DCP onto untreated and Fe‐treated Nostoc sp. biomass conformed to Freundlich isotherms. Iron treatment of Nostoc sp. biomass increased the value of ln K from 8.07 to 8.59 for 4‐NP and from 8.04 to 8.51 for 2,4‐DCP but decreased their desorption. An increase in ionic strength (0.003–0.03) increased the biosorption of both substituted phenols and decreased their percent desorption. An increase in temperature in the range of 15–35°C decreased the sorption of 4‐NP and 2,4‐DCP onto both untreated and Fe‐treated Nostoc sp. biomass and increased their desorption, indicating that the biosorption of both substituted phenols onto untreated and Fe‐treated Nostoc sp. biomass was principally a physical process. The results of this study suggest that Fe‐treated dried Nostoc sp. biomass could be explored as an inexpensive and eco‐friendly material for the effective removal of these phenols and, potentially, other chemicals from industrial wastewater and contaminated groundwater.     

声化学氧化－间歇式活性污泥法处理染料废水的研究

介绍了声化学氧化反应机理。采用声化学氧化法作预处理，可使生物难降解的靛兰染料废水的ＢＯＤ＿５／ＣＯＤ由０．２１—０．２３提高到０．４４—０．５１，再经间歇式活性污泥法处理后，各项水质指标均符合ＧＢ８９７８—８８《污水综合排放标准》。     

Removal of Reactive Blue 19 dye from synthetic wastewater using UV/H2O2 and UV/Cl advanced oxidation processes

The textile and dyeing industries are among the largest water-consuming and polluting industries in the world. The most important feature of the textile dyeing industry wastewater is its color, due to the use of colored materials. Most of these dye compounds are resistant to conventional purification methods and their biodegradation is very low through secondary purification processes, resulting in incomplete removal. Therefore, selecting the optimal method to remove these color compounds is essential. In this study, we studied the removal of an organic dye contaminant (Reactive Blue dye 19 [RB19]) using advanced oxidation processes (AOPs). For this purpose, ultraviolet (UV) mercury lamps with a wavelength of 254 nm and a voltage of W16 inside a reactor were used as an energy source. The experiments were performed in a collimated beam reactor inside a dark chamber. Two oxidizers, sodium hypochlorite (NaOCl) and hydrogen peroxide (H₂O₂), were used to remove RB19 from the artificial sewage stream. Removal of RB19 with a concentration of 20 mg/L with variable pH (5, 7, and 9), oxidant concentrations (5, 10, and 20 mg/L), and time (5, 10, 15, and 30 min) were investigated during the processes of photolysis, chemical oxidation (by H₂O₂ and NaOCl), and UV/NaOCl and UV/H₂O₂ AOPs. The photolysis process did not remove the RB19. The highest removal efficiencies of RB19 by chemical oxidation processes with NaOCl and H₂O₂, UV/NaOCl, and UV/H₂O₂ at optimal conditions (pH = 5, [oxidant] = 20 mg/L, RB19 = 20 mg/L, and radiation intensity of 1005 mJ/cm²) were 64.49%, 0.88%, 99.7%, and 13.31%, respectively. These results indicate that the hydroxyl radical was produced, under optimum conditions, more in the acidic medium; thus, the RB19 removal efficiency was higher in the acidic medium. The combination of UV rays with oxidants resulted in the production of more hydroxyl radicals and increased removal efficiency.     

盐酸-次氯酸钙氧化法去除贫泥磷中的黄磷

分别采用次氯酸钙单一体系和盐酸-次氯酸钙复合体系对贫泥磷中的黄磷进行氧化处理,重点考察了盐酸浓度、次氯酸钙加入量、反应温度和反应时间等因素对贫泥磷中黄磷去除率的影响。实验结果表明:与单一次氯酸钙体系相比,盐酸的加入有效地破除了贫泥磷中的胶质结构,盐酸-次氯酸钙复合体系能有效地去除贫泥磷中的黄磷;在反应温度为60℃、盐酸浓度为2.4 mol/L、破胶反应时间为30 min、次氯酸钙加入量为250 g/L、氧化反应时间为3 h的最佳条件下,黄磷的去除率达到99.6%以上。     

Synthetic Media: A Promising New Treatment Technology for 1,4‐Dioxane

1,4‐Dioxane (14DX) is classified as a probable human carcinogen by the US Environmental Protection Agency (EPA), and it has toxic effects on the kidney and liver. EPA's Health Advisory Level (HAL) for 14DX is 0.35 micrograms per liter (μg/L). Accordingly, several states have lowered their drinking water advisory levels and site cleanup levels. The widespread occurrence of 14DX in contaminated groundwater has contributed to a growing demand for remediation services. Treating 14DX is a challenge due to its very low Henry's law constant, low sorption potential, and strong ether linkages. The primary solution for 14DX remediation has been various forms of advanced oxidation processes (AOP), namely pump and treat followed by ex situ treatment with catalyzed ultraviolet light oxidation or ozone‐peroxidation. Many of the available advanced oxidation systems are complex, requiring careful monitoring and maintenance to adjust for variable source water and operating conditions. Synthetic media is a relatively new 14DX treatment technology that overcomes many of the operating challenges faced by existing technologies. AMBERSORB? 560 (AMBERSORB) has recently demonstrated the effective removal of 14DX over a wide range of concentrations and operating conditions, including those created by in situ thermal remediation. Consistent and reliable treatment down to sub‐0.3 μg/L levels differentiates synthetic media technology from other 14DX treatment technologies. AMBERSORB provides a solution to the problem of “stranded capital” by offering a 14DX treatment system capable of meeting regulatory standards today and in the foreseeable future. © 2014 Wiley Periodicals, Inc.     

Ex‐situ efficacy analysis of brine remediation products in clay loam soil

This study evaluated the effectiveness of gypsum and three proprietary products to remediate brine‐contaminated soil. The research objective was to determine if additives could increase plant cover germination in soils without costly prior soil‐washing or dilution techniques. The soil was shredded using a soil shredder equipped with a spray bar to apply the individual treatments of DeSalt Plus, SoilTech, Chlor*rid, and calcium sulfate (gypsum). Treatments were placed in 40‐mm high‐density polyethylene cells and small drainage systems were installed to allow removal of excess water. An initial 10‐point soil composite was taken from bulk untreated soils at a depth of more than 2.5 cm. Five‐point composite samples were collected from the same depth at weekly intervals and analyzed for: electrical conductivity, sodium adsorption ratio, cation exchange capacity, sodium, calcium, magnesium, potassium, chlorides, and pH. The Gapon selectivity coefficient was calculated and utilized to quantify the affinity for binding between ionic alkali salt constituent groups Na⁺, Ca ⁺⁺, and Mg ^++. Soil analysis indicated product‐related improvements in and bioavailability of salts. The nature of the products requires some prior treatment such as soil washing or dilution using clean soil to lower electroconductivity levels and allow the site to vegetate.