Remediation of alpha-methylnaphthalene-contaminated sediments using peroxy acid

Laboratory experiments have been conducted to elucidate the degradation of alpha-methylnaphthalene in lake sediments using an advanced oxidation process (AOP) employing peroxy-acids as oxidizing agents. Abiotic degradation of alpha-methylnaphthalene was observed in sediment samples exposed to a 1:1:1 v/v/v mixture of water/organic acid/hydrogen peroxide solution. Sediment samples were collected from Lake Macatawa (Holland, MI) and ranged in total organic carbon content from 2.1% (sandy sediment sample III) to 12.8% (silty-clay sediment sample I) and surface area, which ranged from 3.2m(2)/g (sandy sediment sample III) to 22.0m(2)/g (silty-clay sediment sample I). Analytical measurements performed by gas chromatography revealed varied rates of degradation, depending on the type of acid and the characteristics of the sediment sample. Within 24h, alpha-methylnaphthalene was reduced to 70% and 100% of its original concentration when propionic acid and acetic acid were used as the organic acids, respectively. The formation of products was explored using a gas chromatograph equipped with a mass spectrometer and indicated mainly the formation of lower molecular weight compounds, such as alkyl chains. This AOP method of PAH degradation in sediment/liquid slurry was fast acting and products were most likely biodegradable.     

Precipitation of enzyme-catalyzed phenol oxidative coupling products: background ion and pH effects

The effects of solution pH and background ion types and concentrations on the precipitation of polymeric products generated in the catalytically facilitated oxidative coupling of phenol were investigated systematically. The coupling reactions mediated by horseradish peroxidase were carried out under a specific predetermined experimental condition. Acids, bases, and/or selected salts of ions having different valences were then added to the resulting product solutions to adjust pH and ionic conditions. Subsequent analyses of product distributions between dissolved and precipitated forms revealed that ionic conditions and pH significantly impact those distributions, and associated mechanisms are discussed. The findings reported will assist feasibility assessments and process optimization with respect to engineering applications of catalyzed oxidative coupling reactions for wastewater treatment and soil decontamination.     

Ozonation products of triclosan in advanced wastewater treatment

Triclosan is an antimicrobial agent widely used in many household and personal care products. Widespread use of this compound has led to the elevated concentrations of triclosan in wastewater, wastewater treatment plants and receiving waters. In this study removal of triclosan by aqueous ozone was investigated and the degradation products formed during ozonation of an aqueous solution of triclosan were analyzed by GC-MS and HPLC-MS/MS. The following transformation products have been identified: 2,4-dichlorophenol, chloro-catecol, mono-hydroxy-triclosan and di-hydroxy-triclosan during treatment process. Cytotoxicity and genotoxicity of pure triclosan and 2,4-dichlorophenol have been investigated and the results showed reduced genotoxic effects after ozonation, though the respective chlorophenol is harmful to aquatic organisms.     

Ozone and oxygen induced oxidative coupling of aqueous phenolics

The present research concerns results pertaining to oxidative coupling/polymerization of aqueous phenolics by ozone and oxygen. Catechol, resorcinol, catechin, gallic acid and tannic acid were all found to undergo oxidative coupling on ozone/oxygen treatment as evidenced by bathychromic shifts, increased color intensities, functional group analysis, size exclusion chromatography and mechanistic considerations. An oxidative coupling pathway was favored by conditions of high pH and low ozone dose. Reactions of phenolics with ozone were accomplished in a shorter time frame than those with oxygen. Mechanisms consistent with oxidative coupling are presented and the ramifications of the research to natural water systems and water treatment are discussed.     

Electrochemical treatment of industrial wastewater containing 5-amino-6-methyl-2-benzimidazolone: toward an electrochemical-biological coupling

We studied the electrochemical oxidation, on Pt anodes, of industrial wastewaters containing 5-amino-6-methyl-2-benzimidazolone (AMBI). Electrolysis of this non-biodegradable effluent produces simultaneous oxidation of AMBI and chloride ions. Highly oxidative chlorine intermediate species further boost the degradation of AMBI. Solution temperature, pH and current density affect little the degradation of AMBI. At our best conditions, AMBI was 100% degraded in 45 min. However, because the reaction intermediates exhibited high toxicity and non-biodegradability, the electrolysis had to continue for 3 more hours in order to obtain a biocompatible solution. Then, complete mineralization of the outputs from the electrolytic cells was readily achieved in a fixed bed biological reactor.     

消防接口产品质量改进的探讨

介绍了我国消防接口产品的现状，阐述了消防接口生产工艺、技术要求的质量改进，对指导生产企业改进和提高消防接口产品质量起到积极的作用。     

A reliable monitoring of the biocompatibility of an effluent along an oxidative pre-treatment by sequential bioassays and chemical analyses

A new approach to assess biocompatibility of an effluent, based on combination of different bioassays and chemical analyses, has been tested using a mixture of four commercial pesticides treated by a solar photo-Fenton as target effluent. A very fast elimination of the pesticides occurred (all of them were below detection limit at t_30W = 36 min), but mineralisation was a more time-consuming process, due to the formation of organic intermediates and to the presence of solvents, as shown by GC-MS analysis. Measurements based on activated sludge indicated that detoxification was coincident with the removal of the active ingredients, while more sensitive Vibrio fischeri bacterium showed significant toxicity until the end of the experiment, although the effluent might be compatible with biological processes. Biodegradability of the solutions was enhanced by the photochemical process, to reach BOD₅/COD ratios above 0.8. Longer time bioassays, such as the Zahn-Wellens' test, support the applicability of coupling photochemical with activated sludge-based biological processes to deal with these effluents.     

Impact of soil-chemical interactions on the bioavailability of naphthalene and 1-naphthol

The bioavailability of sorbed naphthalene and 1-naphthol was determined for two sandy soils differing primarily in organic matter content. Different sorption conditions were maintained over a 2 d equilibration period to estimate the extent that oxidative coupling contributed to the strong binding of these compounds to the soils. Weakly sorbed test compounds were removed through 50 successive water extractions and the bioavailability of the remaining sorbed fraction was determined by the addition of aerobic, test compound-degrading bacteria to soil slurry reactors. Soils were then incubated under aerobic conditions for 90 d. Biodegradation rates were determined by monitoring ¹⁴CO₂ evolution and the soil-associated non-mineralized residue was measured by combustion of the soil after the 90 d period. Successive water extractions removed 38.7–64.3% of 1-naphthol and 62.4% of naphthalene from the high NOM soil and 67.2–82.9% of 1-naphthol and 72.3% of naphthalene from the low NOM soil. Of the remaining material, 5.7–16.9% of 1-naphthol and 73.3% of naphthalene in the high NOM soil and 3.7–6.0% of 1-naphthol and 34.2% of naphthalene in the low NOM soil was mineralized after 90 d. In contrast, >85% of both test compounds were mineralized in the absence of soil. Experimental evidence suggests that oxidative coupling reactions limited the bioavailability of 1-naphthol in both soils. Naphthalene bioavailability was not greatly limited because it can not directly participate in strong binding reactions.     

多相催化臭氧氧化法处理甲萘酚废水

以活性炭为载体、钾为助催化剂,采用浸渍法制备了Cu-K/AC催化剂,并考察了该催化剂催化臭氧氧化处理甲萘酚废水的效能.结果表明,当甲萘酚废水的COD为3 000 mg/L、含油量为120 mg/L时,在室温、pH=3、反应时间为120 min、催化剂投量为100 g/L、臭氧流量为5.2mg/min的条件下,催化臭氧氧化对COD及油类物质的去除率分别达到了93%和98%;臭氧氧化和催化臭氧氧化对COD的降解过程均符合表观一级反应动力学方程.     

Photodegradation study of three dipyrone metabolites in various water systems: identification and toxicity of their photodegradation products

The photochemical behaviour of three relevant metabolites of the analgesic and antipyretic drug dipyrone, 4-methylaminoantipyrine (4-MAA), 4-formylaminoantipyrine (4-FAA) and 4-acetylaminoantipyrine (4-AAA), was evaluated under simulated solar irradiation (Suntest system). For 4-MAA, different aqueous solutions (synthetic seawater, freshwater and Milli-Q water) as well as different operational conditions were compared. According to the experimental results, 4-MAA resulted as being an easily degraded molecule by direct photolysis, with half-life times (t1/2) ranging from 0.12 to 0.58 h, depending on the irradiation conditions. Faster degradation was observed in synthetic waters, suggesting that the photolysis was influenced by the salt composition of the waters. However, no effect on the degradation rate was observed by the presence of natural photosensitizers (dissolved organic matter, nitrate ions). 4-FAA and 4-AAA showed slower photodegradation kinetics, with t1/2 of 24 and 28 h, respectively. A study of photoproduct identification was carried out by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-time-of-flight mass spectrometry (LC-TOF-MS) (ESI positive mode), which allowed us to propose a tentative photodegradation pathway for 4-MAA and the identification of persistent by-products in all the cases. Finally, the application of an acute toxicity test (Daphnia magna) showed an increase in toxicity during the photolytic process, a consequence of the formation of toxic photoproducts.     

1-萘酚对斑马鱼的亚急性毒性效应和抗氧化酶活性的影响

将斑马鱼暴露于含有不同浓度的1-萘酚水环境,通过检测斑马鱼体内的超氧化物歧化酶(SOD)、过氧化氢酶(CAT)和乙酰胆碱酯酶(AchE)三种酶的生物活性的变化,探讨了1-萘酚对斑马鱼的亚急性生物毒性。结果表明,三种酶在低于1-萘酚安全浓度(0.1倍的96hLC50,即0.4 mg/L)较长时间暴露下,斑马鱼体内的SOD、CAT和AchE三种酶均出现不同程度的抑制,存在一定的生物毒性隐患。     

Remediation of PCB contaminated soils in the Canadian Arctic: excavation and surface PRB technology

The site BAF-5 is located on the summit of Resolution Island, Nunavut, just southeast of Baffin Island at 61 degrees 35'N and 60 degrees 40'W. The site was part of a North American military defense system established in the 1950s that became heavily contaminated with PCBs during and subsequent, its operational years. Remediation through excavation of the PCB contaminated soil at Resolution Island began in 1999 and at its completion in 2006 approximately 5 tonnes of pure PCBs in approximately 20,000 m3 of soil were remediated. Remediation strategies were based on both quantity of soil and level of contamination in the soil. Excavation removed 96% of the PCB contaminated soil on site. In 2003, a surface funnel-and-gate permeable reactive barrier was design and constructed to treat the remaining contamination left in rock crevices and inaccessible areas of the site. Excavation had destabilized contaminated soil in the area, enabling contaminant migration through erosion and runoff pathways. The barrier was designed to maximize sedimentation through settling ponds. This bulk removal enabled the treatment of highly contaminated fines and water through a permeable gate. The increased sediment loading during excavation required both modifications to the funnel and a shift to a more permeable, granular system. Granulated activated charcoal was chosen for its ability to both act as a particle retention filter and adsorptive filter. The reduction in mass of PCB and volume of soils trapped by the funnel of the barrier indicate that soils are re-stabilizing. In 2007, nonwoven geotextiles were re-introduced back into the filtration system as fine filtering could be achieved without clogging. Monitoring sites downstream indicate that the barrier system is effective. This paper describes the field progress of PCB remediation at Resolution Island.     

Transport of two naphthoic acids and salicylic acid in soil: experimental study and empirical modeling

In contrast to the parent compounds, the mechanisms responsible for the transport of natural metabolites of polycyclic aromatic hydrocarbons (PAH) in contaminated soils have been scarcely investigated. In this study, the sorption of three aromatic acids (1-naphthoic acid (NA), 1-hydroxy-2-naphthoic acid (HNA) and salicylic acid (SA)) was examined on soil, in a batch equilibrium single-system, with varying pH and acid concentrations. Continuous flow experiments were also carried out under steady-state water flow. The adsorption behavior of naphthoic and benzoic acids was affected by ligand functionality and molecular structure. All modeling options (equilibrium, chemical nonequilibrium, i.e. chemical kinetics, physical nonequilibrium, i.e. surface sites in the immobile water fraction, and both chemical and physical nonequilibrium) were tested in order to describe the breakthrough behavior of organic compounds in homogeneously packed soil columns. Tracer experiments showed a small fractionation of flow into mobile and immobile compartments, and the related hydrodynamic parameters were used for the modeling of reactive transport. In all cases, the isotherm parameters obtained from column tests differed from those derived from the batch experiments. The best accurate modeling was obtained considering nonequilibrium for the three organic compounds. Both chemical and physical nonequilibrium led to appropriate modeling for HNA and NA, while chemical nonequilibrium was the sole option for SA. SA sorption occurs mainly in mobile water and results from the concomitancy of instantaneous and kinetically limited sites. For all organic compounds, retention is contact condition dependent and differs between batch and column experiments. Such results show that preponderant mechanisms are solute dependent and kinetically limited, which has important implications for the fate and transport of carboxylated aromatic compounds in contaminated soils.     

Elevated concentrations of 1-hydroxypyrene in schoolchildren during winter in Christchurch, New Zealand

Particulate air pollution is significantly elevated during the winter in Christchurch, New Zealand, largely attributable to use of wood burners for domestic home heating, topography, and meteorological conditions. Polycyclic aromatic hydrocarbons (PAHs) are a key component of airborne particulate matter (PM) and urinary 1-hydroxypyrene (1-OHP) has previously been used to assess exposure of people to PAHs. We examined urinary 1-OHP in Christchurch male non-smoking schoolchildren (12-18 yr) on two occasions after high pollution events (48 and 72 microg PM(10)/m(3) 24-h average) and two occasions during periods of low pollution (19 and 12 microg PM(10)/m(3)). Concentrations of urinary 1-OHP were significantly elevated in the students during high pollution events (median (mean+/-SD) 0.043 (0.051+/-0.032) and 0.042 (0.060+/-0.092) micromol OHP/mol creatinine respectively) compared with low pollution periods (median (mean+/-SD) 0.019 (0.026+/-0.032) and 0.025 (0.028+/-0.018) micromol/mol creatinine respectively). The observed 1-OHP concentrations are at the lower end of those determined in children and non-occupationally exposed adults in international studies and suggest a generally low exposure to PAHs. The increased urinary 1-OHP concentrations following nights of elevated particulate concentrations in ambient air suggest increased exposure to ambient air pollution during winter time, and could potentially be used as a biomarker of exposure in this population.     

Effect of ZnO particles on activated sludge: role of particle dissolution

The release of nanoparticles (NPs) into the environment, including wastewater treatment plants, is expected to increase in the future. Therefore, it is important to understand the potential effects of these NPs on activated sludge treatment processes. A pulse-flow respirometer was used to study the toxicity of nano-ZnO on activated sludge endogenous respiration, BOD biodegradation, and nitrification. In addition, toxicities of bulk ZnO particles and Zn ion (e.g. soluble Zn) were also studied. All three Zn forms were found to adversely impact the activity of activated sludge, with soluble Zn exhibited the greatest toxicity. The effects of nano-ZnO and bulk ZnO on activated sludge were caused by soluble Zn resulting from ZnO particle dissolution. The IC₅₀ values of soluble Zn on activated sludge endogenous respiration, BOD biodegradation, ammonia oxidation, and nitrite oxidation were 2.2, 1.3, 0.8, and 7.3 mg-Zn/L, respectively. Therefore, the first step of nitrification was most sensitive to Zn.     

Potential of zero-valent iron in remediation of Cd(II) contaminated soil: From laboratory experiment,mechanism study to field application

This study investigates the potential of ZVI on Cd(II) contaminated soil remediation through laboratory experiment, mechanism study and field application. The results show that the dosage of ZVI, the initial concentration level and the reaction time have significant impacts on Cd(II) adsorption and about 88% of aqueous Cd(II) can be removed from soils. The ZVI is observed to promote the increase of Cd(II) residual fraction in Cd(II) contaminated soils according to the sequential extraction procedure (SEP) results. Regression of the laboratory experimental data based on the Langmuir isotherm equation shows the adsorption capacity can reach 34.7 mg/g. Such a high value is attributed to physical and chemical adsorption, which is proved by X-ray diffraction patterns (XRD), scanning electron microscope images (SEM), and Brunner-Emmet-Teller & Barret–Joyner–Halenda (BET-BJH) analysis. The field application shows that the ZVI can reduce the Cd(II) content in soils and brown rice by 51% and alleviate soil acidification, resulting in a 9.4% increase in rice yields.     

Heterogeneous UV/Fenton degradation of TBBPA catalyzed by titanomagnetite: catalyst characterization, performance and degradation products

Tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant, could negatively affect various aspects of mammalian and human physiology, which triggers effective techniques for its removal. In this work, the degradation characteristics of TBBPA in heterogeneous UV/Fenton reaction catalyzed by titanomagnetite (Fe_3−xTi_xO₄) were studied. Batch tests were conducted to evaluate the effects of titanomagnetite dosage, H₂O₂ concentration and titanium content in magnetite on TBBPA degradation. In the system with 0.125 g L⁻¹ of Fe_2.02Ti_0.98O₄ and 10 mmol L⁻¹ of H₂O₂, almost complete degradation of TBBPA (20 mg L⁻¹) was accomplished within 240 min UV irradiation at pH 6.5. The titanium incorporation obviously enhanced the catalytic activity of magnetite. As shown by the XRD and XANES results, titanomagnetite had a spinel structure with Ti⁴⁺ occupying the octahedral sites. On the basis of the degradation products identified by GC-MS, the degradation pathways of TBBPA were proposed. TBBPA possibly underwent the sequential debromination to form TriBBPA, DiBBPA, MonoBBPA and BPA, and β-scission to generate seven brominated compounds. All of these products were finally completely removed from reaction solution. In addition, the reused catalyst Fe_2.02Ti_0.98O₄ still retained the catalytic activity after three cycles, indicating that titanomagnetite had good stability and reusability. These results demonstrated that heterogeneous UV/Fenton reaction catalyzed by titanomagnetite is a promising advanced oxidation technology for the treatment of wastewater containing TBBPA.     

Fire smoke toxicity: The effect of nitrogen oxides

Measurements of the toxic potency of fire effluents are required for fire-safety engineering and fire-hazard assessments. Toxic potency values may be generated using chemical analysis data and/or by animal protocols. The current ISO methods of calculating toxic potency values from chemical analysis data assume that the nitrogen oxides present in inhaled fire effluents are nitrogen dioxide, a highly irritant acid gas. Observations from real scale fire tests and bench scale tests which simulate the different fire stages show that, in some situations and particularly in proximity of the fire, the nitrogen oxides will be predominately nitric oxide but this can gradually change to nitrogen dioxide as the effluent moves away from the fire. Nitric oxide has a very different toxic potency and effect when compared to nitrogen dioxide. This paper considers the formation of nitric oxide and nitrogen dioxide in fire effluents, their potential toxic effects and the consequential need to reconsider the methods of calculating toxic potency values.     

Use of iron-based technologies in contaminated land and groundwater remediation: a review

Reactions involving iron play a major role in the environmental cycling of a wide range of important organic, inorganic and radioactive contaminants. Consequently, a range of environmental clean-up technologies have been proposed or developed which utilise iron chemistry to remediate contaminated land and surface and subsurface waters, e.g. the use of injected zero zero-valent iron nanoparticles to remediate organic contaminant plumes; the generation of iron oxyhydroxide-based substrates for arsenic removal from contaminated waters; etc. This paper reviews some of the latest iron-based technologies in contaminated land and groundwater remediation, their current state of development, and their potential applications and limitations.     

Slow and very slow desorption of organic compounds from sediment: influence of sorbate planarity

The kinetics of desorption of in situ chlorobenzenes, PAHs, and PCBs from four different sediments was studied employing Tenax beads as an infinite sink for sorbates. Rate constants for slow desorption were 2.9+/-0.4 x 10(-2) x h(-1), irrespective of the extent of sorbate planarity. Rate constants for very slow desorption were 2.1+/-0.5 x 10(-4) and 6.7+/-1.4 x 10(-4) x h(-1) for planar and non-planar compounds, respectively. Comparison with literature data suggests a priori estimates for rate constants for slow desorption to be 3 x 10(-2) x h(-1), and to be 2 x 10(-4) and 7 x 10(-4) x h(-1) for very slow desorption of planar and non-planar compounds, respectively. The ratio between the fractions in the very slowly desorbing domain and the rapidly desorbing domain was 15-38 for planar compounds which is higher than for non-planar compounds for which the ratio was 2.8-5.2. The ratio between the fractions in the slowly desorbing domain and the rapidly desorbing domain was 1.3-1.8 and independent of the sorbate planarity. The difference in influence of sorbate planarity on the very slowly desorbing domain as compared to the slowly desorbing domain points to different environments for the slowly and the very slowly desorbing fractions.