Hydrodechlorination of dichlorobiphenyls over Ni-Mo/Al2O3 catalysts prepared by spray-drying method

The hydrodechlorination (HDCl) process of 2,3-, 2,4- and 2,5-dichlorobiphenyls was studied over a sulphided Ni-Mo/Al(2)O(3) catalyst in a stirred autoclave at a hydrogen pressure of 3 MPa. The catalysts were prepared by spray-drying. They were characterized by N(2) adsorption, thermogravimetry and scanning electron microscopy with X-ray microanalysis. The reaction temperature of the catalytic HDCl process was varied in the range of 230-290 degrees C. Polychlorinated biphenyls (PCBs) free transformer oil was used as reaction medium. The HDCl degree of dichlorobiphenyl isomers was in the range of 82-93%. The efficiency in the chlorine removal was found to be related to the position of the substituted chlorine atom and decreased as follows 2,4-dichlorobiphenyl approximately 2,5-dichlorobiphenyl>2,3-dichlorobiphenyl. For comparison, the HDCl process of 2,3-dichlorobiphenyl (2,3-PCB) without catalyst was also studied. The chlorine removal was 85% for the catalytic HDCl of 2,3-PCB whereas non-catalytic process led only to 16% of dechlorination in the same operating conditions, i.e. at 290 degrees C after 120 min. Monodichlorobiphenyls were not detected in the reaction products. The data for both catalytic and non-catalytic conversion of 2,3-PCB fit to a first-order model. Kinetic constants and the activation energy of the overall HDCl reaction of 2,3-PCB to biphenyl were evaluated. Compared to non-catalytic process, a nearly threefold decrease in the activation energy was observed in the presence of Ni-Mo/Al(2)O(3) catalyst prepared by spray-drying (48 kJ mol(-1) vs. 124 kJ mol(-1)).     

A multiple testing approach for hazard evaluation of complex mixtures in the aquatic environment: the use of diesel oil as a model

Traditional single species toxicity tests and multiple component laboratory-scaled microcosm assays were combined to assess the toxicological hazard of diesel oil, a model complex mixture, to a model aquatic environment. The immediate impact of diesel oil dosed on a freshwater community was studied in a model pond microcosm over 14 days: a 7-day dosage and a 7-day recovery period. A multicomponent laboratory microcosm was designed to monitor the biological effects of diesel oil (1.0 mg litre(-1)) on four components: water, sediment (soil + microbiota), plants (aquatic macrophytes and algae), and animals (zooplanktonic and zoobenthic invertebrates). To determine the sensitivity of each part of the community to diesel oil contamination and how this model community recovered when the oil dissipated, limnological, toxicological, and microbiological variables were considered. Our model revealed these significant occurrences during the spill period: first, a community production and respiration perturbation, characterized in the water column by a decrease in dissolved oxygen and redox potential and a concomitant increase in alkalinity and conductivity; second, marked changes in microbiota of sediments that included bacterial heterotrophic dominance and a high heterotrophic index (0.6), increased bacterial productivity, and the marked increases in numbers of saprophytic bacteria (10 x) and bacterial oil degraders (1000 x); and third, column water acutely toxic (100% mortality) to two model taxa: Selenastrum capricornutum and Daphnia magna. Following the simulated clean-up procedure to remove the oil slick, the recovery period of this freshwater microcosm was characterized by a return to control values. This experimental design emphasized monitoring toxicological responses in aquatic microcosm; hence, we proposed the term 'toxicosm' to describe this approach to aquatic toxicological hazard evaluation. The toxicosm as a valuable toxicological tool for screening aquatic contaminants was demonstrated using diesel oil as a model complex mixture.     

Toxicity of crude oil to the mayfly, Hexagenia bilineata (Ephemeroptera: Ephemeridae)

Effects of crude oil on survival and behavior of the mayfly Hexagenia bilineata were evaluated in laboratory studies. Mayfly nymphs were exposed to the water soluble and oil residue fractions of crude oil. Mayfly survival was not reduced by a 96-h exposure to either the water soluble fraction or the oil residue mixed with sediment. However, significant mortality did result from a 21-day exposure to oil residue mixed with sediment at concentrations as low as 500 microg g(-1). Survival was also reduced after a 21-day exposure to oil-contaminated sediments (1905 microg g(-1)) collected 6 weeks after a crude oil spill in the Chariton River, Missouri. In a behavioral test measuring habitat exclusion, organisms did not avoid contact with sediment containing oil residue (50-800 microg g(-1)). Collectively, results from these studies indicate that exposure to oil residue in sediment will reduce survival of H. bilineata in the laboratory and may reduce survival in the environment for 6 weeks or more after an oil spill.     

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlorination of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc)2+i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls.     

Application of microwave irradiation in the removal of polychlorinated biphenyls from soil contaminated by capacitor oil

The applicability of microwave irradiation in the removal of polychlorinated biphenyls (PCBs) from the soil heavily contaminated by capacitor oil was studied. Granular activated carbon (GAC) was added into the soil as a microwave-absorbing material to rapidly increase the temperature of the reaction system. Effects of sodium hypophosphite (SHP) and iron powder (IP) as reductants on PCB removal, as well as the effects of water content in soil, microwave power and the amount of GAC added were investigated. The results indicated that in the presence of SHP and GAC, about 80% of PCBs in soil were effectively removed by 10 min microwave irradiation, and the further addition of IP could raise the average removal efficiency to a higher level, more than 95%. In the removal of PCBs with the microwave/GAC/IP/SHP system, an appropriate amount of water proved to be helpful in promoting the removal of PCBs from soil by steam distillation and in acting as a co-solvent of SHP and H-donor of IP.     

Transport of chlorinated dioxins and furans in soil columns: modeling pentachlorophenol pole-treating oil influence

Column experiments were conducted to validate a screening model predicting the influence of pentachlorophenol (PCP) pole-treating oil on the vertical migration of its impurities, chlorinated dioxins and furans (PCDD/Fs). PCP pole-treating oil (15 mL d⁻¹) and water (20 mL d⁻¹) were added daily to the top of sand and organic soil columns during 35 d. Column soil samples were analyzed to determine concentrations of hydrocarbons and PCDD/Fs at several depths in the columns (0-30 cm) and their evolution in time (7, 14, 21 and 35 d).The model predicted a significant vertical migration of PCDD/Fs due to the presence of oil as a free phase and PCDD/Fs were found in the different column layers at concentrations consistent with model predictions (same order of magnitude). Measured PCDD/Fs concentrations are in total disagreement with literature data and with model prediction in the absence of oil free phase, which implies PCDD/F properties alone cannot be used to predict their fate in the current context: the influence of PCP pole-treating oil must be accounted for to properly explain their migration.     

PNN破乳剂的合成及其乳化液废水处理

由氨,仲胺与伯胺及表卤代醇合成制备了合成制备了高效破乳剂ＰＮＮ,并用以处理乳化油废水,取得了较好的效果。结果表明,在ＰＨ＝６．０－７．５,投量为１．８８‰３．０‰的条件下,用ＰＮＮ处理ＣＯＤｃｒ为７１８４０ｍｇ／Ｌ、ｉｍｇ ｏ １５５３４ｍｇ／Ｌ、油为１５５３４ｍｇ／Ｌ的某乳化油废水,最佳ＣＯＤｃｒ去除率达９２．７％,最佳油去除率达９９．９％。,浊度去除率达到９９．９％,该药剂破乳后固液分离性能较     

Photoenhanced toxicity of a weathered oil onCeriodaphnia dubia reproduction

Traditionally, the toxic effects of petroleum have been investigated by conducting studies in the absence of ultraviolet radiation (UV). Photomediated toxicity is often not considered, and the toxic effects of an oil spill can be grossly underestimated. The toxicity of a weathered oil collected from a monitoring well at an abandoned oil field toCeriodaphnia dubia was examined in the presence of UV. A solar simulator equipped with UVB, UVA, and cool white lamps was used to generate environmentally comparable solar radiation intensities.C. dubia were exposed to six concentrations of water accommodated fractions (WAF) of weathered oil in conjunction with three levels of laboratory simulated UV (Reference = < 0.002 μW/cm²UVB; 3.0 μW/cm² UVA; Low = 0.30 μW/cm² UVB; 75.0 μW/cm² UVA; High = 2.0 μW/cm² UVB; 340.0 μW/cm² UVA) and visible light. Seven day static renewal bioassays were used to characterize WAF/UV toxicity. WAF toxicity significantly (p < 0.05) increased when the organisms were exposed to WAF in the presence of UV. The photoenhanced toxicity of the WAF increased with WAF concentration within each UV regime. Relative to the reference light regime, the average number of neonates from adults exposed to 1.6 mg TPH/L decreased significantly by 20% within the low light regime, and by 60% within the high light regime. These results indicate that organisms exposed to dissolved-phase weathered oil in the presence of environmentally realistic solar radiation, exhibit 1.3–2.5 times greater sensitivity, relative to organisms exposed under traditional laboratory fluorescent lighting.     

In vitro effect of dimethoate on the activity of tryptophan pyrrolase in rat liver

Total and holo-enzyme activities of tryptophan 2,3-dioxygenase were measured in vitro in the presence and absence of the organophosphorous insecticide, dimethoate. Addition of dimethoate to the reaction mixture decreased the activities of both total and holo-forms. Total and holo-enzyme activities were decreased by 34% and 26%, respectively, by 1 mM dimethoate. On the other hand, 5 mM dimethoate resulted in 56% and 34% inhibition to total and holo-enzyme activities, respectively. Lineweaver-Burk plot of the total-enzyme activity at different tryptophan concentration in the presence of 2 mM dimethoate gave uncompetitive type of inhibition.     

Weathering of crude oil in natural marine environments: The concentration of polar degradation products in water under oil as measured in several field studies

The concentration of oil derived material in the water column under an oil slick has been monitored. In an enclosed natural ecosystem the composition of the material in the water column was found, by liquid chromatography, to be dominated by polar degradation products, indicating that photooxidation of oil hydrocarbons is a major degradation pathway.     

Ozonation of oil sands process water removes naphthenic acids and toxicity

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).     

A protocol for assessing the effectiveness of oil spill dispersants in stimulating the biodegradation of oil

Dispersants are important tools in oil spill response. Taking advantage of the energy in even small waves, they disperse floating oil slicks into tiny droplets (<70 μm) that entrain in the water column and drift apart so that they do not re-agglomerate to re-form a floating slick. The dramatically increased surface area allows microbial access to much more of the oil, and diffusion and dilution lead to oil concentrations where natural background levels of biologically available oxygen, nitrogen, and phosphorus are sufficient for microbial growth and oil consumption. Dispersants are only used on substantial spills in relatively deep water (usually >10 m), conditions that are impossible to replicate in the laboratory. To date, laboratory experiments aimed at following the biodegradation of dispersed oil usually show only minimal stimulation of the rate of biodegradation, but principally because the oil in these experiments disperses fairly effectively without dispersant. What is needed is a test protocol that allows comparison between an untreated slick that remains on the water surface during the entire biodegradation study and dispersant-treated oil that remains in the water column as small dispersed oil droplets. We show here that when this is accomplished, the rate of biodegradation is dramatically stimulated by an effective dispersant, Corexit 9500®. Further development of this approach might result in a useful tool for comparing the full benefits of different dispersants.     

Removal by sorption and in situ biodegradation of oil spills limits damage to marine biota: a laboratory simulation

This study examined the efficiency of cotton grass fibers in removing diesel oil from the surface of water in conditions prevailing in the Baltic Sea. The effect of low temperature, salinity, and bacterial amendments were tested in laboratory-scale set-ups, whereas 600-L mesocosms filled with Baltic Sea water were used for testing the effects of diesel oil and rapid removal of the oil on microorganisms, phytoplankton, and mussels. Cotton grass proved to be an excellent sorbent for diesel oil from the water surface at a low temperature. Inoculation with diesel-enriched microorganisms enhanced degradation of oil significantly in laboratory-scale experiments. In mesocosm experiments, the addition of diesel oil (0.66 mg L(-1), 0.533 L m(-2)) to the basins resulted in higher microbial density than in all other basins, including inoculated ones, suggesting that the Baltic Sea contains indigenous hydrocarbon degraders. The removal of oil with cotton grass significantly improved the survival of mussels in the mesocosm tests: 100% mortality in diesel basins versus 0% mortality in basins with cotton grass, respectively. However, the surviving mussels suffered from histopathological changes such as inflammatory responses, degenerations, and cell death. The observed rescuing effect was observable even when the cotton grass-bound oil was left in the water. The results underline the importance of rapid action in limiting damage caused by oil spills.     

Effects of dissolved oxygen, pH, and anions on the 2,3-dichlorophenol degradation by photocatalytic reaction with anodic TiO(2) nanotube films

In this study, the highly-ordered TiO(2) nanotube (TNT) arrays on titanium sheets were prepared by an anodic oxidation method. Under UV illumination, the TNT films demonstrated the higher photocatalytic activity in terms of 2,3-dichlorophenol (2,3-DCP) degradation in aqueous solution than the conventional TiO(2) thin films prepared by a sol-gel method. The effects of dissolved oxygen (DO) and pH on the photocatalytic degradation of 2,3-DCP were investigated. The results showed that the role of DO in the 2,3-DCP degradation with the TNT film was significant. It was found that 2,3-DCP in alkaline solution was degraded and dechlorinated faster than that in acidic solution whereas dissolved organic carbon removal presented an opposite order in dependence of pH. In the meantime, some main intermediate products from 2,3-DCP degradation were identified by a (1)H NMR technique to explore a possible degradation pathway. A major intermediate, 2-chlororesorcinol, was identified from the 2,3-DCP decomposition as a new species compared to the findings in previous reports. Photocatalytic deactivation was also evaluated in the presence of individual anions (NO(3)(-), Cl(-), SO(4)(2-), and H(2)PO(4)(-)). The inhibition degree of photocatalytic degradation of 2,3-DCP caused by these anions can be ranked from high to low as SO(4)(2-)>Cl(-)>H(2)PO(4)(-)>NO(3)(-). The observed inhibition effect can be attributed to the competitive adsorption and the formation of less reactive radicals during the photocatalytic reaction.     

Factors affecting biosurfactant production by oil degrading Aeromonas spp. isolated from a tropical environment

An Aeromonas spp. was isolated from tropical estuarine water. The organism grew on crude oil and produced biosurfactant that could emulsify hydrocarbons. The peak growth and biosurfactant production was on the 8th day. The organism grew on a range of hydrocarbons that include crude oil and hexadecane while no growth was recorded on some hydrocarbons that include benzene. The biosurfactant produced by the organism emulsified a range of hydrocarbons with diesel (E24=65) as the best substrate and hexane (E24=22) as the poorest. After purification, the biosurfactant was found to contain about 38% carbohydrate and an unidentified lipid. No protein was present in the purified biosurfactant. Production of biosurfactant was highest in medium with glucose and lowest in the medium with diesel+acetate. Soybean was the best nitrogen source for biosurfactant production. The activity of the biosurfactant was enhanced optimally at NaCl concentration of 5%, pH of 8.0 and temperature of 40 degrees C. The biosurfactant retained 77% of its original activity after 120 min of exposure to heat at a temperature of 100 degrees C. Biosurfactant may be produced with this organism using non-hydrocarbon substrates such as glucose and soybean that are readily available and would not require extensive purification for use in food and pharmaceutical industries.     

木屑处置漏油事故的室内模拟

用锯木屑作为吸附材料，0#柴油为吸附对象进行室内模拟实验，研究了木屑对纯油、水中浮油的吸附以及吸油后的木屑在水中的漂浮性能；并以木屑粒径、木屑投加量、振荡频率、油膜厚度为研究指标，设计了5因素4水平的正交实验，考察了各因素对0#柴油的吸附量、去除率以及木屑漂浮率的影响并对优化条件进行了讨论。结果表明，在实验研究范围内，木屑对水中柴油的吸附速度极快，1min即可达到饱和，饱和吸附量为8．08g／g；木屑在水中漂浮性能良好，静态时经72h漂浮，漂浮率维持在92％左右；振荡频率为150r／min时，72h内漂浮率维持在68％以上；最佳吸油条件组合为吸附剂粒径10～20目，振荡频率120r／min，木屑投加量0．7g，油膜厚度1．65mm。     

Effects of beach sand properties, temperature and rainfall on the degradation rates of oil in buried oil/beach sand mixtures

Lysimeters located outdoors have been used to evaluate the decomposition of buried oily beach sand waste (OBS) prepared using Forties light crude oil and sand from different locations around the British coast. The OBS (5% oil by weight) was buried as a 12-cm layer over dune pasture sub-sand and overlain by 20 cm of dune pasture topsoil. Decomposition rates of oil residues averaged 2300 kg ha(-1) in the first year and the pattern of oil decomposition may be represented by a power curve. Oil decomposition was strongly related to the temperature in the OBS layer, but was also significantly affected by rainfall in the previous 12 h. The CO(2) flux at the surface of the treatment lysimeters followed the relationship [log(10) CO(2) (mg C m(-2) h(-1))=0.93+0.058x OBS temp. (degrees C)-0.042x12 h rain (mm)]. There was considerable variation in the rate of oil decomposition in sands collected from different sites. Sand from Askernish supported most microbial activity whilst sand from Tain was relatively inactive. The decomposition process appeared to cease when the sand became saturated with water, i.e. temporarily anaerobic. However, decomposition recommenced when the soil dried out. The fastest rate of decomposition occurred in sand from one of the two sites predicted to have high populations of hydrocarbon-degrading bacteria. Larger particle size and higher Ca content may also be significant factors governing the rate of decomposition.     

Influence of modified soils on the removal of diesel fuel oil from water and the growth of oil degradation micro-organism

Three soils were modified with two kinds of cationic surfactants in order to increase their sorptive capabilities for organic contaminants. Sorption of diesel fuel oil in water by these modified soils had been investigated. Modified soils can effectively sorb diesel fuel oil from water. The sorption capability of modified soils is: HDTMA-black soil > HDTMA-yellow brown soil > HDTMA-red soil > TMA-black soil > TMA-yellow brown soil > TMA-red soil. Sorption of diesel fuel oil by natural soils and HDTMA modified soils is via partition, the sorption isotherms can be expressed by Henry equation, and logK(SOM) is 2.42-2.80, logK(HDTMA) is 3.37-3.60. Sorption isotherms of TMA modified soils can be expressed by Langmuir equation, the saturation sorption capacities are 1150 (TMA-black soil), 750 (TMA-yellow-brown soil), 171 mg/kg (TMA-red soil), respectively. A diesel fuel oil degradation micro-organism (Pseudomonas sp.) was isolated in the lab. To test the influence of the modified soils on the micro-organism, various growth curves of Pseudomonas in different conditions were drawn. Pseudomonas can grow very well with natural soils and TMA modified soils. The acclimation period of Pseudomonas is reduced. As to HDTMA modified soils, HDTMA loading amount is very important. When HDTMA loading amount is no higher than 0.5 CEC, the micro-organism can grow very well after a long acclimation period.     

Dispersibility of crude oil in fresh water

The effects of surfactant composition on the ability of chemical dispersants to disperse crude oil in fresh water were investigated. The objective of this research was to determine whether effective fresh water dispersants can be designed in case this technology is ever considered for use in fresh water environments. Previous studies on the chemical dispersion of crude oil in fresh water neither identified the dispersants that were investigated nor described the chemistry of the surfactants used. This information is necessary for developing a more fundamental understanding of chemical dispersion of crude oil at low salinity. Therefore, we evaluated the relationship between surfactant chemistry and dispersion effectiveness. We found that dispersants can be designed to drive an oil slick into the freshwater column with the same efficiency as in salt water as long as the hydrophilic-lipophilic balance is optimum.     

Impact of edible oil injection on the permeability of aquifer sands

Recent laboratory and field studies have shown that food-grade edible oils can be injected into the subsurface for installation of in-situ permeable reactive barriers. However to be effective, the oil must be distributed out away from the oil injection points without excessive permeability loss. In this work, we examine the distribution of soybean oil in representative aquifer sediments as non-aqueous phase liquid oil (NAPL oil) or as an oil-in-water emulsion. Laboratory columns packed with sands or clayey sands were flushed with either NAPL oil or a soybean emulsion followed by plain water, while monitoring permeability loss and the final oil residual saturation. NAPL oil can be injected into coarse-grained sands. However NAPL injection into finer grained sediments requires high injection pressures which may not be feasible at some sites. In addition, NAPL injection results in high oil residual saturations and moderate permeability losses. In contrast, properly prepared emulsions can be distributed through sands with varying clay content without excessive pressure buildup, low oil retention and very low to moderate permeability loss. For effective transport, the emulsion must be stable, the oil droplets must be significantly smaller than the mean pore size of the sediment and the oil droplets should have a low to moderate tendency to stick to each other and the aquifer sediments. In our work, oil retention and associated permeability loss increased with sediment clay content and with the ratio of droplet size to pore size. For sandy sediments, the permeability loss is modest (0-40% loss) and is proportional to the oil residual saturation.