零价铁还原脱氯污染土壤中PCBs的实验研究

利用零价铁或铁的双金属对模拟污染土中多氯联苯(PCBs)在常温常压下的还原脱氯情况进行实验研究.采用高效离子色谱分析样本,结果表明:零价铁或者镍(Ni)铁双金属对土壤中浓度为5 mg·g-1的PCBs有一定的脱氯效果;当PCBs浓度降低为1 mg·g-1时只有钯(Pd)含量为0.05%的钯铁处理具有显著的脱氯效果;升高土壤温度到45℃,或者简单加入醋酸、活性炭、石墨以及硫粉等处理均不能有效提高脱氯效果;先添加硫粉和水培养,使土壤氧化还原电位降低后,添加含铜(Cu)为2%的铜铁及含钴(Co)为1%的钴铁双金属对土壤中的PCBs有明显的脱氯效果.     

Chemical dechlorination of polychlorinated biphenyls (PCBs) from dielectric oils

We studied the chemical dechlorination of the polychlorinated biphenyls (PCBs) in some dielectric oils via nucleophilic substitution of the chloro atoms by polyethylene alkoxide. The influence of temperature, ultrasounds, polyethylene glycol (PEG) and base type was investigated. Our findings show that dechlorination of PCBs by chemical treatment is effective at moderate temperature (90–100°C) and is strongly dependent on the nature of matrix oil. Stirring affects the process yield by influencing the homogeneity of the oil/glycol two-phase system. Ultrasounds can improve the process efficiency by making operating conditions less severe. Selected article from the 6th European Meeting on Environmental Chemistry, University of Belgrade, Serbia and Montenegro organized by Prof. Dr. Branimir Jovancicevic ().     

Development and characterization of an anaerobic microcosm for reductive dechlorination of PCBs

The toxic and recalcitrant polychlorinated biphenyls (PCBs) adversely affect human and biota by bioaccumulation and biomagnification through food chain. In this study, an anaerobic microcosm was developed to extensively dechlorinate hexa- and hepta-CBs in Aroclor 1260. After 4 months of incubation in defined mineral salts medium amended PCBs (70 mmol·L^–1) and lactate (10 mmol·L^–1), the culture dechlorinated hexa-CBs from 40.2% to 8.7% and hepta-CBs 33.6% to 11.6%, with dechlorination efficiencies of 78.3% and 65.5%, respectively (all in moL ratio). This dechlorination process led to tetra-CBs (46.4%) as the predominant dechlorination products, followed by penta-(22.1%) and tri-CBs (5.4%). The number of meta chlorines per biphenyl decreased from 2.50 to 1.41. Results of quantitative real-time PCR show that Dehalococcoides cells increased from 2.39 ×10⁵±0.5 × 10⁵ to 4.99 × 10⁷±0.32 × 10⁷ copies mL^–1 after 120 days of incubation, suggesting that Dehalococcoides play a major role in reductive dechlorination of PCBs. This study could prove the feasibility of anaerobic reductive culture enrichment for the dehalogenation of highly chlorinated PCBs, which is prior to be applied for in situ bioremediation of notorious halogenated compounds.

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Benthic oxygen uptake and carbon cycling under aphotic and resource-limiting conditions in a submarine cave

To establish relationships between organic input to the benthos and decreases in benthic population biomass and density, benthic oxygen uptake was measured in an oligotrophic submarine cave in the northwestern Mediterranean Sea (Marseille, France), on seven separate occasions in 1987, using an in situ bell-jar respirometer. Oxygen uptake was measured in both the outer twilight section and the dark inner section of the cave during an annual survey (seven recording periods from February 1987 to November 1988). The mean annual benthic oxygen uptake was 80.9 litres O₂ m^–2 yr^–1 for the twilight outer section and 15.5 litres O₂ m^–2 yr^–1 for the dark inner section. The results are discussed and the biogeochemical budget for particulate organic carbon at the sediment-water interface calculated. Respiration rates (expressed as carbon equivalents), together with previously published data on vertical fluxes and burial of organic carbon, revealed that anaerobic pathways accounted for 14% and aerobic pathways for 86% of the total benthic metabolism in the outer part of the cave. In the inner section of the cave, degradation of organic carbon occurred only through aerobic degradation, indicating a strongly carbon-limited ecosystem. The low respiration rates recorded in the dark section were similar to values recorded for some oligotrophic deep-sea environments (1 000 to 2 000 m). Such budgets are essential preliminary steps in order to accurately model benthic metabolic pathways. The determination of annual fluxes linked to the acquisition of long-term data will yield better knowledge of the recycling processes at the water-sediment interface.     

活性炭辅助微波热解污泥反应条件的试验研究

针对微波不能直接实现原污水污泥高温热解的问题,采用活性炭作为微波能吸收物质辅助污泥热解。对影响污泥热解效能的3个主要因素：污泥样品量、活性炭掺杂量和微波辐射功率,各做了3个水平的考察,得到了试验条件下的最优方案：污泥样品量30g、活性炭掺杂量6g、微波辐射功率1200W。结果表明：在最优试验方案下,污泥能在7min内升至920℃的高温,实现污泥快速、高效热解。通过分析3个因素对污泥热解效能的影响,进一步对最优试验方案下的固体产物吸收微波的性能及用其作为掺杂物辅助微波热解污水污泥的可行性进行了研究,结果表明：固体残渣吸收微波性能良好,可以代替活性炭作为更经济、高效的污泥微波热解辅助材料。     

Promotive effect of pyridine on indole degradation by activated sludge under anoxic conditions

Batch experiments were carried out to investigate the promotive effect of pyridine on indole degradation under denitrifying conditions. The seed sludge was obtained from a local coal-coking wastewater treatment facility and was acclimated in the laboratory. Indole and pyridine were supplemented to the synthetic wastewater at different ratios. The optimum ratio of chemical oxygen demand (COD) to nitrate (C/N) was 8.4–8.9 for both denitrification and indole and pyridine degradation. At a temperature of 28°C and pH of 7.0–7.5, the nitrate reductase activity (NRA) was in the best state. The addition of pyridine could promote NRA and the degradation of indole. When the initial concentration of indole was 150 mg/L, the concentration ratio of indole to pyridine was in the range of 1–10. Under optimum C/N conditions, the degradation of indole could be described with pseudo-zero-order kinetics. There was no accumulation of nitrite during the reaction. When the concentration ratio of pyridine to indole was less than 0.25 with an increase in the pyridine proportion, there were more significant augment rates for NRA and the degradation of indole than the situation when the concentration ratio was more than 0.25.     

Stable isotope study of sedimentary carbon utilization by Capitella spp.: effects of two carbon sources and geochemical conditions during their diagenesis

Two experiments were conducted to determine the effect of the type of sediment organic matter and geochemical conditions during diagenesis on the stable carbon isotope ratio ¹³C of the deposit-feeding polychaete worms Capitella spp. Laboratory experiments showed ¹³C values of-13.5 to-13.9%. for worms grown on fresh and aged kelp, Macrocystis pyrifera. Field experiments on worms in the Santa Barbara Channel, California (USA), in 1986 revealed more negative ¹³C values (to-19%.) when oil and kelp were added to sediments. The more negative values suggest the incorporation of oil carbon into worm tissues, supporting previous indications of the importance of hydrocarbons in food webs near oil seeps.     

氧化锌表面的Fe(Ⅱ)对三氯乙烯的还原脱氯研究

通过批量实验研究了在氧化锌-Fe(Ⅱ)混合体系中,束缚在氧化锌表面的Fe(Ⅱ)对三氯乙烯的还原脱氯作用。结果表明,这种束缚在氧化锌表面的Fe(Ⅱ)对三氯乙烯有一定的还原脱氯作用,且脱氯反应符合准一级反应动力学方程。与均质溶液中的Fe(Ⅱ)相比,束缚在氧化锌表面的Fe(Ⅱ)对三氯乙烯有更强的还原脱氯作用。实验还发现三氯乙烯在氧化锌-Fe(Ⅱ)混合体系中的还原脱氯速率受pH值和Fe(Ⅱ)浓度的影响。Fe(Ⅱ)浓度为1mmol·L-1,在pH值5.0～9.0范围内,还原脱氯反应速率常数kobs及三氯乙烯去除率随着pH值的升高而增大。维持pH值7.0不变,在Fe(Ⅱ)浓度1～4mmol·L-1范围内,kobs及三氯乙烯去除率随Fe(Ⅱ)浓度的增大而增大,但是Fe(Ⅱ)浓度进一步升高,kobs及三氯乙烯去除率反而降低。当Fe(Ⅱ)初始浓度为4mmol·L-1、pH=7.0时,三氯乙烯在氧化锌-Fe(Ⅱ)混合体系中的kobs及三氯乙烯去除率均达到最大值,分别为0.260h-1、71.7%。     

Biocatalytic dechlorination of hexachlorocyclohexane by immobilized bio-Pd in a pilot scale fluidized bed reactor

Lindane (??-hexachlorocyclohexane, ??-HCH) is a recalcitrant and toxic organochlorine insecticide. Due to its non-selective production process and widespread use, HCH isomers and their degradation products have been detected frequently in soils and groundwater. An innovative technology using microbial produced Pd(0) nanoparticles, i.e. bio-Pd, was developed to treat groundwater containing a mixture of HCHs and chlorobenzenes. In a first step, the groundwater was de-ironized and most of the chlorobenzenes were removed in a biological trickling filter. The ??g?L^?1 levels of HCHs and chlorobenzenes were removed in a second step by the bio-Pd-based technology. Therefore, a 200-L pilot scale reactor was developed with 100?mg?L^?1 bio-Pd encapsulated in alginate beads. Hydrogen gas was bubbled at the bottom of the reactor and served to charge the bio-Pd catalyst. The reactor influent contained 5.2???g?L^?1 HCHs and 51.1???g?L^?1 chlorobenzenes. During a test period of 10?days, 29% of the HCH isomers and 63% of the chlorobenzenes were removed applying a nominal hydraulic residence time of 4?h. These removal percentages could be increased to 75 and 68% by doubling the nominal hydraulic residence time to 8?h. This study demonstrated that biologically produced nanoparticles of Pd can be applied for the large-scale remediation of groundwater contaminated with HCHs.     

Efficient dechlorination of 2,4-dichlorophenol in an aqueous media with a mild pH using a Pd/TiO2NTs/Ti cathode

In this study, palladium-loaded titania nanotubes was fabricated on a titanium plate (Pd/TiO₂NTs/Ti) for efficient electrodechlorination of 2,4-chlorophenol with a mild pH condition. The nature of Pd/TiO₂NTs/Ti electrodes was characterized by field-emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) techniques. The characterization results indicated the generation of Pd⁰ nanoparticles which were evenly dispersed on titania nanotubes arrays on the Pd/TiO₂NTs/Ti surface. An effective degradation efficiency of up to 91% was achieved within 60 min at cathode potential of −0.7 V (vs. SCE) and initial pH of 5.5. The effects of the applied cathode potential and initial pH on the degradation efficiency were studied. A near neutral condition was more favorable since very low and very high pHs were not conducive to the dechlorination process. Furthermore, the intermediates analysis showed that the Pd/TiO₂NTs/Ti electrode could completely remove chlorine from 2, 4-dichlorophenol since only phenol was detected as the byproduct and the concentration of released chlorine ions indicated near-complete dechlorination. This work presents a good alternative technique for eliminating persistent chlorophenols in polluted wastewater without maintaining strong acidic environment.     

Degradation of chemical alarm cues under natural conditions: risk assessment by larval woodfrogs

Summary. Many aquatic species use chemosensory information to assess predation risk. The cues used in such risk assessment can come either from the predator (predator odour) or from injured prey (alarm cues). The information conveyed through chemicals may, however, be inaccurate both spatially and temporally, as chemicals may persist in the environment long after the predator is gone. Thus, the level of accuracy of the cues for risk assessment may depend on the persistency of the chemicals in the habitat. Here, we investigated the persistency of alarm cues of a larval amphibian, the woodfrog (Rana sylvatica) in a ephemeral pond, their natural habitat. We introduced either alarm cues or control water in enclosed sleeves (~10 L) installed in the pond. The sleeve water was then sampled after 5 min and every two hours for eight hours. We used the behavioural response of woodfrog tadpoles to alarm cues as a bioassay to assess how long the alarm cues persisted in the environment. We found that tadpoles responded with an antipredator response to the pond water containing alarm cues 5 min after the injection of the cues in the sleeves but did not respond to that same pond water after two hours. Our results indicate that biodegradation and/or photodegradation of alarm cues in natural habitats might occur relatively quickly as the loss of a response to the cues in our experiment was independent of a dilution effect. This contrasts with previous laboratory results indicating that chemicals may be active after several hours.     

Numerical simulation of benzene transport in shoreline groundwater affected by tides under different conditions

● An approach for assessing the transport of benzene on the beach was proposed. ● The behavior of benzene in the subsurface of the beach was impacted by tide. ● Tidal amplitude influenced the travel speed and the benzene biodegradation. ● Hydraulic conductivity had the impact on plume residence time and biodegradation. ● Plume dispersed and concentration decreased due to high longitudinal dispersivity. The release and transport of benzene in coastal aquifers were investigated in the present study. Numerical simulations were implemented using the SEAM3D, coupled with GMS, to study the behavior of benzene in the subsurface of tidally influenced beaches. The transport and fate of the benzene plume were simulated, considering advection, dispersion, sorption, biodegradation, and dissolution on the beach. Different tide amplitudes, aquifer characteristics, and pollutant release locations were studied. It was found that the tide amplitude, hydraulic conductivity, and longitudinal dispersivity were the primary factors affecting the fate and transport of benzene. The tidal amplitude influenced the transport speed and percentage of biodegradation of benzene plume in the beach. A high tidal range reduced the spreading area and enhanced the rate of benzene biodegradation. Hydraulic conductivity had an impact on plume residence time and the percentage of contaminant biodegradation. Lower hydraulic conductivity induced longer residence time in each beach portion and a higher percentage of biodegradation on the beach. The plume dispersed and the concentration decreased due to high longitudinal dispersivity. The results can be used to support future risk assessment and management for the shorelines impacted by spill and leaking accidents. Modeling the heterogeneous beach aquifer subjected to tides can also be further explored in the future study.     

Enhanced dechlorination of chlorobenzene by microwave-induced zero-valent iron: particle effects and activation energy

Organic compounds such as chlorobenzene cannot be effectively decomposed with currently available biological and chemical treatment methods. Preliminary studies show that nano-scale zero-valent iron particles irradiated by microwave is effective in decomposing chemically refractive organic compounds such as chlorobenzene. In this study, microwave is applied to enhance chlorobenzene removal using micron-scale iron particles and nano-scale zero-valent iron particles suspended in the chlorobenzene solution as the dielectric media. The results show that better chlorobenzene removal can be achieved when the chlorobenzene solution is irradiated with 250 W microwave for 150 s than without microwave irradiation. The microwave radiation increases iron reaction rate and surface activity, thus enhancing the chlorobenzene removal. The microwave-induced iron particles cause the chlorobenzene activation energy to drop 34.0% for micron-scale iron and 16.1% for nano-scale zero-valent iron. They can remove 13.6 times more chlorobenzene for micro iron, and 3.6 times more chlorobenzene for nano iron. We have demonstrated that the microwave-induced nano-scale iron particles are effective in treating toxic organic substances as demonstrated in this laboratory study.     

Detection of polychlorinated biphenyls employing chemical dechlorination followed by biphenyl whole cell sensing system

Polychlorinated biphenyls (PCBs) are a mixture of 209 individual chlorinated compounds commonly known as PCB congeners. These compounds are hydrophobic and are persistent in the environment. Their use was banned in the US a few decades ago because of harmful health effects. Therefore, detection of PCBs in environmental samples is increasingly important. To that end, we have developed a two-step simple and sensitive method for the detection of total PCBs. Specifically, our method involves dechlorination of PCBs to biphenyl followed by detection of biphenyl using a whole cell sensing system as the detection system. The whole cell sensing system consists of cells of the strain Pseudomonas pseudoalcaligenes KF707 harboring plasmid pSD7000. Plasmid pSD7000 contains the gene of lacZ, a reporter protein under the control of the bph operon. The detection is achieved through the emission of light afforded by the expression of reporter protein triggered by the presence of biphenyl. Due to the fact that this operon is activated only by few PCB congeners, a chemical dechlorination method was employed to convert all PCBs to biphenyl, and thus all the PCBs present in a given sample are able to be detected. The results showed that PCB congeners were rapidly (30?min) and efficiently (>98.5%) dechlorinated to biphenyl using a Mg/K₂PdCl₆ catalyst, and the biphenyl could be subsequently quantified using the whole cell sensing system. This hybrid analytical method that combines classical dechlorination with novel biosensing methods may find applications in the on-site monitoring of PCBs contamination levels.     

Breeding and moulting of barnacles under rearing conditions

The reproductive parameters of three species of barnacles common in warm-water regions,Balanus amphitrite Darwin,B. eburneus Gould andB. trigonus Darwin, cultured singly or in pairs for 2 1/2 yr, were compared. All specimens, collected from Tokyo Bay and studied between 1985 and 1987, were fed on newly hatchedArtemia sp. larvae (Tetra strain) and phytoplankton culture and were maintained under constant temperature (20°C) and controlled photoperiods (10 h light:14 h dark). The breeding frequencies of these three species were equally high, from 2 to 4 broods mo^–1 in the first year; they were relatively high between October and February, averaging 3 broods mo^–1.B. amphitrite, B. eburneus andB. trigonus produced 24, 21 and 11 broods yr^–1, respectively. Brood size was quite variable among the three species examined, yielding 4000 embryos brood^–1 inB. amphitrite andB. eburneus and 6000 inB. trigonus. Brood interval averaged 4 to 9 d. The moult occurred over short intervals of 4 to 10 d moult^–1. Both breeding and moulting frequencies were influenced by low temperature and starvation. Self-fertilization was observed in all species and was more frequent inB. amphitrite than inB. eburneus andB. trigonus. Nutritional condition and temperature seemed to be the main external factors regulating both breeding and moulting processes in barnacles.     

Oxidisability of environmental sulphur under different catalytic conditions

The oxidation of elemental sulphur in the catalytic presence of selected metal ions [Cr(III), Ce(III), Cu(II), Hg(II), Ni(II), Co(II), Mo(VI), Cd(II), Zn(II), Ti(IV), and V(V)], and hydrocarbons (benzene, gasoline, and kerosene) was studied in an alkaline medium buffered by marble powder. The catalytic efficiencies of metal ions were: Cr(III) > Ce(III) > Cu(II) > Hg(II) > Ni(II). The oxidation process was inhibited in the presence of other ions, and the inhibitive effect was in the following order: Co(II) < Mo(VI) < Cd(II) < Zn(II) < Ti(IV) < V(V). In the case of hydrocarbons, the efficiencies were as follows: gasoline > benzene > kerosene. The oxidation of sulphur in sulphur-loaded soils obtained from near a textile mill and a distillery were also carried out in the c both cases was significantly enhanced.To whom all correspondence should be addressed.     

Optimal timing of carbon capture policies under learning-by-doing

Using a standard Hotelling model of resource exploitation, we determine the optimal energy consumption paths from three options: dirty coal, which is non-renewable and carbon-emitting; clean coal, which is also non-renewable but carbon-free thanks to carbon capture and storage (CCS); and solar energy, which is renewable and carbon-free. We assume that the atmospheric carbon stock cannot exceed an exogenously given ceiling. Taking into account learning-by-doing in CCS technology, we show the following results: (i) clean coal exploitation cannot begin before the outset of the carbon constrained phase and must stop strictly before the end of this phase; (ii) the energy price path can evolve non-monotonically over time; and (iii) when the solar cost is low enough, an unusual energy consumption sequence along with solar energy is interrupted for some time and replacement by clean coal may exist.     

Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions

The mobility of phenanthrene (PHE) in soils depends on its sorption and is influenced by either the existing soil humus or exogenous humic substances. Exogenous humic acids (HAs) were added to soil to enhance the amount of soil organic carbon (SOC) by 2.5, 5.0, and 10.0 g kg⁻¹. PHE desorption of the treated soils was determined at two pH levels (3.0 and 6.0) and temperatures (15 and 25 °C). Soil PHE adsorption was related to pH and the type and quantity of added HAs. Humic acid (HA) and fulvic acid (FA) derived from peat had different effects on adsorption of PHE. Adsorption increased at first and then decreased with increasing quantity of exogenous FA. When the soil solution pH (in 0.005 M CaCl₂) was 4.5 or 3.0, the turning points were 2.5 g FA kg⁻¹ at pH 3.0 and 5 g FA kg⁻¹ at pH 4.5. When soil solution pH was 6, the amount of adsorbed PHE was enhanced with increasing exogenous HAs (HA or FA) and amount of adsorption by soil treated with FA was higher than with HA. Adsorption of PHE in the FA treatment at 10.0 g kg⁻¹ was lower than the controls (untreated soil or treatment with HAs at 0 g kg⁻¹) when the soil solution pH was 3.0. This suggests that FA adsorbed by soil was desorbed at low pH and would then increase PHE solubility, and PHE then combined with FA. PHE adsorption was usually higher under lower pH and/or lower temperature conditions. PHE sorption fitted the Freundlich isotherm, indicating that exogenous humic substances influenced adsorption of phenanthrene, which in turn was affected by environmental conditions such as pH and temperature. Thus, exogenous humic substances can be used to control the mobility of soil PAHs under appropriate conditions to decrease PAH contamination.     

常温常压KBH4还原法快速脱除水煤浆中的硫

使用KBH4还原法脱除水煤浆中的硫.在常温常压,KBH4浓度为2.0 mmol.L-1、煤炭粒径109μm、处理时间10 min、搅拌速度为200 r.min-1的条件下,低硫水煤浆中煤炭的总脱硫率可以达到43.0%.而且硫酸盐硫的脱除率约47.8%,黄铁矿硫的脱除率约55.4%;同时有机硫的脱除率约23.9%.硼氢化钾还原法相比其它传统化学脱硫方法,对有机硫和无机硫脱除均有作用,试剂用量少,反应条件温和,脱硫速度快,热值的损耗小,处理后水煤浆中煤炭的热值有所提高,起燃温度降低.