臭氧水中传质模型的研究

在传统鼓泡塔中对臭氧在水中的传质过程进行实验研究。利用实验改变进水流量、臭氧进气流量以及臭氧进气浓度等，得到臭氧传质系数、臭氧传质效率和臭氧消耗等有关参数。建立一个臭氧传质模型，可以预测不同操作条件下臭氧传质效率，从而优化控制臭氧化反应动力学。     

Uptake of Aromatic Hydrocarbon Vapors (Benzene and Phenanthrene) at the Air-Water Interface of Micron-Size Water Droplets

Abstract

Uptake of aromatic hydrocarbon vapors (benzene and phenanthrene) by typical micrometer-sized fog-water droplets was studied using a falling droplet reactor at temperatures between 296 and 316 K. Uptake of phenan-threne vapor greater than that predicted by bulk (air-water)-phase equilibrium was observed for diameters less than 200 μm, and this was attributed to surface adsorption. The experimental values of the droplet-vapor partition constant were used to obtain the overall mass transfer coefficient and the mass accommodation coefficient for both benzene and phenanthrene. Mass transfer of phenanthrene was dependent only on gas-phase diffusion and mass accommodation at the interface. However, for benzene, the mass transfer was limited by liquid-phase diffusion and mass accommodation. A large value of the mass accommodation coefficient, α = (1.4 ± 0.4) × 10^?2 was observed for the highly surface-active (hydrophobic) phenanthrene, whereas a small α = (9.7 ± 1.8) × 10^?5 was observed for the less hydrophobic benzene. Critical cluster numbers ranging from 2 for benzene to 5.7 for phenanthrene were deduced using the critical cluster nucleation theory for mass accommodation. The enthalpy of mass accommodation was more negative for phenanthrene than it was for benzene. Consequently, the temperature effect was more pronounced for phenanthrene. A linear correlation was observed for the enthalpy of accommodation with the excess enthalpy of solution. A natural organic carbon surrogate (Suwannee Fulvic acid) in the water droplet increased the uptake for phenanthrene and benzene, the effect being more marked for phenanthrene. A characteristic time constant analysis showed that uptake and droplet scavenging would compete for the fog deposition of phenanthrene, whereas deposition would be unimpeded by the uptake rate for benzene vapor. For both compounds, the characteristic atmospheric reaction times were much larger and would not impact fog deposition.     

污泥浓度对微孔曝气氧传质过程的影响

污泥浓度是影响微孔曝气氧传质过程的重要因素之一。在小试及中试规模上,研究了不同污泥浓度对微孔曝气氧传质过程的影响,得出曝气性能随污泥浓度的变化规律。结果表明,当污泥浓度低于2000mg／L时,曝气性能随浓度的增大而增强,在2000～3000mg／L时,KLa达到最大值;当污泥浓度大于2000～3000mg／L时,曝气性能随污泥浓度增大而降低,当污泥浓度大于5000mg／L时,曝气性能急剧降低。这一规律对于在设计和运行中合理确定污水处理中的污泥浓度,在达到处理效果的前提下,尽量降低电耗具有重要意义。     

填料塔中Na2CO3吸收高浓度H2S的传质特性

在填料吸收塔中考察了Na2CO3溶液吸收高浓度H2S气体的气液传质特性。通过测量填料塔进出口气体中H2S浓度计算了Na2CO3溶液吸收高浓度H2S气体的总体积传质系数（KGa）,并研究了进气流速、吸收液流量、吸收温度和吸收液浓度对KGa的影响。结果表明,KGa随Na2CO3浓度、吸收液流量的增加而增加,随吸收温度、进气流速的升高而降低;在高浓度H2S吸收过程中液相传质阻力不能忽略。     

水体中化学需氧量的快速测定

介绍了一种快速测定水体中COD的新方法，该法将近红外光谱分析技术中的化学计量学方法应用到紫外可见光区域，对水体进行COD测试，并将结果和标准试验方法进行比较，取得了令人满意的结果。     

Terbuthylazine Contamination of the Aquifer North of Vicenza (North-East Italy) (5 pp)

- DOI: http://dx.doi/10.1065/espr2006.01.016 Background and Goal Agricultural practices can affect the quality of aquifers given that they are often located in cropped areas, so significant amounts of pesticides can be found in the water. In particular, triazine herbicides are always carefully checked by the official monitoring systems. The goal of this study was to find the mean concentration of terbuthylazine in an Italian aquifer and to set up a mass balance of this compound. Methods Terbuthylazine concentrations in the aquifer were measured in various check-wells during 1998–2004, and the value of censored data were estimated using a Gompertz inverse in order to evaluate the overall mean concentration. The total terbuthylazine load in the recharge area was calculated on the basis of surveys of cropped land and the main weed control techniques applied in the area. Data on aquifer water balance were obtained from previous studies. Results and Discussion The herbicide terbuthylazine applied in the recharge zone can be transported by surface water and enter the aquifer. Detected concentrations were always well below the EU drinking water limit and the fraction that can reach the groundwater under normal cropping practices is small, very likely less than 0.2%. Recommendations and Outlook The use and application rates of pesticides should be strictly regulated in recharge areas. Vegetated buffer strips can mitigate the impact of herbicides on surface water through reducing drift and early-spring runoff. Attention should also be paid to the fate of the main metabolites from soil biochemical processes.     

填料塔中Na_2CO_3吸收高浓度H_2S的传质特性

在填料吸收塔中考察了Na2CO3溶液吸收高浓度H2S气体的气液传质特性。通过测量填料塔进出口气体中H2S浓度计算了Na2CO3溶液吸收高浓度H2S气体的总体积传质系数(KGa),并研究了进气流速、吸收液流量、吸收温度和吸收液浓度对KGa的影响。结果表明,KGa随Na2CO3浓度、吸收液流量的增加而增加,随吸收温度、进气流速的升高而降低;在高浓度H2S吸收过程中液相传质阻力不能忽略。     

Transformation and Ecotoxicity of Carbamic Pesticides in Water (5 pp)

Background N-methylcarbamate insecticides are widely used chemicals for crop protection. This study examines the hydrolytic and photolytic cleavage of benfuracarb, carbosulfan and carbofuran under natural conditions. Their toxicity and that of the corresponding main degradation products toward aquatic organisms were evaluated. Methods Suspensions of benfuracarb, carbosulfan and carbofuran in water were exposed to sunlight, with one set of dark controls, for 6 days, and analyzed by 1H-NMR and HPLC. Acute toxicity tests were performed on Brachionus calyciflorus, Daphnia magna, and Thamnocefalus platyurus. Chronic tests were performed on Pseudokirchneriella subcapitata, and Ceriodaphnia dubia. Results and Discussion Under sunlight irradiation, benfuracarb and carbosulfan gave off carbofuran and carbofuran-phenol, while only carbofuran was detected in the dark experiments. The latter was degraded to phenol by exposure to sunlight. Effects of pH, humic acid and KNO3 were evaluated by kinetics on dilute solutions in the dark and by UV irradiation, which evidenced the lability of the pesticide at pH 9. All three pesticides and phenol exhibited acute and higher chronic toxicity towards the aquatic organisms tested. Conclusion Investigation on the hydrolysis and photolysis of benfuracarb and carbosulfan under natural conditions provides evidence concerning the selective decay to carbofuran and/or phenol. Carbofuran is found to be more persistent and toxic. Recommendations and Outlook The decay of benfuracarb and carbosulfan to carbofuran and the relative stability of this latter pesticide account for many papers that report the detection of carbofuran in water, fruits and vegetables.     

Biosorption and Biovolatilization of Arsenic by Heat-Resistant Fungi (5 pp)

Goal, Scope and Background

The aim of this work is to show the ability of several fungal species, isolated from arsenic polluted soils, to biosorb and volatilize arsenic from a liquid medium under laboratory conditions. Mechanisms of biosorption and biovolatilization play an important role in the biogeochemical cycle of arsenic in the environment. The quantification of production of volatile arsenicals is discussed in this article.

Methods

Heat-resistant filamentous fungi Neosartorya fischeri, Talaromyces wortmannii, T. flavus, Eupenicillium cinnamopurpureum, originally isolated from sediments highly contaminated with arsenic (more than 1403 mg.l-1 of arsenic), and the non-heat-resistant fungus Aspergillus niger were cultivated in 40 mL liquid Sabouraud medium (SAB) enriched by 0.05, 0.25, 1.0 or 2.5 mg of inorganic arsenic (H3AsO4). After 30-day and 90-day cultivation under laboratory conditions, the total arsenic content was determined in mycelium and SAB medium using the HG AAS analytical method. Production of volatile arsenic derivates by the Neosartorya fischeri strain was also determined directly by hourly sorption using the sorbent Anasorb CSC (USA).

Results

Filamentous fungi volatilized 0.025–0.321 mg of arsenic from the cultivation system, on average, depending on arsenic concentrations and fungal species. The loss of arsenic was calculated indirectly by determining the sum of arsenic content in the mycelium and culture medium. The amount of arsenic captured on sorption material was 35.7 ng of arsenic (22nd day of cultivation) and 56.4 ng of arsenic (29th day of cultivation) after one hour's sorption. Biosorption of arsenic by two types of fungal biomass was also discussed, and the biosorption capacity for arsenic of pelletized and compact biomass of Neosartorya fischeri was on average 0.388 mg and 0.783 mg of arsenic, respectively.

Discussion

The biosorption and amount of volatilized arsenic for each fungal species was evaluated and the effect of initial pH on the biovolatilization of arsenic was discussed.

Conclusions

The most effective biovolatilization of arsenic was observed in the heat-resistant Neosartorya fischeri strain, while biotransformation of arsenic into volatile derivates was approximately two times lower for the non-heat-resistant Aspergillus niger strain. Biovolatilization of arsenic by Talaromyces wortmannii, T. flavus, Eupenicillium cinnamopurpureum was negligible. Results from biosorption experiments indicate that nearly all of an uptaken arsenic by Neosartorya fischeri was transformed into volatile derivates.

Recommendations and Perspective

. Biovolatilization and biosorption have a great potential for bioremediation of contaminated localities. However, results showed that not all fungal species are effective in the removal of arsenic. Thus, more work in this research area is needed.

     

Photocatalytic Treatment of RDX Wastewater with Nano-Sized Titanium Dioxide (5 pp)

Background, Aim and Scope The polynitramines, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are important military explosives and regulated toxic hazardous compounds. Production, testing and use of the compounds has resulted in numerous acres of contaminated soils and groundwater near many munitions facilities. Economical and efficient methods for treatment of wastewater and cleanup of soils or groundwater containing RDX and HMX are needed. This study focuses on the photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide (nano-TiO2) under simulated sunlight, whose intensity and wavelength are similar to that of the real sunlight in Xi'an at noon. The objective is to determine the potential for RDX destruction with nano-TiO2 in aqueous solution. Materials and Methods: An activated carbon fiber (ACF) cloth-loaded with nano-TiO2 was put into the RDX containing solution, and the concentration of RDX was measured (by HPLC–UV) at regular time intervals under simulated sunlight. Results: The RDX degradation percentage of the photocatalytic process is higher than that of Fenton oxidation before 80 min, equivalent after 80 min, and it reaches 95% or above after 120 min. The nano-TiO2 catalyst can be used repeatedly. Discussion: The photocatalytic degradation kinetics of RDX under simulated sunlight can be described by a first-order reaction kinetics equation. The possible degradation mechanism of RDX was presented and the degradation performance was compared with that of biological method. Conclusions: It was demonstrated that the degradation of RDX wastewater is very effective with nano-TiO2 as the photocatalytic catalyst under simulated sunlight. The efficiency of the nano-TiO2 catalyst for RDX degradation under simulated sunlight is nearly identical to that of Fenton oxidation. Recommendations and Perspectives: To date, a number of catalysts show poor absorption and utilization of sunlight, and still need ultraviolet light irradiation during wastewater degradation. The nano-TiO2 used in the described experiments features very good degradation of RDX under simulated sunlight, and the manufacturing costs are rather low (around 10 Euro/m2). Moreover, the degradation efficiency is higher compared to that of the biological method. This method exhibits great potential for practical applications owing to its easiness and low cost. If it can be applied extensively, the efficiency of wastewater treatment will be enhanced greatly.     

Distribution and Fractionation of Copper in Soils of Apple Orchards (5 pp)

Background Frequent application of Bordeaux mixture, which includes copper, as a fungicide in fruit and grape orchards may lead to copper accumulation in the soil, especially when orchard age and application times increase. The objectives of this study were: (i) to investigate the copper content and its spatial distribution in orchard soils; (ii) to identify the copper fractionation in soil and its relationship with plant uptake; (iii) to understand the characteristics of copper contamination in orchard soils. Materials and Methods Soil profile samples were taken in apple orchards with ages of 0, 5, 10, 20, 30 years and pot experiments were also carried out to study the effects of external copper input on copper fractionation. All soil samples were air-dried, ground and extracted with 0.43 mol L–1 HNO3 for the total absorbed copper. Fractionation determination was conducted following Tessier and Shuman sequential extraction methods, and copper was measured with AAS. Plant samples were first dry ashed, dissolved with 6 mol L–1 HCl and then copper and other elements were measured with ICP-MS.Results and Discussion Soil total Cu was higher in the apple orchards than that in non-orchard fields and was seen to have increased with orchard age. Soil Cu increased substantially with the average annual copper increase, ranging from 2.5 to 9 mg Cu kg–1. The distribution of copper in the soil profile was uneven, decreasing from surface to deeper layers, and the differences were significant, but the contents in every layer were also significantly correlated with those in the next layers. For all copper fractions, the organically bound, crystalline Mn oxide bound, and amorphous Fe bound fractions extracted with the Shuman method were much higher than the exchangeable and residual fractions. Using the Tessier method, organically bound, carbonate bound and Fe-Mn oxide bound fractions were much higher. With an increase in external copper input, the organically bound, crystalline Mn oxide bound and amorphous Fe bound fractions in the Shuman method and organically bound, carbonate bound and Fe-Mn oxide bound fractions in the Tessier method all increased significantly, while the changes in other fractions were not significant. Soil total copper and copper fractions were found to have good correlations with apple tree uptake. Copper in fruit flesh had significant correlations with soil total content in the 0–10 cm layer, all the copper fractions in the 0–5 cm layer, and some fractions in the deeper layers. Conclusion Copper content in orchard soils increased significantly with intensive application of Bordeaux mixtures and orchard age. Copper content decreased sharply from the topsoil to deeper soil layers. The copper contents in different layers also significantly correlated with those in the next layers. Dominant fractions of the copper in soil were mainly associated with organic matter, iron and manganese oxides and carbonates. A close relationship was found between the copper content in soils and in apple tree organs (which contained 8.9 to 66mg kg–1 Cu). Recommendation and Perspective Though most copper in the soil was specifically adsorbed or immobilized, and copper was mainly distributed in topsoil, which was essentially devoid of roots, the copper concentration of fruit still had significantly positive correlations with soil copper and most copper fractions. Therefore, measures must be taken to control copper accumulation in orchard soils and to make the apple fruit production sustainable.     

Uptake and Modeling of Pesticides by Roots and Shoots of Parrotfeather (Myriophyllum aquaticum) (5 pp)

Intention, Goal, Scope, Background Aquatic plants have a great potential to function as in situ, on-site biosinks and biofilters of pollutants. They are used for phytoremediation and phytotoxicity studies. Pesticide uptake studies are very important to predict contaminant accumulation, translocation, and transformation. There are a lot of models which have been developed for emergent plants, but there are not any existing models for submerged aquatic plants for assessing pesticide uptake. Objective In this study, uptake of selected pesticides in parrotfeather (Myriophyllum aquaticum) were studied and the results were modeled with the aid of Log Kow and the concentration of pesticides. At the end, the developed model was compared to other existing models. Methods The test was conducted with parrotfeather as a model plant. The bioassay and cultivation of this plant were examined. Pesticide uptake by roots and shoots was determined using 14C-radiolabeled materials. Results and Discussion The results were fitted with an equation that showed a relationship between uptake and lipophilicity of pesticides. The model was compared with other pesticide uptake models developed for other plants. Atrazine and cycloxidim were taken up more by roots than by shoots in comparison to other pesticides used. The total uptake, both in shoots and roots, was lower than for terbutryn and trifluralin. The best appropriate model was developed from the results against the other models seen in the literature. The concentration factors (Root Concentration Factor (RCF) and Submerged Shoot Concentration Factor (SSCF)) increased with a higher Kow of the substances. The Submerged Shoot Concentration Factor (SSCF) revealed a better relationship of the chemicals than did the Root Concentration Factor (RCF). Conclusions In this study, an uptake model was developed for rooted, submerged aquatic plants. Further studies are necessary to develop and compare models with different plants and pesticides. Recommendation and Outlook Such studies as this one may be extended to other environmental pollutants in the aquatic ecosystem and may be employed to evaluate the possibility of using different plants in phytoremediation studies.     

Life Cycle Assessment as Part of Sustainability Assessment for Chemicals (5 pp)

Background LCA is the only internationally standardized environmental assessment tool (ISO 14040-43) for product systems, including services and processes. The analysis is done ‘from cradle-to-grave’, i.e. over the whole life cycle. LCA is essentially a comparative method: different systems fulfilling the same function (serving the same purpose) are compared on the basis of a ‘functional unit’ - a quantitative measure of this function or purpose. It is often believed that LCA can be used for judging the (relative) sustainability of product systems. This is only partly true, however, since LCA is restricted to the environmental part of the triad ‘environment/ecology - economy - social aspects (including intergenerational fairness)’ which constitutes sustainability. Standardized assessment tools for the second and the third part are still lacking, but Life Cycle Costing (LCC) seems to be a promising candidate for the economic part. Social Life Cycle Assessment still has to be developed on the basis of known social indicators.Method and Limitations LCA is most frequently used for the comparative assessment or optimization analysis of final products. Materials and chemicals are difficult to analyse from cradle-to-grave, since they are used in many, often innumerable product systems, which all would have to be studied in detail to give a complete LCA of a particular material or substance! This complete analysis of a material or chemical is evidently only possible in such cases where one main application exists. But even if one main application does exist, e.g. in the case of surfactants (chemicals) and detergents (final products), the latter may exist in a great abundance of compositions. Therefore, chemicals and materials are better analysed ‘from cradle-to-factory gate’, leaving the analysis of the final product(s), the use phase and the ‘end-of-life’ phases to specific, full LCAs.Conclusion A comparative assessment of production processes is possible, if the chemicals (the same is true for materials) produced by different methods have exactly the same properties. In this case, the downstream phases may be considered as a ‘black box’ and left out of the assessment. Such truncated LCAs can be used for environmental comparisons, but less so for the (environmental) optimization analysis of a specific chemical: the phases considered as ‘black box’ and left out may actually be the dominant ones. A sustainability assessment should be performed at the product level and contain the results of LCC and social assessments. Equal and consistent system boundaries will have to be used for these life cycle tools which only together can fulfil the aim of assessing the sustainability of product systems.     

Phytoremediation of Cadmium-Contaminated Soils by Rorippa globosa Using Two-Phase Planting (5 pp)

Background Phytoextraction of contaminated soils by heavy metals can provide a great promise of commercial development. Although there are more than 400 species of hyperaccumulators found in the world, phytoremediation technology is rarely applied in field practice for remedying contaminated soils, partially due to low biomass and long growth duration for most of discovered hyperaccumulating plants. In order to enhance the metal-removing efficiency in a year, the two-phase planting countermeasure of phytoextraction by harvesting anthesis biomass was investigated on the basis of the newly found Cd-hyperaccumulator Rorippa globosa (Turcz.) Thell. with 107.0 and 150.1 mg/kg of the Cd accumulation in stems and leaves, respectively, when soil Cd added was concentrated to 25.0 mg/kg. Methods The field pot-culture experiment was used to observe the distribution property of R. globosa aboveground biomass and to examine characteristics of accumulating Cd by the plant at different growth stages. The concentration of Cd in plants and soils was determined using atomic absorption spectrophotometry (AAS). Results and Discussion The results indicated that the total dry stem and leaf biomass of R. globosa harvested at the flowering phase was up to 92.3% of that at its full maturity and the concentration of Cd in stems and leaves harvested at the flowering phase was up to 73.8% and 87.7% of that at the mature phase, respectively. The Cd-removing ratio by shoots of R. globosa harvested at the flowering phase was up to 71.4% of that at the mature phase. It was also found, by observing the growth duration of R. globosa, that the frostless period at the experiment site was twice as long as the growth time from the seedling-transplanted phase to the flowering phase of the hyperaccumulator. Conclusion R. globosa could be transplanted into contaminated soils twice in one year by harvesting the hyperaccumulator at its flowering phase based on climatic conditions of the site and traits of the plant growth. In this sense, the extraction efficiency of Cd in shoots of R. globosa increased 42.8% compared to that of at its single maturity when the plant was transplanted into contaminated soils after it had been harvested at its flowering phase and the plant accumulated Cd from soil at the same extraction ratio at its second flowering phase. Thus, the method of anthesis biomass regulation by the two-phase planting is very significant to increase the Cd-removing efficiency by phytoremediation used in practice over the course of a year. Recommendation and Outlook As for some hyperaccumulators that the growth duration from the seedling-transplanted phase to the flowering phase are short and the concentrations of heavy metals accumulated in their shoots at the flowering phase are high, the efficiency of phytoremediation can greatly be improved using the method of the two-phase planting.     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

Impact of Bioaugmentation with a Consortium of Bacteria on the Remediation of Wastewater-Containing Hydrocarbons (5 pp)

Goals, Scope and Background It has been observed that hydrocarbon treated wastewaters still contain high COD and a number of intermediates. This suggests that the required catabolic gene pool for further degradation might be absent in the system or, that its titer value is not significant enough. By providing the desired catabolic potential, the overall efficiency of the treatment system can be improved. This study aims to demonstrate this concept by bioaugmentation of a lab-scale reactor treating refinery wastewater with a consortium having the capacity to complement the alkB genotype to the available microbial population. Methods Two reactors were set up using activated biomass collected from a refinery treatment plant and operated at a continuous mode for a period of 8 weeks. The feed to both reactors was kept constant. Crude oil was spiked regularly. One reactor was bioaugmented with a consortium previously described for crude oil spill remediation. The efficiency of the bioaugmented reactor was demonstrated by reduced COD. The changes in the microbial population over a period of time were analyzed by RAPD. Catabolic activity of the biomass in both reactors was monitored by PCR. The presence of the catabolic loci was confirmed by Southern Hybridization. Results and Discussion 52.2% removal of COD was observed in the bioaugmented reactor while only 15.1% reduction of COD was observed in the reactor without bioaugmentation. The change in microbial population can be seen from the 4th week, which also corresponds to improved catabolic activity. The presence of the bedA locus was seen in all samples, which indicates the presence of aromatic degraders, but the appearance of the alkB locus, from the 6th week onwards, which was observed only in the samples from the bioaugmented reactor. The results suggest that the gene pool of the bioaugmented reactor has catabolic loci that can degrade accumulated intermediates, thus improving the efficiency of the system. Conclusions In this study, improvement of efficiency of bioremediation was demonstrated by addition of catabolic loci that are responsible for degradation. Bioaugmentation was carried out in biomass that was collected from an ETP (effluent treatment plant) treating hydrocarbon containing wastewater to study the strategies for improvement of the treatment system. Biostimulation, only marginally improved the efficiency, when compared to bioaugmentation. The improved efficiency was demonstrated by COD removal. The presence of the alkB locus suggests the importance of a catabolic gene pool that acts on accumulated intermediates. It is well documented that straight chain aliphatics and intermediates of aromatic compounds after ring cleavage, accumulate in refinery wastewater systems, thereby hindering further degradation of the wastewater. Supplementation of a catabolic gene pool that treats the lower pathway compounds and alkanes will improve the overall efficiency. In this study, results suggest that the alkB locus can also be used to monitor the degradative mode of the activated biomass. Recommendations and Perspective . Pollution from petroleum and petroleum products around the globe are known to have grave consequences on the environment. Bioremediation, using activated sludge, is one option for the treatment of such wastes. Effluent treatment plants are usually unable to completely degrade the wastewater being treated in the biological unit (the aerator chambers). The efficiency of degradation can be improved by biostimulation and bioaugmentation. This study demonstrates the improved efficiency of a treatment system for wastewater containing hydrocarbons by bioaugmentation of a consortium that supports degradation. Further experiments on a pilot scale are recommended to assess the use of bioaugmentation on a large scale. The use of molecular tools, like DNA probes for alkB, to monitor the system also needs to be explored.     

The Orange-Brown Patina of Salisbury Cathedral (West Porch) Surfaces: Evidence of its Man-Made Origin (5 pp)

Goal, Scope and Background In this paper, we attempt to elucidate the composition and origin of the orange patina on the surfaces of the West-Porch of Salisbury Cathedral by comparison to other known patinas: (i) the orange-brown patina on the marble surfaces of the Acropolis in Athens and the Arch of Titus in Rome whose analyses have shown very high amounts of phosphates, and generally amino acids from animal-skin glue or other protein binders; (ii) the phosphated patinas which also contain oxalates, found in 1996 on Catalonian calcareous sandstones and in the calcareous dolomites of the Monastery of Silos, Spain, whose origin is either the application of calcium caseinate, or egg yolk and animal glue; and (iii) the patinas with only oxalates found in some of Verona's monuments (St Zeno) and Spanish sites as in the Monastery of Guadalupe and Cuenca cathedral, formed either by the mineralization of algal filaments or by biological reactions yielding oxalate from yolk egg (added to stone as part of preservative empirical treatments). Methods In the winter of 2003, the West-Porch of Salisbury Cathedral received conservation works, but the old patina was not entirely removed. This fact has allowed us to collect the samples for its study. The IR spectra were registered with a Golden Gate ATR Mk II system using attenuated total reflectance Fourier transform infrared (ATR/FTIR) spectrometry. Mineral composition was determined by XRD (Philips PW 1710 spectrometer with Cu tube), whereas major and trace elements analyses were performed by XRF (Philips PW1480 PW). Microscopy examination was performed on a Leica M655 microscope. Phosphate, oxalate, calcium and sulphate contents were analysed by usual chemical methods. Results ATD-FTIR spectra of the Salisbury's patina exhibit peaks at 2361, 2341 and 671 cm–1 (assigned to phosphates); 3410, 1680, 1620, 1122 and 602 cm–1 (assigned to sulphates); and 1447/1437 and 876 cm–1 (attributed to carbonates). The little peaks at 1620 and 798 cm–1 could be assigned to oxalates. XRD and XRF have led to identify the carbonates, phosphates and sulphates as pertaining to the species dolomite, hydroxyapatite and gypsum, respectively. Oxalates are detected only in small amounts by chemical analyses but wewellite and weddellite have not been well identified. The interface between the patina and the calcareous dolomite is very uneven and full of cavities in certain cases, but well-defined and rather smooth in other cases. In accord with the very small amounts of the oxalates found, remnants of micro-organisms are not detected in the patinas. Discussion The Salisbury's patina is a composite material formed by particulates and matrix constituents. Regarding the patina particulate, e.g. animal bones, it is necessary to refer to the apatite phase composition. The bone mineral contains 4–8 wt % of carbonate in animal body and its presence in the apatite phase is advantageous as it increases the mechanical strength. We think that FTIR bands at around 1440 and 876 cm–1 arise from vibration of CO32– ions, but not necessarily from the limestone. They could be attributed to carbonated hydroxyapatite through the substitution of groups PO43– for CO32– in the lattice of hydroxyapatite. Concerning the matrix and also from the FTIR spectra, the absence of specific bands of the following species: proteins (3350–3225, 1660, 1550–1535, 1270–1230 and 620 cm–1), oils (1778, 1738 and 1051 cm–1), bee waxes (3000, 1470, 720–730 and 1700 cm–1) and aged egg-yolk (2954, 2920, 2850, 1650, 1549, 1465 and 1240 cm–1) had led us to exclude these usual binders. On the other hand, the amount of sulphates in the paste that covers the walls of the Salisbury's Cathedral is excessively high (above 20% in weight) to consider it as a biotransformation product of calcium oxalate from fungal biofilms. Consequently, we must think that the gypsum found in the samples has a man-made origin (it was deliberately added as part of a protective paste) and that it is the matrix searched for. Thus, we deduce that the patina of Salisbury's Cathedral is a special stucco made mixing plaster with powdered bone (the colour of the bones is the same that it exhibits in the patina), low quantities of an uncharacterized binder (collagen, possibly) and water. Conclusion We believe that the patina of the Salisbury's Cathedral is a variant of the Greco-Latin empirical protective treatment that included bone as a hardening material. Nevertheless, we also think that the presence of the bones in the paste could be related to an aesthetical intention: gaining a warm tone for the original stone through the ochre colour of the bones. Recommendation and Perspective Our results have been an excuse to contribute to the controversy started at the 80's on the origin of orange-brown patinas observed on stone surfaces of Greco-Latin and medieval monuments. There are two major theories on provenance: biological vs. man-made. In Salisbury Cathedral, neither of them has been proven through scientific evidence as yet. Our opinion is that Salisbury patina can be classified into the man-made group.     

Influence of Phenanthrene on Cadmium Toxicity to Soil Enzymes and Microbial Growth (5 pp)

Background Many contaminated sites contain a variety of toxicants. Risk assessment and the development of soil quality criteria therefore require information on the interaction among toxicants. Interactions between heavy metals are relatively well studied, but little is known about those between heavy metals and polycyclic aromatic hydrocarbons (PAHs). Methods 0.1 mg/kg dry soil phenanthrene alone or phenanthrene plus 10 mg/kg cadmium (Cd) were added to soil to determine the influence of phenanthrene on Cd toxicity to soil enzymes (invertase, urease, dehydrogenase and phosphatase) and microorganisms (fungi, bacteria and actinomycete) in paddy soil. Results and Discussion 0.1 mg/kg phenanthrene did not reduce the number of microorganisms. However, the addition of phenanthrene to soil with Cd enhanced the Cd toxicity to soil enzymes and microorganisms. This deleterious effect was seen to mainly affect the growth of fungi and the activity of invertase, urease and dehydrogenase. The order of combined inhibition of Cd and phenanthrene was fungi>bacteria>actinomycete. Conclusion The presence of phenanthrene might enhance the toxicity of Cd to soil microorganisms. Phenanthrene can easily be used by the soil actinomycetes as a source of carbon and energy and the finding may be supportive to the development of bioremediation techniques.     

基于低频振动强化物质传递过程的污水处理效能提升机制

考察了在低溶解氧(DO)条件下,低频机械振动(LFMVs)的加入对AO工艺脱氮效果的影响,从氧在气—液—固三相之间的传质效率、污泥絮体结构变化以及理化特性等方面进行了机理探究。结果表明：在(1.5±0.3) mg·L⁻¹的低DO浓度下,随着振动频率的增加,系统 COD和TN的去除率有所提高,在40 Hz时达到最高,平均去除率分别为94.86%和76.88%,相比于对照组R0分别提升了5.42%和23.46%,此时,气-液间氧传递系数增加约140.46%,液-固间氧扩散系数增加了255.26%;理化特性分析结果表明,气-液间氧传递系数的增加是由于LFMVs强化了液相的湍流流态造成的,而液-固间氧扩散系数的提升主要是因为LFMVs的引入降低了污泥粒径,增大了絮体间孔隙和刺激了胞外聚合物(EPS)的分泌。此外,经济性评估结果表明,荷载 LFMVs的AO反应器比传统模式AO反应器的综合用电量低0.12 kW·(m³·h)⁻¹。     

Uncertainty analysis using a fugacity-based multimedia mass-balance model: Application of the updated EQC model to decamethylcyclopentasiloxane (D5)

The EQuilibrium Criterion (EQC) model developed and published in 1996 was recently revised to include improved treatment of input partitioning and reactivity data, temperature dependence and an easier sensitivity and uncertainty analysis. This New EQC model was used to evaluate the multimedia, fugacity-based fate of decamethylcyclopentasiloxane (D5; CAS No. 541-02-6) in the environment over a temperature range of 1–25 °C. In addition, Monte Carlo uncertainty analysis was used to quantitatively determine the influence of temperature and input partitioning and reactivity data on the behavior of D5 under various emission scenarios. Results indicated that emission mode was the most influential factor determining the fate and distribution of D5 in the model environment. When emitted to air and soil, D5 partitioned to and remained in the air compartment where rates of removal from degradation and advection processes were relatively rapid. In contrast, D5 emitted to water resulted in a substantial mass fraction of D5 being accumulated in the sediment compartment, where rates of removal from degradation and advection processes were slow. The mass distributions and fate of D5 in the model environment were strongly influenced by multiple input parameters, including temperature, the mode of emission (especially emission rate to water), K_OC and half-life in air. As temperature decreased from 25 °C to 1 °C, K_OC and half-life in air became increasingly more influential such that the mass distribution of D5 increased in air and decreased in sediment, resulting in decreased overall persistence.