Photocatalytic degradation of gaseous perchloroethylene: products and pathway

Batch photocatalytic degradation of 1000-ppm gaseous perchloroethylene (PCE) was conducted with UV irradiation such that nearly 100% was decomposed within 10 min. The main intermediate and final product were identified as trichloroacetylchloride (TCAC) and hydrogen chloride (HCl), respectively, and minor ones as dichloroacetic acid (DCAC), monochloroacetic acid (MCAC), carbon tetrachloride, chloroform, and phosgene. More than 90% of Cl- equivalent, i.e., the sum of the chlorine number in PCE, intermediates, and HCl, was compensated for during the time of PCE degradation; a result indicating that no other major chlorinated intermediates are present during the time of PCE degradation. In a similar experiment, 500 ppm of gaseous TCAC degraded into HCl within 3 h without producing DCAC or MCAC, where like PCE, more than 90% of Cl- equivalent, i.e., the sum of the chlorine number in TCAC and HCl, was compensated for during time of TCAC degradation. Accordingly, gaseous PCE is concluded to predominantly follow a degradation pathway of PCE --> TCAC --> HCl.     

The viability of professional wet cleaning as a pollution prevention alternative to perchloroethylene dry cleaning

The vast majority of dry cleaners worldwide use the toxic chemical perchloroethylene (PCE), which is associated with a number of adverse health and environmental impacts. Professional wet cleaning was developed as a nontoxic alternative to PCE dry cleaning but has not been widely adopted as substitute technology. In the greater Los Angeles, CA, region, a demonstration project was set up to showcase this technology and evaluate its commercial viability by converting seven cleaners from PCE dry cleaning to professional wet cleaning. The demonstration site cleaners who switched to professional wet cleaning were able to maintain their level of service and customer base while lowering operating costs. The cleaners were able to transition to professional wet cleaning without a great degree of difficulty and expressed a high level of satisfaction with professional wet cleaning. Crucial to this success was the existence of the demonstration project, which helped to develop a supporting infrastructure for professional wet cleaning that had otherwise been lacking in the garment care industry.     

Assessing the relationship between personal particulate and gaseous exposures of senior citizens living in Baltimore, MD

We conducted a multi-pollutant exposure study in Baltimore, MD, in which 15 non-smoking older adult subjects (> 64 years old) wore a multi-pollutant sampler for 12 days during the summer of 1998 and the winter of 1999. The sampler measured simultaneous 24-hr integrated personal exposures to PM2.5, PM10, SO4(2-), O3, NO2, SO2, and exhaust-related VOCs. Results of this study showed that longitudinal associations between ambient PM2.5 concentrations and corresponding personal exposures tended to be high in the summer (median Spearman's r = 0.74) and low in the winter (median Spearman's r = 0.25). Indoor ventilation was an important determinant of personal PM2.5 exposures and resulting personal-ambient associations. Associations between personal PM2.5 exposures and corresponding ambient concentrations were strongest for well-ventilated indoor environments and decreased with ventilation. This decrease was attributed to the increasing influence of indoor PM2.5 sources. Evidence for this was provided by SO4(2-) measurements, which can be thought of as a tracer for ambient PM2.5. For SO4(2-), personal-ambient associations were strong even in poorly ventilated indoor environments, suggesting that personal exposures to PM2.5 of ambient origin are strongly associated with corresponding ambient concentrations. The results also indicated that the contribution of indoor PM2.5 sources to personal PM2.5 exposures was lowest when individuals spent the majority of their time in well-ventilated indoor environments. Results also indicate that the potential for confounding by PM2.5 co-pollutants is limited, despite significant correlations among ambient pollutant concentrations. In contrast to ambient concentrations, PM2.5 exposures were not significantly correlated with personal exposures to PM2.5-10, PM2.5 of non-ambient origin, O3, NO2, and SO2. Since a confounder must be associated with the exposure of interest, these results provide evidence that the effects observed in the PM2.5 epidemiologic studies are unlikely to be due to confounding by the PM2.5 co-pollutants measured in this study.     

Microwave-induced nanoscale zero-valent iron degradation of perchloroethylene and pentachlorophenol

Microwave (MW) is applied to enhance perchloroethylene (PCE) or pentachlorophenol (PCP) removal using zero-valent iron (ZVI; Fe⁰) as the dielectric medium. ZVI has a much higher dielectric loss factor (39.5) than other media; it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rises of the ZVI particle surface temperature. If the MW power is continued, excessive electricity will accumulated inside ZVI particles, resulting in sparks. The results show that during the initial 5 sec (700 W), the linear aliphatic PCE has a faster decomposing rate than the ringed PCP (82.0% vs. 4.8%) because less energy is required for decomposing the linear-chlorine bond (90 kcal mol^?1) than ring-chlorine bonds (95 kcal mol^?1). Later, the removal rate for either PCE or PCP remains the same when the exposure time is between 5 and 60 sec. Without MW irradiation, linear PCE molecules have larger surface area to contact ZVI, and hence they have better removal efficiencies than PCP molecules. Using Fe⁰ as a microwave dielectric medium to treat PCE or PCP is a new and worthwhile treatment technology; it is environmentally friendly, and its use will eliminate the secondary pollution.

Implications Nanoscale iron particles are characterized by high surface-area-to-volume ratios, high specific surface area, and high surface reactivity. With a much higher dielectric loss factor, it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rise in temperature. The time needed to achieve a satisfactory treatment is also reduced, leading to significant saving of energy consumption to make this method cost-effective and also environmentally friendly for the industry to pursuit sustainable development.     

Experimental determination of the kinetic rate law for the oxidation of perchloroethylene by potassium permanganate

Flushing soils contaminated with trichloroethylene (TCE) and perchloroethylene (PCE) with a permanganate (MnO₄⁻) solution has been shown to reduce the solvent content of the soil. Experiments were performed to quantify the rate at which KMnO₄ oxidizes aqueous solutions of PCE over a range of concentrations. In a series of homogeneous reactors, aqueous phase PCE concentrations were monitored over time in nine experimental trials with excess oxidant concentrations ranging from 5 to 30 g/l. Analysis of the data was performed to quantify the oxidation reaction order with respect to PCE and KMnO₄ and the reaction rate constant. The reaction between PCE and KMnO₄ was determined to be first-order with respect to both PCE and KMnO₄ with an overall specific reaction rate coefficient of 2.45±0.65 M⁻¹ min⁻¹.     

Shift of microbial diversity and function in high-efficiency performance biotrickling filter for gaseous xylene treatment

ABSTRACT

Xylene is the main component of many volatile industrial pollution sources, and the use of biotechnology to remove volatile organic compounds (VOCs) has become a growing trend. In this study, a biotrickling filter for gaseous xylene treatment was developed using activated sludge as raw material to study the biodegradation process of xylene. Reaction conditions were optimized, and long-term operation was performed. The optimal pH was 7.0, gas-liquid ratio was 15:1 (v/v), and temperature was 25 °C. High-throughput sequencing technique was carried out to analyze microbial communities in the top, middle, and bottom layers of the reactor. Characteristics of microbial diversity were elucidated, and microbial functions were predicted. The result showed that the removal efficiency (RE) was stable at 86%–91%, the maximum elimination capacity (EC) was 303.61 g·m^?3·hr^?1, residence time was 33.75 sec, and the initial inlet xylene concentration was 3000 mg·m^?3, which was the highest known degradation concentration reported. Kinetic analysis of the xylene degradation indicated that it was a very high-efficiency-activity bioprocess. The r_max was 1059.8 g·m^?3·hr^?1, and K_s value was 4.78 g·m^?3 in stationary phase. In addition, microbial community structures in the bottom and top layers were significantly different: Pseudomonas was the dominant genus in the bottom layer, whereas Sphingobium was dominant in the top layer. The results showed that intermediate metabolites of xylene could affect the distribution of community structure. Pseudomonas sp. can adapt to high concentration xylene–contaminated environments.

Implications: We combined domesticated active sludge and reinforced microbial agent on biotrickling filter. This system performed continuously under a reduced residence time at 33.75 sec and high elimination capacity at 303.61 g·m^?3·hr^?1 in the biotrickling reactor for about 260 days. In this case, predomestication combined with reinforcing of microorganisms was very important to obtaining high-efficiency results. Analysis of microbial diversity and functional prediction indicated a gradient distribution along with the concentration of xylene. This implied a rational design of microbial reagent and optimizing the inoculation of different sites of reactor could reduce the preparation period of the technology.     

Wastewater treatment to enhance the economic viability of microalgae culture

Microalgae culture is still not economically viable and it presents some negative environmental impacts, concerning water, nutrient and energy requirements. In this context, this study aims to review the recent advances on microalgal cultures in wastewaters to enhance their economic viability. We focused on three different culture concepts: (1) suspended cell systems, (2) cell immobilization, and (3) microalgae consortia. Cultures with suspended cells are the most studied. The nutrient removal efficiencies are usually high for wastewaters of different sources. However, biomass harvesting is difficult and a costly process due to the small cell size and lower culture density. On the other hand, the cell immobilization systems showed to be the solution for this problem, having as main limitation the nutrient diffusion from bulk to cells, which results in a reduced nutrient removal efficiency. The consortium between microalgae and bacteria enhances the growth of both microorganisms. This culture concept showed to be a promising technology to improve wastewater treatment, regarding not only nutrient removal but also biomass harvesting by bioflocculation. The aggregation mechanism must be studied in depth to find the process parameters that would lead to an effective and cheap harvesting process.     

Application of gaseous ozone for inactivation of Bacillus subtilis spores

The effectiveness of gaseous ozone (O3) as a disinfectant was tested on Bacillus subtilis spores, which share the same physiological characteristics as Bacillus anthracis spores that cause the anthrax disease. Spores dried on surfaces of different carrier material were exposed to O3 gas in the range of 500-5000 ppm and at relative humidity (RH) of 70-95%. Gaseous O3 was found to be very effective against the B. subtilis spores, and at O3 concentrations as low as 3 mg/L (1500 ppm), approximately 3-log inactivation was obtained within 4 hr of exposure. The inactivation curves consisted of a short lag phase followed by an exponential decrease in the number of surviving spores. Prehydration of the bacterial spores has eliminated the initial lag phase. The inactivation rate increased with increasing O3 concentration but not >3 mg/L. The inactivation rate also increased with increase in RH. Different survival curves were obtained for various surfaces used to carry spores. Inactivation rates of spores on glass, a vinyl floor tile, and office paper were nearly the same. Whereas cut pile carpet and hardwood flooring surfaces resulted in much lower inactivation rates, another type of carpet (loop pile) showed significant enhancement in the inactivation of the spores.     

Polarity effect of pulsed corona discharge for the oxidation of gaseous elemental mercury

The effect of polarity on the oxidation of Hg⁰ was examined in the presence of O₂ via a pulsed corona discharge (PCD). The experimental result showed no difference in the energy yield of Hg⁰ oxidation at both positive and negative PCDs (∼8 μg Hg W h⁻¹ at following conditions: total flow rate = 2 L min⁻¹ (Hg⁰ = 50 μg N m⁻³, O₂ = 10%, and N₂ balance), temperature = 150 °C, and specific energy density = 5-15 W h N m⁻³). This suggests that the positive PCD process used to control gaseous air pollutants may play an essential key role in Hg⁰ oxidation because it consumes enough energy (∼15 W h N m⁻³) but an electrical precipitator could not because it consumes less energy (∼0.3 W h N m⁻³) to oxidize Hg⁰.     

Methods for sampling and analysis of tropospheric ethanol in gaseous and aqueous phases

In this paper, we report on techniques for sampling and measuring ethanol in both the gas and aqueous phases of the lower troposphere. In the gas phase, the best sampling conditions were ensured by adsorption on Hayesep Q with a Chromosorb W AW coated with LiCl dryer (method 1) or by cryogenic trapping (method 2). An intercomparison campaign showed good agreement between both methods under various conditions. Method 1 (adsorption on Hayesep Q with dryer) is easier to set up and to carry away from the laboratory. Method 2 (cryogenic trapping) requires longer sampling time (up to 60 min while method 1 requires only 10-15 min). Method 1 is adapted to high concentrations of ethanol (>20 ppb) and low relative humidity (<30%). Method 2 gives more accurate results than method 1 for low ethanol concentrations (1-20 ppb). Comparing these results to previous studies, it is clear that sampling with appropriate solid adsorbents or with stainless steel canisters (with appropriate humidified air and short storage time) is adapted to urban or industrial environments where ethanol concentrations are high. Cryogenic sampling must be preferred for remote places where ethanol concentrations are low. Three techniques were tested for sampling ethanol in the liquid phase, namely solid phase microextraction, purge and trap injection, and direct injection. Among those, the latter was chosen for field measurements of ethanol in rain samples at an urban location. These first ever results at an urban location show concentrations ranging from <1 to 5 microM in rains, which agree with the expected range of concentrations. However, the purge and trap method showed detection limits that were 50 times lower and should be preferred for liquid phase ethanol measurements in rural and remote locations. Combining cryogenic trapping for the gas phase (method 2) and direct injection for the liquid phase is convenient and well adapted for a multiphase study of ethanol in the atmosphere, where simultaneous measurements in both phases are needed.     

Evaluation of an offline method for the analysis of atmospheric reactive gaseous mercury and particulate mercury

Reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected in Milwaukee, WI, between April 2004 and May 2005, and in Riverside, CA, between July 25 and August 7, 2005 using sorbent and filter substrates. The substrates were analyzed for mercury by thermal desorption analysis (TDA) using a purpose-built instrument. Results from this offline-TDA method were compared with measurements using a real-time atmospheric mercury analyzer. RGM measurements made with the offline-TDA agreed well with a commercial real-time method. However, the offline TDA reported PHg concentrations 2.7 times higher than the real-time method, indicating evaporative losses might be occurring from the real-time instrument during sample collection. TDA combined with reactive mercury collection on filter and absorbent substrates was cheap, relatively easy to use, did not introduce biases due to a semicontinuous sample collection strategy, and had a dynamic range appropriate for use in rural and urban locations. The results of this study demonstrate that offline-TDA is a feasible method for collecting reactive mercury concentrations in a large network of filter-based samplers.     

高温载硫活性炭的制备及脱汞能力研究

研究了载硫温度、硫炭比(简称S/C),吸附温度等因素对载硫活性炭的硫含量、脱汞能力以及硫损失的影响,探讨载硫活性炭制备的工艺条件优化。结果表明,不同载硫温度下制备的载硫活性炭的气态Hg0吸附能力远强于原料活性炭;载硫温度不同时,负载到活性炭孔隙或表面上的硫的形态不同,导致了脱汞能力的差异,较合适的载硫温度为350℃;S/C为5%(质量分数,下同)时,随着吸附温度的升高,载硫活性炭的气态Hg0吸附量降低;在一定的载硫温度下,原料中S/C越高时,制备的载硫活性炭的硫含量越高、气态Hg0吸附能力越强,但其硫损失率也越高,从实际的使用效果来看,较合适的S/C为10%。     

Biological treatment of a contaminated gaseous emission from a leather industry in a suspended-growth bioreactor

A suspended-growth bioreactor (SGB) was operated for the treatment of a gaseous stream mimicking emissions generated at a leather industrial company. The main volatile organic compounds (VOCs) present in the gaseous stream consisted of 1-methoxy-2-propanol, 2,6-dimethyl-4-heptanone, 2-butoxyethanol, toluene and butylacetate. A microbial consortium able to degrade these VOCs was successfully enriched. A laboratory-scale SGB was established and operated for 210-d with an 8h cycle period and with shutdowns at weekends. Along this period, the SGB was exposed to organic loads (OL) between 6.5 and 2.3 x 10(2) g h(-1) m(-3). Most of the compounds were not detected at the outlet of the SGB. The highest total VOC removal efficiency (RE) (ca 99%) was observed when an OL of 1.6 x 10(2) g h(-1) m(-3) was fed to the SGB. The maximum total VOC elimination capacity (1.8 x 10(2) g h(-1) m(-3)) was achieved when the OL applied to the SGB was 2.3 x 10(2) g h(-1) m(-3). For all the operating conditions, the SGB showed high levels of degradation of toluene and butylacetate (RE approximately equal to 100%). This study also revealed that recirculation of the gaseous effluent improved the performance of the SGB. Overall, the SGB was shown to be robust, showing high performance after night and weekend shutdown periods.     

Sources and deposition of reactive gaseous mercury in the marine atmosphere

Observations of reactive gaseous mercury (RGM) in marine air show a consistent diurnal cycle with minimum at night, rapid increase at sunrise, maximum at midday, and rapid decline in afternoon. We use a box model for the marine boundary layer (MBL) to interpret these observations in terms of RGM sources and sinks. The morning rise and midday maximum are consistent with oxidation of elemental mercury (Hg⁰) by Br atoms, requiring <2 ppt BrO in most conditions. Oxidation of Hg⁰ by Br accounts for 35–60% of the RGM source in our model MBL, with most of the remainder contributed by oxidation of Hg⁰ by ozone (5–20%) and entrainment of RGM-rich air from the free troposphere (25–40%). Oxidation of Hg⁰ by Cl is minor (3–7%), and oxidation by OH cannot reproduce the observed RGM diurnal cycle, suggesting that it is unimportant. Fitting the RGM observations could be achieved in the model without oxidation of Hg⁰ by ozone (leaving Br as the only significant oxidant) by increasing the entrainment flux from the free troposphere. The large relative diurnal amplitude of RGM concentrations implies rapid loss with a lifetime of only a few hours. We show that this can be quantitatively explained by rapid, mass-transfer-limited uptake of RGM into sea-salt aerosols as HgCl₃^? and HgCl₄^2?. Our results suggest that 80–95% of Hg^II in the MBL should be present in sea-salt aerosol rather than gas-phase, and that deposition of sea-salt aerosols is the major pathway delivering Hg^II to the ocean.     

Effects of dietary and gaseous fluoride on the aphid Aphis fabae

A large proportion of leaf fluoride consists of surface deposits and a sucking herbivore would be expected to take in a smaller load of fluoride in its food than a chewing herbivore. In these experiments, fluoride was applied aerially, through the leaves, and systemically, via the roots, to compare uptake by aphids and effects on their fecundity. Fluoride applied via roots was taken up by both the plants and the aphids, but at high treatment rates the aphids had much lower concentrations than the foliage. When the plants and aphids were fumigated with HF the aphids had much greater loads than the plant shoots, which was due to deposition of F on the insect surfaces. There were no effects of the treatments on aphid reproduction or development time. The aphids obtained some fluoride through their diet which suggests that fluoride is present in the phloem sap, previously thought to be of minor importance.     

应用POMS复合膜分离去除废气中挥发性有机污染物

依靠POMS平板单层膜或POMS卷式膜上选择性分离层的选择性溶解和渗透作用,常温负压分离回收废气中乙酸乙酯等挥发性有机污染物(VOC)组分.结果表明,膜两侧操作压差和原料气流量对乙酸乙酯分离效率影响较大;当原料气处理量为1.770 0～2.810 0 m3/(m2·h)、膜两侧操作压差为0.08 MPa,POMS卷式膜乙酸乙酯渗透速率可达7.86 × 10-7 mol/(s·m2·Pa);乙酸乙酯为1 500～4 500 mg/m3时,其去除率可达80%.测得几种VOC组分在POMS复合膜中的溶解吸附量都比较可观,由此预测该膜处理废气中VOC可取得很好的净化效果.甲苯在POMS复合膜中的溶解吸附量低于乙酸乙酯,其实验测得渗透速率也小于乙酸乙酯.甲苯去除率也能达到80%.     

Theoretical evaluation of a method for locating gaseous emission hot spots

This paper describes and theoretically evaluates a recently developed method that provides a unique methodology for mapping gaseous emissions from non-point pollutant sources. The horizontal radial plume mapping (HRPM) methodology uses an open-path, path-integrated optical remote sensing (PI-ORS) system in a horizontal plane to directly identify emission hot spots. The radial plume mapping methodology has been well developed, evaluated, and demonstrated. In this paper, the theoretical basis of the HRPM method is explained in the context of the method's reliability and robustness to reconstruct spatially resolved plume maps. Calculation of the condition number of the inversion's kernel matrix showed that this method has minimal error magnification (EM) when the beam geometry is optimized. Minimizing the condition number provides a tool for such optimization of the beam geometry because it indicates minimized EM. Using methane concentration data collected from a landfill with a tunable diode laser absorption spectroscopy (TDLAS) system, it is demonstrated that EM is minimal because the averaged plume map of many reconstructed plume maps is very similar to a plume map generated by the averaged concentration data. It is also shown in the analysis of this dataset that the reconstructions of plume maps are unique for the optimized HRPM beam geometry and independent of the actual algorithm applied.