Photocatalytic degradation of PCP-Na with TiO2 photocatalysis loaded with platinum

Titanium dioxide(TiO2) samples of different crystal forms were prepared by hydrolysis tetrbutyl titanate in various water to alkoxide ratios and sintering the hydrolysis product at different temperatures.The photocatalysts coated on hollow glass beads and loaded with platinum varying from 0.2% to 2.4% by weight.The photocatalytic degradation rate of sodium pentachlorophenolate (PCP-Na) depends on the preparing conditions such as:sintering temperatures,water to alkoxide ratios(R),platinum content and the size.The proper conditions of preparation photocatalysts are as follows:the ratio of tiO2:sodium silicate:hollow glass beads:platinum is 10:5:20:0.15(w/w),R is 100,sintering temperature is 650℃,and the size of hollow glass is 0.5-1mm.Under these conditions,the ratio between acatase and rutile of the photocatalyst is 2:1,and the photocatalytic activity is high.     

An experimental set up of a PAH vapour generator and its use to test an annular denuder

The aim of this work is to develop and test a dynamic gas generator for semi-volatile organic compounds (SVOC). A single compound, naphthalene, is used as a surrogate PAH to test the system. The dynamic generation of PAH is based on the permeation technique [Analyst 106 (1981) 817; Am. Ind. Hyg. Assoc. J. 38 (1977) 712]. Monitoring the temperature and measuring the mass of PAH present in the permeation chamber every 48 h gives a direct measurement of the sublimation rate of the PAH. Knowing the flow rate, gives an accurate value of the concentration of PAH from the generator. It was found stable over a period of time under constant operating conditions. This concentration is diluted down to between 0.3 and 30 ppbv by a controlled flow of pure air. The diluting airflow is a mixture of dry and wet air, making it possible to control the relative humidity of the flow from the generator as well as its concentration in PAH. We used this generator to calibrate an annular denuder tube, based on the study by Gundel et al. [Atmos. Environ. 29 (1995) 1719]. Although this technique has been shown to be artefact-free for sampling gaseous PAH [Polycyclic Aromatic Compounds 9 (1996) 67; Atmos. Environ. 28 (1994) 3083], its trapping efficiency still depends on environmental parameters (temperature, relative humidity and sampling duration). Accordingly, we used our generator to calibrate a single annular denuder under controlled conditions (T degrees C, HR%, CPAH, sampling duration). The trapping efficiency of the denuder was calculated by two independent methods. Firstly, by comparing the amount trapped on a denuder with the measured mass sublimated in the generator. Secondly, by putting two denuders in series and comparing the mass collected on the first and the second tube. These two methods gave similar results, within the 10% relative uncertainties of both methods. The first results obtained show that, in environmental conditions, the efficiency ranges between 90 and 100%.     

Prediction of complete bioremediation periods for PAH soil pollutants in different physical states by mechanistic models

Mass-transfer models and biodegradation models were developed for three theoretical physical states of polycyclic aromatic hydrocarbons (PAHs) in soil. These mechanistic models were used to calculate the treatment periods necessary for complete removal of the PAH pollutants from the soil under batch conditions. Results indicate that the bioremediation of PAHs in such systems is mainly mass-transfer limited. The potential for bioremediation as a treatment technique for PAH contaminated soils is therefore mainly determined by the mass-transfer dynamics of PAHs. Under mass-transfer limited conditions simplified mathematical models, based on the assumption of a zero dissolved PAH concentrations, can be used to predict the period of time needed for complete bioremediation.     

Nutrient dynamics in shallow lakes of northern greece

GOAL, SCOPE, BACKGROUND: Shallow lakes display a number of features that set them apart from the more frequently studied deeper systems. The majority of lakes in Northern Greece are small to moderate in size with a relatively low depth and are considered as sites of high value of the wetland habitat. However, the water quality of these lakes has only been evaluated segmentally and occasionally. OBJECTIVE: The objectives of this study were to thoroughly investigate nitrogen and phosphorus speciation in lakes of a high ecological significance located in N. Greece, in order to evaluate their eutrophication status and possible nutrient limitation factors, and to investigate the main factors/sources that affect the water quality of these systems. METHODS: An extensive survey was carried out during the period from 1998-1999. Water samples were collected on a monthly basis from lakes Koronia, Volvi, Doirani, Mikri Prespa and Megali Prespa located in N. Greece. Water quality parameters (temperature, dissolved oxygen, pH and conductivity), organic indices (COD, BOD5), and N- and P-species (NO3(-), NO2(-), NH4(+), and PO4(3-), Kieldahl nitrogen and acid-hydrolysable phosphorus) were determined according to standard methods for surface water. Statistical treatment of the data was employed. RESULTS AND CONCLUSIONS: The physicochemical parameters determined in the lakes studied revealed a high temporal variation. The trophic state of the lakes ranged from meso- to hypertrophic. The nutrient limiting factor varied among lakes suggesting either P-limitation conditions or mixed conditions changing from P- to N-limitation throughout the year. Urban/industrial activities and agricultural runoff are the major factors affecting all lakes, although with a varying contribution. RECOMMENDATION AND OUTLOOK: This lake-specific research offers valuable information about water quality and nutrient dynamics in lakes of significant ecological value located in N. Greece that can be useful for an effective pollution control/management of these systems. Due to the large intra-annual variability of certain physicochemical parameters, a properly designed monitoring program of lake water is recommended.     

Natural attenuation/phytoremediation in the vadose zone of a former industrial sludge basin

The natural attenuation of polyaromatic hydrocarbons (PAHs) in the vadose zone of a naturally revegetated former industrial sludge basin (0.45 ha) was examined. This was accomplished by comparing the concentration of 16 PAH contaminants present in sludge collected below the root zone of plants with contaminants present at 3 shallower depths within the root zone. Chemical analysis of 240 samples from 60 cores showed the average concentration of total and individual PAHs in the 0-30 cm, 30-60 cm, and bottom of the root zone strata were approximately 10, 20, and 50%, respectively, of the 16, 800 ppm average total PAH concentration in deep non-rooted sludge. Statistically significant differences in average PAH concentrations were observed between each strata studied and the non-rooted sludge except for the concentrations of acenaphthene and chrysene present at the bottom of the root zone in comparison to sludge values. The rooting depth of the vegetation growing in the basin was dependent on both vegetation type and plant age. Average rooting depths for trees, forbs (herbaceous non-grasses), and grasses were 90, 60, and 50 cm, respectively. The deepest root systems observed (100-120 cm) were associated with the oldest (12-14 year-old) mulberry trees. Examination of root systems and PAH concentrations at numerous locations and depths within the basin indicated that plant roots and their microbially active rhizospheres fostered PAH disappearance; including water insoluble, low volatility compounds, i.e. benzo(a)pyrene and benzo(ghi)perylene. The reduced concentration of PAHs in the upper strata of this revegetated former sludge basin indicated that natural attenuation had occurred. This observation supports the concept that through appropriate planting and management practices (phytoremediation) it will be possible to accelerate, maximize, and sustain natural processes, whereby even the most recalcitrant PAH contaminants (i.e. benzo(a)pyrene) can be remediated over time.     

The effect of oils on PAH, PCDD, PCDF, and PCB emissions from a spark engine fueled with leaded gasoline

The effect of synthetic and mineral oils on the formation of polyaromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in emissions from a spark ignition engine was studied on a Skoda Favorit engine fueled with leaded gasoline. The test cycle simulated urban traffic conditions on a chassis dynamometer, in accordance with the ECC 83.00 test. The data for selected PAHs as well as PCDDs, PCDFs, and PCBs congener profiles are presented. PCDD/Fs emissions for an unused oil and the oil after 10000-km operation varied from 300 to 2000 fmol/m3, PCBs emissions from 75 to 178 pmol/m3, and PAHs emissions from 150 to 420 microg/m3. The content of PCBs in oils varied from 2 to 920 mg/kg.     

Analysis of particle-associated semi-volatile aromatic and aliphatic hydrocarbons in urban particulate matter on a daily basis

PM_2.5 Particle-associated semi-volatile organic compounds (SVOC) were determined in the city of Augsburg, Germany. Daily samples were collected at a central monitoring station from late summer to late autumn 2002. The concentrations of polycyclic aromatic hydrocarbons (PAH), oxidized PAH (O-PAH), n-alkanes, hopanes and long chain linear alkylbenzenes were determined by direct thermal desorption-gas chromatography-time of flight mass spectrometry (DTD-GC-TOFMS). Additionally, PM_2.5 particle mass and number concentrations were measured. The sampling campaign can be divided into two parts, distinguished by a lower temperature level in the second part of the campaign. The particulate mass concentration showed no significant changes, whereas most of the SVOC had significant higher mean and peak concentrations in the colder period. The analysis of the data showed an increased influence of non-traffic sources in the colder period, reflected by a weak shift in the PAH profile and a significant shift in the hopane pattern. Statistical analysis of the inter-group correlations was carried out. Eight clusters partly representing different sources of the aerosol have been identified.     

Effects of lipids on the sorption of hydrophobic organic compounds on geosorbents: a case study using phenanthrene

The impact of the lipid fraction of natural geosorbents on the sorption of a polycyclic aromatic hydrocarbon was assessed using several experiments. In the first set of experiments phenanthrene was sorbed on a coastal sediment as well as on its humin and humic acid fractions before and after lipid extraction. Before lipid extraction, sorption shows dominantly partitioning characteristics. However, the extraction of lipids from sediment and humin drastically increases, by up to one order of magnitude, their sorption affinity for phenanthrene at low sorbate concentrations, resulting in increased isotherm nonlinearity. This effect is less pronounced for humic acids. One mechanism proposed for the increasing sorption is that lipids, despite their very low relative abundance in the sediments, can compete with phenanthrene for specific high affinity sorption sites (e.g., matrix pores and adsorption sites). This competition is not surprising considering the similar hydrophobic nature of lipids and phenanthrene. Lipids, or any non-polar molecules, could also act like plasticizers by swelling rigid domains and disrupting high affinity sites. In both cases, the removal of lipids (and extraction solvents) makes those sites available for phenanthrene. These provide alternative explanations to the previously proposed “solvent conditioning effect” believed to occur when geosorbents are treated with non-polar solvents modifying the matrix structure, an effect yet to be proven at molecular scale. To further investigate the impact of lipids on sorption, other independent experiments were performed. In a second experiment, re-addition of lipids to the extracted sediment restored the sorption isotherm linearity observed in the native material supporting the absence of irreversible extraction artifacts. However, high addition of lipids (i.e., after saturation of high affinity sites) seems to also enlarge the low affinity partitioning domain. These results are consistent with dual-mode, hole-filling, sorption models involving diffusion. In the final set of experiments, solid-state ¹⁹F-NMR using F-labeled lipids sorbed onto the sediments confirmed that lipids may be in different domains (mobile or rigid) that interact or not with phenanthrene. The possible effects of lipid removal on sorption have been overlooked and should be considered when geosorbents are pretreated.     

基于动态质量平衡的室内颗粒物沉降规律研究

目前室内颗粒物污染问题已经受到广泛关注.越来越多的流行病学研究表明,大气悬浮颗粒物浓度对人体健康存在显著的负影响.由于个人在室内滞留的时间可能超过全天时间的90％,因此剖析室外颗粒物向室内的传输渗透机理,对掌握室内微环境下的颗粒浓度水平至关重要.本实验以青岛一办公室为研究对象,使用具有4个尺寸间隔的光学计数器同时测量室内和室外的颗粒物浓度,粒径分布范围在0.3~2.5μm,采集时间为2016年4月~9月.根据实验数据,采用基于时间的动态质量平衡模型,估算了换气次数在0.03~0.25h^-1范围内的室内颗粒物渗透率和沉降速率分别为0.45~0.82h^-1和0.94~2.82m/h,并分析了这些参数随粒径大小的变化规律.其结论为进一步研究颗粒物在室内的传输机理和运动轨迹提供参数.     

聚酰肼接枝改性活性炭除甲醛材料的制备及其影响因素

为解决甲醛污染问题,开展了多胺高分子接枝活性炭环境材料制备研究.采用质量比为1:1的硫酸和硝酸的混合液对活性炭表面改性,再以DCC（N,N-二环己基碳二亚胺）为胺化反应的缩水剂,通过PAH（聚酰肼）和活性炭缩聚反应制备了除甲醛材料ACm-g-PAH（聚酰肼接枝改性活性炭）,通过单因素试验探讨了影响ACm-g-PAH除甲醛的因素,再由正交试验得出ACm-g-PAH制备的最佳工艺为活化温度为90℃,w（DCC）为2.0%,c（PAH）为12 mmol/L.结果表明:在温度为10~50℃与相对湿度为45%~85%区间内,温度和相对湿度对甲醛去除率影响并不明显.吸附甲醛的ACm-g-PAH经弱酸还原再生技术处理后,再生5次的ACm-g-PAH对甲醛的去除率仍能达到初生材料的89.2%.FTIR（红外光谱）证明了在DCC存在下,聚酰肼高分子PAH与ACm（改性活性炭）表面羧基缩聚反应的事实.随着c（PAH）的增加,SEM（扫描电镜）显示活性炭孔内的PAH呈堆积的现象;TG（热重分析）图谱的测试结果表明,ACm-g-PAH的降解温度在330~420℃之间.研究显示,ACm-g-PAH对甲醛的去除率最高为99.4%.