色谱-质谱联机测定厦门港和员当湖表层沉积物中的石油烃和多环芳香烃的含量

2002年4月厦门港沿岸设九个站,员当湖设两个站采集表层积物,用有机溶剂萃取,硅胶柱色层分离,气相色谱-质谱联机带SIM数据采集系统对样品的石油烃类(M/Z=55),多环芳香烃类(15个典型的多环芳香烃,9个甲基化多环芳香烃作外标)进行分析,结果显示员当湖石油烃和多环芳香浓度分别高达1397微克/克(干)和1376.5纳克/克(干)。厦门港沉积物石油烃和多环芳香浓度范围为:石油烃133.3～943.3微克/克(干)多环芳香烃97.6～308.5纳克/克(干)。厦门港船只活动,厦门港四周工业废水、车辆燃油滴漏是石油烃污染的主要来源。厦门工业用煤、用油、生活用煤及船只、车辆燃料泄漏是沉积物多环芳香烃的主要来源,其工业排废、生活废水排放,市区雨水冲刷和大气灰尘沉降是多环芳香烃进入海湾的主要途径。     

The influence of baking fuel on residues of polycyclic aromatic hydrocarbons and heavy metals in bread

The influence of fuel type used to bake bread on the spectrum and concentrations of some polycyclic aromatic hydrocarbons and heavy metals in baked bread was assessed. Bread samples were collected from different bakeries operated by either electricity, solar, mazot or solid waste and their residue content of PAHs and heavy metals was assessed. The total concentration of PAHs detected in mazot, solar, solid waste and electricity operated bakeries had an average of 320.6, 158.4, 317.3 and 25.5 μg kg⁻¹, respectively. Samples collected from mazot, solar and solid waste operated bakeries have had a wide spectrum of PAHs, in comparison to that detected in bread samples collected from electricity operated bakeries. Lead had the highest concentrations in the four group of bread samples, followed by nickel, while the concentrations of zinc and cadmium were the least. The concentration of lead detected in bread samples produced from mazot, solar, solid waste and electricity fueled bakeries were 1375.5, 1114, 1234, and 257.3 μg kg⁻¹, respectively. Estimated daily intake of PAHs based on bread consumption were 48.2, 28.5, 80.1, and 4.8 μg per person per day for bread produced in bakeries using mazot, solar, solid waste and electricity, respectively. Meanwhile, the estimated daily intake of benzo (a) pyrene were 3.69, 2.65, 8.1, and 0.81 μg per person per day for bread sample baked with mazot, solar, solid waste and electricity, respectively. The daily intake of lead, based on bread consumption was 291, 200.5, 222, and 46.31 μg per person per day for bread sample baked with mazot, solar, solid waste and electricity, respectively. The present work has indicated the comparatively high level of daily intake of benzo (a) pyrene and lead in comparison to levels reported from many other countries and those recommended by international regulatory bodies. It is probable that residues detected in bread samples are partially cereal-borne but there is strong evidence that the process of baking and the gases emitted are responsible for most of the contamination load.     

Characterization of PM10 fraction of road dust for polycyclic aromatic hydrocarbons (PAHs) from Anshan, China

Nineteen road dust samples were collected during 2005 in different parts of the urban area of Anshan, Liaoning Province, China, and 11 polycyclic aromatic hydrocarbons (PAHs) species were quantitatively analyzed using GC–MS. The results indicated that the total average concentration of PAHs over the investigated sites ranged from 48.73 to 638.26 μg/g, with a mean value of 144.25 μg/g, higher than the concentrations measured in previous studies. PAHs concentrations were higher with high molecular weight homologues (4–6 rings PAHs), accounting for 83.24–96.98%, showing combustion of petroleum fuels was a potential source. Organic carbon in road dust was considered one of the important factors that influenced the concentrations of PAHs in this study, and it was found that concentrations of total PAHs were correlated with those of organic carbon in road dust. The results of diagnostic ratios analysis showed traffic emission (gasoline or diesel) was one of the most important sources of road dust PAHs. Principal component analysis (PCA) indicated that the major sources of road dust PAHs might be emission from traffic, steel industry, cooking and coal combustion.     

Source identification and health risk of polycyclic aromatic hydrocarbons associated with electronic dismantling in Guiyu town, South China

In this study the concentrations and distribution of sixteen polycyclic aromatic hydrocarbons (PAHs) were investigated in gas and total suspended particle (TSP) samples collected during daytime and night time. The sampling locations included an electronic waste dismantling workshop (EW), a plastic recycling workshop (PW) and a waste incineration field (WF) in Guiyu, China. A large residential area (RA) in this region was used as a control site. In the daytime, the highest concentration was found at WF (1041 ng m⁻³); while in the night time the highest concentration was found outside of EW (744 ng m⁻³). Comparison between work hours (daytime) and rest hours (night time) displayed that the total PAHs (gas + particulate phase) concentrations and the percentages of PAHs associated with TSP were higher at night than those in the daytime in all sampling workshops except WF. Source diagnostic-ratio analysis revealed that unwanted materials and smoldering honeycomb coals were the main sources of PAHs in EW, WF and PW. Benzo[a]pyrene equivalent [BaPeq] concentrations calculated by using the toxic equivalent factors [TEFs] suggested that the occupational exposure levels were not significantly high when compared with other occupational exposure. Additionally, our study suggested that the smoldering of unwanted materials could produce much more toxic PAHs compounds.     

DK型纳滤膜对水中微量邻苯二甲酸酯的吸附及截留特性

邻苯二甲酸酯(PAEs)是一类典型的环境激素,对人体健康具有较大的危害。本文采用DK型纳滤膜去除水中微量邻苯二甲酸酯,分析了水中微量邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸正二丁酯(DNBP)和邻苯二甲酸异二丁酯(DIBP)等在DK型纳滤膜表面的吸附行为,考察了4种邻苯二甲酸酯的辛醇/水分配系数(logKow)和相对分子质量(Mw)对其在DK型纳滤膜表面的吸附和膜的截留特性的影响。结果表明Freundlich吸附方程能较好地描述4种邻苯二甲酸酯在DK型纳滤膜表面的动态吸附行为;DK型纳滤膜对水中微量邻苯二甲酸酯的截留特性表现为膜面吸附作用和膜孔筛分效应,吸附平衡后的截留机理取决于膜孔的筛分效应,DK型纳滤膜对DMP、DEP、DNBP、DIBP的截留率分别为55%、78%、96%和96.8%(0.5 MPa,30℃,DMP、DEP、DNBP、DIBP浓度均为300μg/L),表明DK型纳滤膜能高效去除水中的DNBP和DIBP。     

Gas-particle concentrations of atmospheric polycyclic aromatic hydrocarbons at an urban and a residential site in Osaka, Japan: effect of the formation of atmospherically stable layer on their temporal change

A comparative study on atmospheric polycyclic aromatic hydrocarbons (PAHs) in particulate matter and the gaseous phase was performed at an urban and a residential site in Osaka, Japan, during 2005-2006. PAH concentrations at the urban site were found to be approximately twice higher than those at the residential site. At both sites, particulate PAH concentrations increased mainly in winter while the trends of temporal change in gaseous PAH concentrations were not clearly observed. The main sources of PAHs were estimated to be local traffic, e.g., diesel engines with catalytic converter. PAH concentrations did not significantly negatively correlate with ozone concentrations and meteorological parameters. Gas-particle partitioning coefficients of representative PAHs with low molecular weight (LMW) significantly negatively correlated with ambient temperature, showing that temporal change in the LMW PAH concentrations in PM could be attributable to the shift of their gas-particle distribution caused by the change in ambient temperature. For the first time, we studied the effect of the formation of atmospherically stable layer following an increase in PAH concentrations in Japan. At the urban site, PAHs showed a significant positive correlation with potential temperature gradients, indicating that temporal variability in PAH concentrations would be dominantly controlled by the formation of atmospherically stable layer in Osaka area.     

The effects of carbon sources and micronutrients in whey and fermented whey on the kinetics of phenanthrene biodegradation in diesel contaminated soil

This paper demonstrates significant effects on phenanthrene degradation in diesel contaminated soil by the addition of organic amendments such as whey and fermented whey. Both amount of amendment added and mode of administration was shown to be decisive. There was a strong positive effect on the ¹⁴C-mineralization of phenanthrene by multiple (bi-weekly) additions of fermented whey 210 mg dw kg⁻¹ soil dw (FW multi) and also by single dose addition of 2100 mg dw sweet whey kg⁻¹ soil dw (SW high). The most prominent effects on phenanthrene degradation kinetics were a five to fifteen fold increase in the linear growth term (k₂) and a 23-27% increase in bioavailability factor S₀ for SW high and FW multi respectively. Also, total mineralization at the end of the experiment increased from 46% in the control to 66 and 71% respectively and the lag time was reduced from 21 to 15 days by multiple addition of fermented whey. The most significant stimulating effects on phenanthrene degradation kinetics could be attributed to lactate and vitamins. This study demonstrates a more complex dependence of carbon sources and growth factors for an aromatic compound such as phenanthrene in comparison to hexadecane.     

Pollution patterns of polycyclic aromatic hydrocarbons in tobacco smoke

Concentrations of polycyclic aromatic hydrocarbons (PAHs) in tobacco smoke of 12 commercial brand cigarettes were determined in a simulated chamber of 20.25 m3 in size. The total concentrations of 17 PAHs (summation operatorPAHs) in the chamber were 3500 and 1152 ng/m3 in vapor phase and particulate phase, respectively. In vapor phase, the yield of naphthalene (NA) appeared to be the most abundant (2462 ng/cig) followed by fluorene (FLUOR) and acenaphthylene (ACY), while the yield of benzo[ghi]perylene (BP) was the most abundant (259.7 ng/cig) in particulate phase followed by phenanthrene (PHEN) and FLUOR. The proportion of PAHs in particulate phase increased with increasing molecular weight. PAHs with two to six rings accounted for 40.2%, 35.3%, 11.7%, 7.6%, 5.2% of summation operatorPAHs, respectively. There was no obvious correlation between PAHs, benzo[a]pyrene (BaP) concentrations in tobacco smoke and smoking tar contents, nicotine contents. With the source fingerprint of PAHs in tobacco smoke, NA could be regarded as the marker of tobacco smoke source because of its largest contribution to summation operatorPAHs (40.2%), followed by FLUOR (12.7%) and ACY (9.8%). Further study indicated that more than 80% of BaP in indoor air of resident homes in Hangzhou was from tobacco smoke.     

Effect of sequestration on PAH degradability with Fenton's reagent: roles of total organic carbon,humin, and soil porosity

The phenomenon of contaminant sequestration—and the physicochemical soil parameters which drive this process—has recently been studied by several authors with regard to microbial contaminant degradation. Very little work has been done to determine the effects of contaminant sequestration on the chemical treatability (oxidizability) of soil contaminants; the current study was conducted to address this data gap. A suite of six model soils, ranging in organic matter content from 2.32 to 24.28%, were extensively characterized. Measured parameters included: (1) levels of total organic carbon (TOC); (2) contents of humic acid (HA); fulvic acid (FA) and humin; and (3) total porosity and surface area. Each soil was then spiked with coal tar and, after varying periods of aging/sequestration, subjected to slurry-phase Fenton’s reagent oxidation. Percent recoveries of 12 PAHs, ranging from 3 to 6 aromatic rings, were determined. Results indicated that the susceptibility of each PAH to chemical oxidation was a function of TOC in four of the soils (those with TOC greater than approximately 5%), but was strongly dependent on soil porosity for low-TOC soils. The importance of these two parameters changed with increasing sequestration time, with the relative contribution of porosity-mediated sequestration becoming more important over time. Porosity-mediated effects were more rapid and significant with lower-molecular-weight PAHs (e.g. those with three or four aromatic rings) than with higher-molecular-weight, more hydrophobic compounds. These observations are discussed in light of current physicochemical models of the contaminant sequestration process.     

Accumulation of polycyclic aromatic hydrocarbons and heavy metals in lettuce grown in the soils contaminated with long-term wastewater irrigation

Accumulation of polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs) by crop plants from contaminated soils may pose health risks. A greenhouse pot experiment using lettuce (Lactuca satuva L.) as a representative vegetable was conducted to assess the concentrations of PAHs and HMs in vegetables grown in wastewater-contaminated soils. The concentrations of total PAHs were ranged from 1.5 to 3.4 mg kg(-1) in the contaminated soils, while 1.2 mg kg(-1) in the reference soil. Linear regression analyses showed that the relationships between soil and shoot PAH concentrations were stronger for LMW-PAHs (R(2) between 0.51 and 0.92) than for HMW-PAHs (R(2) 0.02 and 0.60), suggesting that translocation for LMW-PAHs is faster than HMW-PAHs. Furthermore, the data imply that root uptake was the main pathway for HMW-PAHs accumulation. The plant shoots were also highly contaminated with HMs, particularly Cd (0.4-0.9 mg kg(-1)), Cr (3.4-4.1 mg kg(-1)), Ni (11.7-15.1 mg kg(-1)) and Pb (2.3-5.3 mg kg(-1)), and exceed the guidance limits set by State Environmental Protection Administration (SEPA), China and the World Health Organization (WHO). This study highlights the potential health risks associated with cultivation and consumption of leafy vegetables on wastewater-contaminated soils.     

Particle-phase dry deposition and air-soil gas exchange of polycyclic aromatic hydrocarbons (PAHs) in Izmir, Turkey

Ambient air and dry deposition samples were collected at suburban and urban sites in Izmir, Turkey. Atmospheric total (particle+gas) ∑(14)PAHs concentrations were 36±39 and 144±163 ng m(-3) for suburban and urban sites, respectively. Phenanthrene was the most abundant compound at all sites, and all samples were dominated by low molecular weight PAHs. Average particulate ∑(14)PAH dry deposition fluxes were 8160±5024 and 4286±2782 ng m(-2) day(-1) and overall average particulate dry deposition velocities were 1.5±2.4 and 1.0±2.3 cm s(-1) for suburban and urban sites, respectively. Soil samples were collected at suburban site. Average soil concentration for ∑(14)PAH was 55.9±14.4 ng g(-1) dry weight. Calculated gas-phase air-soil exchange fluxes indicated that fluorene, phenanthrene, anthracene, and carbazole were deposited to soil in winter while they were volatilized in summer. Other compounds (fluoranthene-benzo[g,h,i]perylene) were deposited to soil in both periods. Annual average fluxes of PAHs representing soil to air (i.e., gas volatilization) and air to soil transfer (i.e., gas absorption, dry deposition, and wet deposition) processes were also compared. All processes were comparable for Σ(14)PAHs however their input was dominated by gas absorption. Gas absorption dominated for lower molecular weight PAHs, however dry deposition dominated for higher molecular weight PAHs. The results have suggested that for fluorene, soil and air may be approaching a steady state condition. For the remaining compounds, there was a net accumulation into the soil.     

Hot water extraction with in situ wet oxidation: kinetics of PAHs removal from soil

Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions--with and without in situ wet oxidation--were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 degrees C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and oxidation no PAHs could be detected in the liquid phase after the first 30 min of the experiments. Based on these results, extraction with hot water, if combined with oxidation, should reduce the cost of remediation and can be used as a feasible alternative technique for remediating contaminated soils and sediments.     

Direct photolysis of polycyclic aromatic hydrocarbons in drinking water sources

The widely used low pressure lamps were tested in terms of their efficiency to degrade polycyclic aromatic hydrocarbons listed as priority pollutants by the European Water Framework Directive and the U.S. Environmental Protection Agency, in water matrices with very different compositions (laboratory grade water, groundwater, and surface water). Using a UV fluence of 1500 mJ/cm², anthracene and benzo(a)pyrene were efficiently degraded, with much higher percent removals obtained when present in groundwater (83-93%) compared to surface water (36-48%). The removal percentages obtained for fluoranthene were lower and ranged from 13 to 54% in the different water matrices tested. Several parameters that influence the direct photolysis of polycyclic aromatic hydrocarbons were determined and their photolysis by-products were identified by mass spectrometry. The formation of photolysis by-products was found to be highly dependent on the source waters tested.     

Organic/inorganic hybrid nanospheres based on hyperbranched poly(ethylene imine) encapsulated into silica for the sorption of toxic metal ions and polycyclic aromatic hydrocarbons from water

Organic–inorganic hybrid silica nanospheres were prepared through a biomimetic silicification process in water at ambient conditions by the interaction of low cost poly(ethylene imine) hyperbranched polymer with silicic acid. The characterization of these nanoparticles by FTIR spectroscopy, scanning electron microscopy (SEM), zeta-potential and dynamic light scattering (DLS) experiments confirmed that the dendritic polymer was incorporated into the silica network. Preliminary experiments show that these hybrid nanoparticles can be employed for the removal of toxic water contaminants. Hybrid nanospheres’ sorption of two completely different categories of pollutants, i.e. metal ions such as Pb²⁺, Cd²⁺, Hg²⁺, Cr₂O₇²⁻, and polycyclic aromatic hydrocarbons such as pyrene and phenanthrene, was largely enhanced in comparison with the corresponding polymer-free silica nanospheres. This was attributed to the to the formation of conventional metal-ligand and charge-transfer complexes proving that although integrated into the silica network poly(ethylene imine) retains its chemical properties.     

Degradation of polycyclic aromatic hydrocarbons by the Chilean white-rot fungus Anthracophyllum discolor

The degradation of three- and four-ring polycyclic aromatic hydrocarbons (PAHs) in Kirk medium by Anthracophyllum discolor, a white-rot fungus isolated from the forest of southern Chile, was evaluated. In addition, the removal efficiency of three-, four- and five-ring PAHs in contaminated soil bioaugmented with A. discolor in the absence and presence of indigenous soil microorganisms was investigated. Production of lignin-degrading enzymes and PAH mineralization in the soil were also determined. A. discolor was able to degrade PAHs in Kirk medium with the highest removal occurring in a PAH mixture, suggesting synergistic effects between PAHs or possible cometabolism. A high removal capability for phenanthrene (62%), anthracene (73%), fluoranthene (54%), pyrene (60%) and benzo(a)pyrene (75%) was observed in autoclaved soil inoculated with A. discolor in the absence of indigenous microorganisms, associated with the production of manganese peroxidase (MnP). The metabolites found in the PAH degradation were anthraquinone, phthalic acid, 4-hydroxy-9-fluorenone, 9-fluorenone and 4,5-dihydropyrene. A. discolor was able to mineralize 9% of the phenanthrene. In non-autoclaved soil, the inoculation with A. discolor did not improve the removal efficiency of PAHs. Suitable conditions must be found to promote a successful fungal bioaugmentation in non-autoclaved soils.     

Destruction of organic pollutants by cerium(IV) MEO process: a study on the influence of process conditions for EDTA mineralization

The mediated electrochemical oxidation (MEO) process with cerium(IV) and nitric acid as the oxidizing medium was employed for the destruction of various model organic pollutants in continuous organic feeding mode. A near complete destruction was observed for all the organics studied. The effects of various experimental conditions were evaluated with respect to EDTA mineralization. The key parameters varied in the process were concentration of EDTA (67–268 mM), temperature (70, 80 and 95 °C), concentrations of Ce(IV) (0.7, 0.8 and 0.95 M), nitric acid (2, 3 and 4 M) and duration of organic addition (30 and 120 min). Under the experimental conditions of 80 °C and 0.95 M Ce(IV) in 3 M nitric acid, nearly 90% destruction was achieved based on CO₂ production and 95% based on TOC analyses for all the organic compounds studied. The in situ regeneration of mediator ion by the electrochemical cell was found to be good during the organic destruction within the range of experimental conditions studied. In the case of long term organic feeding (120 min) the destruction was calculated after the CO₂ evolution attained the steady state and under this condition the destruction efficiency was found to be 85% based on CO₂ evolution.     

Migration of Mineral Oil into Noodles from Recycled Fibres in the Paperboard Box and the Corrugated Board Transport Box as well as from Printing Inks: A Case Study

From the toxicological evaluation of mineral oils as used in offset printing inks by the Joint Food and Agriculture Organization of the United Nations/World Health Organization Expert Committee on Food Additives (JECFA), a specific migration limit of 0.6 mg/kg in food can be derived. Experimental packs for taglioline (fine noodles) were investigated, aiming at respecting this limit. This ended with four conclusions. First, during the 65 day test (shelf life of 2 years), the transport box of corrugated board contaminated the bottom packs in the box with 6.1 mg/kg mineral oil saturated hydrocarbons (MOSH) and had the potential of contaminating all the 10 packs on average at about 10 mg/kg. Second, the migration from an improved recycled paperboard (five times less mineral oil than average) still amounted to 4.9 mg/kg, indicating that optimization of recycling is not promising to respect the 0.6 mg/kg limit. Third, a printing ink containing 3 g/kg MOSH (about 100 times less than conventional offset inks) still contaminated the taglioline with 0.6 mg/kg MOSH. Finally, the taglioline were contaminated with 2.5 mg/kg MOSH already before packing, illustrating that there are other sources of mineral oil violating the 0.6 mg/kg limit. Copyright © 2011 John Wiley & Sons, Ltd.     

Size-controlled synthesis of hydroxyapatite nanorods in the presence of organic modifiers

Size-controlled synthesis of hydroxyapatite nanorods was carried out by chemical precipitation followed by hydrothermal treatment using trisodium citrate, Tween 20, and polyethylene glycol (MW 600) as organic modifiers and starting from calcium nitrate and phosphoric acid. The particle sizes of the resultant hydroxyapatite nanorods varied with the chemical structures of the present organic modifiers and the crystallinity of the hydroxyapatite increased with an increasing autoclaving temperature.     

用气相色谱法对水中有机磷农药的测定

本文采用固相萃取法预处理,然后用带有火焰光度检测器(FPD)的气相色谱仪测定有机磷农药。结果表明,该法具有简单、快速、准确的持点。     

Studies on the electronic transport properties of some organic semiconductors in thin films

The investigated compounds are some derivatives of orthotolidin-N,N-bis (4-aminobenzene-2-sulphonic) acid. The temperature dependences of the electrical conductivity and Seebeck coefficient are studied on the thin films deposited from dimethylformamide solution onto glass substrates. It is known that the investigated compounds have typical semiconducting properties. The values of some important parameters of the films (thermal activation energy of electrical conduction, concentrations and mobilities of charge carriers) have been determined. The correlations between some of these parameters and molecular structure of the respective compounds are discussed.