Compound-specific carbon and hydrogen isotope analysis of sub-parts per billion level waterborne petroleum hydrocarbons

Compound-specific carbon and hydrogen isotope analysis (CSCIA and CSHIA) has been increasingly used to study the source, transport, and bioremediation of organic contaminants such as petroleum hydrocarbons. In natural aquatic systems, dissolved contaminants represent the bioavailable fraction that generally is of the greatest toxicological significance. However, determining the isotopic ratios of waterborne hydrophobic contaminants in natural waters is very challenging because of their extremely low concentrations (often at sub-parts ber billion, or even lower). To acquire sufficient quantities of polycyclic aromatic hydrocarbons with 10 ng/L concentration for CSHIA, more than 1000 L of water must be extracted. Conventional liquid/liquid or solid-phase extraction is not suitable for such large volume extractions. We have developed a new approach that is capable of efficiently sampling sub-parts per billion level waterborne petroleum hydrocarbons for CSIA. We use semipermeable membrane devices (SPMDs) to accumulate hydrophobic contaminants from polluted waters and then recover the compounds in the laboratory for CSIA. In this study, we demonstrate, under a variety of experimental conditions (different concentrations, temperatures, and turbulence levels), that SPMD-associated processes do not induce C and H isotopic fractionations. The applicability of SPMD-CSIA technology to natural systems is further demonstrated by determining the delta13C and deltaD values of petroleum hydrocarbons present in the Pawtuxet River, RI. Our results show that the combined SPMD-CSIA is an effective tool to investigate the source and fate of hydrophobic contaminants in the aquatic environments.     

针织物厚度的精确测量

织物厚度采用织物厚度仪进行测量,由一定质量的压脚对织物表面施加一定压强,通过压脚的升降测量压脚停止时的位置高度.机织物采用这种测量方法能得到实际的数值,而对针织物而言,预加载荷对测试结果有很大的影响.最近的一个研究项目旨在估计这种误差,以判定该位置高度是否适合推断空载状态下的织物的厚度.     

Monod kinetics for aerobic biodegradation of petroleum hydrocarbons in unsaturated soil microcosms

We use Monod kinetics to calibrate previously published data that documentthe aerobic biodegradation of hydrocarbon vapors in soil microcosms from a weathered petroleum spill site. Monod kinetics offer insight into biodegradation mechanics because they address biomass growth as well as substrate depletion. A blend of five aromatics and five alkanes dose the microcosm sets at four strengths, and a finite difference model describes the response superimposed across the constituent substrates. An observed initial biomass X0 of 125 g biomass/m(3) soil moisture and an endogendous decay rate b of 0.102 day(-1) calibrate all four dosages and agree with heterotrophic plate counts. Common maximum specific growth rates microMJ and half saturation constants KSJ calibrate each constituent across the four dosages. The biodegradable alkanes exhibit microMJ values ranging from 0.0190 to 0.0996 day(-1), while the aromatic rates vary from 0.0946 to 0.322 day(-1). One of the alkanes (2,2,4-trimethylpentane) is recalcitrant. The half saturation constants range from 0.000083 to 0.000355 g substrate/m(3) soil moisture for the biodegradable alkanes, which imply zero-order kinetics. The aromatic KSJ values vary from 5.02 to 14.3 g substrate/m(3) soil moisture, and suggest first-order kinetics. The yield YJ increases with dosage concentration for all the biodegradable constituents, varying from 0.0533 to 1.58 g biomass/g substrate.     

Optimizing detection limits for the analysis of petroleum hydrocarbons in complex environmental samples

To evaluate the sources, transport, bioremediation, fate, and effects of spilled petroleum and petroleum products, environmental studies often measure parent and alkylated polycyclic aromatic hydrocarbons (PAH), alkanes, and chemical biomarkers (e.g., triterpanes). Accurate data for low analyte concentrations are required when environmental samples contain hydrocarbons from multiple sources that need to be resolved and quantified. The accuracy and usefulness of the analyses can be improved by lowering the method detection limits (MDLs) for these compounds. Misidentification of hydrocarbon source can result when the MDLs are too high. Modifications to standard analytical methods (i.e., U.S. Environmental Protection Agency Method 8270) can lower MDLs by factors ranging from 10 to 1000. This reduction has important implications for ecological-risk assessments. Modifications having the greatest impact on the MDL include GCMS analysis in the selected-ion-monitoring mode (SIM), increased sample size, column cleanup of the extract, and decreased preinjection volume (volume of final extract prior to injection into instrument). In one study in which a benthic sediment sample was spiked with low levels of topped (heated to remove more volatile PAH that are naturally enriched in crude oil) Alaska North Slope crude, MDLs for individual PAH analytes and biomarkers were determined to be less than 0.5 ng/g (ppb) dry weight and less than 5 ppb dry weightfor individual alkanes. Similar results were obtained when the sediment was spiked with the 16 EPA priority pollutants. In addition, a method has been developed to estimate MDLs for source-specific alkylated PAH analytes and chemical biomarker compounds for which standards are not commercially available or are prohibitively expensive. These improved analytical techniques have been used to identify and quantify low levels of hydrocarbons, derived from both natural and anthropogenic sources, found in the benthic sediments of Prince William Sound, AK.     

The West Falmouth oil spill after thirty years: the persistence of petroleum hydrocarbons in marsh sediments

The long-term fate of petroleum hydrocarbons in marsh sediments (West Falmouth, MA) contaminated in 1969 by the spill of the barge Florida was investigated. A 36-cm-long sediment core was collected in August 2000, and sediment extracts were analyzed by gas chromatography (GC) and comprehensive two-dimensional gas chromatography (GC x GC). The latter technique is capable of separating 1 order of magnitude more compounds than the former and was used to observe whether any compositional changes in the unresolved complex mixture (UCM) occurred. No evidence of petroleum residues was detected in the top 6 cm (0-6 cm) and the lower 8 cm (28-36 cm) of the core. However, the central sections 16-28 cm) were dominated by a UCM in the boiling range of n-C13-n-C25 alkanes, consistent with a No. 2 fuel oil source. The 12-14- and 14-16-cm sections had the highest concentrations of UCM approximately 8 mg g(-1)). These values are similar to concentrations observed shortly after the spill. Initial GC x GC analysis revealed that only the n-alkanes were completely degraded, and contrary to previous studies, pristane and phytane as well as numerous other branched alkanes are still present in the sediments. These results suggestthatatthis site hydrocarbon contamination will persist indefinitely in the sedimentary record.     

Field study of pulsed air sparging for remediation of petroleum hydrocarbon contaminated soil and groundwater

Recent laboratory-scale studies strongly suggested an advantage to operating air-sparging systems in a pulsed mode; however, little definitive field data existed to support the laboratory-scale observations. This study aimed to evaluate the performance of a field-scale pulsed air-sparging system during a short-term pilot test and during long-term system operation. The air-sparging system consisted of 32 sparging points and had been previously operated in a continuous mode for two years before the field study was performed. The field study used instruments with continuous data logging capabilities to monitor the dynamic responses of groundwater and soil vapor parameters to air injection. The optimum pulsing frequency was based on the evidence that the hydrocarbon volatilization and oxygen dissolution rates dramatically dropped after the air-sparging system reached steady state. The short-term pilot test results indicated a substantial increase in hydrocarbon volatilization and biodegradation in pulsed operation. On the basis of the results of the pilottest, the air-sparging system was set to operate in a pulsed mode at an optimum pulsing frequency. Operation parameters were collected 2, 8, and 12 months after the start of the pulsed operation. The long-term monitoring results showed thatthe pulsed operation increased the average hydrocarbon removal rate (kg/day) by a factor of up to 3 as compared to the previous continuous operation. The pulsed air sparging has resulted in higher reduction rates of dissolved benzene, toluene, ethylbenzene, and xylenes (BTEX) than were observed during the continuous operation. Among BTEX, benzene's reduction rate was the highest during the pulsed air-sparging operation.     

磷酸酯改性水性聚氨酯胶黏剂的制备及表征

以聚酯二元醇(PBA)、异佛尔酮二异氰酸酯(IPDI)、磷酸酯、2,2-二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)、三乙胺(TEA)和水等为基本原料,合成了一系列磷酸酯改性的水性聚氨酯(WPU)胶粘剂.利用红外光谱(FT-IR)、热重(TG)分析等测试方法对胶粘剂的结构和性能进行了分析、测试和表征,并研究了磷酸...     

Adsorption of polycyclic aromatic hydrocarbons by carbon nanomaterials

Carbon nanomaterials are novel manufactured materials, having widespread potential applications. Adsorption of hydrophobic organic compounds (HOCs) by carbon nanomaterials may enhance their toxicity and affect the fate, transformation, and transport of HOCs in the environment. In this research, adsorption of naphthalene, phenanthrene, and pyrene onto six carbon nanomaterials, including fullerenes, single-walled carbon nanotubes, and multiwalled carbon nanotubes was investigated, which is the first systematic study on polycyclic aromatic hydrocarbons (PAHs) sorption by various carbon nanomaterials. All adsorption isotherms were nonlinear and were fitted well by the Polanyi-Manes model (PMM). Through both isotherm modeling and constructing "characteristic curve", Polanyi theory was useful to describe the adsorption process of PAHs by the carbon nanomaterials. The three fitted parameters (Q0, a, and b) of PMM depended on both PAH properties and the nature of carbon nanomaterials. For different PAHs, adsorption seems to relate with their molecular size, i.e., the larger the molecular size, the lower the adsorbed volume capacity (Q0), but higher a and b values. For different carbon nanomaterials, adsorption seems to relate with their surface area, micropore volume, and the volume ratios of mesopore to micropore. Quantitative relationships between these sorbent properties and the estimated parameters of PMM were obtained. These relationships may represent a first fundamental step toward establishing empirical equations for quantitative prediction of PAH adsorption by carbon nanomaterials and possibly other forms of carbonaceous (geo-) sorbents, and for evaluating their environmental impact. In addition, high adsorption capacity of PAHs by carbon nanotubes may add to their high environmental risks once released to the environment, and result in potential alteration of PAHs fate and bioavailability in the environment.     

羟基硅油改性水性聚氨酯涂料的制备及其印花性能

为探究羟基硅油对改性水性聚氨酯涂料印花性能的影响,制备了不同质量分数的羟基硅油改性聚氨酯,并进行了红外表征,分析了羟基硅油质量分数对改性聚氨酯涂料的黏度、固化速度、耐摩擦牢度、印花图案清晰度的影响。结果表明,当羟基硅油的质量分数小于10%时,异氰酸根与羟基硅油的反应较完全,羟基硅油质量分数在10%~20%之间,水性聚氨酯固化膜的耐水性、柔韧性、耐化学性较好。当羟基硅油质量分数增大时,水性聚氨酯涂料的黏度降低、固化速度增加,耐摩擦牢度变好,印花图案清晰度降低。     

Reliability of ultrasonographic measurements of bovine sole structures in relation to sole horn thickness,measured by computed tomography,and sole horn hardness

The goal of the present study was to determine the effect of sole horn thickness (SHT) and sole horn hardness (SHD) on ultrasonographic visualization of sole structures in the inner and outer claws of 150 Holstein-Friesian cows, and to evaluate different ultrasound frequencies for this purpose. Ultrasonographic views of the sole structure were considered complete when 3 echogenic lines, representing the ventral surface of the sole horn, the borders of the sole horn and soft-tissue layer, and the ventral surface of the distal phalanx, were seen. The proportion of complete ultrasonographic views of the sole structures, designated as the ultrasonographic visualization proportion (UVP), and the measurement errors of SHT were evaluated by comparing images from computed tomography (CT) and ultrasonography. The latter images were generated using 3 different probes, frequencies of 6.5 and 5.0 MHz, and 2 different ultrasound machines (#1 and #2) to assess the apex, middle, and heel regions of the claws. The UVP were 60.8 to 77.9% for the 6.5-MHz probe in ultrasound machine #1 (probe A), which were lower than those (>90%) for both the 5.0-MHz probe in ultrasound machine #1 (probe B) and the 5.0-MHz probe in ultrasound machine #2 (probe C). The UVP was significantly lower in claws with an SHD ≥50 units than in claws with an SHD <40 or 40 to <50 units (UVP: 77.1% compared with 93.7 and 91.4%, respectively) when measured with probe B. In claws with an SHT <10 mm, the UVP was significantly lower when SHD was ≥50 units compared with <40 or 40 to >50 units; the values were 69.0% versus 91.3 and 85.9%, respectively, for probe A, and 89.7% versus 100 and 100%, respectively, for probe B. When SHT were measured by either probes A or B in ultrasound machine #1, the proportions of claws in which ultrasonographic values were within a ±1 mm range compared with the values obtained by CT were 84.9 to 91.3% for CT-determined SHT <5 mm, 66.7 to 71.9% for CT-determined SHT 5 to <7 mm, 28.9 to 51.2% for CT-determined SHT 7 to <10 mm, and 6.2 to 19.7% for CT-determined SHT ≥10 mm. The data indicated that increased SHT was associated with a decrease in ultrasonographic measurement accuracy. In claws with an SHT <5 mm, the high proportion of ultrasonographic values that were accurate within a ±1 mm range suggests that this imaging modality would be useful in cows with thin soles.     

Emission of polycyclic aromatic hydrocarbons in China by county

Quantitative relationships among social, economic, and climate parameters, and energy consumption for Chinese provinces, provide data for regression models' estimated rates of energy consumption and emission of polycyclic aromatic hydrocarbons (PAHs) by county. A nonlinear model was used for domestic coal combustion with total population and annual mean temperature as independent variables. Linear regression models were utilized for all other types of fuel consumption. Monte Carlo simulation demonstrated that emission factors, rather than the regression modeling, constitute the main source of uncertainty in prediction. Models were validated using available energy data of several northern and southern counties of China from the literature. The total PAHs produced by each county is approximately equivalent to the sum of the total emission from energy, coke, and aluminum production.     

Field measurements of aerosol particle dry deposition on tropical foliage at an urban site

This paper presents dry deposition of major ions on tropical foliage (leaves of Ashok (Polyalthia longifolia) and Cassia (Cassia siamea)) at St. John's, Agra, an urban site of tropical India on nonrainy, nondewy, and nonfoggy days. The deposition flux was higher on Cassia leaf than Ashok leaf probably due to a rougher surface as shown by scanning electron microscopy. Dry deposition of cations varies from 0.46 to 12.16 mg m(-2) day(-1) while anions vary from 0.04 to 3.24 mg m(-2) day(-1). The percentage contribution of alkaline components is greater than that of acidic components, indicating the alkaline nature of dry deposition. Two-way analysis of variance results reveal significant seasonal variation only for K+, SO4(2-), and F-; however, values varied season to season for Na+, Ca2+, Mg2+, Cl-, NO3-, and NH4+ also. The large seasonal variation in deposition flux may be due to meteorological conditions, diameter of particles, and variation in atmospheric level. SO42- and NO3- show significant correlation, indicating their origin from similar sources while significant correlation between Ca2+ and Mg2+ implies their origin from soil. Poor correlation between Ca2+ and SO4(2-), Ca2+ and NO3-, and Mg2+ and SO4(2-) indicates that in addition to soil other sources also contribute to dry deposition. Low dry deposition fluxes of SO2- and NO3- compared to Ca2+ and Mg2+ may be due to low mass medium diameters of SO4(2-) and NO3- and may be due to uptake through the stomatal pores abundant on leaf surfaces. Factor analysis was employed to identify the sources. F-, Cl, SO4(2-), NO3-, and K+ are grouped together in the first factor, indicating their probable contribution from combustion, Ca2+, Mg2+, and NH4+ are grouped in factor II, which may be attributed to road dust and soil, and factor III includes mainly Na+ and F-, probably contributed from brick-kiln industries. Atmospheric concentrations of F-, Cl-, NOs-, SO4(2-), Na+, K+, Ca2+, Mg2+, and NH4+ were found to be 0.38, 2.28, 1.31, 2.74, 0.44, 0.59, 1.21, 1.2, and 2.29 microg m(-3), respectively.