Oil Identification Based on a Goodness-of-Fit Metric Applied to Hydrocarbon Analysis Results

Assessment of environmental damage following accidental oil spills requires reliable oil identification methods. Results from hydrocarbon analyses of environmental samples are often difficult to interpret, because of the changes in oil composition (or weathering) that follows release into the environment, and because of confounding by hydrocarbons from other sources. To a first-order approximation, weathering proceeds according to simple first-order loss-rate (FOLR) kinetics for polycyclic aromatic hydrocarbons (PAH) based on molecular size. This relationship between relative weathering rate and molecular size can be exploited to infer the initial PAH composition of spilled oils, and this information can be combined with results for weathering-invariant analytes to substantially increase the precision and accuracy of hydrocarbon source recognition methods. The approach presented here evaluates a goodness-of-fit metric between the measured hydrocarbon composition of an environmental sample and a suspected source, after correcting for PAR weathering losses based on FOLR kinetics. Variability from analytical and sampling error may thus be accounted for, and source identifications can be expressed as objective probability statements. This approach is illustrated by application to four independent case studies.     

Pattern Recognition Based Software for Oil Spills Identification by Gas-Chromatography and IR Spectrophotometry

For environmental control purposes, floating oil spills in harbours, off shore areas and their sources must often be identified. Pattern recognition, applied to IR spectrophotometric data (600–2000 cm⁻¹ range), and to chromatographic data (n -alkanes) for the spill and various suspected sources such as oil and fuels from ships bunkers and harbour installations, can lead to definite conclusions; particularly after artificial weathering formula are used. The software application provides quick and accurate identification of the pollution source. The identification algorithm has a learning stage in which the user creates a minimal database. This database has a tree structure with classes (fuels, crude, etc.) and members representing samples from already known sources. A sample contains IR and chromatographic data and information of the originating source. A larger database means more knowledge, which conveys a better identification. When the origin of an unknown sample is searched for, the software looks for the best match through the database and displays the results in two lists; sorted by calculated similarity. One list displays the classes in which the unknown sample could be included and the other displays the possible sources. An extra check can be done by visual inspection of the overlapped graphics (unknown sample and each of the identified sources).     

Pattern Recognition Based Software for Oil Spills Identification by Gas-Chromatography and IR Spectrophotometry

For environmental control purposes, floating oil spills in harbours, off shore areas and their sources must often be identified. Pattern recognition, applied to JR spectrophotometric data (600-2000 cm m 1 range), and to chromatographic data ( n -alkanes) for the spill and various suspected sources such as oil and fuels from ships bunkers and harbour installations, can lead to definite conclusions; particularly after artificial weathering formula are used. The software application provides quick and accurate identification of the pollution source. The identification algorithm has a learning stage in which the user creates a minimal database. This database has a tree structure with classes (fuels, crude, etc.) and members representing samples from already known sources. A sample contains JR and chromatographic data and information of the originating source. A larger database means more knowledge, which conveys a better identification. When the origin of an unknown sample is searched for, the software looks for the best match through the database and displays the results in two lists; sorted by calculated similarity. One list displays the classes in which the unknown sample could be included and the other displays the possible sources. An extra check can be done by visual inspection of the overlapped graphics (unknown sample and each of the identified sources).     

Forensic Analysis of Chlorinated Hydrocarbon Plumes in Groundwater: a Multi-Site Perspective

Forensic analyses of chlorinated hydrocarbon plumes typically entail reviews of site records, flow and transport modeling, and analysis of indicator compounds to gain insights into the behavior of a contaminant plume in the subsurface. Such approaches are directed toward unraveling the specific circumstances associated with the disposal history and hydrogeology of a site. A complimentary approach is to compare the behavior of a particular plume with a population of plumes from other sites that may be influenced by similar mechanisms (e.g. transformation processes such as reductive dehalogenation). In other words, hypotheses pertaining to plume behavior can be tested against a knowledge base of what is typical behavior and what is not. To address this proposed methodology, three example applications of statistical techniques to a multi-site data set are presented to provide background for problems that may be pertinent to forensic analyses. These examples include measuring the frequency of association between selected chlorinated hydrocarbon compounds, assessing the effects of transformation processes on temporal concentration trends in populations of groundwater monitoring wells, and dating plumes, in a relative sense, by concentration correlation analyses. In each case, the results of the statistical analyses are consistent with expectation, indicating that meaningful trends in chlorinated hydrocarbon plume behavior may be discerned from a diverse multi-site data set.     

Net Waste Reduction Analysis Applied to Air Pollution Control Technologies

Post-combustion air pollution control technologies were evaluated to determine total waste produced by the operation of these systems. A continuum of air pollution control technology choices providing increasing levels of control is presented and the quantity of waste produced by each air pollution control option has been calculated. In addition, this analysis accounts for waste produced indirectly by the generation of energy required for operation of the control technologies. This type of analysis can be used to select optimal control levels and to demonstrate why a goal of zero air emissions may not be environmentally desirable.     

Hydrocarbon pollution fixed to combined sewer sediment: a case study in Paris

Over a period of two years (2000-2001), sediment samples were extracted from 40 silt traps (STs) spread through the combined sewer system of Paris. All sediment samples were analysed for physico-chemical parameters (pH, organic matter content, grain size distribution), with total hydrocarbons (THs) and 16 polycyclic aromatic hydrocarbons (PAHs) selected from the priority list of the US-EPA. The two main objectives of the study were (1) to determine the hydrocarbon contamination levels in the sediments of the Paris combined sewer system and (2) to investigate the PAH fingerprints in order to assess their spatial variability and to elucidate the PAH origins. The results show that there is some important inter-site and intra-site variations in hydrocarbon contents. Despite this variability, TH and PAH contamination levels (50th percentile) in the Parisian sewer sediment are estimated at 530 and 18 microg g(-1), respectively. The investigation of the aromatic compound distributions in all of the 40 STs has underlined that there is, at the Paris sewer system scale, a homogeneous PAH background pollution. Moreover, the study of the PAH fingerprints, using specific ratios, suggests the predominance of a pyrolytic origin for those PAHs fixed to the sewer sediment.     

离子色谱法在大气降水监测中的应用研究

研究了用离子色谱法直接测定大气降水中阳离子的色谱条件、线性范围.实验研究表明,Na+、NH+4、K+、Mg2+、Ca2+方法的最小检出限分别为0.049、0.043、0.011、0.004、0.056 mg·L-1;相对标准偏差分别为4.1%、0.6%、3.7%、1.0%、1.2%;加标回收率为97%～105%.用离子色谱法直接测定大气降水中的阳离子,操作简单、快捷,具有可靠的准确度和良好的精密度,且灵敏度高,实验结果令人满意.     

Interaction Effects of Metals and Salinity on Biodegradation of a Complex Hydrocarbon Waste

Abstract

The presence of high levels of salts because of produced brine water disposal at flare pits and the presence of metals at sufficient concentrations to impact microbial activity are of concern to bioremediation of flare pit waste in the upstream oil and gas industry. Two slurry-phase biotreatment experiments based on three-level factorial statistical experimental design were conducted with a flare pit waste. The experiments separately studied the primary effect of cadmium [Cd(II)] and interaction effect between Cd(II) and salinity and the primary effect of zinc [Zn(II)] and interactioneffect between Zn(II) and salinity on hydrocarbon biodegradation. The results showed 42–52.5% hydrocarbon removal in slurries spiked with Cd and 47–62.5% in the slurries spiked with Zn. The analysis of variance showed that the primary effects of Cd and Cd–salinity interaction were statistically significant on hydrocarbon degradation. The primary effects of Zn and the Zn-salinity interaction were statistically insignificant, whereas the quadratic effect of Zn was highly significant on hydrocarbon degradation. The study on effects of metallic chloro-complexes showed that the total aqueous concentration of Cd or Zn does not give a reliable indication of overall toxicity to the microbial activity in the presence of high salinity levels.     

生物标志物在环境评价中的应用研究概况与趋向

生物标志物在环境评价中的应用日显重要，近几年国内已有这一领域的文献综述，但若干基本方面还有待阐述。文章在回顾文献的基础上，旨在提出侧重于这些方面的全面评述，包括：生物标志物及相关术语的基本概念；暴露生物标志物，反应或毒性效应生物标志物和易感性生物标志物的性质和实例；生物标志物对污染物的特异性和生物标志物有害效应的关系；生物标志物在环境评价中的作用和发展趋向。     

活性炭纤维(ACF)应用于有机废气回收和净化的进展

活性炭纤维(ACF)有比普通活性炭吸附量大、吸附和脱附速度快等优点,因此应用于有机废气的回收和净化,具有良好的经济、环境和社会效益。文中介绍了ACF的微观结构、表面化学以及吸附性能,并综述了近年来ACF在有机废气回收和治理方面的国内概况。     

Identification of methyl chloride-emitting plants and atmospheric measurements on a subtropical island

A survey of methyl chloride (CH3Cl)-emitting plants was performed at a subtropical island in Japan (Iriomote Island). Among the 187 species of tropical/subtropical plants investigated, 33 species from a variety of families were identified as CH3Cl-emitting plants. The strongest emitters were Osmunda banksiifolia, Cibotium balometz, Angiopteris palmiformis, Vitex rotundifolia, Vitex trifolia, and Excoecaria agalloch, each with CH3Cl emission rates exceeding 1microg (gdrywt)(-1)h(-1). The first three species are ferns, and the last three are halophilous plants. Based on our results, the character of CH3Cl emission is likely to be shared at the genus level but not always at the family level. The atmospheric CH3Cl distribution measured on Iriomote Island showed significant enhancement in forested sites (up to 2750 ppt) and a higher concentration on the downwind shore than on the upwind shore. As previously reported, our findings provide strong evidence for the high emission of CH3Cl from tropical/subtropical forests.     

Evaluation of a Probabilistic Exposure Model Applied to Carbon Monoxide (pNEM/CO) Using Denver Personal Exposure Monitoring Data

The probabilistic National Ambient Air Quality Standards (NAAQS) Exposure Model applied to carbon monoxide (pNEM/CO) was developed by the U.S. Environmental Protection Agency (EPA) to estimate frequency distributions of population exposure to carbon monoxide (CO) and the resulting carboxyhemoglobin (COHb) levels. To evaluate pNEM/CO, the model was set up to simulate CO exposure data collected during a Denver Personal Exposure Monitoring Study (PEM) conducted during the winter of 1982-1983. This paper compares computer-simulated exposure distributions obtained by pNEM/CO with the observed cumulative relative frequency distributions of population exposure to CO from 779 people in the Denver PEM study.

The subjects were disaggregated into two categories depending upon whether they lived in a home with a gas stove or an electric stove. The observed and predicted population exposure frequency distributions were compared in terms of 1-hr daily maximum exposure (1DME) and 8-hr daily maximum moving average exposure (8DME) for people living in homes with gas stove or an electric stove. For 1DME, the

computer-simulated results from pNEM/CO agreed most closely within the range of 6-13 ppm, but overestimated occurrences at low exposure (<6 ppm) and underestimated occurrences at high exposure (>13 ppm). For 8DME, the predicted exposures agreed best with observed exposures in the range of CO concentration between 5.5 and 7 ppm, and over-predicted occurrences below 5.5 ppm and under-predicted occurrences above 7 ppm.     

A Feasibility Study on the Predictive Emission Monitoring System Applied to the Hsinta Power Plant of Taiwan Power Company

Abstract

The continuous emission monitoring system (CEMS) can monitor flue gas emissions continuously and instantaneously. However, it has the disadvantages of enormous cost, easily producing errors in sampling periods of bad weather, lagging response in variable ambient environments, and missing data in daily zero and span tests and maintenance. The concept of a predictive emission monitoring system (PEMS) is to use the operating parameters of combustion equipment through thermodynamic or statistical methods to construct a mathematic model that can predict emissions by a computer program. The goal of this study is to set up a PEMS in a gas-fired combined cycle power generation unit at the Hsinta station of Taiwan Power Co. The emissions to be monitored include nitrogen oxides (NO_x) and oxygen (O₂) in flue gas. The major variables of the predictive model were determined based on the combustion theory. The data of these variables then were analyzed to establish a regression model. From the regression results, the influences of these variables are discussed and the predicted values are compared with the CEMS data for accuracy. In addition, according to the cost information, the capital and operation and maintenance costs for a PEMS can be much lower than those for a CEMS.     

Identification of rice cultivar with exclusive characteristic to Cd using a field-polluted soil and its foreground application

Using low-accumulative plant, especially excluder crop, to safely produce food is one of the very important technologies of phytoremediation, which is practical to safe production and long-term remediation of heavy metal-contaminated soil. A pot experiment using field cadmium (Cd)-contaminated soil (Cd concentration was 0.75 mg?kg^?1) was conducted to compare Cd accumulation differences among 39 normal rice cultivars (Japonica) in Shenyang region of China for food safety and high grain yield aim. The results showed that brown grain Cd concentration in 12 rice cultivars of a total of 39 tested cultivars was lower than 0.2 mg?kg^?1 (Agricultural Trade Standard of Nonpollution Food for Rice of China, NY 5115–2008). In these 12 cultivars, Cd enrichment factors (Cd concentration ratio in shoot to that in soil) of nine cultivars were lower than 1. Likewise, Cd translocation factors (Cd concentration ratio in shoot to that in root) of eight cultivars were lower than the 0.28 average. Furthermore, grain yield per pot of seven cultivars were higher than the average 18.4 g?pot^?1. Four cultivars, i.e., Shendao 5, Tianfu 1, Fuhe 90, and Yanfeng 47 showed Cd-exclusive characteristic and better foreground application.     

Identification of various laccases induced by anthracene and contribution to its degradation in a Mediterranean coastal pine litter

Mediterranean coastal ecosystems are known to be highly subject to natural and anthropic environmental stress. In this study, we examine the effects of anthracene as a common pollutant on the total microbial communities from a Pinus halepensis litter of a typical Mediterranean coastal site (Les Calanques, Marseille). The main objective was to identify the microbial factors leading the resilience of this ecosystem. Two questions were addressed: (i) how lignin-degrading enzymes (Laccase, Lignin-peroxidase and Mn-peroxidase) are affected by the presence of this molecule, (ii) whether the indigenous consortia are involved in its degradation in mesocosms under favorable incubation conditions (25 °C, 60% WHC) and after different time intervals (1 and 3 month(s)). We found a strong increase in laccase production in the presence of anthracene after 3 months, together with anthracene degradation (28% ± 5). Moreover 9,10-anthraquinone is detected as the product of anthracene oxidation after 3 months. However neither lignin-peroxidase activity nor Mn-peroxidase activity is detected. Laccase proteins directly extracted from litter were sequenced via Nano-LC-MS/MS and reveal twelve different peptide sequences induced by the presence of anthracene in the mesocoms. Our study confirms the major detoxification role of this enzymatic system and highlights the high degradation potential of fungal species inhabiting P. halepensis litter, a factor in the resilience of Mediterranean ecosystems.     

Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.     

Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.