‘Emulsion locks’ for the containment of hydrocarbons during surfactant flushing

Reversible double water in oil in water (W/O/W) emulsions were developed to contain subsurface hydrocarbon spills during their remediation using surfactant flushing. Double emulsions were prepared by emulsifying CaCl₂ solutions in canola oil, and subsequently by emulsifying the W/O emulsions in aqueous sodium alginate solutions. The formation of double emulsions was confirmed with confocal and optical microscopy. The double emulsions reversed and gelled when mixed with the surfactants sodium dodecyl sulfate (SDS) and cocamidopropyl betaine (CPB). Gels can act as ‘emulsion locks’ to prevent spreading of the hydrocarbon plume from the areas treated with surfactant flushing, as shown in sand column tests. Shear rheology was used to quantify the viscoelastic moduli increase (gelation) upon mixing the double emulsion with SDS and CPB. SDS was more effective than CPB in gelling the double emulsions. CPB and SDS could adsorb at the interface between water and model hydrocarbons (toluene and motor oil), lowering the interfacial tension and rigidifying the interface (as shown with a Langmuir trough). Bottle tests and optical microscopy showed that SDS and CPB produced W/O and O/W emulsions, with either toluene or motor oil and water. The emulsification of motor oil and toluene in water with SDS and CPB facilitated their flow through sand columns and their recovery. Toluene recovery from sand columns was quantitated using Gas-Chromatography Mass-Spectroscopy (GC-MS). The data show that SDS and CPB can be used both for surfactant flushing and to trigger the gelation of ‘emulsion locks’. Ethanol also gelled the emulsions at 100 mL/L.     

膜、柱串联固相萃取-高效液相色谱法测定水中多环芳烃(PAHs)的研究

建立了用膜-柱串联固相萃取(SPE)技术,甲醇和水作为流动相进行梯度洗脱,紫外和荧光检测器串联的高效液相色谱法(HPLC)分析水中EPA优先监控的16种PAHs的方法.     

济南市环境空气中多环芳烃的来源识别和解析

根据环境空气污染源标识物的确定和多环芳烃降解行为,利用CMB受体模型进行拟合计算,确定多环芳烃污染源贡献率,并在比较多环芳烃实测值和CMB受体模型计算值的基础上,得出可吸入颗粒物中多环芳烃源解析结果,确定机动车污染源是济南市可吸入颗粒物中多环芳烃的主要贡献源。     

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.     

WATER QUALITY IN A MEDITERRANEAN MARINE PROTECTED AREA (NORTH SPORADES ISLANDS, GREECE)

Pollution in the marine protected area of North Sporades Islands was investigated in July 1997. Salinity, temperature, dissolved oxygen, dissolved inorganic nutrients, organic carbon, hydrocarbons as well as dissolved and particulate trace metals were determined at 15 offshore and coastal stations. Dissolved organic carbon and inorganic nutrient concentrations indicate the mesotrophic character of the investigated waters. The dissolved forms of nitrogen were slightly higher at coastal stations. Dissolved and particulate Cu, Zn and Ni, were higher in coastal stations, whereas concentrations of Pb were generally low and likely of atmospheric origin. Dissolved/Dispersed petroleum hydrocarbons (DDPH) were close to detection limits at all stations. Temperature and salinity vertical profiles, nutrient and trace metal concentrations revealed the presence of a slight influence of the Black Sea water coming from Dardanelles straits.     

The Distribution and Sources of Polycyclic Aromatic Hydrocarbons in Surface Sediments Along the Egyptian Mediterranean Coast

Coastal marine sediment samples were collected from 31 sampling stations along the Egyptian Mediterranean Sea coast. All sediment samples were analyzed to determine aliphatic and polycyclic aromatic hydrocarbons (PAHs) as well as total organic carbon (TOC) contents and grain size analysis. Total concentrations of 16 EPA-PAHs in the sediments were varied from 88 to 6338 ng g⁻¹ with an average value of 154 ng g⁻¹ (dry weight). However, the concentrations of total aliphatic were varied from 1.3 to 69.9 ng g⁻¹ with an average value of 15.6 ng g⁻¹ (dry weight). The highest contents of PAHs were found in the Eastern harbor (6338 ng g⁻¹), Manzala (5206 ng g⁻¹) and El-Jamil East (4895 ng g⁻¹) locations. Good correlations observed between a certain numbers of PAH concentrations allowed to identify its origin. The average total organic carbon (TOC) percent was varied from 0.91 to 4.54%. Higher concentration of total pyrolytic hydrocarbons (∑COMB) than total fossil hydrocarbons (∑PHE) declared that atmospheric fall-out is the significant source of PAHs to marine sediments of the Egyptian Mediterranean coast. The selected marked compounds, a principal component analysis (PCA) and special PAHs compound ratios (phenanthrene/anthracene vs fluoranthene/pyrene; ∑COMB/∑EPA-PAHs) suggest the pyrogenic origins, especially traffic exhausts, are the dominant sources of PAHs in most locations. Interferences of rather petrogenic and pyrolytic PAH contaminations were noticed in the harbors due to petroleum products deliveries and fuel combustion emissions from the ships staying alongside the quays.     

Bioaccumulation of anthropogenic contaminants by detritivorous fish in the Río de la Plata estuary: 1-aliphatic hydrocarbons

The temporal variability and bioaccumulation dynamics of C_12–25 n-alkanes, isoprenoids and unresolved aliphatic hydrocarbons (UCM) were studied in a detritivorous fish (Sábalo: Prochilodus lineatus) collected from 1999 to 2005 in the sewage impacted Buenos Aires coastal area. Fish muscles contain huge amounts of n-C_12–25 (165 ± 93, 70 ± 48 or 280 ± 134 μg g⁻¹, dry, fresh and lipid weight, respectively) and UCM (931 ± 560, 399 ± 288 and 1567 ± 802 μg g⁻¹) reflecting the chronic bioaccumulation of fossil fuels from sewage particulates. On a temporal basis, lipid normalized aliphatic concentrations peaked by the end of 2001–2002 during the rainiest period over the last four decades (1750 vs. 1083 ± 4.6 mm in 1999, 2004 and 2005), reflecting an enhanced exposition due to massive anthropogenic fluxes from Metropolitan Buenos Aires in wet years. The hydrocarbon composition in fish muscles is enriched in n-C_15–17 and isoprenoids relative to a fresh crude oil and settling particulates, with fresher signatures during the 2001–2002 maxima. Fish/settling material bioaccumulation factors (BAFs: 0.4–6.4 dry weight or 0.07–0.94 lipid-organic carbon) plotted against K_ow showed a parabolic pattern maximizing at n-C_14–18 and isoprenoids. The optimal bioaccumulation window corresponds to highly hydrophobic (log K_ow: 7.2–9.9), intermediate-size C_14–18 n-alkanes and C_15–20 isoprenoids (MW: 198–282; length: 17.9 to 25.4 Å) with melting points ranging from −19.8 to 28 °C. The uptake efficiency is inversely correlated to melting points and increased from 75% for n-C₂₅ to above 90% for n-C_14–15 and isoprenoids.     

Predicting bioremediation of hydrocarbons: Laboratory to field scale

There are strong drivers to increasingly adopt bioremediation as an effective technique for risk reduction of hydrocarbon impacted soils. Researchers often rely solely on chemical data to assess bioremediation efficiently, without making use of the numerous biological techniques for assessing microbial performance. Where used, laboratory experiments must be effectively extrapolated to the field scale. The aim of this research was to test laboratory derived data and move to the field scale. In this research, the remediation of over thirty hydrocarbon sites was studied in the laboratory using a range of analytical techniques. At elevated concentrations, the rate of degradation was best described by respiration and the total hydrocarbon concentration in soil. The number of bacterial degraders and heterotrophs as well as quantification of the bioavailable fraction allowed an estimation of how bioremediation would progress. The response of microbial biosensors proved a useful predictor of bioremediation in the absence of other microbial data. Field-scale trials on average took three times as long to reach the same endpoint as the laboratory trial. It is essential that practitioners justify the nature and frequency of sampling when managing remediation projects and estimations can be made using laboratory derived data. The value of bioremediation will be realised when those that practice the technology can offer transparent lines of evidence to explain their decisions.     

重点流域水系沉积物中多环芳烃标准样品制备

环境标准样品是监测过程中重要的质量控制手段,中国受天然基体标准样品制备技术的制约,尚未拥有自己的沉积物中多环芳烃标准样品。为制备符合中国重点流域沉积物类型及多环芳烃浓度水平的沉积物标准样品,对中国6个重点流域的沉积物进行了采样,获得了制备多环芳烃标准样品的原料。分析常温及冷冻2种干燥方式对多环芳烃的影响,为制备大批量多环芳烃标准样品提供数据支持。对11个点位样品采用气相色谱质谱法测定16种优控多环芳烃化合物浓度,结果表明,样品均匀性良好,样品中多环芳烃检出率在99%以上,江河沉积物样品中多环芳烃浓度区间为664~2.91×103μg/kg,湖泊样品最高值达到1.25×105μg/kg,其主要污染源是化学燃料的燃烧。为中国制备水系沉积物中多环芳烃标准样品积累了技术基础。     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.