The removal of Polycyclic Aromatic Hydrocarbons in the wastewater treatment process: experimental calculations and model predictions

The removal of PAHs during the wastewater treatment process was examined in an activated sludge mode conventional facility. Concentrations reported are taken from an earlier measuring campaign. Removals of PAHs ranged between 28 and 67% in the primary, <1-61% in the secondary stage, and 37-89% in the whole process. Significant positive relationships were observed for removal efficiencies and the log K(ow) of PAHs in the primary and the log K(H) of PAHs in the secondary stage. Experimental removals were compared to those obtained from the FATE model. In the primary stage, predicted removals were lower than those experimentally calculated while in the secondary stage were higher. Predicted removals were apportioned mainly to sorption with negligible contribution from volatilization and biodegradation. Remarkable consistency between experimental and modeled removal efficiencies (-20-+20%) was observed for almost all PAHs in the whole treatment process.     

Sources of hydrocarbons in sediments of the Mandovi estuary and the Marmugoa harbour, west coast of India

Surface sediments were collected from various locations of the Mandovi estuary and the Marmugoa harbour. Sediments were analysed for organic carbon (OC), total lipids, n-alkanes concentration and composition. Concentrations of OC, total lipids and n-alkanes varied spatially and ranged from 1 to 2.5%, 176 to 1413 microg/g dry weight (dw) sediments, and 0.8 to 3.2 microg/g dw sediments of the Mandovi estuary, respectively; and from 0.6 to 2.9%, 233 to 1448 microg/g dw sediments, and 1.6 to 10.7 microg/g dw sediments in the Marmugoa harbour, respectively. Long chain, odd carbon n-alkanes (C(23)-C(33)) in the Mandovi estuary, whereas short chain, even carbon n-alkanes (C(11)-C(21)) in the Marmugoa harbour sediments were more abundant. The total HC concentrations, n-alkane composition, CPI, UCM and other evaluation indices suggest the dominance of terrestrial hydrocarbons in the estuarine while petroleum derived hydrocarbons in the harbour sediments. This conclusion was further supported by the abundance of hopanes with C(29) to C(34) alpha, beta compounds and steranes with C(27), C(28) and C(29) compounds in the harbour sediments.     

焦化厂不同粒径土壤中PAHs的赋存特征

为分析典型焦化污染场地不同粒径土壤中PAHs的累积及其与土壤有机碳含量（TOC）、比表面积（SA）等土壤性质的相关性,对北京焦化厂长期受PAHs污染的土壤进行粒度分级[P1（0.5~1.0 mm）、P2（0.25~0.5 mm）、P3（0.15~0.25 mm）、P4（0.106~0.15 mm）、P5（0.075~0.106 mm）、P6（<0.075 mm）],测定了各粒径土壤的理化性质及土壤中USEPA优先控制的16种PAHs的浓度,探究PAHs在不同粒径土壤中的累积特征,并通过PAHs质量分数及土壤部分理化性质的曲线拟合结果分析PAHs的赋存特征。结果表明：各粒径土壤中16种PAHs均有检出,其最高质量分数大多出现在P1粒径土样,最低质量分数出现在 P4、P5中。各粒径土壤中2~3（低）环 PAHs、ΣPAHs16质量分数变化趋势相似,均为 P1>P2>P3、P4、P6>P5(P<0.05),4（中）、5~6（高）环PAHs趋势类似,均为P1、P2>P3>P6>P4、P5(P<0.05)。比表面积（SA）、总有机碳（TOC）、可溶解性有机碳（DOC）与各类PAHs的质量分数呈现一定的相关性,各类PAHs质量分数随SA的增大呈先增大随后减小趋势,最大质量分数所对应的SA为38~41 m2·g-1,随TOC的增加呈先减小随后增大趋势,最小质量分数所对应的TOC为7.0~8.7 g·kg-1。不同粒径土壤颗粒中,基于污染物毒性当量因子（TEF）的等效质量分数与污染物实际质量分数变化趋势并不相同,ΣPAHs16实际质量分数变化趋势为P1>P2、P3、P4、P6>P5(P<0.05),而其等效质量分数则为P1、P2、P3、P4、P6>P5(P<0.05)。     

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.     

Subsurface sediment contamination during borehole drilling with an air-actuated down-hole hammer

Drilling methods can severely alter physical, chemical, and biological properties of aquifers, thereby influencing the reliability of water samples collected from groundwater monitoring wells. Because of their fast drilling rate, air-actuated hammers are increasingly used for the installation of groundwater monitoring wells in unconsolidated sediments. However, oil entrained in the air stream to lubricate the hammer-actuating device can contaminate subsurface sediments. Concentrations of total hydrocarbons, heavy metals (Cu, Ni, Cr, Zn, Pb, and Cd), and nutrients (particulate organic carbon, nitrogen, and phosphorus) were measured in continuous sediment cores recovered during the completion of a 26-m deep borehole drilled with a down-hole hammer in glaciofluvial deposits. Total hydrocarbons, Cu, Ni, Cr and particulate organic carbon (POC) were all measured at concentrations far exceeding background levels in most sediment cores. Hydrocarbon concentration averaged 124 +/- 118 mg kg(-1) dry sediment (n = 78 samples) with peaks at depths of 8, 14, and 20 m below the soil surface (maximum concentration: 606 mg kg(-1)). The concentrations of hydrocarbons, Cu, Ni, Cr, and POC were positively correlated and exhibited a highly irregular vertical pattern, that probably reflected variations in air loss within glaciofluvial deposits during drilling. Because the penetration of contaminated air into the formation is unpreventable, the representativeness of groundwater samples collected may be questioned. It is concluded that air percussion drilling has strong limitations for well installation in groundwater quality monitoring surveys.     

Biodegradation of Kupferschiefer black shale organic matter (Fore-Sudetic Monocline, Poland) by indigenous microorganisms

This study provides the first evidence for the direct biodegradation of persistent organic matter extracted from the organic-rich polymetallic black shale ore Kupferschiefer, one of the most important sources of metals in the world. It was demonstrated that an enriched community of indigenous heterotrophic microorganisms isolated from black shale grown under aerobic conditions could utilize shale organic matter as the sole carbon and energy source. Colonization of shale organic matter was observed. The main biodegradation intermediates and products such as phosphonic acid dioctadecyl ester and isoindole-1,3 were detected in the aqueous phase of cultures. The bacterial community showed the ability to PAH biodegradation, assimilation of organic acids and esters as well as lipase activity. The intracellular accumulation of phosphorus by bacteria during growth on organic matter was confirmed. Strains within the genus Pseudomonas were found to dominate the bacterial population at the end of the experiment. The results of this study confirm that indigenous bacteria are likely to play a role in the biotransformation of black shale and can influence the geochemical cycles of ancient organic carbon in the deep terrestrial subsurface. This process may also occur in tailings ponds containing black shale, and cause the mobilization of potentially toxic compounds to the soil and groundwater.     

二维气相色谱法测定空气中的总烃及非甲烷总烃

采用单一进样口六通阀进样、毛细管柱二维气相色谱仪三通路分离塔柱分离系统、采用氢离子化检测器分别产生信号,测定环境空气中的非甲烷总烃。通过柱分离系统将样品平均分配到不同类型的两个毛细管色谱柱,分别测定总烃及甲烷。方法简单、快速,最大程度地保证了进样的一致性,从而保证了分析结果的准确性。     

Low-maturity Kulthieth Formation Coal: A Possible Source of Polycyclic Aromatic Hydrocarbons in Benthic Sediment of the Northern Gulf of Alaska

The successful application of forensic geology to contamination studies involving natural systems requires identification of appropriate endmembers and an understanding of the geologic setting and processes affecting the systems. Studies attempting to delineate the background, or natural, source for hydrocarbon contamination in Gulf of Alaska (GOA) benthic sediments have invoked a number of potential sources, including seep oils, source rocks, and coal. Oil seeps have subsequently been questioned as significant sources of hydrocarbons present in benthic sediments of the GOA in part because the pattern of relative polycyclic aromatic hydrocarbon (PAH) abundance characteristic of benthic GOA sediments is inconsistent with patterns typical of weathered seep oils. Likewise, native coal has been dismissed in part because ratios of labile hydrocarbons to total organic carbon (e.g. PAH: TOC) for Bering River coal field (BRCF) sources are too low--i.e. the coals are over mature--to be consistent with GOA sediments. We present evidence here that native coal may have been prematurely dismissed, because BRCF coals do not adequately represent the geochemical signatures of coals elsewhere in the Kulthieth Formation. Contrary to previous thought, Kulthieth Formation coals east of the BRCF have much higher PAH: TOC ratios, and the patterns of labile hydrocarbons in these low thermal maturity coals suggest a possible genetic relationship between Kulthieth Formation coals and nearby oil seeps on the Sullivan anticline. Analyses of low-maturity Kulthieth Formation coal indicate the low maturity coal is a significant source of PAH. Source apportionment models that neglect this source will underestimate the contribution of native coals to the regional background hydrocarbon signature.     

Improved and Standardized Methodology for Oil Spill Fingerprinting

The existing Nordtest methodology for oil spill Identification has over the past 10 years formed an important "platform" for solving oil spill identification cases both in the Scandinavian countries as well as other countries in Europe, the USA and Canada. " Revision of the Nordtest Methodology for Oil Spill Identification " is a cooperative project between the National Oil Spill Identification laboratories in Norway, Sweden, Finland, Denmark and the Battelle Memorial Institute (Duxbury) in the USA. The goals of the project are: (1) to refine the existing Nordtest methodology into a technically more robust and defensible oil spill identification methodology with focus on determination of quantitative diagnostic indices (ratios) and (2) to adjust the revised Nordtest methodology into guidelines for the European Committee for Standardization (CEN). This paper presents the recommended methodology for the analytical oil spill identification part. The sampling techniques and handling of oil samples and background (reference) samples prior to their arrival at the environmental forensic laboratory is not covered in this paper. The recommended methodology approach is a result of documented analytical improvements and a more quantitative treatment of analytical data from gas chromatographic-flame ionization detector (GC/FID) and gas chromatographic-mass spectrometer methods (GC/MS-SIM) and the operational experiences over past few years among the participating forensic laboratories. The experience and literature in the field of oil exploration and production geochemistry have also played an important role for the recommended methodology. The results from a recent Round Robin test carried out among 12 laboratories using this new methodology are presented in a separate paper in this issue (Faksness et at ., 2002d).     

Mineralisation of target hydrocarbons in three contaminated soils from former refinery facilities

This study investigated the microbial degradation of ¹⁴C-labelled hexadecane, octacosane, phenanthrene and pyrene and considered how degradation might be optimised in three genuinely hydrocarbon-contaminated soils from former petroleum refinery sites. Hydrocarbon mineralisation by the indigenous microbial community was monitored over 23 d. Hydrocarbon mineralisation enhancement by nutrient amendment (biostimulation), hydrocarbon degrader addition (bioaugmentation) and combined nutrient and degrader amendment, was also explored. The ability of indigenous soil microflora to mineralise ¹⁴C-target hydrocarbons was appreciable; ≥16% mineralised in all soils. Generally, addition of nutrients or degraders increased the rates and extents of mineralisation of ¹⁴C-hydrocarbons. However, the addition of nutrients and degraders in combination had a negative effect upon ¹⁴C-octacosane mineralisation and resulted in lower extents of mineralisation in the three soils. In general, the rates and extents of mineralisation will be dependent upon treatment type, nature of the contamination and adaptation of the ingenious microbial community.