Identification of estrogen-like alkylphenols in produced water from offshore oil installations

Produced water released into the sea from oil installations contains a vast number of organic compounds. This work focuses on the analysis and identification of phenols in produced water, in particular long-chain para-substituted alkylphenols, which act as endocrine disruptors for marine biota. Some alkylphenol standards, unavailable commercially, have been synthesised and some compounds of interest identified. However, a complete identification is not possible since conventional GC techniques cannot achieve the desired degree of separation. An overview of the levels of the 52 known alkylphenols in produced water from nine oil installations in the North and Norwegian Seas has been made. The previously unidentified alkylphenols in produced water have been characterised by means of alkylphenol retention indices (APRI) and mass spectrometry, and their total amounts estimated for the same nine locations. Our results confirm the presence of naphthols and other as yet unidentified compounds in produced water, while thiophenols were not detected by the used technique.     

Bioconcentration and distribution of 4-tert-octylphenol residues in tissues of the rainbow trout (Oncorhynchus mykiss)

Branched chain alkylphenols are weak oestrogen mimics which are present in the aquatic environment and have been implicated in the feminisation of fish. This study reports the biotransformation, bioconcentration and tissue distribution of the xenoestrogen 4-tert-octylphenol (t-OP) in juvenile rainbow trout. Fish were exposed for 10 days to a concentration of 4 micrograms/l of [14C] t-OP in a flow-through system and were sampled after 1, 4, 7 and 10 days of exposure. t-OP residues were extracted from all tissues and analysed by radio-high-performance liquid chromatography. After 1 day of exposure radioactive residues were detected in all tissues and reached steady state conditions in the whole fish after 4 days of exposure. The concentration of t-OP residues were highest in bile, followed by faeces, pyloric caeca, liver and intestine. In these tissues the majority of alkylphenol was in the form of two metabolites which were identified by gas chromatography-mass spectroscopy as the glucuronide conjugates of t-OP and t-octylcatechol. t-OP accumulated as the parent compound in fat with a bioconcentration factor (BCF) of 1190, and in brain, muscle, skin, bone, gills, and eye with BCFs of between 100 and 260. This study suggests that exposure to water-borne alkylphenols results in rapid conjugation and elimination of the chemical via the liver/bile route, but that high amounts of the parent xenoestrogen can accumulate in a variety of other fish tissues.     

聚合物驱采出污水深度处理的实验研究

以大庆某采出液处理站含聚污水为研究对象,应用UV/H2O2／O3组合对二次除油、过滤后的污水进行了处理实验,实验分析了H2O2、O3投加量、紫外灯强度、初始pH值以及处理时间对HPAM去除率影响,确定了合理的组合参数量;结合初始污水中含油量变化对聚合物和污油去除率的影响进行了实验,确定了初始污水含油量范围。并对处理前后污水对岩心渗透率伤害程度进行实验,结果表明,短用高级氧化处理技术处理最的含聚污水水质可以满足污水回注油层要求,在现场比较经济可行。     

Identification of dissolved and particulate carbonyl compounds produced by marine harmful algal bloom species

Carbonyl compounds, especially polyunsaturated aldehydes (PUAs), are increasingly reported as teratogenic to grazers and deleterious to phytoplankton. While PUAs have been considered to be mainly produced by diatoms after cell wounding, little is known about whether microalgae other than diatoms, particularly harmful algal bloom (HAB)-forming species, produce carbonyl compounds. In this study, we analyzed the carbonyl compounds from eight common HAB-forming species ( Akashiwo sanguinea , Karenia mikimotoi , Karlodinium venefi cum , Margalefi dinium polykrikoides , Prorocentrum donghaiense , P . minimum , Scrippsiella trochoidea , and Heterosigma akashiwo ) using gas chromatography-mass spectrometry in full scan and selected ion monitoring (SIM) modes. Our results show a ubiquitous presence of carbonyl compounds in both dissolved and particulate forms in all species we examined. In the full scan mode, 133 chromatographic peaks were detected from 51 samples altogether. Both the varieties of carbonyl compounds and their quantities were algal species dependent, although most of the carbonyl compounds could not be fully identifi ed according to the mass spectral database only due to the unavailability of enough standards for all analytes. Aided with nine standards in SIM mode, we further identifi ed and quantifi ed all nine aldehydes (2-methyl-2-pentenal, trans-2-nonenal, cis-6-nonenal, 2,6-dimethyl-5-heptenal, trans-2-hexenal, trans-2- decenal, 2,4-heptadienal, trans-trans-2,4-octadienal, and trans-trans-2,4-decadienal). Four of these nine aldehydes were detected in particulate form, which confi rmed that trans-2-nonenal could be produced by K . mikimotoi , Karl . venefi cum , P . donghaiense , P . minimum , S . trochoidea , and H . akashiwo , 2,4-heptadienal and trans-trans-2,4-decadienal by A . sanguinea , M . polykrikoides , and S . trochoidea , and trans, trans-2,4- octadienal by S . trochoidea , respectively. We proved that some dinofl agellate and raphidophyte species could contribute to the pool of carbonyl compounds including PUAs in a marine ecosystem. Some carbonyl compounds, particularly those in high cell quota and/or dissolved concentration, may be related to fi shkilling or allelopathy which needs further identifi cation and quantifi cation.     

Biochemical and histological responses in mussel (Mytilus edulis) exposed to North Sea oil and to a mixture of North Sea oil and alkylphenols

Several environmental chemicals are suspected to be responsible for adverse health effects on the reproductive system in various organisms. During this work, environmentally relevant concentrations of North Sea oil were used alone or in combination with alkylphenols and additional PAH to study the effect on vitellogenin-like protein expression and gonadal development in mussels. North Sea oil (0.5 ppm) induced the expression of phospho-proteins in both sexes indicating that some compounds are oestrogen-mimics. This induction was not seen in samples dosed with the mixture but signs of toxic effects were observed in the gonads. Indeed, numerous degenerating ovarian follicles in females and foci, similar to vertebrate melanomacrophage centres, were observed in testes.     

多环芳烃油指纹应用于船舶溢油鉴别研究

溢油种类主要包括船舶燃料油和原油,二者性质的差异决定了鉴别方法也相应不同,寻求适合于船舶溢油的鉴别方法具有重要意义。在使用柱色谱层析方法对样品进行分离前处理的基础上,以气相色谱/质谱方法(GC-MS)为主要分析手段,对溢油样品和可疑船舶溢油源样品的多环芳烃油指纹特征进行对比,并在多环芳烃油指纹参数的基础上进一步进行多环芳烃内组成三角图分布特征与聚类分析研究,成功为珠江口水域某船舶溢油事故追踪到肇事溢油源。结果表明:取自丁船的油样和现场溢油样芳烃油指纹特征最为相近,是此次溢油事故的溢油源。受风化作用后的船舶燃料油中饱和烃类化合物数量稀少,且含量极低,不适合用于溢油鉴别,而多环芳烃类化合物较饱和烃类化合物而言具有含量高、种类丰富的特点,是该类溢油鉴别的主要油指纹依据。使用油指纹参数进行可疑溢油源识别时,充分考虑油品中有机分子所受风化影响程度的不同是风化条件下溢油鉴定的关键。因此,多环芳烃油指纹可以有效应用于船舶燃料油溢油的鉴别。     

Biochemical and histological responses in mussel (Mytilus edulis) exposed to North Sea oil and to a mixture of North Sea oil and alkylphenols

Several environmental chemicals are suspected to be responsible for adverse health effects on the reproductive system in various organisms. During this work, environmentally relevant concentrations of North Sea oil were used alone or in combination with alkylphenols and additional PAH to study the effect on vitellogenin-like protein expression and gonadal development in mussels. North Sea oil (0.5 ppm) induced the expression of phospho-proteins in both sexes indicating that some compounds are oestrogen-mimics. This induction was not seen in samples dosed with the mixture but signs of toxic effects were observed in the gonads. Indeed, numerous degenerating ovarian follicles in females and foci, similar to vertebrate melanomacrophage centres, were observed in testes.     

Oil well produced water discharges to the North Sea. Part II: comparison of deployed mussels (Mytilus edulis) and the DREAM model to predict ecological risk

Large volumes of water often are produced with oil and gas from offshore platforms. The produced water is separated from the oil and gas and either reinjected into a deep formation or discharged to the ocean. The Norwegian oil and gas industry advocates ecological risk assessment as the basis for managing produced water discharges to the North Sea. In this paper, we compare estimates of ecological risks to water-column communities based on data on hydrocarbon residues in soft tissues of blue mussels deployed for a month near offshore platforms and based on predictions of the Dose related Risk and Effect Assessment Model (DREAM). The study was performed near produced water discharges to the Tampen and Ekofisk Regions of the Norwegian Sector of the North Sea. Because polycyclic aromatic hydrocarbons (PAH) are considered the most important contributors to the ecological hazard posed by produced water discharges, comparisons made here focus on this group of compounds. The mussel approach is based on predicted environmental concentrations (PECs) of individual PAH, estimated from PAH residues in mussels following deployment for a month near several produced water discharges, and predicted no effects concentrations (PNECs) based on a K(ow) regression model. In the DREAM method, PECs for three PAH fractions are estimated in the three-dimensional area around produced water discharge with the DREAM model. PNECs for each fraction are based on the chronic toxicity of a representative PAH from each fraction divided by an assessment factor to account for uncertainty in the chronic value. The mussel method gives much lower estimates of ecological risk than the DREAM method. The differences are caused by the much lower PNECs used in DREAM than derived from the regression model, and by the lower concentrations of aqueous PAH predicted by DREAM than estimated from PAH residues in mussel tissues. However, the two methods rank stations at different distances from produced water discharges in the same order and both identify 2- and 3-ring PAHs as the main contributors to the ecological risk of produced water discharges. Neither method identifies a significant ecological risk of PAH in the upper water column of the oil fields. The DREAM model may produce an overly conservative estimate of ecological risk of produced water discharges to the North Sea.     

Environmental risk assessment of alkylphenols from offshore produced water on fish reproduction

Concern has been raised over whether environmental release of alkylphenols (AP) in produced water (PW) discharges from the offshore oil industry could impose a risk to the reproduction of fish stocks in the North Sea. An environmental risk assessment (ERA) was performed to determine if environmental exposure to PW APs in North Sea fish populations is likely to be high enough to give effects on reproduction endpoints. The DREAM (Dose related Risk and Effect Assessment Model) software was used in the study and the inputs to the ERA model included PW discharge data, fate information of PW plumes, fish distribution information, as well as uptake and elimination information of PW APs. Toxicodynamic data from effect studies with Atlantic cod (Gadus morhua) exposed to APs were used to establish a conservative environmental risk threshold value for AP concentration in seawater. By using the DREAM software to 1) identify the areas of highest potential risk and 2) integrate fish movement and uptake/elimination rates of APs for the chosen areas we found that the environmental exposure of fish to APs from PW is most likely too low to affect reproduction in wild populations of fish in the North Sea. The implications related to risk management of offshore PW and uncertainties in the risk assessment performed are discussed.     

海面水包油乳化液溢油量等效估算方法研究

激光诱导荧光(LIF)是一种主动光学探测技术,该技术已在海面未乳化溢油油种鉴别及油膜厚度评估方面取得了一定的研究成果,但乳化溢油的监测理论基础和探测方法尚未成熟。溢油乳化物的量化会直接影响溢油污染的应急处理和灾害评估,但目前对溢油乳化液溢油量的计算尚未有研究报道。本文以水包油乳化液为研究对象,基于等效思想,根据油量相等建立了水包油乳化液与油膜的荧光检测等效模型,并依据光的辐射传输机理推导出等效油膜厚度的估算公式,最后采用仿真实例对估算方法的适用性和有效性进行了验证。实验结果表明,当水包油乳化液含油率小于12×10^-6,厚度小于5.98 cm时,利用所提出的等效方法能有效计算出水包油实际溢油厚度。该方法可为海面乳化溢油量的估算提供一种创新性的方法,具有良好的借鉴意义和实际应用价值。     

A chemical investigation of the transport and fate of petroleum hydrocarbons in littoral and benthic environments: The TSESIS oil spill

The fate of saturated and aromatic hydrocarbons discharged into the coastal Baltic Sea environment from the TSESIS oil spill has been studied in the acute and postacute (one year) phases of the spill. Periodic samples of Mytilus edulis (mussels) from eight littoral zone stations and Macoma balthica from nine soft bottom stations were obtained as well as sediment trap samples and surface sediment samples. Glass capillary gas chromatography and gas chromatographic mass spectrometry were used as the analytical tools to determine saturated and aromatic hydrocarbon composition and concentrations in these samples.Sediment trap samples indicated that sizable quantities of chemically and microbially weathered oil were sedimented, and available for benthic uptake shortly after the spill. After initial uptake of sedimented oil (500 to 1000 μ/g dry weight), Macoma populations appear to have begun slow depuration through the first winter after the spill, but TSESIS oil was again introduced to the benthic stations studied during the following summer. Mytilus populations in the region were severely impacted by the oil. Initial depuration of spilled oil during the first month was rapid and nearly complete at all but the most heavily impacted stations one year after the spill. The post-spill depuration of assimilated hydrocarbons was characterised by a relative retention of alkylated dibenzothiophenes and alkylated phenanthrenes compared to their unsubstituted parent compounds and compared with the entire homologous naphthalene series.These data suggest that petroleum hydrocarbons from the TSESIS spill have become a chronic source of degraded saturated and aromatic hydrocarbons to the soft bottom benthic communities. Petroleum hydrocarbons in the benthic environment from this spill appear to reside in the difficulty sampled and mobile flucculent layer at the sediment/water interface and may affect epifaunal communities for an extended period of time.     

Assessment of lysosomal membrane stability and peroxisome proliferation in the head kidney of Atlantic cod (Gadus morhua) following long-term exposure to produced water components

There is a need for sensitive biological effect methods by which to detect impacts of chronic exposure to low concentrations of contaminants. Two methods shown to be potentially useful for monitoring purposes in fish include lysosomal membrane stability and peroxisome proliferation. These biological endpoints were assessed in Atlantic cod (Gadus morhua) head kidney following exposure to a mixture of produced water components including polycyclic aromatic hydrocarbons, phenol, and alkylphenols. Lysosomal damage of head kidney cells occurred within the first two weeks and did not recover during the entire exposure period (32 weeks). Lysosomal membrane stability was not affected by gender and was responsive at low concentrations of contamination, indicating that lysosomal membrane stability measured in the head kidney could be a useful biomarker for effects of offshore pollution. Peroxisome proliferation, measured as acyl-CoA oxidase activity in the head kidney, appeared to be a potential biomarker in male cod exposed less than 16 weeks.     

The effects of oil exploration and production in the northern north sea: Part 1–The levels of hydrocarbons in water and sediments in selected areas, 1978–1981

In the light of increasing oil exploration and production in the northern North Sea, the Brent, Beryl and Forties oil fields, representing three different types of operation, and a number of stations between the Forties field and the Firth of Forth, were sampled to determine the levels of total (by fluorescence), alkane (by glass capillary gas chromatography) and aromatic (by gas chromatography-mass spectrometry) hydrocarbons in water and sediments. Close to the Beryl platform, where diesel-washed drill cuttings have been dumped, there was an accumulation of petrogenic hydrocarbons in the sediment, resulting in a build up of certain aryl hydrocarbons, notably the dibenzthiophenes and 3- and 4-ring aromatic compounds. In all the sediment samples analysed for aromatic hydrocarbons, relatively large amounts of 5- and 6-ring compounds were found in areas expected to be free of pollution, as well as from areas around oil platforms and from the Firth of Forth. Their source is likely to be windborne combustion products.     

综合风化条件下渤海原油中PAHs 变化特征研究

以渤海某原油作为研究对象进行50 d综合模拟风化实验,探讨了原油中五类PAHs组分的分布情况及其风化规律.结果表明:经过50 d风化,原油中PAHs的分布发生了较大的改变:萘系列化合物损失最为严重,相对浓度的损失达到56.78%;菲系列所占的比例有所提高,二苯并噻吩、屈、芴系列则保持相对稳定,其分布特征变化规律为进一步筛选溢油来源鉴别新诊断比值参数提供了一定的导向性;经风化检验,现有常用6种PAHs诊断比值在风化50 d后稳定性良好,可用于风化溢油的鉴别.     

适于高温高盐油藏的聚合物性能指标评价

我国多数油田经过多年注水开发,综合含水已超过90%,而采出程度低于35%,如何提高油田采收率是高含水油田急需解决的难题。目前,聚合物驱油是工业化应用程度最高的一项提高采收率技术,但由于聚合物产品性能差异和油田现场对污水处理的需要,多数聚合物不适宜高温高盐油田的现场驱油试验。本文以胜坨高温高盐油藏的地质条件为依托,在对聚合物驱油效果影响因素分析的基础上,研究了适合于高温高盐油藏强化采油的聚合物性能指标,优选了具有梳形结构的KYPAM聚合物为胜坨油田的驱替剂。该性能指标的提出对国内外高温高盐油藏进行聚合物驱油具有重要的指导意义。     

中国近海海区污损生物研究现状及展望

近海海区通常是指离岸3n mile以上或水深超过25m的水域(Relini et al.，1994)；海洋污损生物是海洋环境中栖息或附着在船舶和各种水下人工设施上，对人类经济活动产生不利影响的动物、植物和微生物的总称，它不仅是影响海洋设施安全与使用寿命的重要因素，也是人类开始接触海洋时所关注的问题。本文就污损生物对海洋结构物的影响和我国近海污损生物研究的进展状况、存在问题等方面进行了综合论述，并对未来几年内为研究方向和重点进行了探讨，以期为下一阶段研究工作提供一些具有参考价值的依据和建议。     

Candidate biomarker discovery in plasma of juvenile cod (Gadus morhua) exposed to crude North Sea oil, alkyl phenols and polycyclic aromatic hydrocarbons (PAHs)

In this study we have investigated protein changes in plasma of juvenile Atlantic cod (Gadus morhua) induced by crude North Sea oil and North Sea oil spiked with alkyl phenols and polycyclic aromatic hydrocarbons, a surrogate produced water composition. Using a proteomic approach, we identified 137 differentially expressed proteins at different levels of crude oil exposure. Many of the induced protein changes occurred at low levels of exposure. The results obtained with protein expression profiles after exposure to oil and surrogate produced water indicate effects on fibrinolysis and the complement cascade, the immune system, fertility-linked proteins, bone resorption, fatty acid metabolism as well as increased oxidative stress, impaired cell mobility and increased levels of proteins associated with apoptosis. Although the number of individuals and samples in this study is limited within each treatment group, the protein changes observed in this study represent a first screening for potential biomarker candidates in cod plasma reflecting potential effects of crude oil and produced water exposure on fish.     

Seasonal survey of copper-complexing ligands and thiol compounds in a heavily utilized, urban estuary: Elizabeth River, Virginia

Concentrations of thiol compounds, copper-complexing ligands, and total dissolved copper were followed over the course of 1 year (October 2002 until September 2003) in the Elizabeth River, Virginia to evaluate seasonality. Copper-complexing ligand concentrations were determined by competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE/ACSV). Thiol detection was carried out by high performance liquid chromatography (HPLC) and calibration using a suite of nine thiol compounds (cysteine, glutathione, mercaptoacetic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, and monothioglycerol). Total dissolved copper concentrations reached a January low of 13.1 nM to a June high of 24.7 nM and were found to vary seasonally with higher concentrations occurring from June to September. With a low of 26 nM during April to a high of 56 nM in October, copper-complexing ligand (average log K′_CuL of 12.0 ± 0.2) concentrations displayed a similar seasonal pattern to that of total dissolved copper. Free cupric ion concentrations remained below 1.5 pM for a majority of the year except during March, April, and December when values reached pM levels greater than 1.5. Six of the nine thiol compounds surveyed were detected in the Elizabeth River samples and ranged in concentration from below detectable concentrations (< 5 nM) to individual highs ranging from 25.3 to168.5 nM. The thiol compound concentrations displayed a clear seasonality fluctuating at below detection limits during November to February then increasing with increasing surface water temperatures from March to July. CLE/ACSV was used to assess whether or not the suite of thiol compounds detected by HPLC could contribute to the copper-complexing ligand pool. Conditional stability constants for each one of six thiol standards (average log K′_CuL  12.1 ± 0.5) were found to be statistically equivalent to the naturally occurring copper-complexing ligands (average log K′_CuL  12.0 ± 0.2). This suggests that these thiol compounds could act as copper-complexing ligands in natural samples and could contribute to the copper-complexing ligand pool detected by CLE/ACSV. This study involving seasonality of copper-complexing ligands and thiols in an industrialized, urban estuary underscored several points that have to be substantiated in future research efforts including copper-complexing ligands sources and the role that thiol compounds as well as other unidentified organic compounds play in the copper-complexing ligand pool.     

An “Olympic” framework for a green decommissioning of an offshore oil platform

Oil and gas offshore platform and installations have a limited life of operations. When oil runs out, many terms are used to describe the situation: abandonment, removal, disposal, decommissioning, etc. Even the issue of decommissioning is now at the forefront of deep water oil drilling for many reason (the enormous costs required for disposal, the increasing number of rigs which required removal, the need to protect the marine environment, legal frameworks), there are very few published researchers studying the problem according to its different facets (legal, environmental, economical etc.). In this paper, we apply the concept of “Olympic” supply chain developed by Lakhal et al. Lakhal, SY, H'Mida S, Islam R. Green Supply Chain parameters for a Canadian Petroleum Refinery Company. International Journal of Environmental Technology and Management, IJETM 2007:7;56–67. to provide feedback for life-cycle offshore platforms. Our approach starts from platform development projects environmentally, exploit it in the respect of the environment and have an efficient decommissioning project.     

深层砂砾岩储层测井精细评价

储层岩石物理相是储层岩性和物性特征的综合反映,它对油水分布具有重要的控制作用,同类岩石物理相具有相似的岩石学特征,孔—渗关系呈现出规律性变化,表现出相似的岩电关系和测井响应特征。为此充分分析核磁共振、成像测井等新技术,采用测井相分析技术,将储集层划分为不同类型的岩石物理相,在此基础上分类建立了该区块测井参数精细评价模型和油水层判别标准,使研究区的油水层判别精度从原来的60%提高到了80%以上,基本解决了本区油水层判别困难的难题。