Evaluating legacy contaminants and emerging chemicals in marine environments using adverse outcome pathways and biological effects-directed analysis

Natural and synthetic chemicals are essential to our daily lives, food supplies, health care, industries and safe sanitation. At the same time protecting marine ecosystems and seafood resources from the adverse effects of chemical contaminants remains an important issue. Since the 1970s, monitoring of persistent, bioaccumulative and toxic (PBT) chemicals using analytical chemistry has provided important spatial and temporal trend data in three important contexts; relating to human health protection from seafood contamination, addressing threats to marine top predators and finally providing essential evidence to better protect the biodiversity of commercial and non-commercial marine species. A number of regional conventions have led to controls on certain PBT chemicals over several years (termed ‘legacy contaminants’; e.g. cadmium, lindane, polycyclic aromatic hydrocarbons [PAHs] and polychlorinated biphenyls [PCBs]). Analytical chemistry plays a key role in evaluating to what extent such regulatory steps have been effective in leading to reduced emissions of these legacy contaminants into marine environments. In parallel, the application of biomarkers (e.g. DNA adducts, CYP1A-EROD, vitellogenin) and bioassays integrated with analytical chemistry has strengthened the evidence base to support an ecosystem approach to manage marine pollution problems. In recent years, however, the increased sensitivity of analytical chemistry, toxicity alerts and wider environmental awareness has led to a focus on emerging chemical contaminants (defined as chemicals that have been detected in the environment, but which are currently not included in regulatory monitoring programmes and whose fate and biological impacts are poorly understood). It is also known that natural chemicals (e.g. algal biotoxins) may also pose a threat to marine species and seafood quality. Hence complex mixtures of legacy contaminants, emerging chemicals and natural biotoxins in marine ecosystems represent important scientific, economic and health challenges. In order to meet these challenges and pursue cost-effective scientific approaches that can provide evidence necessary to support policy needs (e.g. the European Marine Strategy Framework Directive), it is widely recognised that there is a need to (i) provide marine exposure assessments for priority contaminants using a range of validated models, passive samplers and biomarkers; (ii) integrate chemical monitoring data with biological effects data across spatial and temporal scales (including quality controls); and (iii) strengthen the evidence base to understand the relationship between exposure to complex chemical mixtures, biological and ecological impacts through integrated approaches and molecular data (e.g. genomics, proteomics and metabolomics). Additionally, we support the widely held view that (iv) that rather than increasing the analytical chemistry monitoring of large number of emerging contaminants, it will be important to target analytical chemistry towards key groups of chemicals of concern using effects-directed analysis. It is also important to evaluate to what extent existing biomarkers and bioassays can address various classes of emerging chemicals using the adverse outcome pathway (AOP) approach now being developed by the Organization for Economic Cooperation and Development (OECD) with respect to human toxicology and ecotoxicology.     

On the determination of marine magnetotelluric receiver orientation using land magnetic observatory data

Marine magnetotelluric measurements using “free‐fall’’ instruments without effective compasses suffer from the problem of unknown orientation of the receivers at the seafloor. While past works indicate that marine magnetotelluric orientation of the instruments can be estimated by reference to land deployments of known orientation using the transfer tensor method, there is limited published information on how this is implemented in practice. We document this method and propose a set of new time‐ and frequency‐domain approaches to solve this orientation problem of the seafloor receivers. We test these methodologies in onshore and offshore magnetotelluric data whose orientations are well known and apply these techniques to marine magnetotelluric data with unknown orientation. For the controlled tests, both time‐ and frequency‐domain approaches produce overall comparable results. To investigate the effects of the subsurface structure distribution on the orientation process, a dimensionality analysis of a controlled dataset is carried out. In subsequent analysis using the available disoriented marine magnetotelluric data from offshore Brazil and from the Vassouras magnetic observatory on the mainland for remote referencing, frequency‐domain methods yield approximate orientation angles among themselves with low standard deviation each. Time‐domain results are consistent for most cases but differ from frequency‐domain results for some situations.     

Monitoring of toxic substances in the Hong Kong marine environment

A long-term programme for monitoring toxic substances in the marine environment was established in Hong Kong in 2004, focusing on chemicals of potential ecological and health concern. The programme ran on 3-year cycles, with the first two years monitoring marine water, sediment, biota, and the third year monitoring pollution sources. Twenty-four priority chemicals were measured, including dioxins/furans, dioxin-like PCBs, total PCBs, PAHs, DDTs, HCHs, TBTs, phenol, nonylphenol (NP), NP ethoxylates, PBDEs and metals. Results from the first three years of monitoring indicate that toxic substances in the Hong Kong marine environment were within the range reported for the coastal waters in China and other regions, but generally lower than in the Pearl River Estuary. The levels met the standards for protecting aquatic life and human consumption. Sewage effluent, stormwater and river water were possible sources of phenolic compounds; whereas air deposition or regional pollution, rather than local discharges, may contribute to the dioxins/furans, PAHs and PCBs found in the marine environment.     

Introduced marine species: Management arrangements of consideration for the Torres Strait

Introduced marine species (IMS) can have significant impacts on economic, ecological, social and cultural aspects of coastal marine environments. There is, therefore, a need to minimise these impacts through the implementation of comprehensive and consistent management strategies and monitoring processes that work towards preventing introductions, detecting introductions if they were to occur and managing incursions should they be detected. There is also the need to ensure that approaches taken are comparable to provide consistency of IMS management effort, particularly across areas that are multi-jurisdictional (e.g. spanning State or Territory borders).     

Long-term marine litter monitoring in the remote Great Australian Bight, South Australia

The Anxious Bay beach litter clearance is the longest running annual survey of ocean-based litter in Australia. It's remoteness from centres of human population and location (with respect to prevailing winds and currents) make it an ideal place for monitoring ocean or ship-based litter in Australia's southern oceans and particularly, the Great Australian Bight. Over the 1991-1999 period, a large but gradual decline in the amount of beach washed litter was recorded (with minor peaks recorded during the 1992 and 1994 surveys). Beach washed litter decreased by approximately 86%, from 344 kg recorded in 1991 (13.2 kg/km) to 49 kg in 1999 (i.e. 1.9 kg/km), reaching a maximum of 390 kg in 1992 (or 15 kg/km of beach). However, a sharp increase in litter was recorded in 2000 (i.e. 252 kg or 9.7 kg/km). This increase in litter yield in 2000 is probably due to stronger than average onshore surface flow (or Ekman Transport) in the western Eyre Peninsula and Bight region. Prior to the survey in 2000, the results appeared to indicate that ocean litter on Anxious Bay beach was beginning to level out at around 50-70 kg/year (i.e. 2-3 kg/km). As the beach surveys involve the assumption that the beach is completely cleared of litter, this may represent a baseline level for ocean-based litter in the region. The yields and type of litter collected from the annual survey indicates that the majority of litter washed ashore originates from commercial fishing activities within the Great Australian Bight. Most of the fishing-related litter was directly sourced to the Southern Rock Lobster Fishery (i.e. bait buckets, baskets, pots), the Great Australian Bight Trawl Fishery (i.e. codends, trawl nets) and the Southern Shark Fishery (i.e. monofilament gillnets and longlines). Between 1994 and 1999, large reductions were observed in the amount of bait straps (77% reduction), lobster bait baskets/buckets (86% reduction), nets/ropes (62% reduction) and floats/buoys (83% reduction). Significantly, fishing-related litter in the Bight has reduced at a slower rate than domestic litter. While the level of glass and soft plastics on the beach have both reduced by almost 93% (i.e. 103-7 kg and 119-8 kg, respectively), the level of hard plastics, has diminished at a slower rate, with reductions of only 75% (i.e. 122-30 kg). Some fisheries (i.e. rock lobster, Southern Shark Fishery) have shown marked reductions in fishing-related litter. This is probably due, to some extent, to significant reductions in fishing effort in the region, although this requires further investigation. The information from the Anxious Bay beach litter survey is crucial in monitoring trends in ocean litter in Australia's southern oceans and compliance with international litter regulations. While fishing-related litter remains the major source of ship-based or ocean litter in Australia's southern oceans, the continued reduction in ship-based litter since 1991 supports increasing compliance to MARPOL (Annex V) by commercial fisheries and shipping in the Great Australian Bight. While Australia participates in marine debris monitoring programs in the Antarctic (under CCAMLR), there is currently no national program or management framework to assess, manage and monitor ocean-based litter along Australia's coasts, and monitor compliance with MARPOL. Apart from the commitments under CCAMLR for Antarctic (and sub-Antarctic) marine environments, there are no other regional programs, guidelines or monitoring protocols or to assess and manage ocean litter in the Southern Ocean.     

Monitoring ship noise to assess the impact of coastal developments on marine mammals

The potential impacts of underwater noise on marine mammals are widely recognised, but uncertainty over variability in baseline noise levels often constrains efforts to manage these impacts. This paper characterises natural and anthropogenic contributors to underwater noise at two sites in the Moray Firth Special Area of Conservation, an important marine mammal habitat that may be exposed to increased shipping activity from proposed offshore energy developments. We aimed to establish a pre-development baseline, and to develop ship noise monitoring methods using Automatic Identification System (AIS) and time-lapse video to record trends in noise levels and shipping activity. Our results detail the noise levels currently experienced by a locally protected bottlenose dolphin population, explore the relationship between broadband sound exposure levels and the indicators proposed in response to the EU Marine Strategy Framework Directive, and provide a ship noise assessment toolkit which can be applied in other coastal marine environments.     

Biosensors for marine pollution research,monitoring and control

Measurement of ecological, climatic and anthropogenic changes underpins the formulation of effective management strategies for sustainable use and protection of the marine environment. Sensors are traditionally used in marine studies to determine physical parameters, but there is increasing demand for real-time information about chemical and biological parameters. These parameters are currently measured in samples collected at sea and subsequently analysed in the laboratory. Biosensors fuse the exquisite sensitivity and specificity of living systems with the processing power of microelectronics to deliver simple, inexpensive measurement systems for use in the field or deployment in situ. While their potential for use in the marine environment is enormous, much published work to date has focussed on applications in freshwater and wastewater. Marine applications pose a substantial challenge in the robustness required for remote application, but recent developments in portable medical devices and receptor design suggest that these demands can now be realistically tackled.     

Best practice methodology for 14C calibration of marine and mixed terrestrial/marine samples

There is a lack of detailed guidance in the published literature on how to calibrate ¹⁴C measurements made on marine or mixed marine/terrestrial (primarily human remains) samples. We describe what we consider to be the best approach towards achieving the most accurate calibrated age ranges, using the most appropriate ΔR and percentage marine diet estimates, and associated, realistic error terms on these values. However, this approach will increase the calibrated age range(s) by fully accounting for the variability in both the model and the material. While the discussion is based on examples from the UK and Iceland, the same fundamental arguments can be applied in any geographic location largely devoid of C₄ plants as the high δ¹³C values from such plants can make identification of marine intake difficult to determine.     

The pollution of the marine environment by plastic debris: a review

The deleterious effects of plastic debris on the marine environment were reviewed by bringing together most of the literature published so far on the topic. A large number of marine species is known to be harmed and/or killed by plastic debris, which could jeopardize their survival, especially since many are already endangered by other forms of anthropogenic activities. Marine animals are mostly affected through entanglement in and ingestion of plastic litter. Other less known threats include the use of plastic debris by "invader" species and the absorption of polychlorinated biphenyls from ingested plastics. Less conspicuous forms, such as plastic pellets and "scrubbers" are also hazardous. To address the problem of plastic debris in the oceans is a difficult task, and a variety of approaches are urgently required. Some of the ways to mitigate the problem are discussed.     

Actually achieving marine sustainability demands a radical re-think in approach, not 'more of the same'

The UK is committed to meeting a series of ‘high-level marine objectives’ which are required to satisfy national obligations and to meet international commitments for the marine environment. There are more than 16 such international high-level policy driven obligations and commitments, together with more than 18 European and more than 12 of national origin. In the UK, there is an assumption that the current and planned monitoring will provide evidence to demonstrate achievement against these high-level objectives.     

电导率各向异性的海洋电磁三维有限单元法正演

本文提出了一种基于非结构化网格的海洋电磁有限单元正演算法.为了回避场源奇异性,文中选用二次场算法,将背景电阻率设置为水平层状且各向异性,场源在水平层状各向异性介质中所激发的一次场通过汉克尔积分得到.基于Coulomb规范得到二次矢量位和标量位所满足的Maxwell方程组,通过Galerkin加权余量法形成大型稀疏有限元方程,采用不完全LU分解(ILU)预条件因子的quasi-minimum residual(QMR)迭代解法对有限元方程进行求解得到二次矢量位和标量位;进而,利用滑动平均方法得到二次矢量位和标量位在空间的导数,由此得到二次电磁场;通过一维模型对算法的可靠性进行验证,与此同时,针对实际复杂海洋电磁模型,比较有限元模拟结果与积分方程模拟结果,进一步验证算法精度.若干计算结果均表明,文中算法具有良好的通用性,适用于井中电磁、航空电磁,环境地球物理等非均匀且各向异性介质中的电磁感应基础研究.     

南黄海海底大地电磁测深试验研究

针对南黄海盆地深层地震地质条件差,地震波受屏蔽,能量严重衰减,在海洋反射地震资料中很难识别反映中-古生界的反射地震波组,不能满足南黄海盆地前第三系油气资源前景评价的需要等问题,于2006年5月,开展了南黄海海域海底大地电磁测深试验,在盆地内五莲斜坡和胶州凹陷区布设了3个海底大地电磁测深点,取得了可靠的海底观测数据.本文详细阐述了海底大地电磁测深与常规大地电磁测深在数据处理方法上的差别,论述了海洋电磁噪声对海底大地电磁场观测的影响,提出了海底大地电磁场实测资料“水平姿态”校正、“方位”校正和“海洋电磁噪声”校正的方法.通过对试验观测资料的处理和反演,并结合地质、物性资料进行综合分析,结果表明在南黄海盆地海底以下深部还存留有古生代地层,这对于南黄海前第三系含油气前景的评价具有重要意义.试验结果也证明了海底大地电磁测深技术在研究古生代残留盆地方面的问题可以发挥相当好的作用.     

On the potential for climate change impacts on marine anthropogenic radioactivity in the Arctic regions

Current predictions as to the impacts of climate change in general and Arctic climate change in particular are such that a wide range of processes relevant to Arctic contaminants are potentially vulnerable. Of these, radioactive contaminants and the processes that govern their transport and fate may be particularly susceptible to the effects of a changing Arctic climate. This paper explores the potential changes in the physical system of the Arctic climate system as they are deducible from present day knowledge and model projections. As a contribution to a better preparedness regarding Arctic marine contamination with radioactivity we present and discuss how a changing marine physical environment may play a role in altering the current understanding pertaining to behavior of contaminant radionuclides in the marine environment of the Arctic region.     

海洋拖曳式水平电偶源数值模拟与电场接收机研制

海洋天然气水合物资源调查中,电磁法已成为地震勘探最有效的补充手段之一,而我国海洋水合物电磁探测中的拖曳式电场接收机此前是空白.本文从方法原理、仪器设备和海洋试验等方面,对海洋拖曳式水平电偶极-偶极方法进行研讨.建立三维电阻率模型,进行数值模拟,讨论收发距、发射频率、拖曳装置离海底高度等参数与电场异常响应的关系,针对特定模型给出了最佳观测参数以指导仪器硬件设计与海洋测试.在此基础上,采用高级嵌入式计算机的智能化控制、前端低噪声斩波放大、高精度同步采集等技术,研制了由拖体、承压舱、采集电路、低噪声电场传感器等组成的海洋拖曳式水平轴向电场接收机,其系统噪声达到2 nV/√HZ @(1~100Hz).将自主研制的电场接收机用于国内首次拖曳式电偶极-偶极方法的海洋试验与评估,并对海试资料进行了处理与分析.研究结果表明,所研发的仪器达到了设计指标,能够用于海洋天然气水合物调查.     

Adriatic coast as a microcosm for global genotoxic marine contamination--a long-term field study

Global changes in the marine environment and the continuing disposal of genotoxic xenobiotics are increasing the importance of environmental pollution monitoring and of biomonitoring programs. Current approaches focus on investigations at regional and local levels in an attempt to precisely define the nature and extent of any potential environmental crisis. We have initiated, for the first time, a long-term biomonitoring program focusing on the Croatian coast of the Adriatic Sea to contribute to a more detailed understanding of marine genotoxic effects using the mussels Mytilus galloprovincialis Lam., collected along the eastern Adriatic coast over a period of five years (1998-2002), as a key test organism. The integrity of DNA in its gill homogenate was examined by the Fast Micromethod. The strand scission factor (SSF) values, as a measure of DNA integrity, DNA damage or incomplete repair have been used for the ranking of sampling sites with respect to significant genotoxic stress due to the influence or effects of genotoxic xenobiotics. The region of Split (Kastela Bay) proved to be the area with the heaviest load of genotoxic agents. The investigation of harmful effects in the ecosystem based on biomonitoring of genetic and other agents, not only on local levels but also on a wider scale, is considered as an important step in marine environmental management.     

Signal detectability of marine electromagnetic methods in the exploration of resistive targets

We compare selected marine electromagnetic methods for sensitivity to the presence of relatively thin resistive targets (e.g., hydrocarbons, gas hydrates, fresh groundwater, etc.). The study includes the conventional controlled‐source electromagnetic method, the recently introduced transient electromagnetic prospecting with vertical electric lines method, and the novel marine circular electric dipole method, which is still in the stage of theoretical development. The comparison is based on general physical considerations, analytical (mainly asymptotic) analysis, and rigorous one‐dimensional and multidimensional forward modelling. It is shown that transient electromagnetic prospecting with vertical electric lines and marine circular electric dipole methods represent an alternative to the conventional controlled‐source electromagnetic method at shallow sea, where the latter becomes less efficient due to the air‐wave phenomenon. Since both former methods are essentially short‐offset time‐domain techniques, they exhibit a much better lateral resolution than the controlled‐source electromagnetic method in both shallow sea and deep sea. The greatest shortcoming of the transient electromagnetic prospecting with vertical electric lines and marine circular electric dipole methods comes from the difficulties in accurately assembling the transmitter antenna within the marine environment. This makes these methods significantly less practical than the controlled‐source electromagnetic method. Consequently, the controlled‐source electromagnetic method remains the leading marine electromagnetic technique in the exploration of large resistive targets in deep sea. However, exploring laterally small targets in deep sea and both small and large targets in shallow sea might require the use of the less practical transient electromagnetic prospecting with vertical electric lines and/or marine circular electric dipole method as a desirable alternative to the controlled‐source electromagnetic method.     

利用微分进化法确定海洋磁场向下延拓中的最优参数

位场的解析延拓是实现不同高度海洋地磁场相互转换的主要途径,是构建海洋三维磁空间背景场模型的关键技术.针对位场向下延拓迭代法中最优正则化参数及最佳迭代次数难以确定问题,尝试引入微分进化法,以正则化参数及迭代次数为种群变量,以延拓结果的熵值为目标函数,以目标函数最小化为搜索准则,实现两种参数的并行全局寻优.采用实测数据对微分进化法在几种常用的迭代法中最优正则化参数及最佳迭代次数的确定进行了分析,与传统L-曲线准则确定的最优正则化参数及多次试验确定的最佳迭代次数进行对比,结果表明：微分进化法确定的最优参数能使三种迭代法取得最佳迭代效果,延拓结果与真实地磁场最为接近,并且该法计算稳定、自适应强,建议在海洋磁场数据向下延拓中应用.     

Alkylphenols in marine environments: Distribution monitoring strategies and detection considerations

The presence of alkylphenols (APs) in coastal and marine ecosystems is not as well-documented as it is in freshwater ecosystems. This paper reviews reported concentrations of alkylphenol ethoxylates (APEOs) and APs in seawater, sediments and organisms of marine environments such as estuaries, coastal lagoons, bights, harbours or deep sea in order to study their distribution. Overall contamination of marine aquatic compartments by APs and APEOs has been observed, while coastal areas in the vicinity of wastewater discharges are more impacted than deep sea environments, but to a lesser extent than freshwater sites. Sediments act as sinks for APs and APEOs, especially around wastewater discharge sites. Reported AP concentrations in marine organisms are higher in bivalves and gastropods than in fishes. As nonylphenols and octylphenols are estrogenomimetic, biological responses induced in marine organisms are discussed. Finally, we describe the cell bioassay approach for the biodetection of APs.