红枫湖有机氯污染物的生物地球化学

本研究以红枫湖为主要研究对象，对环境各介质中PCBs和OCPs进行了研究，讨论了理化因素TOC、粒度、SPM、微生物等对于PCBs和OCPs的影响，对各介质中PCBs和OCPs的组成进行了分析，讨论了红枫湖地区PCBs和OCPs的来源，并对其污染水平进行了评价，得到以下几点认识： 1、对红枫湖水体和沉积物的理化性质进行了分析，和洱海进行了对比。湖泊沉积物有机质含量和C/N比值表明红枫湖沉积物有机质主要来源于河流输入和湖泊内部，洱海主要以湖泊内源为主，与后面PCBs和OCPs分析结果相符。湖泊沉积物有机质及DNA呈现同一规律，表层是有机质和DNA的含量较高的区域，表层至底层整体呈逐渐降低的趋势，表明表层是微生物量和活性最高的层段，有机质的降解主要发生在此区域。湖泊沉积物粒度与有机质和DNA变化趋势一致，暗示了有机质的降解过程主要发生在表层，SRI和SRB的分析表明微生物在有机质降解过程中起着至关重要的作用。 2、红枫湖沉积物中7种PCBs的含量范围在3.2～31.6ng/g之间，主要以PCB28和PCB52为主。其中PCB28的含量范围在0.5～4.6ng/g，平均为1.8ng/g， PCB52含量在0.4～28.1ng/g。PCB28和PCB52低氯取代的PCBs占PCBs总量的60%以上。各点沉积物中PCBs的组成基本一致，其含量的变化主要与其输入来源和环境条件相关。沉积物中PCBs随深度整体呈现降低的趋势，但表层含量比次表层低，表明近年PCBs的输入降低。PCBs与TOC和粒径呈现较显著的正相关关系，与其自身的理化性质相关，PCBs具有较高的憎水性，倾向于在颗粒态中分布，也暗示了其来源。 3、红枫湖沉积物中13种OCPs的组成主要以HCHs和DDTs为主。其中HCHs的含量范围1.6～8.9ng/g，平均值为3.2ng/g，沉积物柱均值表现为HW>DB>HE>JJD；DDTs的含量范围在0.9～25.7ng/g，平均值为7.8ng/g，沉积物柱均值表现为HW>HE>DB>JJD。HCHs按其组成来看，以β-HCH和γ-HCH为主，DDTs以p,p’-DDE和p,p’-DDT为主。α-HCH/γ-HCH的比值在范围在0.1~3.0之间，表明HCH在环境中发生了改变，而且林丹的用量高于混合HCHs。DDT/DDE+DDD的比值基本都小于1，暗示DDTs在环境中发生了较长期的变化，β-HCH和p,p’-DDE的高含量也暗示了大气来源可能也是红枫湖地区OCPs的主要来源之一。 4、红枫湖湖水、汇入汇出河流及其周边土壤中PCBs和OCPs的分析，显示PCBs和OCPS在过滤后水中含量较低，主要分配在悬浮颗粒物中，悬浮颗粒物中的PCBs和OCPs组成与周边土壤中的组成基本一致。HCHs和DDTs的组成和α-HCH/γ-HCH、DDT/DDE+DDD的比值暗示水中悬浮颗粒物及其PCBs和OCPs主要来源于周边土壤和大气沉降。 5、 红枫湖后五鱼体内PCBs主要以4～6氯取代的PCBs的同系物为主，OCPs以HCHs和DDTs为主。鱼体内PCBs和OCPs对于水体的富集系数达到102～105。PCBs富集系数随氯取代数目的增加而增加，表明其生物有效性随氯取代数目的增加而增加，高氯取代的PCBs更容易通过食物链在高营养级生物体内富集，对人体造成危害。 6、 大气总悬浮颗粒物TSP中及背景区土壤中PCBs和OCPs的分析，与其它环境介质中结果基本一致。红枫湖地区大气、水、沉积物、生物和土壤各环境介质中PCBs和OCPs的组成基本一致，表明其来源具有一致性。α-HCH/γ-HCH和 DDT/DDE+DDD的值，及β-HCH、p,p’-DDE的高的比例，暗示红枫湖地区OCPs在环境中经历了较长时间的变化，而且大气长距离传输对于该区OCPs和PCBs的来源具有一定的贡献。从各因子的分析可以得出，红枫湖为该地区PCBs和OCPs的汇。 7、我国PCBs和DDTs、HCHs的含量除了典型区外，在国内外都处于较低和中等污染水平，红枫湖地区整体处于较低污染水平。根据Long和Chapman等对沉积物中POPs的评价方法，红枫湖沉积物中PCBs只有一个样品处于ERL和ERM之间，其它都低于ERL值，表明PCBs对生物造成不利影响的可能性较低；DDTs的值大部分处于ERL和ERM值之间，对生物造成不利影响的可能性较大；γ-HCH的值都低于TEC值，对生物的潜在影响较小。

Correct identification of polychlorinated biphenyls in temperature-programmed GC with ECD detection

A method has been developed for peak identification of PCBs in GC with ECD detection under different temperature programs and isothermal conditions on two commonly used columns (DB-5 and DB-1701). This was achieved by means of accurate calibration of retention times based on the concept of the relative retention index P-i and retention times of the selected PCB internal standards. The P-i was calculated from the predicted retention times with the database of the retention parameters (A, B) and the migration equations. Through comparison of the calibrated and experimental retention times of PCBs in technical samples, it was shown that the developed method was effective for correct PCB comprehensive, quantitative, congener-specific (CQCS) analyses.

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlormation of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc)(2) + i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls. (c) 2004 Elsevier Ltd. All rights reserved.

An unrecognized source of PCB contamination in schools and other buildings

An investigation of 24 buildings in the Greater Boston Area revealed that one-third (8 of 24) contained caulking materials with polychlorinated biphenyl (PCB) content exceeding 50 ppm by weight, which is the U.S. Environmental Protection Agency (U.S. EPA) specified limit above which this material is considered to be PCB bulk product waste. These buildings included schools and other public buildings. In a university building where similar levels of PCB were found in caulking material, PCB levels in indoor air ranged from 111 to 393 ng/m3; and in dust taken from the building ventilation system, < 1 ppm to 81 ppm. In this building, the U.S. EPA mandated requirements for the removal and disposal of the PCB bulk product waste as well as for confirmatory sampling to ensure that the interior and exterior of the building were decontaminated. Although U.S. EPA regulations under the Toxic Substances Control Act stipulate procedures by which PCB-contaminated materials must be handled and disposed, the regulations apparently do not require that materials such as caulking be tested to determine its PCB content. This limited investigation strongly suggests that were this testing done, many buildings would be found to contain high levels of PCBs in the building materials and potentially in the building environment. The presence of PCBs in schools is of particular concern given evidence suggesting that PCBs are developmental toxins.

Surface Insulation Resistance Degradation and Electrochemical Migration on Printed Circuit Boards

Widespread adoption of lead-free materials and processing for printed circuit board (PCB) assembly has raised reliability concerns regarding surface insulation resistance (SIR) degradation and electrochemical migration (ECM). As PCB conductor spacings decrease, electronic products become more susceptible to these failures mechanisms, especially in the presence of surface contamination and flux residues which might remain after no-clean processing. Moreover, the probability of failure due to SIR degradation and ECM is affected by the interaction between physical factors (such as temperature, relative humidity, electric field) and chemical factors (such as solder alloy, substrate material, no-clean processing). Current industry standards for assessing SIR reliability are designed to serve as short-term qualification tests, typically lasting 72 to 168 hours, and do not provide a prediction of reliability in long-term applications. The risk of electrochemical migration with lead-free assemblies has not been adequately investigated. Furthermore, the mechanism of electrochemical migration is not completely understood. For example, the role of path formation has not been discussed in previous studies. Another issue is that there are very few studies on development of rapid assessment methodologies for characterizing materials such as solder flux with respect to their potential for promoting ECM. In this dissertation, the following research accomplishments are described: 1). Long-term temp-humidity-bias (THB) testing over 8,000 hours assessing the reliability of printed circuit boards processed with a variety of lead-free solder pastes, solder pad finishes, and substrates. 2). Identification of silver migration from Sn3.5Ag and Sn3.0Ag0.5Cu lead-free solder, which is a completely new finding compared with previous research. 3). Established the role of path formation as a step in the ECM process, and provided clarification of the sequence of individual steps in the mechanism of ECM: path formation, electrodeposition, ion transport, electrodeposition, and filament formation. 4). Developed appropriate accelerated testing conditions for assessing the no-clean processed PCBs' susceptibility to ECM: a). Conductor spacings in test structures should be reduced in order to reflect the trend of higher density electronics and the effect of path formation, independent of electric field, on the time-to-failure. b). THB testing temperatures should be modified according to the material present on the PCB, since testing at 85oC can cause the evaporation of weak organic acids (WOAs) in the flux residues, leading one to underestimate the risk of ECM. 5). Correlated temp-humidity-bias testing with ion chromatography analysis and potentiostat measurement to develop an efficient and effective assessment methodology to characterize the effect of no-clean processing on ECM.

Numerical modelling of solder joint formation

Solder materials are used to provide a connection between electronic components and printed circuit boards (PCBs) using either the reflow or wave soldering process. As a board assembly passes through a reflow furnace the solder (initially in the form of solder paste) melts, reflows, then solidifies, and finally deforms between the chip and board. A number of defects may occur during this process such as flux entrapment, void formation, and cracking of the joint, chip or board. These defects are a serious concern to industry, especially with trends towards increasing component miniaturisation and smaller pitch sizes. This paper presents a modelling methodology for predicting solder joint shape, solidification, and deformation (stress) during the assembly process.

Multiphysics modelling for electronics design

The future of many companies will depend to a large extent on their ability to initiate techniques that bring schedules, performance, tests, support, production, life-cycle-costs, reliability prediction and quality control into the earliest stages of the product creation process. Important questions for an engineer who is responsible for the quality of electronic parts such as printed circuit boards (PCBs) during design, production, assembly and after-sales support are: What is the impact of temperature? What is the impact of this temperature on the stress produced in the components? What is the electromagnetic compatibility (EMC) associated with such a design? At present, thermal, stress and EMC calculations are undertaken using different software tools that each require model build and meshing. This leads to a large investment in time, and hence cost, to undertake each of these simulations. This paper discusses the progression towards a fully integrated software environment, based on a common data model and user interface, having the capability to predict temperature, stress and EMC fields in a coupled manner. Such a modelling environment used early within the design stage of an electronic product will provide engineers with fast solutions to questions regarding thermal, stress and EMC issues. The paper concentrates on recent developments in creating such an integrated modeling environment with preliminary results from the analyses conducted. Further research into the thermal and stress related aspects of the paper is being conducted under a nationally funded project, while their application in reliability prediction will be addressed in a new European project called PROFIT.

Computational modeling techniques for reliability of electronic components on printed circuit boards

This paper describes modeling technology and its use in providing data governing the assembly and subsequent reliability of electronic chip components on printed circuit boards (PCBs). Products, such as mobile phones, camcorders, intelligent displays, etc., are changing at a tremendous rate where newer technologies are being applied to satisfy the demands for smaller products with increased functionality. At ever decreasing dimensions, and increasing number of input/output connections, the design of these components, in terms of dimensions and materials used, is playing a key role in determining the reliability of the final assembly. Multiphysics modeling techniques are being adopted to predict a range of interacting physics-based phenomena associated with the manufacturing process. For example, heat transfer, solidification, marangoni fluid flow, void movement, and thermal-stress. The modeling techniques used are based on finite volume methods that are conservative and take advantage of being able to represent the physical domain using an unstructured mesh. These techniques are also used to provide data on thermal induced fatigue which is then mapped into product lifetime predictions.

Correlation of solder paste rheology with computational simulations of the stencil printing process

Soldering technologies continue to evolve to meet the demands of the continuous miniaturisation of electronic products, particularly in the area of solder paste formulations used in the reflow soldering of surface mount devices. Stencil printing continues to be a leading process used for the deposition of solder paste onto printed circuit boards (PCBs) in the volume production of electronic assemblies, despite problems in achieving a consistent print quality at an ultra-fine pitch. In order to eliminate these defects a good understanding of the processes involved in printing is important. Computational simulations may complement experimental print trials and paste characterisation studies, and provide an extra dimension to the understanding of the process. The characteristics and flow properties of solder pastes depend primarily on their chemical and physical composition and good material property data is essential for meaningful results to be obtained by computational simulation.This paper describes paste characterisation and computational simulation studies that have been undertaken through the collaboration of the School of Aeronautical, Mechanical and Manufacturing Engineering at Salford University and the Centre for Numerical Modelling and Process Analysis at the University of Greenwich. The rheological profile of two different paste formulations (lead and lead-free) for sub 100 micron flip-chip devices are tested and applied to computational simulations of their flow behaviour during the printing process.

Polychlorinated Biphenyl DDT And Dieldrin Residues In Grey Seal (Halichoerus-Grypus) Males Females And Mother-Foetus Pairs Sampled At The Farne Islands England During The Breeding-Season

PCB, DDT, DDE, dieldrin and total non-polar organohalogen residues have been determined in the blubber-lipid of grey seals (Halichoerus grypus) sampled during the 1972 breeding season (November) at the Farne Islands off the north eastern coast of England. PCBs were analysed by gas-liquid chromatography linked to a chlorine- and carbon-selective microwave plasma detector and total organohalogen residues were determined by microcoulometry. Total organohalogen residues were negatively correlated with blubber thickness and positively correlated with age in males (aged 1 to 24 y) and females (aged 5 to 38 y). However, the correlation of blubber-lipid residue with age in males depended upon the inclusion of immature (aged < 6 y) animals, and in females reflected only a small residue increment. The mean blubber organohalogen concentration of the males was significantly greater than that of the females. PCB and DDT group residue concentrations were significantly correlated. PCB, DDT, DDE and dieldrin were detected in the liver of mother/foetus pairs demonstrating transplacental movement of these residues. The possibility of the condition of the seals at breeding time influencing residue levels and of these residues influencing the health of the population is discussed.

The effect of pesticides on Byssus formation in the common mussel, Mytilus edulis

Seed mussels (Mytilus edulis) were exposed to a range of pesticides and PCBs, several of which caused a reduction in byssal attachment at higher concentrations. In queen scallops (Chlamys opercularis) byssus formation was similarly affected although this species was more sensitive than M. edulis. The sensitivity of mussels was greater at higher temperatures and decreased with increase in size. Of the compounds tested Endosulfan (organochlorine) was the most toxic, causing a 50% reduction in byssal attachment after 24 h at 0•45 mg/l. Trichlorphon (organophosphate) was the least toxic and did not affect byssal attachment at concentrations up to 30 mg/l. The probable cause of decreased byssal attachment is a reduction in pedal activity, although it is possible that direct interference with the synthesis or combination of byssus components may be involved. It is suggested that byssogenesis tests offer a rapid and convenient technique for the routine screening of potential marine pollutants.

1D-Leaky Wave Antenna Employing Parallel-Plate Waveguide Loaded With PRS and HIS

A new type of one-dimensional leaky-wave antenna (LWA) with independent control of the beam-pointing angle and beamwidth is presented. The antenna is based on a simple structure composed of a bulk parallel-plate waveguide (PPW) loaded with two printed circuit boards (PCBs), each one consisting of an array of printed dipoles. One PCB acts as a partially reflective surface (PRS), and the other grounded PCB behaves as a high impedance surface (HIS). It is shown that an independent control of the leaky-mode phase and leakage rate can be achieved by changing the lengths of the PRS and HIS dipoles, thus resulting in a flexible adjustment of the LWA pointing direction and directivity. The leaky-mode dispersion curves are obtained with a simple Transverse Equivalent Network (TEN), and they are validated with three-dimensional full-wave simulations. Experimental results on fabricated prototypes operating at 15 GHz are reported, demonstrating the versatile and independent control of the LWA performance by changing the PRS and HIS parameters.

PCB congener dynamics in a heavily industrialized river catchment

PCB congener concentrations in the water column of a highly industrialized river catchment, the Aire/Calder, in N.E. England were determined weekly on a routine basis, and 2 hourly through selected high flow (flood) events. Bed, suspended and floodplain sediment PCB congener concentrations were also determined along transects of the rivers investigated. Weekly monitoring revealed that the sum of 11 quantified (Sigma11) PCBs rose in concentration by two orders of magnitude during late summer compared to their winter minimum values. This rise was concurrent with sustained periods of low flow. SigmaPCB concentrations were rapidly diluted during high flow (flood) events. Suspended sediment was, on average, 13 times more contaminated with PCBs than bed sediment, with means of 4.0 and 53.8 ng/g, respectively, while floodplain samples had an intermediate concentration of 29.8 ng/g. Principle components analysis (PCA) of congener profiles showed that all three sediment types were similar, but that congener profiles differed considerably between sediment and whole-water samples. There was no change in the percentage contribution of individual PCB congeners apparent from weekly whole-water monitoring. However, the congener pattern in whole-waters changed systematically during high flow events. PCA showed that whole-water samples collected during high flow events had progressively more sediment characteristics, and then returned to whole-water characteristics on cessation of the event. The PCA evidence, dilution of PCB concentrations during events, and suspended sediments more contaminated than bed sediments, indicate that the major sources of PCBs in this catchment are current inputs from sewage treatment works, rather than remobilization of bed sediments.

Complex Interactions between Dioxin-Like and Non-Dioxin-Like Compounds for in Vitro Cellular Responses: Implications for the Identification of Dioxin Exposure Biomarkers

Despite considerable advances in reducing the production of dioxin-like toxicants in recent years, contamination of the food chain still occasionally occurs resulting in huge losses to the agri-food sector and risk to human health through exposure. Dioxin-like toxicity is exhibited by a range of stable and bioaccumulative compounds including polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), produced by certain types of combustion, and man-made coplanar polychlorinated biphenyls (PCBs), as found in electrical transformer oils. While dioxinergic compounds act by a common mode of action making exposure detection biomarker based techniques a potentially useful tool, the influence of co-contaminating toxicants on such approaches needs to be considered. To assess the impact of possible interactions, the biological responses of H4IIE cells to challenge by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) in combination with PCB-52 and benzo-a-pyrene (BaP) were evaluated by a number of methods in this study. Ethoxyresorufin-O-deethylase (EROD) induction in TCDD exposed cells was suppressed by increasing concentrations of PCB-52, PCB-153, or BaP up to 10 mu M. BaP levels below 1 mu M suppressed TCDD stimulated EROD induction, but at higher concentrations, EROD induction was greater than the maximum observed when cells were treated with TCDD alone. A similar biphasic interaction of BaP with TCDD co-exposure was noted in the AlamarBlue assay and to a lesser extent with PCB-52. Surface enhanced laser desorption/ionization-time of flight mass spectrometry (SELDI-TOF) profiling of peptidomic responses of cells exposed to compound combinations was compared. Cells co-exposed to TCDD in the presence of BaP or PCB-52 produced the most differentiated spectra with a substantial number of non-additive interactions observed. These findings suggest that interactions between dioxin and other toxicants create novel, additive, and non-additive effects, which may be more indicative of the types of responses seen in exposed animals than those of single exposures to the individual compounds.

Storage of sediment-associated nutrients and contaminants in river channel and floodplain systems

Samples of fine-grained channel bed sediment and overbank floodplain deposits were collected along the main channels of the Rivers Aire (and its main tributary, the River Calder) and Swale, in Yorkshire, UK, in order to investigate downstream changes in the storage and deposition of heavy metals (Cr, Cu, Pb, Zn), total P and the sum of selected PCB congeners, and to estimate the total storage of these contaminants within the main channels and floodplains of these river systems. Downstream trends in the contaminant content of the <63 μm fraction of channel bed and floodplain sediment in the study rivers are controlled mainly by the location of the main sources of the contaminants, which varies between rivers. In the Rivers Aire and Calder, the contaminant content of the <63 μm fraction of channel bed and floodplain sediment generally increases in a downstream direction, reflecting the location of the main urban and industrialized areas in the middle and lower parts of the basin. In the River Swale, the concentrations of most of the contaminants examined are approximately constant along the length of the river, due to the relatively unpolluted nature of this river. However, the Pb and Zn content of fine channel bed sediment decreases downstream, due to the location of historic metal mines in the headwaters of this river, and the effect of downstream dilution with uncontaminated sediment. The magnitude and spatial variation of contaminant storage and deposition on channel beds and floodplains are also controlled by the amount of <63 μm sediment stored on the channel bed and deposited on the floodplain during overbank events. Consequently, contaminant deposition and storage are strongly influenced by the surface area of the floodplain and channel bed. Contaminant storage on the channel beds of the study rivers is, therefore, generally greatest in the middle and lower reaches of the rivers, since channel width increases downstream. Comparisons of the estimates of total storage of specific contaminants on the channel beds of the main channel systems of the study rivers with the annual contaminant flux at the catchment outlets indicate that channel storage represents <3% of the outlet flux and is, therefore, of limited importance in regulating that flux. Similar comparisons between the annual deposition flux of specific contaminants to the floodplains of the study rivers and the annual contaminant flux at the catchment outlet, emphasise the potential importance of floodplain deposition as a conveyance loss. In the case of the River Aire the floodplain deposition flux is equivalent to between ca. 2% (PCBs) and 36% (Pb) of the outlet flux. With the exception of PCBs, for which the value is ≅0, the equivalent values for the River Swale range between 18% (P) and 95% (Pb). The study emphasises that knowledge of the fine-grained sediment delivery system operating in a river basin is an essential prerequisite for understanding the transport and storage of sediment-associated contaminants in river systems and that conveyance losses associated with floodplain deposition exert an important control on downstream contaminant fluxes and the fate of such contaminants. © 2003 Elsevier Science Ltd. All rights reserved.