The application of HPLC-F and GC-MS to the analysis of selected hydroxy polycyclic hydrocarbons in two certified fish bile reference materials

Four selected hydroxy polycyclic aromatic hydrocarbons (OH-PAHs), 2-hydroxy-naphthalene (2-OH-NPH), 1-hydroxy-phenanthrene (1-OH-PHE), 1-hydroxy-pyrene (1-OH-PYR) and 3-hydroxy-benzo[a]pyrene (3-OH-BaP) have been analysed in two certified fish bile reference materials (CRMs) for exposure monitoring of PAHs in the aquatic environment. The two materials, BCR 720 and BCR 721, consist of bile from fish exposed to contaminated sediment and dispersed crude oil, respectively. Both bile samples have been analysed by two different analytical techniques, gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography-fluorescence detection (HPLC-F), and the separation performance, detection limits, recoveries and reproducibility for the four target compounds were evaluated. HPLC-F requires a simple sample preparation and the separation capacity is adequate for quantification of 1-OH-PYR and 3-OH-BaP. Detection limits are excellent for 1-OH-PYR (6 pg injected) and 3-OH-BaP (3 pg injected) and generally improved with increasing molecular size. Recoveries ranged from 48 to 99% for the four selected compounds, depending on compound and concentration. Sample preparation prior to GC-MS analysis was more demanding, as reflected by the obtained recoveries for 2-OH-NPH, 1-OH-PHE and 1-OH-PYR (35 to 61%). The sensitivity improved with decreasing molecular size, 2-OH-NPH (1.2 pg injected), 1-OH-PHE (2.4 pg injected) and 1-OH-PYR (6 pg injected). Because of the superior separation power of GC and the extra selectivity of MS detection, GC-MS was the method of choice for the determination of 2-OH-NPH and 1-OH-PHE in both CRMs. In fish bile samples these two compounds are more likely to suffer from chromatographic overlap, and HPLC-F was not sufficiently selective. Determination of 1-OH-PYR was performed with success by both methods, but HPLC-F would be preferred because of the simpler and less time-consuming sample preparation. Detectable concentrations of 3-OH-BaP were present in BCR 720 and could only be determined by HPLC-F. The present work aims to present HPLC-F and GC-MS as complementary methods for the quantitative analysis of OH-PAHs in fish bile.     

Use of cluster and principal component analyses to profile areas in California where ground water has been contaminated by pesticides

An empirical approach to profiling areas of ground water contamination by pesticides was devised that did not rely upon determining the level of vulnerability between land areas and that did not assume any particular pathway for ground water contamination. Climatic and soil data were obtained for 1-square mile sections of land in California where pesticide residues had been found in well water samples and the detection was attributed to legal agricultural applications. These sections were designated as known contaminated (KC) sections. Climate and soil data were also obtained for sections which lacked either well sampling data or a positive pesticide detection. These sections were designated as candidate sections. Statistical procedures were used to cluster groups of KC sections first with respect to climate characteristics and then with respect to soil characteristics. Principal components analysis (PCA) was used to construct a statistical profile of soil variables for each cluster of KC sections. A method based on the PCA was developed to compare the similarity of soil profiles derived for each KC section cluster to individual candidate sections. Since the profiling scheme was based only on data from KC sections, candidate sections that did not match any KC cluster profile could only be considered dissimilar to contaminated sections, receiving a status of not-classified. This profiling method is flexible and it can be revised to incorporate updated well sampling information.     

Matrix diffusion effects in the cleanup of heterogeneous aquifers

Simple mathematical models are developed to account for the rather slow mass transport of nonaqueous phase liquid (NAPL) into aqueous solution in groundwater during flushing operations. The models are based on the assumption that this bottleneck in the process is associated with diffusion in the aqueous phase in the porous medium from the location of the NAPL drops/ganglia in a region of relatively low permeability out into a region of substantially higher permeability, somewhat analogous to diffusion from a block of porous rock into a nearby fracture, where the fracture system overwhelmingly dominates the overall permeability. The models include batch flushing, flushing in a laboratory column, and a one-dimensional model for flushing by means of a single recovery well.     

Optimizing the removal of small fish passage barriers

Removing small artificial barriers that hinder upstream migrations of fish is a major problem in riparian habitat restoration. Because of budgetary limitations, it is necessary to prioritize barrier removal and repair decisions. These have usually been based on scoring and ranking procedures, which, although simple to use, can be very inefficient in terms of increasing the amount of accessible instream habitat. We develop a novel decision-making approach, based on integer programming techniques, which optimizes repair and removal decisions. Results show based on real datasets of barrier culverts located in Washington State that scoring and ranking is over 25% below the optimum on average and a full 100% below in the worst case, producing no net habitat gain whatsoever. This is compared to a dynamic programming method that was able to find optimal solutions in less than a second, even for problems with up to several hundred variables, and a heuristic method, which found solutions with less than a 1% average optimality gap in even less time.     

Migration of pollutants in groundwater: I. reduction of numerical dispersion by conformal mapping

The partial differential equations governing the migration of adsorbable pollutants undergoing 2-dimensional flow in saturated aquifers are presented. The analytical solution of these equations is rarely possible, and the use of mesh or grid techniques for numerical integration leads to so-called numerical dispersion, excessive dispersion which is an artifact associated with the numerical method. We discuss here the use of conformal mapping techniques to develop coordinate systems in which numerical dispersion transverse to the direction of flow is eliminated. Some simple illustrations are presented.     

Measurement of atmospheric concentrations of common household pesticides: A pilot study

Air concentrations of 28 of the most commonly used household pesticides were measured inside nine homes in Jacksonville, Florida, and compared with corresponding outdoor levels. The households selected were sorted into three categories according to the degree of pesticide indoor usage. Personal air monitoring was also performed on one resident of each household by means of a portable sampler, which was kept with the person at all times. Five of the pesticides were found in the air inside of the majority of the homes at concentrations as high as 15 gm^–3 (average concentrations, 12 ngm^–3 to 2.4 gm^–3). Indoor levels were generally one to two ordrrs of magnitude higher than surrounding outdoor air levels and personal air measurements were within ± 50% of corresponding indoor values. All samples were collected over 24-hr periods on polyurethane foam and analyzed by capillary colum gas chromatography with mass spectrometric and/or electron capture detection.     

Declines in organochlorines in eggs of red-breasted mergansers from Lake Michigan, 1977–1978 versus 1990

From 1977–1978 to 1990, concentrations of polychlorinated biphenyls (PCBs) and most organochlorine pesticides declined in eggs of red-breasted mergansers (Mergus serrator) nesting on islands in northwestern Lake Michigan. Total PCBs decreased 60% (from 21 ppm in 1977–1978 to 8.5 ppm in 1990) and p,p-DDE decreased 66% (from 6.5 to 2.2 ppm). Dieldrin decreased only 16% (from 0.82 to 0.69 ppm). In 1990, 79.1% of incubated eggs hatched, which was not significantly different from the 83.5% that hatched in 1977–1978.The U.S. Government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

Association between the mollusc bivalve Loripes lucinalis and a Chlamydia-like organism,with comments on its pathogenic impact,life cycle and possible mode of transmission

Loripes lucinalis is a littoral bivalve which has already been confirmed to harbour endo-cellular sulfur-oxidizing bacteria within its gills. Examination of the digestive gland of L. lucinalis collected from the Moulin Blanc Beach in the Bay of Brest (Brittany, France) revealed the existence of an additional association involving a Chlamydia-like organism. Three different forms of Chlamydia-like bacteria were observed: reticulate rod-shaped cells, electron-dense cells and enlarged cells. The reticulate rod-shaped cells and the electron-dense bodies are thought to represent the germinal initial body and infectious form of the bacteria, respectively. The enlarged cells were always associated with what are believed to be spherical or icosahedral phages. Initial infestation seems to occur by phagocytosis at the apical pole of the digestive cells of the tubule and duct epithelia. Within the host cell, the bacteria undergo binary fission and budding, forming an inclusion which gradually fills up the cell. Inclusions are generally between 15 and 30 m in size, and > 85% of all individuals examined possessed inclusion bodies. The level of infestation varied between individuals, some being heavily colonized, but did not seem to be related to season. Histological and ultrastructural observations suggest that, once developed, the colony has three possible fates: (1) the cells will degenerate due to phage infection; (2) colony overcrowding will occur, causing the development of electron-dense bodies that will be released into the lumen; (3) the entire membrane-bound inclusion will be released into the lumen and subsequently into the pallial cavity. Inclusions within the pallial cavity may be ingested by the host or may even be phagocytized by bacteriocyte cells of the gill. It is proposed that this association could be a form of symbiosis and that L. lucinalis may, therefore, be a rare example of an organism adapted to harbour two very different symbioses.     

安大略基拉尼公园及实验湖泊区浮游生物群落对酸化的响应及其恢复过程

人们普遍推测控制SO2排放可以促进加拿大、美国和欧洲的酸化淡水湖泊的恢复.本文研究了1998～2000年间靠近安大略省基拉尼公园的22个湖泊(pH值范围4.5～7.7)的浮游生物群落变化,将结果与安大略省西北的实验湖泊区(ELA)人工酸化(pH值从6.7降至4.5)又恢复(pH升至6.0)的南302号湖的数据进行了对比,以评价酸化后的恢复效果.根据历史记录,基拉尼地区数个湖泊的pH值由先前酸化的5.0～5.5反弹到6.0.浮游生物量与pH不相关,但其物种的丰富度与pH值间呈显著相关.将所得到的物种多样性数据与历史数据加以组合,可观察到其中6个湖泊中的恢复轨迹.相关分析表明:pH值得到提高后,其中几个湖泊的浮游生物群落开始向中性环境中的典型群落转化.     

让我们积极应对气候变化

气候确实在发生变化。以往人们随意地认为这与温室效应气体排放量的增加有关，现在这种观点已得到充分证实。自1991年以来．已出现了自有记录以来全球气温最高的十个年份．而在上个世纪，温度上升7约0.6摄氏度。在同一期间内，全球的海平面上升了约20厘米．部分原因是陆地上冰层融化．海洋自身发生热膨胀。许多山峰上的冰盖正在消失．最近几十年来，夏秋季节北冰洋的冰层厚