珠江口沉积物酸挥发性硫化物与重金属生物毒性的研究

研究了2003年10月采于珠江口5个站位的沉积物剖面酸挥发性硫化物(AVS)和同时提取的重金属(SEM:Pb,Zn,Cu,Cd,Ni)。其中,站位1、2位于中滩,其沉积物的AVS含量变化范围较小,为0.25—4.06μmol.g-1;站位3、4位于西滩,其沉积物的AVS含量变化范围较大,为0—26.09μmol.g-1。中滩和西滩沉积物的AVS含量均随深度增加。西滩表层沉积物的AVS含量接近于零,这可能与该水域较强的底层流和沉积物的再悬浮作用有关。站位5位于珠江口外侧,其表层沉积物的AVS含量相对较高,且垂向变化较小,可能是还原性沉积物间歇性再悬浮后重新沉积的结果。站位1、2和5沉积物中同时提取的重金属含量大体在0.95±0.2μmol.g-1范围内,随深度增加略呈下降趋势;而西滩沉积物重金属含量相对较高,为1.43—2.42μmol.g-1,且在一定深度范围内随深度增加呈明显下降的趋势,表明珠江口西滩沉积物中的重金属污染有加重的趋势。对AVS/SEM摩尔比值和单个金属的毒性效应研究显示,珠江口内尤其是西滩的表层沉积物存在重金属污染,对其中生活的底栖生物具有潜在的毒性效应。     

Photochemical models of the atmosphere and their application in ozonosphere and climate studies: A review

This review is devoted to problems in the photochemical modeling of atmospheric processes. The physicochemical and mathematical foundations underlying the construction of photochemical models are described, a classification of the atmospheric reactions is presented, and the features of photochemical modeling are considered under various irradiance conditions for various atmospheric layers and geographical regions. Atmospheric processes that are important to photochemical models are discussed. Applications involving photochemical models are outlined. Some results are presented to illustrate the capabilities of photochemical models. Special attention is given to relatively recent directions in photochemical modeling, such as data assimilation and inverse problems. The review can be used by experts in areas related to atmospheric chemistry as a basic source of knowledge on the subject and for the development of photochemical modules for atmospheric models.     

An optimized method for automated analysis of algal pigments by HPLC

A recent development in algal pigment analysis by high-performance liquid chromatography (HPLC) is the application of automation. An optimization of a complete sampling and analysis protocol applied specifically in automation has not yet been performed. In this paper we show that automation can only be successful if the various methodological aspects of the sampling and analysis protocol are considered in coherence. We introduce an optimized protocol that involves freeze-drying of the sample, subsequent extraction in 90% acetone and the application of water-packing during analysis. The method was evaluated on both natural plankton populations and a broad spectrum of microalgal cultures: Thalassiosira weisflogii (Bacillariophyceae), Emiliania huxleyi (Prymnesiophyceae), Phaeocystis globosa and Phaeocystis antarctica (Prymnesiophyceae) and Pyramimonas sp. (Prasinophyceae). Whereas pigment extracts were unstable in methanol, with recorded chlorophyll a losses from 10% to 60% per day, pigment degradation rates in acetone were generally less than 1% over 18 h storage in the autosampler (4 °C). In addition, it was found that the extraction efficiency of acetone significantly increased upon freeze-drying prior to extraction. Increases as high as 50–60% were measured in P. antarctica. The application of water-packing of the sample during injection resulted in improved peak shape and peak separation, without diluting the pigment concentrations. Automation is especially beneficial for application in the field, when mixed algal assemblages and low biomass put a high demand on the sensitivity as well as reproducibility of the method.     

Inhomogeneous substrate analysis using EM300 backscatter imagery

Backscatter reflectivity from multibeam echo-sounders provides a powerful tool to efficiently characterize seafloor substrates. A comprehensive EM300 bathymetric and backscatter survey has been completed of Cook Strait, in central New Zealand. This paper presents a detailed analysis of the realtime corrections applied to the raw EM300 multibeam data and additional corrections required to compute angular variations of the backscatter strength. The corrections, including the local absorption coefficient, the influence of seafloor topography and sound refraction in the water column, are determined for different Cook Strait seafloor substrates. Modifying MB-System software code, we extracted the backscatter signal parameters in order to quantify the raw backscatter strength and apply additional processing. Profiles of backscatter strength versus incidence angle were computed for a variety of sites characterized by flat seafloor and homogeneous substrates, and for which ground-truth data were available. For each homogeneous site, different but characteristic backscatter profiles are observed that can be interpreted in terms of sediment facies. To analyze heterogeneous substrates, we present a statistical technique, based on a 3-dimensional distribution of (incidence angle, backscatter strength) couples that preserves geological information of the substrate components. This analysis, using backscatter data acquired on a submarine volcano, north of New Zealand, clearly differentiates soft sediments and lava flows within a heterogeneous substrate.     

Imaging of Buried Archaeological Materials: The Reflection Properties of Archaeological Wood

Effective marine archaeological site management demands detailed information on not only the spatial distribution of artefacts but also the degradation state of the materials present. Although sonar methods have frequently been used in an attempt to detect buried wooden shipwrecks they are currently unable to indicate their degradation state. To assess the sensitivity of acoustic measurements to changes in the degradation state of such material, and hence the potential for sonars to quantify degradation, laboratory measurements of compressional wave velocity, as well as bulk density for oak and pine samples, in varying states of decay, were undertaken. These data enabled the calculation of theoretical reflection coefficients for such materials buried in various marine sediments. As wood degrades, the reflection coefficients become more negative, resulting in the hypothesis that the more degraded wood becomes, the easier it should be to detect. Typical reflection coefficients of the order of −0.43 and −0.52 for the most degraded oak and pine samples in sand are predicted. Conversely, for wood exposed to seawater the predicted reflection coefficients are large and positive for undegraded material (0.35 for oak, 0.18 for pine) and decrease to zero or slightly below for the most degraded samples. This indicates that exposed timbers, when heavily degraded, can be acoustically transparent and so undetectable by acoustic methods. Corroboration of these experimental results was provided through comparison with high resolution seismic reflection data that has been acquired over two shipwrecks.     

Multi-decadal synthesis of benthic–pelagic coupling in the western arctic: Role of cross-shelf advective processes

Using geographic information systems (GIS) software and geostatistical techniques, we utilized three decades of water-column chlorophyll a data to examine the relative importance of autochthonous versus allochthonous sources of reduced carbon to benthic communities that occur from the northern Bering to the eastern Beaufort Sea shelf. Spatial trend analyses revealed areas of high benthic biomass (>300 g m⁻²) and chlorophyll (>150 mg m⁻²) on both the southern and northern Chukchi shelf; both areas are known as depositional centers for reduced organic matter that originates on the Bering Sea shelf and is advected northward in Anadyr and Bering shelf water masses. We found a significant correlation between biomass and chlorophyll a in the Chukchi Sea, reflective of the strong benthic–pelagic coupling in a system that is utilized heavily by benthic-feeding marine mammals. In contrast, there was no significant correlation between biomass and chlorophyll in the Beaufort Sea, which by comparison, is considerably less productive (biomass and chlorophyll, <75 g m⁻² and <50 mg m⁻², respectively). One notable exception is an area of relatively high biomass (50–100 g m⁻²) and chlorophyll (80 mg m⁻²) near Barter Island in the eastern Beaufort Sea. Compared to other adjacent areas in the Beaufort Sea, the chlorophyll values in the vicinity of Barter Island were considerably higher and likely reflect a long-hypothesized upwelling in that area and close coupling between the benthos and autochthonous production. In the Bering Sea, a drop in benthic biomass in 1994 compared with previous measurements (1974–1993) may support earlier observations that document a decline in biomass that began between the 1980s and 1990s in the Chirikov Basin and south of St. Lawrence Island. The results of this study indicate that the benthos is an excellent long-term indicator of both local and physical advective processes. In addition, this work provides further evidence that secondary production on arctic shelves can be significantly augmented by reduced carbon advected from highly productive adjacent shelves.     

Seasonal variations of alkenones and U37 in the Chesapeake Bay water column

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.     

Management of a shallow temperate estuary to control eutrophication: The effect of hydrodynamics on the system’s nutrient loading

The Mondego estuary, a shallow warm-temperate intertidal system located on the west coast of Portugal, has for some decades been under severe ecological stress, mainly caused by eutrophication. Water circulation in this system was, until 1998, mainly dependent on tides and on the freshwater input of a small tributary artificially controlled by a sluice. After 1998, the sluice opening was effectively minimised to reduce the nutrient loading, and the system hydrodynamics improved due to engineering work in the upstream areas. The objective of the present study was to evaluate the effect of the mitigation measures implemented in 1998. Changes to the hydrodynamics of the system were assessed using precipitation and salinity data in relation to the concentrations of dissolved inorganic nutrients, as well as the linkage between dissolved N:P ratios and the biological parameters (phytoplankton chlorophyll a concentrations, green macroalgal biomass and seagrass biomass). Two distinctive periods were compared, over a ten year period: from January 1993 to January 1997 and from January 1999 until January 2003. The effective reduction in the dissolved N:P atomic ratio from 37.7 to 13.2 after 1998 is a result of lowered ammonia, but not the oxidised forms of nitrogen (nitrate plus nitrite), or increased concentrations of dissolved inorganic phosphorus. Results suggest that the phytoplankton is not nutrient limited, yet maximum and mean biomass of green macroalgae was reduced by one order of magnitude after the mitigation measures. This suggests that besides lowering the water residence time of the system, macroalgal growth became nitrogen limited. In parallel to these changes the seagrass-covered area and biomass of Zostera noltii showed signs of recovery.     

Glucuronidation in the polar bear (Ursus maritimus)

Polar bears bioaccumulate lipophilic pollutants, including polychlorinated biphenyls (PCBs), into their bodies from their exclusive diet of marine organisms. Hydroxylated PCB metabolites (OH-PCBs) have been found in plasma, presumably due to CYP-dependent biotransformation of PCBs in liver. Little is known about the phase 2 metabolism of hydroxylated xenobiotics in polar bears. The objective of this study was to examine UDP-glucuronosyltransferase (UGT) activity with OH-PCBs and a hydroxylated polycyclic aromatic hydrocarbon, 3-hydroxy-benzo(a)pyrene (3-OH-BaP), in polar bear liver. Samples of frozen polar bear liver were used to prepare microsomes. UGT activity with 3-OH-BaP in Brij-treated microsomes, measured by a fluorescence assay, was readily measurable with protein concentrations in assay tubes of up to 10 g/ml, but dropped off very sharply at higher protein concentrations. The apparent Km for 3-OH-BaP was 1.71 +/- 0.04 microM, and Vmax 1.26 +/- 0.16 nmol/min/mg protein (mean +/- SD, n=3). UGT activities with a model tetrachloro-OH-PCB (4'-OH-CB72) and a model hexachloro-OH-PCB (4'-OH-CB159) were assayed with [14-C]-UDPGA and separation of the [14-C]-glucuronide by ion-pair extraction and thin-layer chromatography. [14-C]-glucuronide conjugates were readily formed by polar bear liver microsomes in the absence of added substrate, apparently from contaminants present in liver. This phenomenon was not observed using hepatic microsomes from laboratory-held catfish. Glucuronidation efficiency was much higher with 4'-OH-CB72 (Km 7.3 microM; Vmax 1.55 nmol/min/mg) than 4'-OH-CB159 (Km 16.1 microM; Vmax 0.46 nmol/min/mg). The identities of the aglycones present in polar bear liver are not known, but could include OH-PCBs or hydroxylated metabolites of other persistent organic pollutants. This study demonstrates that UGT with high activity for 3-OH-BaP and other substrates is present in polar bear liver.     

The Dynamics of Covering Behaviour in Dominant Echinoid Populations from American and European West Coasts

Abstract.  The so-called 'covering behaviour' of echinoids is known to vary with habitat according to the types of covering items available, but the full extent of the role played by habitat characteristics in this behaviour is not known. Moreover, whether or not different species inhabiting similar environmental conditions and habitats also show similar patterns of this particular behaviour has yet to be investigated. In this study, two prominent west coast echinoid species, Paracentrotus lividus and Strongylocentrotus purpuratus , were examined with respect to covering behaviour and spatial organisation. Populations of both species are found in exposed intertidal zones, occupying boreholes within tidepools. Important similarities were found in the spatial organisation of both species' populations, with lowest densities in upper shore pools. However, the size distributions of the two populations differed significantly; P. lividus within upper shore pools were significantly larger than those in mid or lower shore pools, whereas S. purpuratus on the lower shore were significantly larger than those at other shore heights. We found significant between-species variability in covering item use, although the number of covering items available at both sites was not significantly different. For example, greater densities of covering items were used by P. lividus than by S. purpuratus . We also found that the percent of echinoid surface area covered varied significantly in space for both species. These data emphasise the complex and multifaceted nature of covering behaviour, but most importantly, they also strongly suggest that habitat characteristics can only partly explain the extent of this behavioural variability amongst echinoid species.