Detection of PAHs in seawater using surface-enhanced Raman scattering (SERS)

The laboratory characterization of a field-operable surface-enhanced Raman scattering sensor (SERS optode) is presented for the detection of aromatic hydrocarbons in seawater. The sensor has been developed for deployment with a robust underwater spectrograph. To meet the demands of the harsh seawater application, sol-gel derived SERS substrates were used. The calibration curves of six PAHs were determined to be of Langmuir adsorption isotherm type with limits of detection ranging from the microg l(-1) to ng l(-1) level. The experimentally determined adsorption constants varied strongly with the molecular weight of the analytes and correlated with their solubility. A mixture of five PAHs dissolved in seawater was investigated to demonstrate the utility of this method for screening. Emphasis was put on the interference from suspended particulate matter (SPM). The Raman measurement with backscattering configuration was shown to be immune against turbidities up to 1000 NTU. The physico-chemical interference arising from adsorption by the sediment was measured on-line by adding sediment to a PAH-spiked solution. According to the calibration curve, the PAH concentration decrease corresponded to more than 98% of the analyte being scavenged by the sediment.     

Carbon dioxide segregation in 1:4 and 1:9 CO2:H2O ices

The mid-infrared spectra of mixed vapor deposited ices of CO₂ and H₂O were studied as a function of both deposition temperature and warming from 15 to 100 K. The spectra of ices deposited at 15 K show marked changes on warming beginning at 60 K. These changes are consistent with CO₂ segregating within the ice matrix into pure CO₂ domains. Ices deposited at 60 and 70 K show a greater degree of segregation, as high as 90% for 1:4 CO₂:H₂O ice mixtures deposited at 70 K. As the ice is warmed above 80 K, preferential sublimation of the segregated CO₂ is observed. The kinetics of the segregation process is also examined. The segregation of the CO₂ as the ice is warmed corresponds to temperatures at which the structure of the water ice matrix changes from the high density amorphous phase to the low density amorphous phase. We show how these microstructural changes in the ice have a profound effect on the photochemistry induced by ultraviolet irradiation. These experimental results provide a framework in which observations of CO₂ on the icy bodies of the outer Solar System can be considered.     

[WR] nuclei of planetary nebulae: Inferences from statistical studies of the nebulae

There are about 50 galactic planetary nebulae know to have [WR] type nuclei. We have compared their nebular properties with those of the other planetary nebulae in the Galaxy. We have found that the nebular morphological types are similarly distributed in the two groups. Bipolar nebulae constitute only 20% of the total in each group. The distribution of the nebular electron densities and abundance ratios N/O, He/H and C/O are the same in the two groups. The only marked difference is that nebular expansion velocities are larger in the group of planetary nebulae with [WR] central stars. We argue that the WR phenomenon does not preferentially occur in more massive central stars of planetary nebulae, contrary to what has been suggested in some former studies. We demonstrate that, for most of the observed [WR] type objects, the WR phenomenon cannot be triggered by a late helium shell flash event.The results of our investigation are published inAstronomy & Astrophysics 303, 893 (1995) and in the proceedings of the 2nd International Colloquium on Hydrogen-deficient Stars, C.S. Jeffery & U. Heber (eds), Astronomical Society of the Pacific Conference Series, Vol. 96, p. 209 (1996).     

Chloropigments a in the Gulf of Gdańsk (Baltic Sea) as markers of the state of this environment

The Gulf of Gdańsk receives the waters of the Wis?a (Vistula), the largest Polish river and the second largest river flowing into the Baltic Sea. Chloropigments a (chlorophyll a and its derivatives) were determined in water and sediments from the Gulf. Samples were collected during cruises of R.V. 'Oceania' at 19 stations located at different water depths and distances from the shore, in May (2003) and October (2004), i.e., at the beginning and at the end of the growing season, respectively. Seawater was also sampled on the beach at Sopot in June, July and August 2004, i.e., during the height of the growing season. All water samples were collected with a bathometer and passed through Whatman GF/F filters. Recent sediments (0-10 cm) were collected with a core sampler and divided into sub-samples (0-1, 1-5 and 5-10 cm). The pigments were determined using HPLC-DAD. The results were first correlated with a set of parameters measured in situ during sample collection (salinity, temperature, oxygen content of seawater) and determined in the same material (organic carbon content, granulometry), then worked up statistically. Although this investigation shows that particular chloropigments a in recent sediments are indicative of the prevailing environmental conditions in the study area and the trends in their variations, they should be treated as a relative and not an absolute measure, since this is the first such study based on a large and coherent set containing both chloropigment a and environmental data. In addition, a chlorophyll a budget is estimated for the Gulf of Gdańsk on the basis of the literature and the authors' own data. Only c. 10% of the chlorophyll a produced annually in the Gulf of Gdańsk is transferred to sediments in the form of chloropigments a; 2.8% is in the form of undecomposed chlorophyll a and 7.2% in the form of chlorophyll a derivatives. About 90% of chlorophyll a is decomposed to colourless products.     

Analysis of nonlinear associations between prenatal methylmercury exposure from fish consumption and neurodevelopmental outcomes in the Seychelles Main Cohort at 17 years

The Seychelles Child Development Study has been examining the relationship between prenatal methylmercury (MeHg) exposure from consuming fish during pregnancy and child development. This study re-analyzes seven outcomes in the 17 year Main Cohort data to determine if there are nonlinear or non-homogeneous (subgroup) associations that were not identified in the linear analysis. We adopted two statistical approaches. First, we carried out an additive nonlinear analysis assuming homogeneous prenatal MeHg-outcome relationships to explore overall associations. Second, we applied the regression tree to the Woodcock–Johnson Calculation subtest (it was significantly associated in earlier analyses) and identified 4 clusters based on covariates. Then we used additive models to assess the prenatal MeHg association in each of the four clusters for all seven outcomes. This approach assumes nonlinear associations in each cluster and non-homogeneous associations between clusters. The additive nonlinear analysis yielded prenatal MeHg curves similar to the linear analysis. For the regression tree analysis, the curves relating prenatal MeHg to outcomes between the 4 clusters differed and some crossed at higher prenatal MeHg levels, suggesting non-homogeneity in the upper range of exposure. Additionally, some of the curves suggested a possible non-linear relationship within the range of exposure we studied. This non-linear analysis supports the findings from the linear analysis. It shows little evidence to support an adverse association of prenatal MeHg exposure through maternal consumption of fish contaminated with natural background levels. However, the tree analysis suggests that the prenatal exposure/outcome relationship may not be homogeneous across all individuals and that some subpopulations may have an adverse association in the upper range of the exposures studied. More robust data in the higher levels of exposure in this cohort are needed to confirm this finding.     

Ultraviolet photolysis of amino acids in a 100 K water ice matrix: Application to the outer Solar System bodies

We report the rates of decomposition by ultraviolet (UV) photolysis of four amino acids in millimeter-thick crystalline water ice matrices at 100 K to constrain the survivability of these important organic molecules within ice lying near the surfaces of outer Solar System bodies. We UV-irradiated crystalline ice samples containing known concentrations of the amino acids glycine, aspartic acid, glutamic acid, and phenylalanine, then we measured the surviving concentrations using high performance liquid chromatography (HPLC) with fluorescence detection. From these experiments, we determine photolytic decomposition rates and half-lives. The half-life varies linearly with the ice thickness for all acids studied here. For example, glycine is the most resistant to photolytic destruction with a half-life of 50, 12, and 3.7 h in 1.6, 0.28, and 0.14 mm thick ices, respectively. We explain this linear variation of half-life with thickness as a consequence of extinction, mostly due to scattering, within these macroscopically thick ice samples. Applied to low latitude surface ice on Jupiter's satellite Europa, this analysis indicates that the concentration of any of these amino acids within the top meter of similar ice will be halved within a ∼10 year timescale.     

Transfer of organic contaminants to the Baltic in the Odra Estuary

This paper describes the transfer of organic contaminants to the sea, using PAHs (12 compounds) and PCBs (11 congeners) as examples, through a eutrophicated coastal lagoon (Szczecin Lagoon, on the Polish-German border). The transfer of contaminants study was based on their concentration in recent sediments (0-10 cm), in relation to different environmental conditions such as temperature, salinity, turbidity, oxygen and nutrients in water, hydrological conditions, organic carbon and biomarkers (pigments and their derivatives) in sediments. Results include the data obtained between 1994 and 2000, also those on before and afterwards the great flood in July 1997, at different stations in the Lagoon and the adjacent Pomeranian Bay. The results indicated that the eutrophic estuary of the shape of lagoon acts as an effective trap for the hydrophobic organic pollutants. The abundance and taxonomy of plankton as well as detritus derived from it play an important role in bonding the studied compounds. The salinity gradient in the lagoon has a significant influence upon deposition of the pollutants from the water column to the sediments and the residence time of the compounds there depends strongly on oxic-anoxic status of the sediments and the strength of interaction with sediments resulting from polarity, the type and stability of associates formed, as well as on hydrological conditions. We conclude that eutrophication in this area prevents pollution of the sea to some extent.     

The effects of spatially distributed ionisation sources on the temperature structure of H <Emphasis Type="SmallCaps">ii</Emphasis> regions

Spatially resolved studies of star-forming regions show that the assumption of spherical geometry is not realistic in most cases, with a major complication posed by the gas being ionised by multiple non-centrally located stars or star clusters. Geometrical effects including the spatial configuration of ionising sources affect the temperature and ionisation structure of these regions. We try to isolate the effects of multiple non-centrally located stars, via the construction of 3D photoionisation models using the 3D Monte Carlo photoionisation code mocassin with very simple gas density distributions, but various spatial configurations for the ionisation sources.Emission-line spectra from H?ii regions are often used to study the metallicity of star-forming regions, as well as for providing a constraint on temperatures and luminosities of the ionising sources. Empirical metallicity diagnostics must often be calibrated with the aid of photoionisation models. However, most studies so far have been carried out by assuming spherical or plane-parallel geometries, with major limitations on the allowed gas and dust density distributions and with the spatial distribution of multiple, non-centrally located ionising sources not being accounted for. We compare integrated emission-line spectra from our models and quantify any systematic errors caused by the simplifying assumption of a single, central location for all ionising sources. We find that the dependence of the metallicity indicators on the ionisation parameter causes a clear bias, due to the fact that models with a fully distributed configuration of stars always display lower ionisation parameters than their fully concentrated counterparts. The errors found imply that the geometrical distribution of ionisation sources may partly account for the large scatter in metallicities derived using model-calibrated empirical methods.