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.     

Abnormal features of Macoma balthica (Bivalvia) in the Baltic Sea: alerting symptoms of environmental adversity?

Recent studies of the Baltic clam Macoma balthica (L.) from the southern Baltic (the Gulf of Gdansk) have revealed striking morphological, histological and cytogenetic features. Strong deformation of the shell, including elongation of the posterior end and the appearance of an easily visible flexure in this part, has been recorded. The population contribution of the deformed blunt shelled ("irregular") clams ranged from 0% to 65% and tended to increase with depth. The morphologically "irregular" clams had higher accumulated tissue concentrations of trace metals (As, Ag, Cd, Pb, Cu and Zn), indicating a different metal handling ability. Adverse conditions in deeper water regions of the Gulf (e.g. hypoxia, hydrogen sulphide, elevated bioavailability of contaminants) have been suggested as inducers of the phenotypical changes (morphological deformation) in part of the population and, in parallel, of the specific physiological adaptations that result in higher metal accumulation in the "irregular" clams. Cytogenetic and histological analyses showed the presence of tumours in gill cells and digestive system of the affected clams, the prevalence of disseminated neoplasia ranging from 0% to 94% depending on the site. The disease was manifested by a modified karyotype (i.e. an abnormal number and morphology of chromosomes), a higher activity of nucleolar organizer regions (AgNORs), and tissue lesions (enlarged cells, actively proliferative with pleomorphic nuclei). Bottom sediments showed acute toxicity and have been proposed as a source of an initialising carcinogenic factor. However, none of the ecotoxicological studies provided was successful in the clear demonstration of a single (or multifactorial) agent that can account for the disseminated neoplasia.     

Anthropogenic iodine-129 in seawater along a transect from the Norwegian coastal current to the North Pole

Variation in the concentrations of iodine-129 (129I, T1/2=15.7 Myr), a low-level radioactive component of nuclear fuel waste, is documented in surface waters and depth profiles collected during 2001 along a transect from the Norwegian Coastal Current to the North Pole. The surface waters near the Norwegian coast are found to have 20 times higher 129I concentration than the surface waters of the Arctic Ocean. The depth profiles of 129I taken in the Arctic Ocean reveal a sharp decline in the concentration to a depth of about 300-500 m followed by a weaker gradient extending down to the bottom. A twofold increase in the 129I concentration is observed in the upper 1000 m since 1996. Based on known estimates of marine transient time from the release sources (the nuclear reprocessing facilities at La Hague, France, and Sellafield, UK), a doubling in the 129I inventory of the top 1000 m of the Arctic Ocean is expected to occur between the years 2001 and 2006. As 129I of polar mixed layer and Atlantic layer of the Arctic Ocean is ventilated by the East Greenland Current into the Nordic Seas and North Atlantic Ocean, further dispersal and increase of the isotope concentration in these regions will be encountered in the near future.     

Concentration and subcellular distribution of trace elements in liver of small cetaceans incidentally caught along the Brazilian coast

Concentrations of trace elements (V, Cr, Mn, Fe, Co, Cu, Zn, Ga, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Cs, Ba, T-Hg, Org-Hg, Tl and Pb) were determined in liver samples of estuarine dolphin (Sotalia guianensis; n = 20), Franciscana dolphin (Pontoporia blainvillei; n = 23), Atlantic spotted dolphin (Stenella frontalis; n = 2), common dolphin (Delphinus capensis; n = 1) and striped dolphin (Stenella coeruleoalba; n = 1) incidentally caught along the coast of Sao Paulo State and Parana State, Brazil, from 1997 to 1999. The hepatic concentrations of trace elements in the Brazilian cetaceans were comparable to the data available in literature on marine mammals from Northern Hemisphere. Concentrations of V, Se, Mo, Cd, T-Hg and Org-Hg increased with increasing age in liver of both estuarine and Franciscana dolphins. Very high concentrations of Cu (range, 262-1970 microg/g dry wt.) and Zn (range, 242-369 microg/g dry wt.) were observed in liver of sucklings of estuarine dolphin. Hepatic concentrations of V, Se, T-Hg, Org-Hg and Pb were significantly higher in estuarine dolphin, whereas Franciscana dolphin showed higher concentrations of Mn, Co, As and Rb. Ratio of Org-Hg to T-Hg in liver was significantly higher in Franciscana dolphin than estuarine dolphin, suggesting that demethylation ability of methyl Hg might be lower in liver of Franciscana than estuarine dolphins. High hepatic concentrations of Ag were found in some specimens of Franciscana dolphin (maximum, 20 microg/g dry wt.), and 17% of Franciscana showed higher concentrations of Ag than Hg. These samples with high Ag concentration also exhibited elevated hepatic Se concentration, implying that Ag might be detoxified by Se in the liver. Higher correlation coefficient between (Hg+0.5 Ag) and Se than between Hg and Se and the large distribution of Ag in non-soluble fraction in nuclear and mitochondrial fraction of the liver also suggests that Ag might be detoxified by Se via formation of Ag2Se in the liver of Franciscana dolphin.     

Applications of C and N stable isotopes to ecological and environmental studies in seagrass ecosystems

Stable isotopes of carbon and nitrogen are increasingly used in marine ecosystems, for ecological and environmental studies. Here, we examine some applications of stable isotopes as ecological integrators or tracers in seagrass ecosystem studies. We focus on both the use of natural isotope abundance as food web integrators or environmental tracers and on the use of stable isotopes as experimental tools. As ecosystem integrators, stable isotopes have helped to elucidate the general structure of trophic webs in temperate, Mediterranean and tropical seagrass ecosystems. As environmental tracers, stable isotopes have proven their utility in sewage impact measuring and mapping. However, to make such environmental studies more comprehensible, future works on understanding of basic reasons for variations of N and C stable isotopes in seagrasses should be encouraged. At least, as experimental tracers, stable isotopes allow the study of many aspects of N and C cycles at the scale of a plant or at the scale of the seagrass ecosystem.     

Identification of heterogeneous aquifer transmissivity using an AE-based method

Determination of hydraulic head, H, as a function of spatial coordinates and time, in ground water flow is the basis for aquifer management and for prediction of contaminant transport. Several computer codes are available for this purpose. Spatial distribution of the transmissivity, T(x,y), is a required input to these codes. In most aquifers, T varies in an erratic manner, and it can be characterized statistically in terms of a few moments: the expected value, the variance, and the variogram. Knowledge of these moments, combined with a few measurements, permits one to estimate T at any point using geostatistical methods. In a review of transmissivity data from 19 unconsolidated aquifers, Hoeksema and Kitanidis (1985) identified two types of the logtransmissivity Y= ln(T) variations: correlated variations with variance sigma2Yc and correlation scale, I(Y), on the order of kilometers, and uncorrelated variations with variance sigma2Yn. Direct identification of the logtransmissivity variogram, Gamma(Y), from measurements is difficult because T data are generally scarce. However, many head measurements are commonly available. The aim of the paper is to introduce a methodology to identify the transmissivity variogram parameters (sigma2Yc, I(Y), and sigma2Yn) using head data in formations characterized by large logtransmissivity variance. The identification methodology uses a combination of precise numerical simulations (carried out using analytic element method) and a theoretical model. The main objective is to demonstrate the application of the methodology to a regional ground water flow in Eagle Valley basin in west-central Nevada for which abundant transmissivity and head measurements are available.     

Transition probability/Markov chain analyses of DNAPL source zones and plumes

At sites where a dense nonaqueous phase liquid (DNAPL) was spilled or released into the subsurface, estimates of the mass of DNAPL contained in the subsurface from core or monitoring well data, either in the nonaqueous or aqueous phase, can be highly uncertain because of the erratic distribution of the DNAPL due to geologic heterogeneity. In this paper, a multiphase compositional model is applied to simulate, in detail, the DNAPL saturations and aqueous-phase plume migration in a highly characterized, heterogeneous glaciofluvial aquifer, the permeability and porosity data of which were collected by researchers at the University of Tübingen, Germany. The DNAPL saturation distribution and the aqueous-phase contaminant mole fractions are then reconstructed by sampling the data from the forward simulation results using two alternate approaches, each with different degrees of sampling conditioning. To reconstruct the DNAPL source zone architecture, the aqueous-phase plume configuration, and the contaminant mass in each phase, one method employs the novel transition probability/Markov chain approach (TP/MC), while the other involves a traditional variogram analysis of the sampled data followed by ordinary kriging. The TP/MC method is typically used for facies and/or hydraulic conductivity reconstruction, but here we explore the applicability of the TP/MC method for the reconstruction of DNAPL source zones and aqueous-phase plumes. The reconstructed geometry of the DNAPL source zone, the dissolved contaminant plume, and the estimated mass in each phase are compared using the two different geostatistical modeling approaches and for various degrees of data sampling from the results of the forward simulation. It is demonstrated that the TP/MC modeling technique is robust and accurate and is a preferable alternative compared to ordinary kriging for the reconstruction of DNAPL saturation patterns and dissolved-phase contaminant plumes.     

Influence of small-scale heterogeneities on contaminant transport in fractured crystalline rock

We present a sequence of purely advective transport models that demonstrate the influence of small-scale geometric inhomogeneities on contaminant transport in fractured crystalline rock. Special weight is placed on the role of statistically generated variable fracture apertures. The fracture network geometry and the aperture distribution are based on information from an in situ radionuclide retardation experiment performed at Grimsel test site (Swiss Alps). The obtained breakthrough curves are fitted with the advection dispersion equation and continuous-time random walks (CTRW). CTRW is found to provide superior fits to the late-arrival tailing and is also found to show a good correlation with the velocity distributions obtained from the hydraulic models. The impact of small-scale heterogeneities, both in fracture geometry and aperture, on transport is shown to be considerable.     

Mediterranean fin whales at risk from fatal ship strikes

This paper reviews and analyzes ship collision records for the relatively isolated population of fin whales in the Mediterranean Sea from 1972 to 2001. Out of 287 carcasses, 46 individuals (16.0%) were certainly killed by boats. The minimum mean annual fatal collision rate increased from 1 to 1.7 whales/year from the 1970s to the 1990s. Fatal strike events (82.2%) were reported in or adjacent to the Pelagos Sanctuary, characterized by high levels of traffic and whale concentrations. Among 383 photo-identified whales, 9 (2.4%) had marks that were attributed to a ship impact. The reported rates are unusually high for baleen whales. The high likelihood of unreported fatal strikes combined with other anthropogenic threats suggests an urgent need for a comprehensive, basin-wide conservation strategy, including ship strike mitigation requirements, like real-time monitoring of whale presence and distribution to re-locate ferry routes to areas of lower cetacean density, and reducing ship speed in high cetacean density areas.