Fatal attraction: synthetic musk fragrances compromise multixenobiotic defense systems in mussels

We studied interactions of nitromusk compounds musk ketone and musk xylene and polycyclic musks Galaxolide trade mark (HHCB), Celestolide trade mark (ADBI), Tetralide trade mark (AHTN), and Traseolide trade mark (AITI) with multixenobiotic resistance (mxr) transporters in gill tissue of the marine mussel Mytilus californianus (Conrad, 1837). A competitive substrate transport test with rhodamine B was used to assay modulation of transport activity by musks. All tested musks inhibited the transport activity in the low microm range as indicated by increased accumulation of rhodamine B in the tissue. Compared to known substrates of mxr transporters, the effective concentration range was similar to quinidine and about 100 times higher than verapamil. Musk ketone and musk xylene also inhibited efflux of rhodamine B from gill tissue which was loaded with the dye and subsequently incubated with these compounds. Synthetic musk compounds are persistent environmental pollutants in aquatic environments with a high potential to bioaccumulate. As potent inhibitors of mxr transporters they may also play a role as chemosensitizers that enable toxic mxr substrates to accumulate in cells of aquatic organisms.     

Palaeo-carbonate seep structures above an oil reservoir, Gryphon Field, Tertiary, North Sea

Petrographic and geochemical analyses performed on a North Sea core from the Gryphon Field reveal the presence of palaeo-degassing features surrounded by injected sandstones in the Eocene interval. The injected sandstones are oil-stained and poorly cemented by carbonate and quartz. ¹⁸O isotope analyses indicate that carbonate cementation occurred during shallow burial (likely less than about 300 m). Depleted ¹³C (around –30 V-PDB) carbonate cement suggests that bicarbonate was derived from the microbial oxidation of oil and gas. Late quartz overgrowths enclose oil present in the injected units. The tubular degassing conduits are composed of zoned cements and have ¹⁸O and ¹³C isotope values similar to the injected sandstones, indicating that oil and gas seepage induced the precipitation of authigenic carbonate in the shallow subsurface. Oil inclusions in inter- and intra-crystal cement sites in both injected sandstones and degassing conduits indicate that oil seepage was an ongoing feature at shallow burial. A proposed model involves oil and gas seepage and the formation of the degassing conduits, followed by a sand injection phase. It seems likely that oil and gas continued to leak towards the seabed by exploiting the network of permeable injected sandstones and the horizons of porous degassing features.     

Climate control on stacked paleosols in the Pleistocene of the Po Basin (northern Italy)

Paleosols are recurrent features in alluvial successions and provide information about past sedimentary dynamics and climate change. Through sedimentological analysis on six sediment cores, the mud-dominated succession beneath the medieval ‘Two Towers’ of Bologna was investigated down to 100 m depth. A succession of weakly developed paleosols (Inceptisols) was identified. Four paleosols (P1, P2, P3 and PH) were radiocarbon-dated to 40–10 cal ka bp . Organic matter and CaCO₃ determinations indicate low groundwater levels during soil development, which spanned periods < 5 ka. The development and burial of soils, which occurred synchronously in the Bologna region and in other sectors of the Po Plain, are interpreted to reflect climatic and eustatic variations. Climatic oscillations, at the scale of the Bond cycles, controlled soil development and burial during Marine Isotope Stage (MIS) 3 (P1 and P2). Rapid sea-level oscillations probably induced soil development at the MIS 3/2 transition (P3) and favored burial of PH after 10 ka bp . Weakly developed paleosols in alluvial successions can provide clues to millennial-scale climatic and environmental variations. In particular, the paleosol-bearing succession of the Po Plain represents an unprecedent record of environmental changes across the Late Pleistocene (MIS 3 and 2) in the Mediterranean region.     

Seep mounds on the Southern Vøring Plateau (offshore Norway)

Multidisciplinary study of seep-related structures on Southern Vøring Plateau has been performed during several UNESCO/IOC TTR cruises on R/V Professor Logachev. High-resolution sidescan sonar and subbottom profiler data suggest that most of the studied fluid discharge structures have a positive relief at their central part surrounded by depression. Our data shows that the present day fluid activity is concentrated on the top of these “seep mounds”. Number of high hydrocarbon (HC) gas saturated sediment cores and 5 cores with gas hydrate presence have been recovered from these structures. δ¹³C of methane (between −68 and −94.6‰ VPDB) and dry composition of the gas points to its biogenic origin. The sulfate depletion generally occurs within the upper 30–200 cm bsf and usually coincides with an increase of methane concentration. Pore water δ¹⁸O ranges from 0.29 to 1.14‰ showing an overall gradual increase from bottom water values (δ¹⁸O ∼ 0.35‰). Although no obvious evidence of fluid seepage was observed during the TV surveys, coring data revealed a broad distribution of living Pogonophora and bacterial colonies on sea bottom inside seep structures. These evidences point to ongoing fluid activity (continuous seepage of methane) through these structures. From other side, considerable number and variety of chemosynthetic macro fauna with complete absence of living species suggest that present day level of fluid activity is significantly lower than it was in past. Dead and subfossil fauna recovered from various seep sites consist of solemyid (Acharax sp.), thyasirid and vesicomyid (cf. Calyptogena sp.) bivalves belonging to chemosymbiotic families. Significant variations in δ¹³C (−31.6‰ to −59.2‰) and δ¹⁸O (0.42‰ and 6.4‰) of methane-derived carbonates collected from these structures most probably related to changes in gas composition and bottom water temperature between periods of their precipitation. This led us to ideas that: (1) seep activity on the Southern Vøring Plateau was started with large input of the deep thermogenic gas and gradually decries in time with increasing of biogenic constituent; (2) authigenic carbonate precipitation started at the near normal deep sea environments with bottom water temperature around +5 °C and continues with gradual cooling up to negative temperatures recording at present time.     

Authigenic carbonate precipitates from the NE Black Sea: a mineralogical,geochemical, and lipid biomarker study

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low δ¹³C values measured on carbonates (−41 to −32‰ V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. δ¹⁸O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly ¹⁸O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.     

Simultaneous identification of the pollutant release history and the source location in groundwater by means of a geostatistical approach

This paper describes an innovative procedure that is able to simultaneously identify the release history and the source location of a pollutant injection in a groundwater aquifer (simultaneous release function and source location identification, SRSI). The methodology follows a geostatistical approach: it develops starting from a data set and a reliable numerical flow and transport model of the aquifer. Observations can be concentration data detected at a given time in multiple locations or a time series of concentration measurements collected at multiple locations. The methodology requires a preliminary delineation of a probably source area and results in the identification of both the sub-area where the pollutant injection has most likely originated, and in the contaminant release history. Some weak hypotheses have to be defined about the statistical structure of the unknown release function such as the probability density function and correlation structure. Three case studies are discussed concerning two-dimensional, confined aquifers with strongly non-uniform flow fields. A transfer function approach has been adopted for the numerical definition of the sensitivity matrix and the recent step input function procedure has been successfully applied.     

Response of single benthic metrics and multi-metric methods to anthropogenic pressure gradients, in five distinct European coastal and transitional ecosystems

In recent times many benthic indices have been proposed to assess the ecological quality of marine waters worldwide. In this study we compared single metrics and multi-metric methods to assess coastal and transitional benthic status along human pressure gradients in five distinct environments across Europe: Varna bay and lake (Bulgaria), Lesina lagoon (Italy), Mondego estuary (Portugal), Basque coast (Spain) and Oslofjord (Norway). Hence, 13 single metrics (abundance, number of taxa, and several diversity and sensitivity indices) and eight of the most common indices used within the European Water Framework Directive (WFD) for benthic assessment were selected: index of size spectra (ISS), Benthic assessment tool (BAT), Norwegian quality index (NQI), Multivariate AMBI (M-AMBI), Benthic quality index (BQI), (Benthic ecosystem quality index (BEQI), Benthic index based on taxonomic sufficiency (BITS), and infaunal quality index (IQI). Within each system, sampling sites were ordered in an increasing pressure gradient according to a preliminary classification based on professional judgement. The different indices are largely consistent in their response to pressure gradient, except in some particular cases (i.e. BITS, in all cases, or ISS when a low number of individuals is present). Inconsistencies between indicator responses were most pronounced in transitional waters (i.e. IQI, BEQI), highlighting the difficulties of the generic application of indicators to all marine, estuarine and lagoonal environments. However, some of the single (i.e. ecological groups approach, diversity, richness) and multi-metric methods (i.e. BAT, M-AMBI, NQI) were able to detect such gradients both in transitional and coastal environments, being these multi-metric methods more consistent in the detection than single indices. This study highlights the importance of survey design and good reference conditions for some indicators. The agreement observed between different methodologies and their ability to detect quality trends across distinct environments constitutes a promising result for the implementation of the WFD’s monitoring plans. Moreover, these results have management implications, regarding the dangers of misclassification, uncertainty in the assessment, use of conflicting indices, and testing and validation of indices.     

Deciphering late Quaternary land snail shell δO and δC from Franchthi Cave (Argolid,Greece)

This paper investigates the stable isotopic composition from late Pleistocene–Holocene (~ 13 to ~ 10.5 cal ka BP) shells of the land snail Helix figulina, from Franchthi Cave (Greece). It explores the palaeoclimatic and palaeoenvironmental implications of the isotope palaeoecology of archaeological shells at the time of human occupation of the cave. Modern shells from around the cave were also analysed and their isotopic signatures compared with those of the archaeological shells. The carbon isotope composition of modern shells depicts the consumption of C₃ vegetation. Shell oxygen isotopic values are consistent with other Mediterranean snail shells from coastal areas. Combining empirical linear regression and an evaporative model, the δ¹⁸Os suggest that modern snails in the study area are active during periods of higher relative humidity and lower rainfall δ¹⁸O, probably at night. Late glacial and early Holocene δ¹⁸Os show lower values compared to modern ones. Early Holocene δ¹⁸Os values likely track enhanced moisture and isotopic changes in the precipitation source. By contrast, lower late glacial δ¹⁸O could reflect lower temperatures and δ¹⁸Op, compared to the present day. Shell carbon isotope values indicate the presence of C₃ vegetation as main source of carbon to late glacial and early Holocene snails.     

Geomaterials related to photovoltaics: a nanostructured Fe-bearing kuramite,Cu<Subscript>3</Subscript>SnS<Subscript>4</Subscript>

The successful synthesis of nanoparticles of Fe-bearing kuramite, (Cu,Fe)₃SnS₄, is reported in this study. Nanocrystalline powders were obtained through a mild, environmentally friendly and scalable solvothermal approach, in a single run. The sample was the object of a multidisciplinary investigation, including X-ray diffraction and absorption, scanning electron microscopy and microanalysis, electron paramagnetic resonance, diffuse reflectance and Mössbauer spectroscopy as well as SQUID magnetometry. The nanoparticles consist of pure Fe-bearing kuramite, exhibiting tetragonal structure. The valence state of the metal cations was assessed to be Cu⁺, Sn⁴⁺ and Fe³⁺. The material presents a band gap value of 1.6 eV, which is fully compatible with solar cell applications. The uptake of Fe by nanokuramite opens a compositional field where the physical properties can be tuned. We thus foster the application of Fe-bearing nanokuramite for photovoltaics and energy storage purposes.