Comparison of gas with liquid chromatography for the determination of benzenepolycarboxylic acids as molecular tracers of black carbon

Existing methods for black carbon (BC) quantification measure different parts of the BC continuum, which complicates the calculation of a global BC budget. Benzenepolycarboxylic acids (BPCA) are used as molecular markers to quantify and characterize BC in soils and sediments using gas chromatography for BPCA separation (GC-BPCA). Recently, this method was refined for BC analysis in seawater using high performance liquid chromatography (LC-BPCA), which omits the cleaning steps and derivatization necessary in GC analysis. As yet it is not clear whether the two analytical methods yield similar results. Here we apply both methods to a suite of laboratory produced charcoals derived from wood and grass. We found systematically lower total BPCA-C contents and larger analytical variability for all tested charcoals when using GC-BPCA compared to LC-BPCA, the latter giving 1.5 ± 0.3 times higher yields for the charcoal samples formed at 275-700 °C. At lower and higher pyrolysis temperatures the differences between the two analytical methods were larger. The main reason for the differences between the two methods is the loss of BPCA during sample preparation for GC analysis. We propose a correction factor of 1.5 to account for at least part of these losses. No qualitative biases, i.e. towards more or less functionalized BPCAs, were observed between the two methods. The relative contribution of mellitic acid C to total BPCA-C, a measure for the degree of condensation of BC, was the same in the two analytical techniques. Qualitative differences between wood and grass charcoals as detected by both methods were small.     

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Surface selection,adhesion, and retention behavior of marine bacteria on synthetic organic surfaces using self-assembled monolayers and atomic force microscopy

Adhesion of two marine bacteria Shewanella sp. strain T1 and Pseudoalteromonas sp. strain T8, on differently terminated alkanethiolate self-assembled monolayers on gold was investigated. The selected model surfaces—terminated by CH₃, OH, NH₂, COOH, OH-terminated oligo(ethylene glycol), and methyl-terminated oligo(ethylene glycol)—are characterized by contact angle measurement using water, methylene iodide, 1-bromonaphthalene, and formamide. Surface free energies were calculated. Cell counting of the two bacterial strains on the model surfaces after different times revealed differences between the two strains by at least one order of magnitude. For the different surfaces, the bacteria showed comparably small selectivity. Atomic force microscopy images of adhered bacteria showed very different fingerprints on the different surfaces. Electronic supplementary material  Supplementary material is available in the online version of this article at and is accessible to authorized users.     

Non-LTE modeling of supernova-fallback disks

We present a first detailed spectrum synthesis calculation of a supernova-fallback disk composed of iron. We assume a geometrically thin disk with a radial structure described by the classical α-disk model. The disk is represented by concentric rings radiating as plane-parallel slabs. The vertical structure and emission spectrum of each ring is computed in a fully self-consistent manner by solving the structure equations simultaneously with the radiation transfer equations under non-LTE conditions. We describe the properties of a specific disk model and discuss various effects on the emergent UV/optical spectrum. We find that strong iron-line blanketing causes broad absorption features over the whole spectral range. Limb darkening changes the spectral distribution up to a factor of four depending on the inclination angle. Consequently, such differences also occur between a blackbody spectrum and our model. The overall spectral shape is independent of the exact chemical composition as long as iron is the dominant species. A pure iron composition cannot be distinguished from silicon-burning ash. Non-LTE effects are small and restricted to few spectral features.     

Curation protocol of Phobos sample returned by Martian Moons eXploration

Japan Aerospace Exploration Agency's Martian Moons eXploration (MMX) mission will launch a spacecraft in 2024 to return samples from Phobos in 2029. Curatorial work for the returned Phobos samples is critical for the sample allocation without degrading the sample integrity and subsequent sample analysis that will provide new constraints on the origin of Phobos and the evolution of the circum-Mars environment. The Sample Analysis Working Team of the MMX is designing the sample curation protocol. The curation protocol consists of three phases: (1) quick analysis (extraction and mass spectrometry for gases), (2) pre-basic characterization (bulk-scale observation), and (3) basic characterization (grain-by-grain observation and allocation of the sample aliquots). Nondestructive analyses within the clean chamber (e.g., visible and near-infrared spectral imaging) and outside the chamber (e.g., gas mass spectrometry) are incorporated into the curation flow in coordination with the MMX mission instrument teams for ground-truthing the remote-sensing data sets. The MMX curation/sample analysis flow enables the seamless integration between the sample and remote-sensing data sets to maximize the scientific value of the collected Phobos samples.     

Thermogenic organic matter dissolved in the abyssal ocean

Formation and decay of thermogenic organic matter are important processes in the geological carbon cycle, but little is known about the fate of combustion-derived and petrogenic compounds in the ocean. We explored the molecular structure of marine dissolved organic matter (DOM) for thermogenic signatures in different water masses of the Southern Ocean. Ultrahigh-resolution mass spectrometry via the Fourier transform-ion cyclotron resonance technique (FT-ICR-MS) revealed the presence of polyaromatic hydrocarbons (PAHs) dissolved in the abyssal ocean. More than 200 different PAHs were discerned, most of them consisting of seven condensed rings with varying numbers of carboxyl, hydroxyl, and aliphatic functional groups. These unambiguously thermogenic compounds were homogenously distributed in the deep sea, but depleted at the sea surface. Based on the structural information alone, petrogenic and pyrogenic compounds cannot be distinguished. Surface depletion of the PAHs and first estimates for their turnover rate (> 1.2 · 10¹² mol C per year) point toward a primarily petrogenic source, possibly deep-sea hydrothermal vents, which is thus far speculative because the fluxes of combustion-derived and petrogenic matter to the ocean are not well constrained. We estimate that > 2.4% of DOM are thermogenic compounds, and their global inventory in the oceans is > 1.4 · 10¹⁵ mol C, significantly impacting global biogeochemical cycles.     

Ion microprobe (SHRIMP) dating of detrital zircon grains from quartzites of the Eckergneiss Complex, Harz Mountains (Germany): implications for the provenance and the geological history

The Eckergneiss Complex (EGC) is a geologically unique medium- to high-grade metamorphic unit within the Rhenohercynian domain of the Mid-European Variscides. A previously, poorly defined conventional lower U–Pb intercept age of about 560 Ma from detrital zircons of metasedimentary rocks has led to speculations about an East Avalonian affinity of the EGC. In order to unravel the provenance and to constrain the age of the sediment protolith, we carried out sensitive high-resolution ion microprobe U–Pb analyses on detrital zircons from five different EGC quartzite occurrences. The obtained age spectrum indicates a SW Baltica provenance of the detritus. Sveconorwegian ages between 0.9–1.2 Ga are particularly well represented by analyses from metamorphic recrystallization/alteration zones penetrating into igneous zircon. Cadomian (Pan-African) ages, which might reflect a metamorphic event, could not be substantiated. Instead, zircons of igneous origin yielded concordant Lower Devonian and Silurian ages of 410±10, 419±10, and 436±6 Ma (1), implying that sedimentation of the EG protolith must have taken place after 410±10 Ma. The lower age limit of the EGC metamorphism is constrained by 295 Ma intrusion ages of the adjacent, nonmetamorphosed Harzburg Gabbronorite and Brocken Granite. Sedimentation and metamorphism must thus have taken place between about 410 Ma and 295 Ma. Given that this time span coincides with most of the sedimentation within the virtually nonmetamorphosed (lowest grade) Rhenohercynian in the Harz Mountains, including the direct vicinity of the EGC, along with the high-grade metamorphism, the EGC can hardly be seen as uplifted local basement. A possible candidate for the root region is an easterly, concealed marginal segment of the Rhenohercynian domain of the Variscides, which is tectonically overridden and suppressed by the Mid-German Crystalline Rise during continent collision. However, based on the concept of strike-slip movement of Variscan terranes with different P–T–t histories as a result of postaccretion intraplate deformation, the EGC could also represent a fault-bounded complex with an origin located far east or south east of the present location.

Analysis of trophic networks and carbon flows in south-eastern Baltic coastal ecosystems

Carbon flows in five south-eastern Baltic coastal ecosystems (Puck Bay, Curonian Lagoon, Lithuanian coast, Gulf of Riga coast and Pärnu Bay) were compared on the basis of ECOPATH models using 12 common functional groups. The studied systems ranged from the hypertrophic Curonian Lagoon to the mesotrophic Gulf of Riga coast. Interestingly, we found that macrophytes were not consumed by grazers, but rather channelled into the detritus food chain. In all ecosystems fisheries had far reaching impacts on their target species and on the food-web in general. In particular, benthic food-webs were partly affected by indirect fisheries effects. For example, fisheries tend to change the biomass of piscivorous fish, causing a cascading effect on benthivorous fish and macrozoobenthos. These cascades are ecosystem specific and need to be considered when using benthic invertebrates as productivity and eutrophication indicators. Odum’s maturity attributes allowed a ranking of costal ecosystems according to their maturity. Namely, the community development decreased in the following order: Pärnu Bay > Gulf of Riga coast > Lithuanian coast > Puck Bay > Curonian Lagoon.     

Trends of persistent organic pollutants in the suspended matter of the River Rhine

Recently amended European (EU) water policies call for an adequate monitoring of the chemical status of sediments and suspended matter (SM) in rivers. In this study, we focus on long‐term time series of particle‐bound hexachlorobenzene (HCB) and selected polychlorinated biphenyls (PCB‐138 and PCB‐153) that were monitored biweekly to monthly at eight stations in the River Rhine catchment. Our aims are (1) to detect trends in the concentration series HCB, PCB‐138 and PCB‐153, (2) to estimate the uncertainty of loads caused by SM collection techniques and load calculation procedures and (3) to detect trends in the subsequently calculated annual load series. HCB concentration in the SM for the period 1995–2008 significantly (p < 0·01) decreased at six of the eight monitoring stations. Decreasing PCB‐138 and PCB‐153 concentrations are significant at six of the eight and seven of the eight monitoring stations, respectively. A two‐way analysis of variance (ANOVA) that tested the effect of two collection techniques and four load calculation procedures on annual loads indicates homogeneity of the methods at four of the five monitoring stations. At Weil, only the loads of HCB, PCB‐138 and PCB‐153 are significantly affected by the collection technique. The trend analysis of an extended series (1985–2007) of annual HCB loads at Koblenz showed a significant decrease from about 110 kg year^?1 to about 15–23 kg year^?1; however, in the shorter period (1995–2007) only at two of the eight monitoring stations decreasing trends of annual contaminant load could be detected. We conclude that any of the tested load calculation procedures can be applied, as loads do no differ systematically. Although a high uncertainty in load estimation exists (e.g. maximum percentage error of E = [18·1, 122·5]% for HCB), the monitoring programme at the Rhine is adequate for analysing the long‐term chemical status of SM. Copyright © 2011 John Wiley & Sons, Ltd.