Reconstruction of contaminant trends in a salt wedge estuary with sediment cores dated using a multiple proxy approach

The Taunton River is a partially mixed tidal estuary in southeastern Massachusetts (USA) which has received significant contaminant inputs, yet little information exists on the history of discharge and the subsequent fate of these contaminants. Three sediment cores taken along a transect were analyzed, reconstructing the spatial and temporal trends of pollution in the estuary. A combination of radiometric dating, contaminant markers, and storm layers from major hurricanes were used to establish age models and sedimentation rates. Age estimates obtained from the different dating methods compared well, establishing an accurate history of contaminant release to the estuary. Polycyclic aromatic hydrocarbons (PAHs) were present in one core at depths corresponding to the early 1860s, earlier than previously established dates of introduction. Temporal and spatial trends of Cr, Cu, Hg and Pb indicated multiple sources of varying input to the river. Polychlorinated biphenyls (PCBs) were present in each of the cores from the 1930s onward, with elevated levels still present in surficial sediments at several sites. A unique organic compound, Topanol, which was produced locally was used as a tracer to track contaminant transport in the river. Tracer data indicates that contaminants are still being transported and deposited to surficial sediments at high concentrations well after their discharge. This reconstruction demonstrates the utility of using multiple dating proxies where often the sole use of radiometric dating techniques is not an option and provides insights into the fate of contaminants discharged decades ago but continue to represent environmental risks.     

Experimental evidence for an effect of early-diagenetic interaction between labile and refractory marine sedimentary organic matter on nitrogen dynamics

In most natural sedimentary systems labile and refractory organic material (OM) occur concomitantly. Little, however, is known on how different kinds of OM interact and how such interactions affect early diagenesis in sediments. In a simple sediment experiment, we investigated how interactions of OM substrates of different degradability affect benthic nitrogen (N) dynamics. Temporal evolution of a set of selected biogeochemical parameters was monitored in sandy sediment over 116 days in three experimental set-ups spiked with labile OM (tissue of Mytilus edulis), refractory OM (mostly aged Zostera marina and macroalgae), and a 1:1 mixture of labile and refractory OM. The initial amounts of particulate organic carbon (POC) were identical in the three set-ups. To check for non-linear interactions between labile and refractory OM, the evolution of the mixture system was compared with the evolution of the simple sum of the labile and refractory systems, divided by two. The sum system is the experimental control where labile and refractory OM are virtually combined but not allowed to interact. During the first 30 days there was evidence for net dissolved-inorganic-nitrogen (DIN) production followed by net DIN consumption. (Here ‘DIN’ is the sum of ammonium, nitrite and nitrate.) After  30 days a quasi steady state was reached. Non-linear interactions between the two types of OM were reflected by three main differences between the early-diagenetic evolutions of nitrogen dynamics of the mixture and sum (control) systems: (1) In the mixture system the phases of net DIN production and consumption commenced more rapidly and were more intense. (2) The mixture system was shifted towards a more oxidised state of DIN products [as indicated by increased (nitrite + nitrate)/(ammonium) ratios]. (3) There was some evidence that more OM, POC and particulate nitrogen were preserved in the mixture system. That is, in the mixture system more particulate OM was preserved while a higher proportion of the decomposed particulate N was converted into inorganic N. It can be concluded that during the first days and weeks of early diagenesis the magnitude and composition of the flux of decompositional dissolved N-compounds from sediments into the overlying water was influenced by non-linear interactions of OM substrates of different degradability. Given these experimental results it is likely that the relative spatial distributions of OM of differing degradability in sediments control the magnitude and composition of the return flux of dissolved N-bearing compounds from sediments into the overlying water column.     

The stellar mass spectrum of the open cluster NGC 3293

We have obtained and analyzed UBVRI CCD frames of the young, 4–10 Myr, open cluster NGC 3293 and the surrounding field in order to study its stellar content and determine the cluster’s IMF. We found significantly fewer lower mass stars, M≤2.5M _⊙, than expected. This is particularly so if a single age for the cluster of 4.6 Myr is adopted as derived from fitting evolutionary models to the upper main sequence. Some intermediate-mass stars near the main sequence in the HR diagram imply an age for the cluster of about 10 Myr. When compared with the Scalo (The stellar initial mass function. ASP conference series, vol. 24, p. 201, 1998) IMF scaled to the cluster IMF in the intermediate mass range, 2.5≤M/M _⊙≤8.0 where there is good agreement, the high mass stars have a distinctly flatter IMF, indicating an over abundance of these stars, and there is a sharp turnover in the distribution at lower masses. The radial density distribution of cluster stars in the massive and intermediate mass regimes indicate that these stars are more concentrated to the cluster core whereas the lower-mass stars show little concentration. We suggest that this is evidence supporting the formation of massive stars through accretion and/or coagulation processes in denser cluster cores at the expense of the lower mass proto-stars. R.W. Slawson and E.P. Horch are guest investigators at the University of Toronto Southern Observatory, Las Campanas, Chile.     

Oxygen and carbon isotope ratios in the martian atmosphere

Oxygen and carbon isotope ratios in the martian CO₂ are key values to study evolution of volatiles on Mars. The major problems in spectroscopic determinations of these ratios on Mars are uncertainties associated with: (1) equivalent widths of the observed absorption lines, (2) line strengths in spectroscopic databases, and (3) thermal structure of the martian atmosphere during the observation. We have made special efforts to reduce all these uncertainties. We observed Mars using the Fourier Transform Spectrometer at the Canada–France–Hawaii Telescope. While the oxygen and carbon isotope ratios on Mars were byproducts in the previous observations, our observation was specifically aimed at these isotope ratios. We covered a range of 6022 to 6308 cm⁻¹ with the highest resolving power of ν/δν=3.5×10⁵ and a signal-to-noise ratio of 180 in the middle of the spectrum. The chosen spectral range involves 475 lines of the main isotope, 184 lines of ¹³CO₂, 181 lines of CO¹⁸O, and 119 lines of CO¹⁷O. (Lines with strengths exceeding 10⁻²⁷ cm at 218 K are considered here.) Due to the high spectral resolution, most of the lines are not blended. Uncertainties of retrieved isotope abundances are in inverse proportion to resolving power, signal-to-noise ratio, and square root of the number of lines. Laboratory studies of the CO₂ isotope spectra in the range of our observation achieved an accuracy of 1% in the line strengths. Detailed observations of temperature profiles using MGS/TES and data on temperature variations with local time from two GCMs are used to simulate each absorption line at various heights in each part of the instrument field of view and then sum up the results. Thermal radiation of Mars' surface and atmosphere is negligible in the chosen spectral range, and this reduces errors associated with uncertainties in the thermal structure on Mars. Using a combination of all these factors, the highest accuracy has been achieved in measuring the CO₂ isotope ratios: ¹³C/¹²C = 0.978 ± 0.020 and ¹⁸O/¹⁶O = 1.018 ± 0.018 times the terrestrial standards. Heavy isotopes in the atmosphere are enriched by nonthermal escape and sputtering, and depleted by fractionation with solid-phase reservoirs. The retrieved ratios show that isotope fractionation between CO₂ and oxygen and carbon reservoirs in the solid phase is almost balanced by nonthermal escape and sputtering of O and C from Mars.     

Unsteady diagenetic processes and sulfur biogeochemistry in tropical deltaic muds: Implications for oceanic isotope cycles and the sedimentary record

Sedimentary S cycling is usually conceptualized and interpreted within the context of steadily accreting (1-D) transport-reaction regimes. Unsteady processes, however, are common in many sedimentary systems and can result in dramatically different S reaction balances and diagenetic products than steady conditions. Globally important common examples include tropical deltaic topset and inner shelf muds such as those extending from the Amazon River ∼1600 km along the Guianas coast of South America. These deposits are characterized by episodic reworking of the surface seabed over vertical depths of ∼0.1-3 m. Reworked surface sediments act as unsteady, suboxic batch reactors, unconformably overlying relict anoxic, often methanic deposits, and have diagenetic properties largely decoupled from net accumulation of sediment. Despite well-oxygenated water and an abundant reactive organic matter supply, physical disturbance inhibits macrofauna, and benthic communities are dominated by microbial biomass across immense areas. In the surficial suboxic layer, molecular biological analyses, tracer experiments, sediment C/S/Fe compositions, and δ³⁴S, δ¹⁸O of pore water indicate close coupling of anaerobic C, S, and Fe cycles. δ¹⁸O- can increase by 2-3‰ during anaerobic recycling without net change in δ³⁴S-, demonstrating reduction coupled to complete anaerobic reoxidation to and a δ¹⁸O- reduction + reoxidation fractionation factor?12‰ (summed magnitudes). S reoxidation must be coupled to Fe-oxide reduction, contributing to high dissolved Fe²⁺ (∼1 mM) and Fe mobilization-export. The reworking of Amazon-Guianas shelf muds alone may isotopically alter δ¹⁸O- equivalent in mass to?25% of the annual riverine delivery of to the global ocean. Unsteady conditions result in preservation of unusually heavy δ³⁴S isotopic compositions of residual Cr reducible S, ranging from 0‰ to >30‰ in physically reworked deposits. In contrast, bioturbated facies adjacent to physically reworked regions accumulate isotopically light S (δ³⁴S to −20‰) in otherwise similar decomposition regimes. The isotopic patterns of both physically and biologically reworked regions can be simulated with simple diagenetic models. Heavy S isotopic signatures are largely a consequence of unsteady diffusion and progressive anaerobic burndown into underlying deposits, whereas isotopically depleted bioturbated deposits predominantly reflect biogenic diffusive scaling and isotopic distillation/diffusive pumping associated with reoxidation in burrow walls immediately adjacent to reduced zones. The S isotopic transition from unsteady physically controlled regions of the Amazon delta moving laterally into bioturbated facies mimics the transition of S isotopic patterns temporally in the geologic record during the rise of bioturbation. No special role for S disproportionation is required to explain these differences. The potential role of unsteady, suboxic diagenesis and dynamic reworking of sediments has been largely ignored in models of the evolution of surficial elemental cycling and interpretations of the geologic record.     

The geochemistry of primary and weathered oil shale and coquina across the Julia Creek vanadium deposit (Queensland, Australia)

A significant resource of vanadium and molybdenum exists near Julia Creek, Australia, where the middle Cretaceous organic-rich Toolebuc Formation lies between 0 and 25 m of the surface. We present and discuss a comprehensive geochemical study of the Toolebuc Formation and its enclosing stratigraphy near Julia Creek to understand this ore deposit. V and Mo contents in fresh facies are strongly associated with total organic carbon (TOC) contents, but not with Al or CaCO₃; this suggests that V and Mo were originally concentrated in the organic fraction. However, chemical extractions using H₂O₂ indicate that Mo was originally concentrated in pyrite. The data also suggest that V was mobilised from organic matter during early diagenesis and became associated with clays as little V was extracted by H₂O₂ in the fresh samples. TOC contents in the Toolebuc Formation were removed during weathering, residually enriching trace metals including V and Mo, and as a result, the TOC relationship with V and Mo disintegrates. With weathering, both V and Mo predominantly became associated with iron oxide/hydroxide phases (and possibly other unidentified phases) as these elements in the weathered facies were highly soluble in the sodium citrate–sodium dithionite digestion. Large shale-hosted V and Mo deposits such as Julia Creek offer a potentially viable alternative to the currently mined magnetite-hosted deposits. A thorough understanding of the formation and host mineral phases for V and Mo of these shale deposits, however, is critical to ensure that these valuable metals can be feasibly extracted.     

Trinitite—the atomic rock

On 16 July 1945, the first atomic bomb was detonated at the Alamogordo Bombing range in New Mexico, USA. Swept up into the nuclear cloud was the surrounding desert sand, which melted to form a green glassy material called ‘trinitite’. Contained within the glass are melted bits of the first atomic bomb and the support structures and various radionuclides formed during the detonation. The glass itself is marvelously complex at the tens to hundreds of micrometre scale, and besides glasses of varying composition also contains unmelted quartz grains. Air transport of the melted material led to the formation of spheres and dumbbell shaped glass particles. Similar glasses are formed during all ground level nuclear detonations and contain forensic information that can be used to identify the atomic device.     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are:

Raman spectroscopic study of PbCO3 at high pressures and temperatures

Cerussite (PbCO₃) has been investigated by high-pressure and high-temperature Raman spectroscopy up to pressures of 17.2 GPa and temperatures of 723 K. Two pressure induced phase transitions were observed at about 8.0(2) and 16.0(2) GPa, respectively. The post-aragonite transition (PbCO₃-II) at 8.0(2) GPa is accompanied by softening of the v ₂-out-of-plane mode of the CO ₃ ^2? group and disappearance of the B_1g (v ₄-in-plane band of the CO ₃ ^2? group) mode. Stronger shifts of the carbonate group modes after the phase transition suggest that the new structure is more compressible. The formation of a second high-pressure polymorph begins at about 10 GPa. It is accompanied by the occurrence of three new bands at different pressures and splitting of the v ₁-symmetric C–O stretching mode of the CO ₃ ^2? group. The transitions are reversible on pressure release. A semi-quantitative phase diagram for PbCO₃ as a function of pressure and temperature is proposed.     

A digitized global flood inventory (1998–2008): compilation and preliminary results

Floods have profound impacts on populations worldwide in terms of both loss of life and property. A global inventory of floods is an important tool for quantifying the spatial and temporal distribution of floods and for evaluating global flood prediction models. Several global hazard inventories currently exist; however, their utility for spatiotemporal analysis of global floods is limited. The existing flood catalogs either fail to record the geospatial area over which the flood impacted or restrict the types of flood events included in the database according to a set of criteria, limiting the scope of the inventory. To improve upon existing databases, and make it more comprehensive, we have compiled a digitized Global Flood Inventory (GFI) for the period 1998–2008 which also geo-references each flood event by latitude and longitude. This technical report presents the methodology used to compile the GFI and preliminary findings on the spatial and temporal distributions of the flooding events that are contained in the inventory.