Late Holocene sea-level changes and isostasy in western Denmark

Cores and exposed cliff sections in salt marshes around Ho Bugt, a tidal embayment in the northernmost part of the Danish Wadden Sea, were subjected to ¹⁴C dating and litho- and biostratigraphical analyses to reconstruct paleoenvironmental changes and to establish a late Holocene relative sea-level history. Four stages in the late Holocene development of Ho Bugt can be identified: (1) groundwater-table rise and growth of basal peat (from at least 2300 BC to AD 0); (2) salt-marsh formation (0 to AD 250); (3) a freshening phase (AD 250 to AD 1600?), culminating in the drying out of the marshes and producing a distinct black horizon followed by an aeolian phase with sand deposition; and (4) renewed salt-marsh deposition (AD 1600? to present). From 16 calibrated AMS radiocarbon ages on fossil plant fragments and 4 calibrated conventional radiocarbon ages on peat, we reconstructed a local relative sea-level history that shows a steady sea-level rise of 4 m since 4000 cal yr BP. Contrary to suggestions made in the literature, the relative sea-level record of Ho Bugt does not contain a late Holocene highstand. Relative sea-level changes at Ho Bugt are controlled by glacio-isostatic subsidence and can be duplicated by a glacial isostatic adjustment model in which no water is added to the world's oceans after ca. 5000 cal yr BP.     

The synergistic effect of calcium on organic carbon sequestration to ferrihydrite

Sequestration of organic carbon (OC) in environmental systems is critical to mitigating climate change. Organo-mineral associations, especially those with iron (Fe) oxides, drive the chemistry of OC sequestration and stability in soils. Short-range-ordered Fe oxides, such as ferrihydrite, demonstrate a high affinity for OC in binary systems. Calcium commonly co-associates with OC and Fe oxides in soils, though the bonding mechanism (e.g., cation bridging) and implications of the co-association for OC sequestration remain unresolved. We explored the effect of calcium (Ca²⁺) on the sorption of dissolved OC to 2-line ferrihydrite. Sorption experiments were conducted between leaf litter-extractable OC and ferrihydrite at pH 4 to 9 with different initial C/Fe molar ratios and Ca²⁺ concentrations. The extent of OC sorption to ferrihydrite in the presence of Ca²⁺ increased across all tested pH values, especially at pH ≥ 7. Sorbed OC concentration at pH 9 increased from 8.72 ± 0.16 to 13.3 ± 0.20 mmol OC g^?1 ferrihydrite between treatments of no added Ca²⁺ and 30 mM Ca²⁺ addition. Batch experiments were paired with spectroscopic studies to probe the speciation of sorbed OC and elucidate the sorption mechanism. ATR-FTIR spectroscopy analysis revealed that carboxylic functional moieties were the primary sorbed OC species that were preferentially bound to ferrihydrite and suggested an increase in Fe-carboxylate ligand exchange in the presence of Ca at pH 9. Results from batch to spectroscopic experiments provide significant evidence for the enhancement of dissolved OC sequestration to 2-line ferrihydrite and suggest the formation of Fe–Ca-OC ternary complexes. Findings of this research will inform modeling of environmental C cycling and have the potential to influence strategies for managing land to minimize OM stabilization.     

Comparative Hydrodynamics during Events along a Barrier Island: Explanation for Overwash

A fairly undeveloped barrier island along the mid-Atlantic coast, Onslow Beach, was exposed to two differing, yet sequential meteorological events in the fall of 2008. The response of the barrier island differed significantly enough to warrant investigation into the causes of aberrant overwash locations. Tropical Storm Hanna generated high significant wave heights for a short period of time and caused overwash events along the southern portion of Onslow Beach. The Nor’easter and subsequent wind shift after TS Hanna generated significant wave heights that were lower than during TS Hanna, yet more locations of overwash were recorded along the beach. Data from NOAA wave buoys and a nearshore deployed AWAC were analyzed to understand the underlying physics behind the recorded differences in barrier island response. These data were also used to validate a coupled hydrodynamic (ADCIRC) and waves (SWAN) model to investigate the alongshore variability. Low frequency variability, on the order of days, and tidal timing of shoreward high significant wave heights contributed to the recorded variability.     

Isotopic and noble gas study of Chalk groundwater in the London Basin, England

The chemical and isotopic composition of groundwater from 52 sites in the London (U.K.) area was determined as part of a project aimed at assessing the spatial variation in the age of Chalk groundwater, and in determining the relationship between fracture and matrix groundwater in this dual porosity system.Systematic changes in groundwater chemistry take place in the downgradient direction in response to several chemical processes. These processes include early concentration by evaporation and congruent dissolution of calcite followed by widespread incongruent dissolution and ion exchange in addition to local oxidation-reduction reactions, gypsum dissolution and saline intrusion. As a result of the above processes, Chalk groundwater follows an evolutionary path from Ca bicarbonate type to Na bicarbonate type.The age of Chalk groundwater was modelled using¹⁴C, δ¹³C,³H, δ²H and δ¹⁸0. There is a general increase in the groundwater age in a downgradient direction with the oldest water found in N central areas of the basin. Groundwater in the unconfined zones and in areas S of the Greenwich fault is almost entirely of unevolved, modem composition. Carbon-14 modelling suggests that Chalk groundwater in the S basin is generally less than 10000 a old while that in the north is generally between 10000 and 25000 a old. The presence of³H in concentrations of up to 7 TU in groundwater which yields ages of several 1000 a, however, indicates that mechanisms exist for the rapid introduction of recent groundwater to the confined aquifer. Results of palaeorecharge temperature determinations using δ²H, δ¹⁸0 and noble gas analytical results suggest that significant Devensian recharge did indeed occur in the aquifer.A model of the development of the Chalk recognizes that it is a classic dual porosity aquifer in which groundwater flow occurs predominantly in the fracture system. The upper 50 m of the aquifer was flushed with fresh water during the 2–3 × 10⁶ a of the Quaternary and therefore meteoric water largely replaced the Tertiary and Cretaceous marine water that previously saturated the system. Most processes which control the chemistry of the groundwater occur in the matrix where the surface area is exceptionally high. Although fracture flow dominates the flow regime, diffusion from the matrix into the fracture porosity controls the chemistry of Chalk groundwater.     

Impacts of hydrous manganese oxide on the retention and lability of dissolved organic matter

Minerals constitute a primary ecosystem control on organic C decomposition in soils, and therefore on greenhouse gas fluxes to the atmosphere. Secondary minerals, in particular, Fe and Al (oxyhydr)oxides—collectively referred to as “oxides” hereafter—are prominent protectors of organic C against microbial decomposition through sorption and complexation reactions. However, the impacts of Mn oxides on organic C retention and lability in soils are poorly understood. Here we show that hydrous Mn oxide (HMO), a poorly crystalline δ-MnO₂, has a greater maximum sorption capacity for dissolved organic matter (DOM) derived from a deciduous forest composite O_i, O_e, and O_a horizon leachate (“O horizon leachate” hereafter) than does goethite under acidic (pH 5) conditions. Nonetheless, goethite has a stronger sorption capacity for DOM at low initial C:(Mn or Fe) molar ratios compared to HMO, probably due to ligand exchange with carboxylate groups as revealed by attenuated total reflectance-Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy and scanning transmission X-ray microscopy–near-edge X-ray absorption fine structure spectroscopy coupled with Mn mass balance calculations reveal that DOM sorption onto HMO induces partial Mn reductive dissolution and Mn reduction of the residual HMO. X-ray photoelectron spectroscopy further shows increasing Mn(II) concentrations are correlated with increasing oxidized C (C=O) content (r = 0.78, P < 0.0006) on the DOM–HMO complexes. We posit that DOM is the more probable reductant of HMO, as Mn(II)-induced HMO dissolution does not alter the Mn speciation of the residual HMO at pH 5. At a lower C loading (2 × 10² μg C m^?2), DOM desorption—assessed by 0.1 M NaH₂PO₄ extraction—is lower for HMO than for goethite, whereas the extent of desorption is the same at a higher C loading (4 × 10² μg C m^?2). No significant differences are observed in the impacts of HMO and goethite on the biodegradability of the DOM remaining in solution after DOM sorption reaches steady state. Overall, HMO shows a relatively strong capacity to sorb DOM and resist phosphate-induced desorption, but DOM–HMO complexes may be more vulnerable to reductive dissolution than DOM–goethite complexes.     

Tracing source and evolution of suspended particles in the Rio Negro Basin (Brazil) using chemical species of iron

Suspended solids found in porewaters obtained in waterlogged soil sequences that included representative laterite–podzol transitions, associated brooks and major rivers of the Rio Negro watershed (Brazil) were studied using electron paramagnetic resonance (EPR) and Fourier-transform infrared spectroscopies. The main goal was to ascertain sources and track the evolution of suspended matter using a ubiquitous chemical species, FeIII complexed to organic matter (FeOM). Three size fractions were separated by tangential-flow (ultra)filtration: particulate (> 0.2 μm), dense (P) and light (Ps), and colloidal (5 kD < Col. < 0.2 μm) fractions. Quantitative results were acquired for Col. and Ps fractions which are predominantly organic in nature.FeOM concentration (in ‰ dry weight) was determined to be relatively low in suspended solids found in black waters from podzol porewaters and brooks whereas in the main rivers it was several times higher. FeOM concentrations were also correlated with Fe(II)/Fe(III) ratios in solution; these ratios were high in podzol porewaters and low in the rivers. Considering that organic complexation of Fe(II) is minor when compared to that of Fe(III), two interpretations were proposed to account for the above observation. First, [FeOM] was assumed to be distributed along a mixing line, with the clear waters from laterites and the black waters from podzols being its end-members. Consequently, [FeOM] can be used to trace the source of suspended material. Second, dissolved Fe(II) from podzol areas was considered to be progressively oxidized as pore waters move towards the mainstream. According to this mechanism, iron is complexed by organic matter or precipitated as oxides, thus producing an evolution of colloidal matter. As a result of these mechanisms' action, both the high production of Fe(II) and organic matter at the waterlogged podzol–laterite transition areas are major factors affecting iron export in the Rio Negro watershed.     

Geochemical characteristics of crustal anatexis during the formation of migmatite at the Southern Sierra Nevada,California

We provide data on the geochemical and isotopic consequences of nonmodal partial melting of a thick Jurassic pelite unit at mid-crustal levels that produced a migmatite complex in conjunction with the intrusion of part of the southern Sierra Nevada batholith at ca. 100 Ma. Field relations suggest that this pelitic migmatite formed and then abruptly solidified prior to substantial mobilization and escape of its melt products. Hence, this area yields insights into potential mid-crustal level contributions of crustal components into Cordilleran-type batholiths. Major and trace-element analyses in addition to field and petrographic data demonstrate that leucosomes are products of partial melting of the pelitic protolith host. Compared with the metapelites, leucosomes have higher Sr and lower Sm concentrations and lower Rb/Sr ratios. The initial ⁸⁷Sr/⁸⁶Sr ratios of leucosomes range from 0.7124 to 0.7247, similar to those of the metapelite protoliths (0.7125–0.7221). However, the leucosomes have a much wider range of initial ε_Nd values, which range from −6.0 to −11.0, as compared to −8.7 to −11.3 for the metapelites. Sr and Nd isotopic compositions of the leucosomes, migmatites, and metapelites suggest disequilibrium partial melting of the metapelite protolith. Based on their Sr, Nd, and other trace-element characteristics, two groups of leucosomes have been identified. Group A leucosomes have relatively high Rb, Pb, Ba, and K₂O contents, Rb/Sr ratios (0.15<Rb/Sr<1.0), and initial ε_Nd values. Group B leucosomes have relatively low Rb, Pb, Ba, and K₂O contents, Rb/Sr ratios (<0.15), and initial ε_Nd values. The low Rb concentrations and Rb/Sr ratios of the group B leucosomes together suggest that partial melting was dominated by water-saturated or H₂O-fluxed melting of quartz + feldspar assemblage with minor involvement of muscovite. Breakdown of quartz and plagioclase with minor contributions from muscovite resulted in low Rb/Sr ratios characterizing both group A and group B leucosomes. In contrast, group A leucosomes have greater contributions from K-feldspar, which is suggested by: (1) their relatively high K concentrations, (2) positive or slightly negative Eu anomalies, and (3) correlation of their Pb and Ba concentrations with K₂O contents. It is also shown that accessory minerals have played a critical role in regulating the partitioning of key trace elements such as Sm, Nd, Nb, and V between melt products and residues during migmatization. The various degrees of parent/daughter fractionations in the Rb–Sr and Sm–Nd isotopic systems as a consequence of nonmodal crustal anatexis would render melt products with distinct isotopic signatures, which could profoundly influence the products of subsequent mixing events. This is not only important for geochemical patterns of intracrustal differentiation, but also a potentially important process in generating crustal-scale as well as individual pluton-scale isotopic heterogeneities.     

Native and artificial radiation-induced defects in montmorillonite. An EPR study

A natural montmorillonite containing radiation-induced defects was studied with Electron Paramagnetic Resonance (EPR) spectroscopy (X- and Q-band). A first dominant native defect, namely native defect 1, is identified. It gives rise to an orthorhombic spectrum with g_x= 2.004 ± 0.005 g_y= 2.010 ± 0.003, g_z= 2.065 ± 0.002. Simulation of the EPR spectrum at X- and Q-band reveals a second native defect with isotropic spectrum at g= 2.019 ± 0.005. Both are electron holes trapped on oxygen atoms of the structure. The native defect 1 is located on an oxygen-silicon bond or a non-bonding orbital parallel to the c* axis. These defects are annealed at 500°C and the half-life determined for native defect 1 is circa 3,000 years. Irradiations with beta rays produced two additional hole centers of lower stability and distinct EPR parameters. Artificial irradiations show that montmorillonite can be used as a dosimeter in a large dose range.     

Wetland Loss,Juvenile Salmon Foraging Performance,and Density Dependence in Pacific Northwest Estuaries

During the transition of juveniles from fresh water to estuarine and coastal environments, the survival of Pacific salmon (Oncorhynchus spp.) can be strongly size selective and cohort abundance is partly determined at this stage. Because quantity and quality of food influence juvenile salmon growth, high rates of prey and energy acquisition during estuarine residence are important for survival. Human activities may have affected the foraging performance of juvenile salmon in estuaries by reducing the area of wetlands and by altering the abundance of salmon. To improve our understanding of the effects of wetland loss and salmon density on juvenile salmon foraging performance and diet composition in estuaries, we assembled Chinook salmon (Oncorhynchus tshawytscha) diet and density data from nine US Pacific Northwest estuaries across a gradient of wetland loss. We evaluated the influence of wetland loss and density on juvenile Chinook salmon instantaneous ration and energy ration, two measures of foraging performance, and whether the effect of density varied among estuaries with different levels of wetland loss. We also assessed the influence of wetland loss and other explanatory variables on salmon diet composition. There was no evidence of a direct effect of wetland loss on juvenile salmon foraging performance, but wetland loss appeared to mediate the effect of density on salmon foraging performance and alter salmon diet composition. Specifically, density had no effect on foraging performance in the estuaries with less than 50 % wetland loss but had a negative effect on foraging performance in the estuaries with greater than 50 % wetland loss. These results suggest that habitat loss may interact with density to constrain the foraging performance of juvenile Chinook salmon, and ultimately their growth, during a life history stage when survival can be positively correlated with growth and size.