Cleaning of lake sediment samples for diatom oxygen isotope analysis

Detrital grain contamination in a diatom sample can considerably influence the δ¹⁸O_diatom signal. In order to obtain a meaningful signal, pure samples must be used. This can be achieved via a series of cleaning stages including organic and carbonate material removal, sieving, differential settling and heavy liquid separation. The method described here works best for sediments with >20% diatom content. Based on testing various clean-up methods, we propose a sequence of four clean-up stages to produce pure diatom samples from a range of lake sediments types starting with a few grams of sediment. The diatom content and the oxygen isotope composition of the samples at each stage were measured in order to assess the effect of differential amounts of contamination. Results show that a four stage clean-up is necessary to produce clean diatom samples and that contamination by silt and clay causes lower δ¹⁸O values.     

Geochemical and biological consequences of groundwater augmentation in lakes of west-central Florida (USA)

We studied sediment cores from four Florida (USA) lakes that have received groundwater hydrologic supplements (augmentation) for >30 years to maintain lake stage. Top samples (0–4 cm) from sediment cores taken in Lakes Charles, Saddleback, Little Hobbs, and Crystal had ²²⁶Ra activities of 44.9, 17.5, 7.6, and 8.5 dpm g⁻¹, respectively, about an order of magnitude greater than values in deeper, older deposits. The surface sample from Lake Charles yielded the highest ²²⁶Ra activity yet reported from a Florida lake core. Several lines of evidence suggest that groundwater augmentation is responsible for the high ²²⁶Ra activities in recent sediments: (1) ²²⁶Ra activity in cores increased recently, (2) the Charles, Crystal, and Saddleback cores display ²²⁶Ra/²¹⁰Pb disequilibrium at several shallow depths, suggesting ²²⁶Ra entered the lakes in dissolved form, (3) cores show recent increases in Ca, which, like ²²⁶Ra, is abundant in augmentation groundwater, and (4) greater Sr concentrations are associated with higher ²²⁶Ra activities in recent Charles and Saddleback sediments. Sr concentrations in Eocene limestones of the deep Floridan Aquifer are high relative to Sr concentrations in surficial quartz sands around the lakes. Historical water quality inferences for the lakes were based on diatom assemblages in sediments. Recent alkalization in Lakes Charles, Saddleback, Little Hobbs, and Crystal was inferred from weighted-averaging calibration (WACALIB). The lakes also show recent trophic state increases based on WACALIB-derived estimates for limnetic total P. Although residential and agricultural sources might contribute to increased P loading, P in augmentation waters probably has had significant influence on eutrophication. Dystrophic diatoms were abundant in the early history of Lakes Saddleback, Little Hobbs, and Crystal, which suggests that these lakes contained more tannic waters during the past than at present, perhaps as a consequence of greater inflows from surrounding wetlands. Ionic content of lake waters increased, as indicated by diatom autecological analysis. Recent geochemical and biological changes detected in cores from these lakes probably are a result of deliberate groundwater augmentation, although inputs of groundwater pumped for agricultural and residential development in the watersheds also might have contributed to limnological changes.     

Limnology of Two Antarctic Epishelf Lakes and their Potential to Record Periods of Ice Shelf Loss

George VI Ice Shelf is the largest ice shelf on the western side of the Antarctic Peninsula and its northern margin marks the southern most latitudinal limit of recent ice shelf retreat. As part of a project to reconstruct the long-term (Holocene) history of George VI Ice Shelf we studied two epishelf lakes impounded by the ice shelf at Ablation Point, on the east coast of Alexander Island. These lakes, Moutonnée and Ablation, are stratified water bodies with a lower marine layer and an upper freshwater layer. To determine if their sediment records could be used to detect past changes in the presence or absence of the ice shelf it was necessary to describe their present-day limnology and sedimentology. We measured water column chemistry and sampled the water column and sediments of the lakes along vertical and horizontal transects. We analysed these samples for diatoms, stable isotopes (δ¹⁸O, δ²H, δ¹³C_DIC, δ¹³C_org), geochemistry (TOC, TN, C/N ratios) and physical sedimentology (grain-size). This was supplemented by chemical and biological reference data from the catchments. Results showed that the water columns of both lakes are nutrient limited and deficient in phytoplankton. Benthic productivity is low and decreases with depth. Comparison of water column chemistry with an earlier survey shows a net increase in the thickness of the freshwater layer in Moutonnée Lake between 1973 and 2001, which could indicate that George VI Ice Shelf has thinned during this period. However, a similar trend was not observed in Ablation Lake (5 km to the north) and an alternative explanation is that the changes are a seasonal phenomena. Data from the surface sediment transects identified a number of proxies that respond to the present day stratification of the water column including diatom species composition, stable isotopes and geochemistry, particularly in Moutonnée Lake. Collectively these data have been used to develop a conceptual model for determining past ice shelf configuration in epishelf lakes. Specifically, periods of past ice shelf loss, and the removal of the ice dam, would see the present stratified epishelf lake replaced by a marine embayment. It is suggested that this change would leave a clear signature in the lake sediment record, notably the deposition of an exclusively marine biological assemblage, increased ice rafted debris and δ¹³C_org values that are indicative of marine derived organic matter. These authors contributed equally to this work     

Modelling surface‐water depression storage in a Prairie Pothole Region

In this study, the Precipitation‐Runoff Modelling System (PRMS) was used to simulate changes in surface‐water depression storage in the 1,126‐km² Upper Pipestem Creek basin located within the Prairie Pothole Region of North Dakota, USA. The Prairie Pothole Region is characterized by millions of small water bodies (or surface‐water depressions) that provide numerous ecosystem services and are considered an important contribution to the hydrologic cycle. The Upper Pipestem PRMS model was extracted from the U.S. Geological Survey's (USGS) National Hydrologic Model (NHM), developed to support consistent hydrologic modelling across the conterminous United States. The Geospatial Fabric database, created for the USGS NHM, contains hydrologic model parameter values derived from datasets that characterize the physical features of the entire conterminous United States for 109,951 hydrologic response units. Each hydrologic response unit in the Geospatial Fabric was parameterized using aggregated surface‐water depression area derived from the National Hydrography Dataset Plus, an integrated suite of application‐ready geospatial datasets. This paper presents a calibration strategy for the Upper Pipestem PRMS model that uses normalized lake elevation measurements to calibrate the parameters influencing simulated fractional surface‐water depression storage. Results indicate that inclusion of measurements that give an indication of the change in surface‐water depression storage in the calibration procedure resulted in accurate changes in surface‐water depression storage in the water balance. Regionalized parameterization of the USGS NHM will require a proxy for change in surface‐storage to accurately parameterize surface‐water depression storage within the USGS NHM.     

Bulk organic δC and C/N as indicators for sediment sources in the Pearl River delta and estuary,southern China

Preservation of organic matter in estuarine and coastal areas is an important process in the global carbon cycle. This paper presents bulk δ¹³C and C/N of organic matter from source to sink in the Pearl River catchment, delta and estuary, and discusses the applicability of δ¹³C and C/N as indicators for sources of organic matter in deltaic and estuarine sediments. In addition to the 91 surface sediment samples, other materials collected in this study cover the main sources of organic material to estuarine sediment. These are: terrestrial organic matter (TOM), including plants and soil samples from the catchment; estuarine and marine suspended particulate organic carbon (POC) from both summer and winter. Results show that the average δ¹³C of estuarine surface sediment increases from −25.0 ± 1.3‰ in the freshwater environment to −21.0 ± 0.2‰ in the marine environment, with C/N decreasing from 15.2 ± 3.3 to 6.8 ± 0.2. In the source areas, C₃ plants have lower δ¹³C than C₄ plants (−29.0 ± 1.8‰ and −13.1 ± 0.5‰ respectively). δ¹³C increases from −28.3 ± 0.8‰ in the forest soil to around −24.1‰ in both riverbank soil and mangrove soil due to increasing proportion of C₄ grasses. The δ¹³C_POC increases from −27.6 ± 0.8‰ in the freshwater areas to −22.4 ± 0.5‰ in the marine-brackish-water areas in winter, and ranges between −24.0‰ in freshwater areas and −25.4‰ in brackish-water areas in summer. Comparison of the δ¹³C and C/N between the sources and sink indicates a weakening TOM and freshwater POC input in the surface sedimentary organic matter seawards, and a strengthening contribution from the marine organic matter. Thus we suggest that bulk organic δ¹³C and C/N analysis can be used to indicate sources of sedimentary organic matter in estuarine environments. Organic carbon in surface sediments derived from anthropogenic sources such as human waste and organic pollutants from industrial and agricultural activities accounts for less than 10% of the total organic carbon (TOC). Although results also indicate elevated δ¹³C of sedimentary organic matter due to some agricultural products such as sugarcane, C₃ plants are still the dominant vegetation type in this area, and the bulk organic δ¹³C and C/N is still an effective indicator for sources of organic matter in estuarine sediments.     

Methane in the southern North Sea: Sources, spatial distribution and budgets

Measurements of methane (CH₄) so far have always shown supersaturation in the entire North Sea relative to the atmospheric partial pressure and the distribution of surface CH₄ reveals a distinct increase towards the shore. Since North Sea sediments presumably are an insignificant source for CH₄ the coastal contribution via rivers and tidal flats gains in importance.In this work, CH₄ data from the River Weser, the back barrier tidal flats of Spiekeroog Island (NW Germany), and the German Bight are presented. Results from the River Weser are compared to other rivers draining into the German Bight. Measurements in the tidal flat area of Spiekeroog Island highlight this ecosystem as an additional contributor to the overall CH₄ budget of the southern North Sea. A tidally driven CH₄ pattern is observed for the water column with maximum values during low tide. Tidal flat sediments turn out to be the dominating source because pore waters discharged during low tide are highly enriched in CH₄. In contrast, the freshwater contribution to the tidal flats by small coastal tributaries has almost no impact on water column CH₄ concentrations. The CH₄ level seems to be disturbed irregularly by wind forcing due to elevated degassing and prevention of advective flow when tidal flats remain covered by water.Based on our data, two model calculations were used to estimate the impact of tidal flats on the CH₄ budget in the German Bight. Our results demonstrate that the back barrier tidal flats of the east Frisian Wadden Sea contribute CH₄ in an order of magnitude between the Wash estuary and River Elbe and thus have to be considered in budget calculations.     

Volatiles in a peralkaline system: Abiogenic hydrocarbons and F–Cl–Br systematics in the naujaite of the Ilímaussaq intrusion, South Greenland

Agpaitic rocks comprise most of the exposed part of the 1.16 Ga old, 8 × 17 km large and about 1700 m thick Ilímaussaq intrusion in South Greenland. Within these, more than 600 m thick sequence of sodalite-rich “naujaites” (mainly sodalite + arfvedsonite + alkali feldspar + nepheline + eudialyte + aenigmatite) are interpreted as a sodalite flotation cumulate. Sodalites show two to three different zones in cathodoluminescence (CL) and at least two zones in thin sections. The CL zones can be related to chemical differences detectable by electron microprobe, whereas relations with optical zonations are less obvious. Compositional trends in sodalite reflect trends in the evolution of volatile contents in the melt. The sodalite at Ilímaussaq is almost free of Ca and closely corresponds to the pure Na–Cl sodalite endmember with about 7 wt.% of Cl; S contents reach up to 0.9 wt.%. Cl/Br ratios range from 500 to 1700. Raman spectroscopy shows that S is present as [SO₄]²⁻ in sodalite, although sphalerite (ZnS) is a stable phase in naujaites. Peralkalinity and fO₂ conditions allow S²⁻ and [SO₄]²⁻ to be present contemporaneously.

The whole naujaite sequence is divided into two parts, an upper part with low, homogeneous S contents and Cl/Br ratios in the sodalite cores, and a lower part with strongly variable and higher S contents and with Cl/Br ratios, which are decreasing downwards. The details of the S content and the Cl/Br ratio evolution show that sodalite strongly influences the halogen contents of the melt by scavenging Cl and Br.

The naujaites were formed from a highly reduced, halogen-rich magma in equilibrium with magmatic methane at about 800 °C, which, upon ascent, cooling and fractionation, exsolved an aqueous fluid phase. Both fluids were trapped in separate inclusions indicating their immiscibility.

Micrometer-sized aegirine crystals and primary hydrocarbon-bearing inclusions are abundant in the crystal cores. The inclusions were trapped at pressures up to 4 kbar, although the emplacement pressure of the intrusion is about 1 kbar. This indicates growth of the sodalite during melt ascent and a very effective mechanism of trace element scavenging during sodalite growth. Sodalite rims are devoid of aegirine or primary hydrocarbon inclusions and probably reflect the emplacement stage.     

Non-conservative behaviour of molybdenum in coastal waters: Coupling geochemical, biological, and sedimentological processes

Non-conservative behaviour of dissolved Mo was observed during specific time periods in the water column of the Wadden Sea of NW Germany. In July 2005 dissolved Mo declined within 36 h from a level only slightly below seawater (82 nM) to a minimum value of 30 nM, whereas in August 2002 dissolved Mo revealed a tidal cyclicity with maximum values up to 158 nM at low tide. In contrast, cruises in August 2003 and 2004 displayed an almost conservative behaviour of Mo. The decrease in dissolved Mo during July 2005 and elevated values in August 2002 were accompanied by Mo enrichments on aggregates in the water column of the Wadden Sea. Along with Mo, dissolved Mn showed unusual concentration patterns in July 2005, with values distinctly below the common summer level (by a factor of five). A direct relation between the loss of Mo and scavenging by freshly formed MnO_x phases could not be inferred from our data because both metals revealed inverse patterns. Parallel to decreasing dissolved Mo concentrations dissolved Mn showed an increasing trend while particulate Mn decreased. Such finding is compatible with the formation of oxygen-depleted zones in aggregates, which provide suitable conditions for the rapid fixation of Mo and parallel release of Mn by chemically and/or microbially mediated processes. Our assumption is supported by biological (e.g. number of aggregate-associated bacteria) and sedimentological (e.g. aggregate abundance and size) parameters. The production of organic components (e.g. TEP) during breakdown of an algae bloom in July 2005 led to the formation of larger Mo-enriched aggregates, thus depleting the water column in dissolved Mo. After deposition on and incorporation into sandy tidal flats these aggregates are rapidly decomposed by microbial activity. Pore water profiles document that during microbial decomposition of these aggregates, substantial amounts of Mo are released and may replenish and even enrich Mo in the open water column. We postulate a conceptual model for the observed non-conservative behaviour of Mo in coastal waters, which is based on the tight coupling of geochemical, biological, and sedimentological processes.