Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

A geochemical investigation of hydrologically derived threats to rare biota: the Drummond Nature Reserve, Western Australia

The Drummond Nature Reserve (DNR), a high-value conservation area 100?km northeast of Perth, Western Australia, contains two rare freshwater claypans and a diverse range of rare and threatened vascular plants. Groundwater/surface-water interactions were investigated via isotopic (??¹⁸O and ??D) and major ion analysis. The groundwater chemical and isotope analyses combined with nutrient data allowed for the assessment of potential hydrologically derived threats to the claypans and their associated conservation values. Groundwater composition is typically Na?CCl to Na?CMg?CCl; whereas the claypan??s ephemeral fresh surface water is Na?CCl?CHCO₃. Distinct ??¹⁸O and ??D isotopic signatures for the claypan surface waters and adjoining groundwaters indicate that there currently is minimal connection between these two hydrological systems. Hence the current threat to the freshwater claypans and associated biota from rising saline and acidic groundwater is minimal. Elevated nutrient (N) levels identified in groundwaters along the reserve??s western boundary may be linked to fertiliser regimes employed in adjoining agricultural lands. The ecosystem associated with the southwest claypan is particularly vulnerable to N and P inputs via surface-water flows, which could cause algal blooms, vegetation degradation and weed infestation.     

Formation of Zn–Ca phyllomanganate nanoparticles in grass roots

It is now well established that a number of terrestrial and aquatic microorganisms have the capacity to oxidize and precipitate Mn as phyllomanganate. However, this biomineralization has never been shown to occur in plant tissues, nor has the structure of a natural Mn(IV) biooxide been characterized in detail. We show that the graminaceous plant Festuca rubra (red fescue) produces a Zn-rich phyllomanganate with constant Zn:Mn and Ca:Mn atomic ratios (0.46 and 0.38, respectively) when grown on a contaminated sediment. This new phase is so far the Zn-richest manganate known to form in nature (chalcophanite has a Zn:Mn ratio of 0.33) and has no synthetic equivalent. Visual examination of root fragments under a microscope shows black precipitates about ten to several tens of microns in size, and their imaging with backscattered and secondary electrons demonstrates that they are located in the root epidermis. In situ measurements by Mn and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) with a micro-focused beam can be quantitatively described by a single-phase model consisting of Mn(IV) octahedral layers with 22% vacant sites capped with tetrahedral and octahedral Zn in proportions of 3:1. The layer charge deficit is also partly balanced by interlayer Mn and Ca. Diffracting crystallites have a domain radius of 33 Å in the ab plane and contain only 1.2 layers (8.6 Å) on average. Since this biogenic Mn oxide consists mostly of isolated layers, basal 00l reflections are essentially absent despite its lamellar structure. Individual Mn layers are probably held together in the Mn–Zn precipitates by stabilizing organic molecules. Zinc biomineralization by plants likely is a defense mechanism against toxicity induced by excess concentrations of this metal in the rhizosphere.     

First record of a Cretaceous cheilostome bryozoan from Hokkaido, Japan

A small collection of recrystallised, encrusting colonies of a single species from the Mikasa Formation (lower Middle Cenomanian), represents the first record of cheilostome (malacostegan or anascan) bryozoans from Hokkaido, Japan.     

The creative reconstruction of the Internet: Google and the privatization of cyberspace and DigiPlace

The Internet has often been portrayed as the ultimate leveler of information where existing hierarchies of power and privilege are undermined by meritocracy. Some websites and functions are, however, more equal than others. In particular, search engines such as Google have been a key means to construct meaning out of disorder. This ordering (or enclosing of the Internet commons), however, comes at a cost as a location within the top 10 Google search results, marks the boundary (albeit a fluid one) between the core and the periphery of the Internet. The recent incorporation of spatial elements into the Google indexing raises fresh and geographically relevant concerns. This article focuses on the construction, access and use of Google derived rankings to deploy geo-referenced information in the physical environment and the way this melding of code and place affects how people interact with place. Using the theoretical concept of DigiPlace this article analyzes how Google Maps and Google Earth are structured and shape what appears (and what does not) in cyberspace and DigiPlace. Of particular concern are the implications of a private corporation controlling this new space.     

Pattern,style and timing of British–Irish Ice Sheet advance and retreat over the last 45 000 years: evidence from NW Scotland and the adjacent continental shelf

Predicting the future response of ice sheets to climate warming and rising global sea level is important but difficult. This is especially so when fast-flowing glaciers or ice streams, buffered by ice shelves, are grounded on beds below sea level. What happens when these ice shelves are removed? And how do the ice stream and the surrounding ice sheet respond to the abruptly altered boundary conditions? To address these questions and others we present new geological, geomorphological, geophysical and geochronological data from the ice-stream-dominated NW sector of the last British–Irish Ice Sheet (BIIS). The study area covers around 45 000 km² of NW Scotland and the surrounding continental shelf. Alongside seabed geomorphological mapping and Quaternary sediment analysis, we use a suite of over 100 new absolute ages (including cosmogenic-nuclide exposure ages, optically stimulated luminescence ages and radiocarbon dates) collected from onshore and offshore, to build a sector-wide ice-sheet reconstruction combining all available evidence with Bayesian chronosequence modelling. Using this information we present a detailed assessment of ice-sheet advance/retreat history, and the glaciological connections between different areas of the NW BIIS sector, at different times during the last glacial cycle. The results show a highly dynamic, partly marine, partly terrestrial, ice-sheet sector undergoing large size variations in response to sub-millennial-scale climatic (Dansgaard–Oeschger) cycles over the last 45 000 years. Superimposed on these trends we identify internally driven instabilities, operating at higher frequency, conditioned by local topographic factors, tidewater dynamics and glaciological feedbacks during deglaciation. Specifically, our new evidence indicates extensive marine-terminating ice-sheet glaciation of the NW BIIS sector during Greenland Stadials 12 to 9 – prior to the main ‘Late Weichselian’ ice-sheet glaciation. After a period of restricted glaciation, in Greenland Interstadials 8 to 6, we find good evidence for rapid renewed ice-sheet build-up in NW Scotland, with the Minch ice-stream terminus reaching the continental shelf edge in Greenland Stadial 5, perhaps only briefly. Deglaciation of the NW sector took place in numerous stages. Several grounding-zone wedges and moraines on the mid- and inner continental shelf attest to significant stabilizations of the ice-sheet grounding line, or ice margin, during overall retreat in Greenland Stadials 3 and 2, and to the development of ice shelves. NW Lewis was the first substantial present-day land area to deglaciate, in the first half of Greenland Stadial 3 at a time of globally reduced sea-level c. 26 kabp , followed by Cape Wrath at c. 24 kabp. The topographic confinement of the Minch straits probably promoted ice-shelf development in early Greenland Stadial 2, providing the ice stream with additional support and buffering it somewhat from external drivers. However, c. 20–19 kabp , as the grounding-line migrated into shoreward deepening water, coinciding with a marked change in marine geology and bed strength, the ice stream became unstable. We find that, once underway, grounding-line retreat proceeded in an uninterrupted fashion with the rapid loss of fronting ice shelves – first in the west, then the east troughs – before eventual glacier stabilization at fjord mouths in NW Scotland by ~17 kabp. Around the same time, ~19–17 kabp , ice-sheet lobes readvanced into the East Minch – possibly a glaciological response to the marine-instability-triggered loss of adjacent ice stream (and/or ice shelf) support in the Minch trough. An independent ice cap on Lewis also experienced margin oscillations during mid-Greenland Stadial 2, with an ice-accumulation centre in West Lewis existing into the latter part of Heinrich Stadial 1. Final ice-sheet deglaciation of NW mainland Scotland was punctuated by at least one other coherent readvance at c. 15.5 kabp , before significant ice-mass losses thereafter. At the glacial termination, c. 14.5 kabp , glaciers fed outwash sediment to now-abandoned coastal deltas in NW mainland Scotland around the time of global Meltwater Pulse 1A. Overall, this work on the BIIS NW sector reconstructs a highly dynamic ice-sheet oscillating in extent and volume for much of the last 45 000 years. Periods of expansive ice-sheet glaciation dominated by ice-streaming were interspersed with periods of much more restricted ice-cap or tidewater/fjordic glaciation. Finally, this work indicates that the role of ice streams in ice-sheet evolution is complex but mechanistically important throughout the lifetime of an ice sheet – with ice streams contributing to the regulation of ice-sheet health but also to the acceleration of ice-sheet demise via marine ice-sheet instabilities.     

Spatial and isotopic analysis of watershed soil loss and reservoir sediment accumulation rates in Lake Anna, Virginia, USA

Soil erosion and associated sedimentation are a threat to the sustainable use of surface water resources through the loss of volume storage capacity and conveyance of pollutants to receiving water bodies. The RUSLE2 empirical model and isotopic sediment core analyses were used to evaluate watershed erosion and reservoir sediment accumulation rates for Lake Anna, in Central Virginia. A sediment flux rate of 66,000 Mg/year was estimated from the upper basin and land use was determined to be the primary factor contributing to soil erosion. Barren lands and agricultural activities were estimated to contribute the most sediment (>20 Mg/ha/year), whereas forested and herbaceous landscapes were less likely to erode (<0.3 Mg/ha/year). Eleven separate ²¹⁰Pb-based estimates of sediment accumulation were used to construct reservoir-scale sedimentation rates. Sedimentation rates in the upper reaches of the reservoir were variable, ranging from 2.3 to 100 Mg/ha/year, with a median rate of 8.4 Mg/ha/year. Historical sedimentation showed an increase in annual accumulation from 1972 to present. Based on these data the reservoir has experienced a 2% loss of volume storage capacity since impoundment in 1972. Results from this study indicate that Lake Anna is not currently experiencing excessive sedimentation and erosion problems. However, the predominance of highly erosive soils (soil erodibility factor >0.30) within the watershed makes this system highly vulnerable to future anthropogenic stressors.