Elm bark beetle in Holocene peat deposits and the northwest European elm decline

The elm decline of 5000 ¹⁴C yr ago has been the most widely discussed phenomenon in post‐glacial vegetation history. This pan‐European reduction of elm populations, echoed in the decimation of elmwoods in Europe during the twentieth century, has attracted a series of interrelated hypotheses involving climate change, human activity, disease and soil deterioration. The elm bark beetle (Scolytus scolytus L.) is an essential component of disease explanations. We present evidence for the presence of the beetle over a prolonged period (ca. 7950–4910 yr BP [8800–5660 cal. yr BP]) from a lowland raised mire deposit in northeast Scotland, with its final appearance at this site, and the first and only appearance in another mire of a single scolytid find, around the time of the elm decline. The subfossil S. scolytus finds are not only the first from Scotland, but they also represent the most comprehensive sequence of finds anywhere. Copyright © 2004 John Wiley & Sons, Ltd.     

High resolution paleoenvironmental and chronological investigations of Norse landnám at Tasiusaq, Eastern Settlement, Greenland

High-resolution paleoenvironmental data from a peat profile with a small pollen source area are used to reconstruct the impacts of landnám on vegetation and soils at a Norse farm complex (∅2 at Tasiusaq) comprising two farms in the Eastern Settlement of Greenland. Analyses include the AMS ¹⁴C dating of plant macrofossil samples and the use of Bayesian radiocarbon calibration to construct improved age-depth models for Norse cultural horizons. The onset of a regional landnám may be indicated by the clearance of Betula pubescens woodland immediately prior to local settlement. The latter is dated to AD 950-1020 (2σ) and is characterised by possible burning of Betula glandulosa scrub to provide grassland pasture for domestic stock. Clearance and grazing resulted in accelerated levels of soil erosion at a westerly farm. This was followed by an easterly migration of settlement and agriculture. Site constraints prevent an assessment of the demise of the easterly farm, but pressures of overgrazing and land degradation may have been the major factors responsible for the abandonment of the earlier farm.     

The geochemistry of gem opals as evidence of their origin

Seventy-seven gem opals from ten countries were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) through a dilution process, in order to establish the nature of the impurities. The results are correlated to the mode of formation and physical properties and are instrumental in establishing the geographical origin of a gem opal. The geochemistry of an opal is shown to be dependant mostly on the host rock, at least for examples from Mexico and Brazil, even if modified by weathering processes. In order of decreasing concentration, the main impurities present are Al, Ca, Fe, K, Na, and Mg (more than 500 ppm). Other noticeable elements in lesser amounts are Ba, followed by Zr, Sr, Rb, U, and Pb. For the first time, geochemistry helps to discriminate some varieties of opals. The Ba content, as well as the chondrite-normalized REE pattern, are the keys to separating sedimentary opals (Ba > 110 ppm, Eu and Ce anomalies) from volcanic opals (Ba < 110 ppm, no Eu or Ce anomaly). The Ca content, and to a lesser extent that of Mg, Al, K and Nb, helps to distinguish gem opals from different volcanic environments. The limited range of concentrations for all elements in precious (play-of-color) compared to common opals, indicates that this variety must have very specific, or more restricted, conditions of formation. We tentatively interpreted the presence of impurities in terms of crystallochemistry, even if opal is a poorly crystallized or amorphous material. The main replacement is the substitution of Si⁴⁺ by Al³⁺ and Fe³⁺. The induced charge imbalance is compensated chiefly by Ca²⁺, Mg²⁺, Mn²⁺, Ba²⁺, K⁺, and Na⁺. In terms of origin of color, greater concentrations of iron induce darker colors (from yellow to “chocolate brown”). This element inhibits luminescence for concentrations above 1000 ppm, whereas already a low content in U (≤ 1 ppm) induces a green luminescence.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Evidence for crustal degassing of CF4 and SF6 in Mojave Desert groundwaters

Dissolved tetrafluoromethane (CF₄) and sulfur hexafluoride (SF₆) concentrations were measured in groundwater samples from the Eastern Morongo Basin (EMB) and Mojave River Basin (MRB) located in the southern Mojave Desert, California. Both CF₄ and SF₆ are supersaturated with respect to equilibrium with the preindustrial atmosphere at the recharge temperatures and elevations of the Mojave Desert. These observations provide the first in situ evidence for a flux of CF₄ from the lithosphere. A gradual basin-wide enhancement in dissolved CF₄ and SF₆ concentrations with groundwater age is consistent with release of these gases during weathering of the surrounding granitic alluvium. Dissolved CF₄ and SF₆ concentrations in these groundwaters also contain a deeper crustal component associated with a lithospheric flux entering the EMB and MRB through the underlying basement. The crustal flux of CF₄, but not of SF₆, is enhanced in the vicinity of local active fault systems due to release of crustal fluids during episodic fracture events driven by local tectonic activity. When fluxes of CF₄ and SF₆ into Mojave Desert groundwaters are extrapolated to the global scale they are consistent, within large uncertainties, with the fluxes required to sustain the preindustrial atmospheric abundances of CF₄ and SF₆.     

Iron isotope fractionation in subterranean estuaries

Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redox-stratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ⁵⁶Fe values between 0.3 and −1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ⁵⁶Fe values down to −5‰. These low δ⁵⁶Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Fe-oxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ⁵⁶Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ⁵⁶Fe values between −2 and 1.5‰. The relationship between Fe concentration and δ⁵⁶Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ⁵⁶Fe values relative to river values.     

Temporal variability in phytodetritus and megabenthic activity at the seabed in the deep Northeast Atlantic

We report a ten-year study of the abundance and activity of megabenthos on the Porcupine Abyssal Plain, northeast Atlantic, together with observations on the occurrence of phytodetritus at the deep-sea floor (4850 m). Using the Southampton Oceanography Centre time-lapse camera system, ‘Bathysnap’, we have recorded a radical change in the abundance and activity of megabenthos between the two periods of study (1991–1994 and 1997–2000). In 1991–1994, the larger megabenthos occurred at an abundance of c. 71.6/ha and were dominated by large holothurians. In addition, there were very substantial populations of smaller megabenthic ophiuroids (c. 4979/ha). Together, the total megabenthos are estimated to track over some 17 cm²/m²/d (exploiting 100% of the surface of the seabed in c. 2.5 years). In 1997–2000, the larger megabenthos increased to an abundance of c. 204/ha and were joined by exceptional numbers of a small holothurian species (Amperima rosea, 6457/ha) and ophiuroids (principally Ophiocten hastatum, 53,539/ha). The total megabenthos population was tracking at an estimnated rate of c. 247 cm²/m²/d (exploiting 100% of seabed in just 6 weeks). Coincident with these increases in the abundance and activity of the megabenthos, there were apparently no mass depositions of aggregated phytodetritus to the seabed in the summers of 1997–1999. Mass occurrences of phytodetritus had been noted during the summer months of the three years previously studied (1991, 1993 and 1994), with covering between 50 and 96% of the sediment surface. There is a statistically significant (p<0.02) negative correlation between maximum extent of this seabed cover of phytodetritus and seabed tracking by megabenthos. Additional studies [Lampitt et al., Progr. Ocean. 50 (2001)], indicate that there were no substantial changes in surface ocean primary productivity, in export flux, or in the composition of the flux that might otherwise account for the apparent absence of observable concentrations of phytodetritus during the summers of 1997–1999. We postulate that the marked increase in megabenthic tracking activity resulted in the removal (via consumption, disaggregation, burial etc.) of the bulk of the incoming phytodetrital flux during these years. A simple conceptual model, based on the apparent phytodetrital fluxes observed in 1991 and 1993, suggests that the megabenthos tracking rates estimated for 1997–1999 are sufficient to account for near-total removal of this flux. However, we are not able to estimate other processes removing phytodetritus (i.e. other elements of the benthos) that may also have increased between 1991–1994 and 1997–1999. Other independent studies [e.g. Ginger et al., Progr. Ocean. 50 (2001)] of flux constituents support the possibility that just a few species of megabenthos (e.g. A. rosea, and O. hastatum) could well have consumed a major proportion of the incoming flux and so substantially modified the composition of the organic matter available to other components of the benthos.     

Sediment-starved sand ridges on a mixed carbonate/siliciclastic inner shelf off west-central Florida

High-resolution side-scan mosaics, sediment analyses, and physical process data have revealed that the mixed carbonate/siliciclastic, inner shelf of west-central Florida supports a highly complex field of active sand ridges mantled by a hierarchy of bedforms. The sand ridges, mostly oriented obliquely to the shoreline trend, extend from 2 km to over 25 km offshore. They show many similarities to their well-known counterparts situated along the US Atlantic margin in that both increase in relief with increasing water depth, both are oriented obliquely to the coast, and both respond to modern shelf dynamics. There are significant differences in that the sand ridges on the west-central Florida shelf are smaller in all dimensions, have a relatively high carbonate content, and are separated by exposed rock surfaces. They are also shoreface-detached and are sediment-starved, thus stunting their development. Morphological details are highly distinctive and apparent in side-scan imagery due to the high acoustic contrast. The seafloor is active and not a relict system as indicated by: (1) relatively young AMS ¹⁴C dates (<1600 yr BP) from forams in the shallow subsurface (1.6 meters below seafloor), (2) apparent shifts in sharply distinctive grayscale boundaries seen in time-series side-scan mosaics, (3) maintenance of these sharp acoustic boundaries and development of small bedforms in an area of constant and extensive bioturbation, (4) sediment textural asymmetry indicative of selective transport across bedform topography, (5) morphological asymmetry of sand ridges and 2D dunes, and (6) current-meter data indicating that the critical threshold velocity for sediment transport is frequently exceeded. Although larger sand ridges are found along other portions of the west-central Florida inner shelf, these smaller sand ridges are best developed seaward of a major coastal headland, suggesting some genetic relationship. The headland may focus and accelerate the N–S reversing currents. An elevated rock terrace extending from the headland supports these ridges in a shallower water environment than the surrounding shelf, allowing them to be more easily influenced by currents and surface gravity waves. Tidal currents, storm-generated flows, and seasonally developed flows are shore-parallel and oriented obliquely to the NW–SE trending ridges, indicating that they have developed as described by the Huthnance model. Although inner shelf sand ridges have been extensively examined elsewhere, this study is the first to describe them in a low-energy, sediment-starved, dominantly mixed siliciclastic/carbonate sedimentary environment situated on a former limestone platform.