The timing of Quaternary calcrete development in semi-arid southeast Spain: Investigating the role of climate on calcrete genesis

Quaternary-aged calcrete horizons are common weathering products in arid and semi-arid regions. It is, however, unclear how calcrete forming processes respond to the major oscillations in climate that occur over the Quaternary period. This paper presents a U-series-based calcrete age database from the Sorbas basin, southeast Spain. The study constructs an age frequency distribution of these ages which is consequently compared to a range of palaeoenvironmental records from the Mediterranean. The age distribution presented here suggests that the formation of pedogenic calcrete horizons in the Sorbas basin primarily occurs during 'warm' isotope stages (MIS 1 and 5), with very few calcrete ages occurring during cold glacial/stadial stages (MIS 2, 3 and 4). It is suggested that this is a function of the environments that existed during 'warm' isotope stages being more conducive to calcrete development than those that existed during cold climate episodes. In a semi-arid region such as the Sorbas basin it is likely that increased aridity during glacial stages, coupled with reduced vegetation and accelerated landscape instability, was crucial in reducing rates of calcrete formation. In a semi-arid region such as southeast Spain, calcrete formation during the Quaternary, therefore, oscillates with climate change but is primarily a "warm" episode phenomenon. It is suggested that further studies are required to see how calcrete genesis responds to environmental change in more humid parts of the Mediterranean. (C) 2009 Elsevier B.V. All rights reserved.

Interpreting the response of a dryland river system to Late Quaternary climate change

A U-series calcrete chronology has been constructed for three Late Quaternary terrace units, termed the D1, D2 and D3 terraces in age descending order, from the Rio Aguas river system of the Sorbas basin, southeast Spain. The D1 terrace formed between 30,300 +/- 4400 year BP and 12,140 +/- 360 year BP, correlating well with the Last Glacial Maximum when rates of sediment supply would have increased greatly, because of higher rates of weathering, reduced vegetation cover and weak soil development. The D2 terrace formed between 12,800 +/- 1100 year BP and 9,600 +/- 530 year BP, correlating well with the Younger Dryas event. The D3 terrace could only be poorly constrained to the early Holocene and no unequivocal cause could be assigned to this period of aggradation. The sedimentology and geomorphology of the D2 terrace suggests, however, that the aggradation of this unit was a response to diapirism/karstic processes occurring within the underlying Messinian gypsum strata and the subsequent damming of the Aguas system. Therefore, despite its coincident occurrence with the Younger Dryas, aggradation of the D2 terrace is unrelated to climate change. The style of this response, controlled predominantly by the characteristics of the underlying bedrock, makes correlating the terrace record of the Aguas with other systems in the Mediterranean unreliable. This study, therefore, highlights the problems of correlating fluvial sequences in regions of variable tectonics, climatic history and bedrock geology and emphasises the need to properly understand the main controls on individual fluvial systems before any attempt is made to correlate their depositional histories. (C) 2004 Elsevier Ltd. All rights reserved.

U-series isochron dating of immature and mature calcretes as a basis for constructing Quaternary landform chronologies for the Sorbas basin, southeast Spain

Immature and mature calcretes from an alluvial terrace sequence in the Sorbas basin, southeast Spain, were dated by the U-series isochron technique. The immature horizons consistently produced statistically reliable ages of high precision. The mature horizons typically produced statistically unreliable ages but, because of linear trends in the dataset and low errors associated with each data point, it was still possible to place a best-fit isochron through the dataset to produce an age with low associated uncertainties. It is, however, only possible to prove that these statistically unreliable ages have geochronological significance if multiple isochron ages are produced for a single site, and if these multiple ages are stratigraphically consistent. The geochronological significance of such ages can be further proven if at least one of the multiple ages is statistically reliable. By using this technique to date calcretes that have formed during terrace aggradation and at the terrace surface after terrace abandonment it is possible not only to date the timing of terrace aggradation but also to constrain the age at which the river switched from aggradation to incision. This approach, therefore, constrains the timing of changes in fluvial processes more reliably than any currently used geochronological procedure and is appropriate for dating terrace sequences in dryland regions worldwide, wherever calcrete horizons are present. (c) 2005 University of Washington. All rights reserved.

Calcrete profile development in quaternary alluvial sequences, southeast Spain: Implications for using calcretes as a basis for landform chronologies

A detailed study of the morphology and micro-morphology of Quaternary alluvial calcrete profiles from the Sorbas Basin shows that calcretes may be morphologically simple or complex. The 'simple' profiles reflect pedogenesis occurring after alluvial terrace formation and consist of a single pedogenic horizon near the land surface. The 'complex' profiles reflect the occurrence of multiple calcrete events during terrace sediment aggradation and further periods of pedogenesis after terrace formation. These 'complex' calcrete profiles are consequently described as composite profiles. The exact morphology of the composite profiles depends upon: (1) the number of calcrete-forming events occurring during terrace sediment aggradation; (2) the amount of sediment accretion that occurs between each period of calcrete formation; and (3) the degree of pedogenesis after terrace formation. Simple calcrete profiles are most useful in establishing landform chronologies because they represent a single phase of pedogenesis after terrace formation. Composite profiles are more problematic. Pedogenic calcretes that form within them may inherit carbonate from calcrete horizons occurring lower down in the terrace sediments. In addition erosion may lead to the exhumation of older calcretes within the terrace sediment. Calcrete 'inheritance' may make pedogenic horizons appear more mature than they actually are and produce horizons containing carbonate embracing a range of ages. Calcrete exhumation exposes calcrete horizons whose morphology and radiometric ages are wholly unrelated to terrace surface age. Composite profiles are, therefore, only suitable for chronological studies if the pedogenic horizon capping the terrace sequence can be clearly distinguished from earlier calcrete-forming events. Thus, a detailed morphological/micro-morphological study is required before any chronological study is undertaken. This is the only way to establish whether particular calcrete profiles are suitable for dating purposes. Copyright (C) 2003 John Wiley Sons, Ltd.

Magnitude of climate variability during middle Pliocene warmth: a palaeoclimate modelling study

The nature and magnitude of climatic variability during the period of middle Pliocene warmth (ca 3.29–2.97 Ma) is poorly understood. We present a suite of palaeoclimate modelling experiments incorporating an advanced atmospheric general circulation model (GCM), coupled to a Q-flux ocean model for 3.29, 3.12 and 2.97 Ma BP. Astronomical solutions for the periods in question were derived from the Berger and Loutre BL2 astronomical solution. Boundary conditions, excluding sea surface temperatures (SSTs) which were predicted by the slab-ocean model, were provided from the USGS PRISM2 2°×2° digital data set. The model results indicate that little annual variation (0.5°C) in SSTs, relative to a ‘control’ experiment, occurred during the middle Pliocene in response to the altered orbital configurations. Annual surface air temperatures also displayed little variation. Seasonally, surface air temperatures displayed a trend of cooler temperatures during December, January and February, and warmer temperatures during June, July and August. This pattern is consistent with altered seasonality resulting from the prescribed orbital configurations. Precipitation changes follow the seasonal trend observed for surface air temperature. Compared to present-day, surface wind strength and wind stress over the North Atlantic, North Pacific and Southern Ocean remained greater in each of the Pliocene experiments. This suggests that wind-driven gyral circulation may have been consistently greater during the middle Pliocene. The trend of climatic variability predicted by the GCM for the middle Pliocene accords with geological data. However, it is unclear if the model correctly simulates the magnitude of the variation. This uncertainty is derived from, (a) the relative insensitivity of the GCM to perturbation in the imposed boundary conditions, (b) a lack of detailed time series data concerning changes to terrestrial ice cover and greenhouse gas concentrations for the middle Pliocene and (c) difficulties in representing the effects of ‘climatic history’ in snap-shot GCM experiments.

Elevated marine deposits in Bermuda record a late Quaternary megatsunami

Deposits of coral-bearing, marine shell conglomerate exposed at elevations higher than 20 m above present-day mean sea level (MSL) in Bermuda and the Bahamas have previously been interpreted as relict intertidal deposits formed during marine isotope stage (MIS) I I, ca. 360-420 ka before present. On the strength of this evidence, a sea level highstand more than 20 m higher than present-day MSL was inferred for the MIS I I interglacial, despite a lack of clear supporting evidence in the oxygen-isotope records of deep-sea sediment cores. We have critically re-examined the elevated marine deposits in Bermuda, and find their geological setting, sedimentary relations, and microfaunal assemblages to be inconsistent with intertidal deposition over an extended period. Rather, these deposits, which comprise a poorly sorted mixture of reef, lagoon and shoreline sediments, appear to have been carried tens of meters inside karst caves, presumably by large waves, at some time earlier than ca. 310-360 ka before present (MIS 9-11). We hypothesize that these deposits are the result of a large tsunami during the mid-Pleistocene, in which Bermuda was impacted by a wave set that carried sediments from the surrounding reef platform and nearshore waters over the eolianite atoll. Likely causes for such a megatsunami are the flank collapse of an Atlantic island volcano, such as the roughly synchronous Julan or Orotava submarine landslides in the Canary Islands, or a giant submarine landslide on the Atlantic continental margin. (c) 2006 Elsevier B.V. All rights reserved.

Reply to "Mega-highstand or megatsunami? Discussion of McMurtry et al. "Elevated marine deposits in Bermuda record a late Quaternary megatsunami": Sed. Geol. 200 (2007) 155-165" by Paul J. Hearty and Storrs L. Olson

Our recent paper [McMurtry, G.M., Tappin, D.R., Sedwick, P.N., Wilkinson, I., Fietzkc, J. and Sellwood, B., 2007a. Elevated marine deposits in Bermuda record a late Quaternary megatsunami. Sedimentary Geol. 200, 155-165.] critically re-examined elevated marine deposits in Bermuda, and concluded that their geological setting, sedimentary relations, micropetrography and microfaunal assemblages were inconsistent with sustained intertidal deposition. Instead, we hypothesized that these deposits were the result of a large tsunami that impacted the Bermuda island platform during the mid-Pleistocene. Hearty and Olson [Hearty, P.J., and Olson, S.L., in press. Mega-highstand or megatsunami? Discussion of McMurtry et al. "Elevated marine deposits in Bermuda record a late Quaternary megatsunami": Sedimentary Geology, 200, 155-165, 2007 (Aug. 07). Sedimentary Geol. 200, 155-165.] in their response, attempt to refute our conclusions and claim the deposits to be the result of a +21 m eustatic sea level highstand during marine isotope stage (MIS) 11. In our reply we answer the issues raised by Hearty and Olson [Hearty, P.J., and Olson, S.L., in press. Mega-highstand or megatsunami? Discussion of McMurtry et al. "Elevated marine deposits in Bermuda record a late Quaternary megatsunami": Sedimentary Geology, 200, 155-165, 2007 (Aug. 07). Sedimentary Geol. 200,155-165.] and conclude that the Bermuda deposits do not provide unequivocal evidence of a prolonged +21 m eustatic sea level highstand. Rather, the sediments are more likely the result of a past megatsunami in the North Atlantic basin. (c) 2008 Elsevier B.V. All rights reserved.

Pliocene seasonality across the North Atlantic inferred from cheilostome bryozoans

Previous studies have shown an inverse correlation between zooid size in cheilostome bryozoans and ambient water temperature. This relationship underlies the MART technique which uses intracolonial variation in zooid size to predict mean annual range in temperature experienced by bryozoan colonies during their life. Here we apply the MART technique to study Early and Mid Pliocene bryozoans from Central America (Panama, Costa Rica), the USA (Florida, South Carolina, North Carolina, Virginia) and the UK (Suffolk) to reconstruct palaeoseasonality across a range of latitudes for the North Atlantic during the Pliocene Epoch. Compared to the present-day, our analyses suggest greater seasonality (ca 4.5 degrees C) in the southern Caribbean at the time of Cayo Agua Formation deposition (ca 4.25 Ma), in keeping with inferred upwelling prior to the closure of the isthmian barrier at 2.7 Ma. Bryozoans also indicate seasonal upwelling on the Gulf Coast of Florida in a similar manner to the present-day. Because upwelling can be highly localised and prone to spatial and temporal variation in the Gulf of Mexico today, it contributes little to a broad understanding of Pliocene North Atlantic waters. However, MART estimates for the coastal plain region indicate a general reduction in the annual range in temperature relative to the present, suggesting that the colder surface waters that today reach south to Cape Hatteras had less influence in Early to Mid Pliocene times. These results, along with evidence from other proxies, strongly support reduced seasonality and warmer conditions along the eastern seaboard of the USA in the Early to Mid Pliocene. Finally, the MART estimates amongst Coralline Crag localities provide evidence for an increased annual range in temperature in the southern North Sea than at present. Our study shows that bryozoan MART estimates provide a powerful, independent proxy for palaeoseasonality and is the first to demonstrate that the MART technique can be applied to infer palaeoclimates across a wide range of latitudes focusing on a variety of geological formations and geographical regions. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Characterization of the quaternary amine transporters of Rhizobium leguminosarum bv. viciae 3841

Rhizobium leguminosarum bv. viciae 3841 contains six putative quaternary ammonium transporters (Qat), of the ABC family. Qat6 was strongly induced by hyperosmosis although the solute transported was not identified. All six systems were induced by the quaternary amines choline and glycine betaine. It was confirmed by microarray analysis of the genome that pRL100079-83 (qat6) is the most strongly upregulated transport system under osmotic stress, although other transporters and 104 genes are more than threefold upregulated. A range of quaternary ammonium compounds were tested but all failed to improve growth of strain 3841 under hyperosmotic stress. One Qat system (gbcXWV) was induced 20-fold by glycine betaine and choline and a Tn5::gbcW mutant was severely impaired for both transport and growth on these compounds, demonstrating that it is the principal system for their use as carbon and nitrogen sources. It transports glycine betaine and choline with a high affinity (apparent K-m, 168 and 294 nM, respectively).

Degradation pathway of bisphenol A: Does ipso substitution apply to phenols containing a quaternary alpha-carbon structure in the para position?

The degradation of bisphenol A and nonylphenol involves the unusual rearrangement of stable carboncarbon bonds. Some nonylphenol isomers and bisphenol A possess a quaternary alpha-carbon atom as a common structural feature. The degradation of nonylphenol in Sphingomonas sp. strain TTNP3 occurs via a type II ipso substitution with the presence of a quaternary alpha-carbon as a prerequisite. We report here a new degradation pathway of bisphenol A. Consequent to the hydroxylation at position C-4, according to a type 11 ipso substitution mechanism, the C-C bond between the phenolic moiety and the isopropyl group of bisphenol A is broken. Besides the formation of hydroquinone and 4-(2-hydroxypropan-2-yl) phenol as the main metabolites, further compounds resulting from molecular rearrangements consistent with a carbocationic intermediate were identified. Assays with resting cells or cell extracts of Sphingomonas sp. strain TTNP3 under an 18 02 atmosphere were performed. One atom of 180, was present in hydroquinone, resulting from the monooxygenation of bisphenol A and nonylphenol. The monooxygenase activity was dependent on both NADPH and flavin adenine dinucleotide. Various cytochrome P450 inhibitors had identical inhibition effects on the conversion of both xenobiotics. Using a mutant of Sphingomonas sp. strain TTNP3, which is defective for growth on nonylphenol, we demonstrated that the reaction is catalyzed by the same enzymatic system. In conclusion, the degradation of bisphenol A and nonylphenol is initiated by the same monooxygenase, which may also lead to ipso substitution in other xenobiotics containing phenol with a quaternary a-carbon.