Photochemical changes in chemical markers of sedimentary organic matter source and age

Several chemical markers of organic matter source and age are shown to be susceptible to light-induced alteration. To test for the photochemical lability of markers previously employed for sediments from the Louisiana coastal zone, we subjected sediments under resuspension conditions to simulated sunlight, and monitored changes in C:N and Br:OC ratios, δ¹³C, Δ¹⁴C, and lignin composition. Markers of terrigenous origin (high C:N, lignin) decreased and δ¹³C became enriched in sediments containing primarily terrigenous organic matter, while a marker of marine organic matter (Br:OC) decreased in samples containing significant contributions from this source. Preferential loss of ¹⁴C from all sediments indicated enhanced photochemical lability of organic matter of relatively recent origin, consistent with the changes in chemical markers. Most, but not all, experimental alterations are consistent with field distributions of these markers. Relatively small experimental changes in the markers in combination with confounding processes in the environment, however, prevent these parallel trends from providing any more than a consistency test for the importance of photochemical reactions in this region.     

Phenological Changes of Blooming Diatoms Promoted by Compound Bottom-Up and Top-Down Controls

Understanding phytoplankton species-specific responses to multiple biotic and abiotic stressors is fundamental to assess phenological and structural shifts at the community level. Here, we present the case of Thalassiosira curviseriata, a winter-blooming diatom in the Bahía Blanca Estuary, Argentina, which displayed a noticeable decrease in the past decade along with conspicuous changes in phenology. We compiled interannual field data to assess compound effects of environmental variations and grazing by the invasive copepod Eurytemora americana. The two species displayed opposite trends over the period examined. The diatom decreased toward the last years, mainly during the winters, and remained relatively constant over the other seasons, while the copepod increased toward the last years, with an occurrence restricted to winter and early spring. A quantitative assessment by structural equation modeling unveiled that the observed long-term trend of T. curviseriata resulted from the synergistic effects of environmental changes driven by water temperature, salinity, and grazing. These results suggest that the shift in the abundance distribution of T. curviseriata toward higher annual ranges of temperature and salinity—as displayed by habitat association curves—constitutes a functional response to avoid seasonal overlapping with its predator in late winters. The observed changes in the timing and abundance of the blooming species resulted in conspicuous shifts in primary production pulses. Our results provide insights on mechanistic processes shaping the phenology and structure of phytoplankton blooms.     

Seismic studies of the Brasília fold belt at the western border of the São Francisco Craton, Central Brazil, using receiver function, surface-wave dispersion and teleseismic tomography

The Tocantins Province in Central Brazil is composed of a series of SSW–NNE trending terranes of mainly Proterozoic ages, which stabilized in the Neoproterozoic in the final collision between the Amazon and São Francisco cratons. No previous information on crustal seismic properties was available for this region. Several broadband stations were used to study the regional patterns of crustal and upper mantle structure, extending the results of a recent E–W seismic refraction profile. Receiver functions and surface wave dispersion showed a thin crust (33–37 km) in the Neoproterozoic Magmatic Arc terrane. High average crustal Vp/Vs ratios (1.74–1.76) were consistently observed in this unit. The foreland domain of the Brasília foldbelt, on the other hand, is characterized by thicker crust (42–43 km). Low Vp/Vs ratios (1.70–1.72) were observed in the low-grade foreland fold and thrust zone of the Brasília belt adjacent to the São Francisco craton. Teleseismic P-wave tomography shows that the lithospheric upper mantle has lower velocities beneath the Magmatic Arc and Goiás Massif compared with the foreland zone of the belt and São Francisco craton. The variations in crustal thickness and upper mantle velocities observed with the broadband stations correlate well with the measurements along the seismic refraction profile. The integration of all seismic observations and gravity data indicates a strong lithospheric contrast between the Goiás Massif and the foreland domain of the Brasília belt, whereas little variation was found across the foldbelt/craton surface boundary. These results support the hypothesis that the Brasília foreland domain and the São Francisco craton were part of a larger São Francisco-Congo continental plate in the final collision with the Amazon plate.     

Petrographic and geochemical characterization of Archaic‐Hellenistic tableware production at Solunto,Sicily

A selected assortment of Archaic‐Hellenistic tableware samples from Solunto, a Phoenician‐Punic site located 20 km east of Palermo (Sicily), has been subjected to thin‐section petrography and chemical analysis (XRF). In this settlement several ceramic kilns remained operative over a long time period (7th to 3rd century B.C.). The main goal of this analytical study is to distinguish the ceramics manufactured locally from regional and off‐island imports. Analytical results were matched to similar data concerning local natural clay sources and to coeval tableware productions from other sites in the same area. The ceramic pastes used by the ancient craftsmen of Solunto in the case of this class of pottery could be differentiated clearly by their petrochemical characteristics. We conclude that ceramics were locally produced far beyond satisfying just internal consumption needs, indicating interaction of Solunto with neighboring Greek colonies, indigenous people, and Phoenician‐Punic colonies of Sicily. © 2009 Wiley Periodicals, Inc.     

Probable causes for cyanobacterial expansion in the Baltic Sea: Role of anoxia and phosphorus retention

This study corroborates the hypothesis that nitrogen-fixing cyanobacteria have probably occurred as an important component of the phytoplankton community in the Baltic Sea at least since brackish water conditions were initiated 8,500¹⁴C yr BP. Pigment analyses indicate that extensive occurrences started prior to a sharp increase in nutrient levels dated to 7,100¹⁴C yr BP. The cyanobacteria could have functioned as a natural trigger for eutrophication in the Baltic Sea by importing nitrogen. This is also verified by a contemporaneous drop in the δ¹⁵N values from 4‰ to around 2‰. We further conclude that the spreading of cyanobacteria was probably caused by a decrease in nitrogen∶phosphorus (N∶P) in the water mass that resulted from the intrusion of oceanic water with high P levels. The fractionation of P in sediments indicated that iron-bound P was efficiently sequestered under anoxic conditions that occurred as a consequence of the establishment of a stable stratification caused by the marine intrusion. This pool only showed minor variations around 3 μmol g⁻¹ at the freshwater-brackish water transition. All P pools except the CaCO₃ fraction showed a distinct increase around 9,300¹⁴C yr BP prior to the transition. We interpreted this increase as a change in preservation of organic matter or in the source of the sediment. Slightly after 4,000¹⁴C yr BP there was a dramatic drop in all P pools without any corresponding decreases in total N and carbon. Total P decreased from around 75 to 25–30 μmol g⁻¹. The most dramatic drop occurred in the organic bound and the detrital apatite fractions, which decreased by a factor of 3–4. We explain this as a preferential regeneration of P, especially organic P, compared to other nutrients due to more prevalent anoxic conditions.     

Carbon cycling in a shallow turbid estuary of southeast Texas: The use of plant pigment biomarkers and water quality parameters

Particulate organic carbon (POC), dissolved organic carbon (DOC), and plant pigments (chlorophylls and carotenoids) were measured approximately bimonthly from March 1992 to October 1993 in the Sabine-Neches estuary (Sabine Lake region), located on the Texas-Louisiana border. High freshwater inflow into this shallow turbid estuary results in the shortest hydraulic residence time (ca. 7 d) of all Texas estuaries (Baskaran et al. in press). Annual averages of chlorophyll-a (3.0 μg l^?1) and particulate organic carbon (1.1 mg l^?1) in the water column were extremely low in comparison to other shallow estuaries. The highest chlorophyll-a concentrations were observed in October 1993, in the mid and lower regions of the estuary, during the lowest river discharge. Zeaxanthin and fucoxanthin concentrations suggested that much of the chlorophyll-a during this low flow period was represented by cyanobacteria and diatoms that entered from the Gulf of Mexico. The range of DOC concentrations was generally high (4.4–20.9 mg l^?1) and were significantly correlated with POC, but not with chlorophyll-a concentrations. When total suspended particulate (TSP) concentrations were below 20 to 30 mg l^?1, there were significant increases in %POC and %PON of the TSP. The unusually high POC: chlorophyll-a ratios (highest value of 1423) suggested that much of the POC contained low concentrations of chlorophyll-a that had degraded during transport from wetlands in the Sabine and Neches rivers. Based on these data, this estuary can be characterized as a predominantly heterotrophic system, with low light penetrance, short particle-residence times, high DOC, and low inputs from autochthonous carbon sources.     

Regional record of a global oceanic anoxic event: OAE1a on the Apulia Platform margin, Gargano Promontory, southern Italy

The Gargano Promontory of southern Italy, located on the eastern margin of the Apulia Platform, represents a peculiar Tethyan area where the transition between carbonate platform and adjacent basins is exposed on land. The Aptian stratigraphic record, represented in shallow-water, slope and deep-water deposits, provides a good opportunity to investigate the regional response to the worldwide documented climatic, biotic and palaeoceanographic changes related to Oceanic Anoxic Event 1a (OAE1a). A synthesis of data previously published (Ischitella and Coppitella sections), together with original data (Val Carbonara and Coppa della Guardia sections), from four stratigraphic sections from different depositional settings (proximal to distal) is provided, using an integrated, high-resolution micropalaeontological (planktonic foraminifera and calcareous nannofossils) and, for one section, geochemical (stable carbon and oxygen isotopes) approach. Organic matter preservation is confined to the more distal areas and consists of two thin intervals of black shales in the Aptian portion of the Marne a Fucoidi Formation. Biostratigraphic data assign the older black shale (5 cm thick) to the Selli Level equivalent (OAE1a, Lower Aptian); this carbon-rich interval is immediately followed by another black shale (7–10 cm thick) of early Late Aptian age.OAE1a is generally interpreted as a high-productivity event during a warming interval, followed by a cooling trend. In the Gargano Promontory, although the oxygen isotope curve indicates the above-mentioned climatic evolution, the micropalaeontological data do not support high fertility of the surface water, whereas micropalaeontological and geochemical data for the younger black shale do record high productivity (radiolarian increase in overall abundance, low nannofossil and foraminiferal species richness, increase in abudance of nannofossil fertility indices) associated with a cooling trend. The carbon and oxygen isotope record is in line with evidence from the curves documented elsewhere, whereas, among the biotic events, only the “nannoconid crisis” preceding OAE1a is revealed to be globally correlable.Environmental models for the two episodes of organic matter preservation are proposed, taking into account both global and local controlling factors.