Antimony(III) complexing with O-bearing organic ligands in aqueous solution: An X-ray absorption fine structure spectroscopy and solubility study

The stability and structure of aqueous complexes formed by trivalent antimony (Sb^III) with carboxylic acids (acetic, adipic, malonic, lactic, oxalic, tartaric, and citric acid), phenols (catechol), and amino acids (glycine) having O- and N-functional groups (carboxyl, alcoholic hydroxyl, phenolic hydroxyl and amine) typical of natural organic matter, were determined at 20 and 60 °C from solubility and X-ray absorption fine structure (XAFS) spectroscopy measurements. In organic-free aqueous solutions and in the presence of acetic, adipic, malonic acids and glycine, both spectroscopic and solubility data are consistent with the dominant formation of Sb^III hydroxide species, , at strongly acid, acid-to-neutral and basic pH, respectively, demonstrating negligible complexing with mono-functional organic ligands (acetic) or those having non adjacent carboxylic groups (adipic, malonic). In contrast, in the presence of poly-functional carboxylic and hydroxy-carboxylic acids and catechol, Sb^III forms stable 1:1 and 1:2 complexes with the studied organic ligands over a wide pH range typical of natural waters (3 < pH < 9). XAFS spectroscopy measurements show that in these species the central Sb^III atom has a distorted pseudo-trigonal pyramidal geometry composed of the lone pair of 5s² electrons of Sb and four oxygen atoms from two adjacent functional groups of the ligand (OC-OH and/or COH), forming a five-membered bidendate chelate cycle. Stability constants for these species, generated from Sb₂O₃ (rhomb.) solubility experiments, were used to model Sb complexing with natural humic acids possessing the same functional groups as those investigated in this study. Our predictions show that in an aqueous solution of pH between 2 and 10, containing 1 μg/L of Sb and 5 mg/L of dissolved organic carbon (DOC), up to 35% of total dissolved Sb binds to aqueous organic matter via carboxylic and hydroxy-carboxylic groups. This amount of complexed Sb for typical natural DOC concentrations is in agreement with that estimated from dialysis experiments performed with commercial humic acid in our work and those available in the literature for a range of standardized IHSS humic acids. Our results imply that a significant part of Sb is likely to be bound with humic acids via hydroxy-carboxylic moieties, in the form of bidendate complexes. However, following the strong chemical affinity of Sb^III for reduced sulfur, some undefined fraction of Sb^III might also be bound to the minor thiol-bearing moieties of humic acids; further studies are required to check this hypothesis.     

Long term monitoring for oil in the Exxon Valdez spill region

In the aftermath of the 1989 Exxon Valdez oil spill, a Long Term Environmental Monitoring Program (LTEMP) has been regularly sampling mussels (and some sediments) for polycyclic aromatic and saturated hydrocarbons (PAH and SHC) at sites in Port Valdez, Prince William Sound, and the nearby Gulf of Alaska region. After 1999, a decreasing trend appears in total PAH (TPAH) in tissues at all sites with current values below 100 ng/g dry weight (many below 50 ng/g). Currently, most samples reflect a predominantly dissolved-phase signal. This new low in TPAH likely represents ambient background levels. Synchrony in TPAH time-series and similarities in the hydrocarbon signatures portray regional-scale dynamics. The five inner Prince William Sound sites show similar composition and fluctuations that are different from the three Gulf of Alaska sites. The two Port Valdez sites represent a unique third region primarily influenced by the treated ballast water discharge from the Alyeska Marine Terminal. Prince William Sound has reverted to a stable environment of extremely low level contamination in which local perturbations are easily detected.     

Estimating monthly surface winds for Scania, southern Sweden, using geostrophic wind (1899–1997)

Wind direction conditions during the 20th century in Scania, southern Sweden, are investigated using an estimated series of monthly wind vector components (east–west u component and north–south v component). The series is developed from a regression relationship between pairwise (1973 to 1997) monthly averages of 10–m surface wind from Scania and a monthly geostrophic wind, based on mean sea level (MSL) pressure data from the National Center of Atmospheric Research (NCAR). The wind conditions during the 20th century are dominated by winds from southwesterly and westerly directions, particularly during summer and autumn. From the 1980s onwards, increased frequencies of westerly winds are evident in spring and summer; however, similarly large frequencies of westerly winds are also found during the early part of the 20th century. Analysis of the estimated wind series indicates large variation in wind direction during the investigated time period, particularly during 1930 to 1960 when large increases of easterly winds are evident in spring. Increased frequencies of easterly winds were also found in other months during this period but not to the same extent as during the spring season. Thus, the presence of periods with quite different wind characteristics suggests that the overall atmospheric circulation has experienced some shifts in this region during the 20th century.     

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Upcoming international events     

A dated volcano-tectonic deformation event in Jan Mayen causing landlocking of Arctic charr

We provide the first documentation of tectonic deformation resulting from a volcanic eruption on the island of Jan Mayen. Vertical displacement of about 14 m southwest of the stratovolcano Beerenberg is associated with an eruption in ad 1732 on its southeastern flank. The age of the uplift event is bracketed by radiocarbon-dated driftwood buried by material deposited due to uplift, and by tephra from this eruption. Constraints, inferred from radiocarbon ages alone, allow for the possibility that uplift was completed prior to the ad 1732 eruption. However, the occurrence of tephra in the sediment column indicates that some displacement was ongoing during the eruption but ceased before the eruption terminated. We attribute the tectonic deformation to intrusion of shallow magma associated with the volcanic eruption. Our results complement previous studies of volcanic activity on Jan Mayan by providing precise age constraints for past volcanic activity. Also, it raises new hypotheses regarding the nature, timing and prevalence of precursor tectonic events to Jan Mayan eruptions. The uplift caused the complete isolation of a coastal lake by closing its outlet to the sea, thus landlocking the facultative migratory fish species Arctic charr (Salvelinus alpinus).     

Ionospheric and geomagnetic disturbances during the 2005 Sumatran earthquakes

This paper investigates the ionospheric and geomagnetic responses during the 28 March 2005 and 14 May 2005 Sumatran earthquakes using GPS and magnetometer stations located in the near zone of the epicenters. These events occurred during low solar and geomagnetic activity. TEC oscillations with periods of 5–10 min were observed about 10–24 min after the earthquakes and have horizontal propagation velocities of 922–1259 m/s. Ionospheric disturbances were observed at GPS stations located to the northeast of the epicenters, while no significant disturbances were seen relatively east and south of the epicenters. The magnetic field measurements show rapid fluctuations of 4–5 s shortly after the earthquake, followed by a Pc5 pulsation of 4.8 min about 11 min after the event. The correlation between the ionospheric and geomagnetic responses shows a good agreement in the period and time lag of the peak disturbance arrival, i.e. about 11–13 min after the earthquake.