Chlorinated pesticides and PCBs in the sea-surface microlayer and seawater samples of Singapore

Sea-surface microlayer (SML) and seawater samples collected from Singapore's coastal marine environment were analyzed for selected chlorinated pesticides and polychlorinated biphenyls (PCBs). The SML is a potential site of enrichment of persistent organic pollutants (POPs) compared to the underlying water column. The concentration ranges of SigmaHCH, SigmaDDT and SigmaPCB in subsurface (1 m depth) seawater were 0.4-27.2 ng/l (mean 4.0 ng/l), 0.01-0.6 ng/l (mean 0.1 ng/l) and 0.05-1.8 ng/l (mean 0.5 ng/l) respectively. In the SML, the concentration ranges of SigmaHCH, SigmaDDT and SigmaPCB were 0.6-64.6 ng/l (mean 9.9 ng/l), 0.01-0.7 ng/l (mean 0.2 ng/l) and 0.07-12.4 ng/l (mean 1.3 ng/l) respectively. High spatial and temporal distribution was observed for all POPs measured. However, overall levels measured in the SML were lower than levels reported in the literature for SML samples from temperate coastal regions-possibly due to loss of semi-volatile compounds in the tropical climate of Singapore. Atmospheric wet deposition during the monsoon season may be an important source of POPs to the SML. This study provides the first scientific data on POP concentrations and enrichment factors in the SML for Southeast Asia.     

The Dual Sources of Io's Sodium Clouds

Io's sodium clouds result mostly from a combination of two atmospheric escape processes at Io. Neutralization of Na⁺ and/or NaX⁺ pickup ions produces the “stream” and the “jet” and results in a rectangular-shaped sodium nebula around Jupiter. Atmospheric sputtering of Na by plasma torus ions produces the “banana cloud” near Io and a diamond-shaped sodium nebula. Charge exchange of thermal Na⁺ with Na in Io's atmosphere does not appear to be a major atmospheric ejection process. The total ejection rate of sodium from Io varied from 3×10²⁶ to 25×10²⁶ atoms/s over seven years of observations. Our results provide further evidence that Io's atmospheric escape is driven from collisionally thick regions of the atmosphere rather than from the exosphere.     

Temperature and solar zenith angle control of D-region positive ion chemistry

A numerical model is utilized to investigate the temperature (T) and solar zenith angle (χ) control of D-region positive ion chemistry between 75 and 90 km. It is assumed that NO^? is the precursor ion in a chain which involves three-body formation of the intermediary cluster ions NO⁺(H₂O)_m?1(X) (m = 1–3), where X can be N₂,O₂, H₂O, or CO₂, switching reactions which convert these weakly bound clusters to hydrates of NO⁺ and reaction of the third hydrate of NO⁺ with H₂O to initiate the chain to form H⁺(H₂O)_n (n = 1–7). Zonal mean and tidal temperatures from rocket observations and theory are synthesized to obtain the best available estimate of mean latitudinal, seasonal and local time variations of temperature in this height region. Relative compositions of NO⁺(H₂O)_m and H⁺(H₂O)_n are found to vary widely over the complete range of realistic conditions; however, the relative ion populations are entirely explicable in terms of the effects of χ and T on the relative life-times of the intermediary ion clusters with respect to recombination, switching and thermal decomposition. For instance, as χ increases (and electron production decreases) beyond 60° for a given temperature, the recombination times of the intermediate ion cluster species lengthen with respect to the formation time of the H⁺ water clusters, causing the relative H⁺ water cluster population to increase and thus raise the level where the cluster ion and NO⁺ concentrations are equal from about 85 km (normal midday) to 90 km. For a given χ the concentrations of NO⁺H₂O and H⁺(H₂O)₄ increase (decrease) for temperatures less than (greater than) 190 and 205 K, respectively. The transition occurs when the temperature becomes sufficiently high that the lifetimes of intermediary ion clusters with respect to thermal decomposition become less than their lifetimes with respect to H₂O switching (which ultimately leads to the third hydrate of NO⁺ and entry into the water chain). At this point, the formation time of H⁺(H₂O)₄ becomes long compared with its lifetime with respect to thermal decomposition and its relative concentration decreases also. Implications of these results with respect to studies of the D-region are discussed.     

Analytical solutions for Euler parameters

Two new analytical solutions for Poinsot motion in terms of Euler parameters are derived. The first solution is a straightforward ‘universal’ (no branches) time series practical for short time motion calculations or as a basis for analytical continuation. The second, more involved solution is also universal but is not restricted to short times; it is in terms of circular, hyperbolic, and elliptic functions and elliptic integrals.     

Revisiting the accurate calculation of block-sample covariances using Gauss quadrature

Block-sample covariances may be calculated by discretizing a block into regularly spaced grid points, computing punctual covariance between each grid point and the sample, then averaging. Gauss quadrature is a better, more accurate method for calculating block-sample covariance as has been demonstrated in the past by other authors (the history of which is reviewed herein). This prior research is expanded upon to provide considerably more detail on Gauss quadrature for approximating the areal or volumetric integral for block-sample covariance. A 4 × 4 Gauss point rule is shown to be optimal for this procedure. Moreover, pseudo-computer algorithms are presented to show how to implement Gauss quadrature in existing computer programs which perform block kriging.     

Asteroid Differentiation: Pyroclastic Volcanism to Magma Oceans

Abstract— Asteroid differentiation was driven by a complex array of magmatic processes. This paper summarizes theoretical and somewhat speculative research on the physics of these processes. Partial melts in asteroids migrate rapidly, taking < 10⁶ years to reach surface regions. On relatively small (<100 km) asteroids with sufficient volatiles in partial melts (<3000 ppm), explosive volcanism accelerated melts to greater than escape velocity, explaining the apparent lack of basaltic components on the parent asteroids of some differentiated meteorites. Partial melting products include the melts (some eucrites, angrites), residues (lodranites, ureilites), and unfractionated residues (acapulcoites). The high liquidus temperatures of magmatic iron meteorites, the existence of pallasites with only olivine, and the fact that enstatite achondrites formed from ultramafic magmas argue for the existence of magma oceans on some asteroids. Asteroidal magma oceans would have been turbulently convective. This would have prevented crystals nucleated at the upper cooling surface (the only place for crystal nucleation in a low-pressure body) from settling until the magma became choked with crystals. After turbulent convection slowed, crystals and magma would have segregated, leaving a body stratified from center to surface as follows: a metallic core, a small pallasite zone, a dunite region, a feldspathic pyroxenite, and basaltic intrusions and lava flows (if the basaltic components had not been lost by explosive volcanism). The pallasite and dunite zones probably formed from coarse (0.5–1 cm) residual olivine left after formation of the magma ocean at >50% partial melting of the silicate assemblage. Iron cores crystallized dendritically from the outside to the inside. The rapid melt migration rate of silicate melts suggests that ²⁶Al could not be responsible for forming asteroidal magma oceans because it would leave the interior before a sufficient amount of melting occurred. Other heat sources are more likely candidates. Our analysis suggests that if Earth-forming planetesimals had differentiated they were either small (<100 km) and poor in volatiles (<1000 ppm) or they were rich in volatiles and large enough (>300 km) to retain the products of pyroclastic eruptions; if these conditions were not met, Earth would not have a basaltic component.     

Factors affecting sulfur incorporation into lake sediments: paleoecological implications

This paper discusses the use of S as a paleolimnological tracer of limnetic sulfate concentration. A positive relationship (p<0.05) was found between limnetic sulfate and sediment S concentrations for the Great Lakes, English Lakes, and lakes from the Adirondack and Northern New England regions. There is a positive correlation (p<0.05) between C and S concentration in sediment across all regions studied. The importance of C in affecting S content in sediment was also examined by a series of cores taken at different water depths in Big Moose Lake (Adirondacks). There was a strong relationship between C and S among cores with sediment from deeper water having higher C and S concentrations (r ²=0.99). Sulfur from the shallower cores had greater concentrations of chromium-reducible S (pyrite), while cores from deeper waters had a greater proportion of organic S fractions including C-bonded S and ester sulfates.For assessing historical changes in S accumulation in sediments, enrichment factors were calculated for the PIRLA lakes. Pre-1900 net sediment accumulation rates of S were very similar across all regions. Sulfur enrichment was greatest in Adirondack sediment which had total post-1900 S accumulation of 1.1 to 7.4 times pre-1900 S accumulation. Sediment from Northern New England (NNE) generally had lower S concentration than Adirondack sediments and S enrichment factors ranged from 1.2 to 2.1. Sediment from the Northern Great Lakes States region had similar S concentration and distribution with depth to NNE sediment. In two Northern Florida lakes, sediment showed little variation in S concentration with depth, but in two other lakes from the same region, there was higher S concentration in deeper layers. Lakes which had the greatest enrichment factors also exhibited the most marked changes in C:S ratios. Ratios of C:N showed little variation (10.6 to 26.1) among the PIRLA lakes. A first order model indicated slow decomposition within these organic rich sediments.Elemental concentrations and ratios of sediment from a variety of lakes and reservoirs were complied. Maximum and minimum elemental ratios for all the data were 28 to 8.1 for C:N, 0.81 to 0.11 for C:H, and 675 to 12.5 for C:S, respectively. For the C:S ratios in all regions except the Great Lakes, the maximum ratio was less than 231. Both the maximum and minimum amount of N and H concentration of organic matter is related to biotic processes. The minimum concentration of S is regulated not only by nutrient demands but also by non-assimilatory processes.Sulfur incorporation into sediments is a function of a complex of factors, but limnetic sulfate concentration and organic matter content play a major role in regulating the S content of sediment. Further quantification of S incorporation pathways will aid in the paleolimnological interpretation of sediment S profiles. Such information is also important in assessing how S sediment pools will respond to decreases in limnetic sulfate concentration which may occur with decreases in inputs from acidic deposition.This is the eighth of a series of papers to be published by this journal which is a contribution to the Paleoecological Investigation of Recent Lake Acidification (PIRLA) project. Drs. D.F. Charles and D.R. Whitehead are guest editors for this series.     

Dating the introduction of cereal cultivation to the British Isles: early palaeoecological evidence from the Isle of Man

The adoption of cereal cultivation is a key benchmark in the transition from Mesolithic hunter–gatherer foraging to Neolithic farming economies, but the nature, timing and ecological–cultural context of the earliest cereal use in the British Isles and northwest Europe is still uncertain. We present AMS radiocarbon dating and fine‐resolution pollen evidence from the Isle of Man for cereal growing in the latter stages of a distinct episode of forest disturbance at almost 6000 yr BP (uncalibrated). The coherent ecological structure of this phase at the fine resolution level suggests that it records cereal cultivation well before the Ulmus decline, rather than wild grass pollen grains. This example is one of a cluster of early dates for cereal‐type pollen near the start of the sixth millenium BP, including several around the Irish Sea, which indicate that the introduction of cereal agriculture probably occurred as early in the central British Isles as in the northern European plain. This early cereal phase is followed later by a probable phase of pre‐Ulmus decline pastoral activity. We also report Mesolithic age woodland disturbance around 7000 yr BP (uncalibrated) and the first radiocarbon dates for mid‐Holocene forest history of the Isle of Man. Copyright © 2003 John Wiley & Sons, Ltd.