Molecular implications of hydrophobic organic partitioning theory

Recent normal phase silica followed by reverse phase XAD separation has led to the identification of several flavonoid and condensed tannin structures in Suwannee River Fulvic Acid (SFRA) (Leenheer, J. A., Rostad, C. (2004) Scientific Investigations Report 2004–5276, U.S. Geological Survey). We have used the molecular properties of one of these structures to define ideal behavior during partitioning of PAHs assuming that these structures function as an immiscible liquid solvent bound to finely dispersed mineral particles. Existing data for the partitioning of PAHs into NOM compared well to this ideal behavior under Raoult/Henry and Flory‐Huggins treatments, and activity coefficients of pyrene in the hypothetical NOM phase and the free energy of transfer were estimated. If experimental data on partitioning of PAHs into synthesized samples of these structures is similar to NOM uptake data, it will be attractive to assume that, a) much smaller components of the NOM complex than suggested by gross molecular weight may be important in environmental properties such as solubility enhancement, and b) the effective molar volumes within the NOM complex responsible for solubility enhancement may be solute, or solute class dependent.     

Soil hydrophobic effects on infiltration and catchment runoff

After dry summers or drought, eucalypt forest soils at two sites in southeastern Australia developed hydrophobic or non-wetting surface characteristics that reduced infiltration, measured using a sprinkling infiltrometer. At one site the development of hydrophobic conditions caused the rainfall to runoff conversion efficiency of a forested catchment to increase from 5 per cent to 15 per cent. Under non-hydrophobic conditions at this site, grassland always generated more runoff than forest. However, one major rainfall-runoff was recorded at a time of highly hydrophobic forest soil conditions and this storm generated greater runoff on the forested catchment than the grassland catchment. At the second site forest soils have naturally highly conductive surface layers because of a dense network of macropores and pathways for preferential flow. Hydrophobic conditions produced by drought caused soil water movement to be confined to only a few of the larger macropores exposed to surface ponded water. Even so, infiltration rates remained relatively high so that the impacts of hydrophobic soils were not translated into increased catchment runoff as at the first site.     

Concentration and distribution of hydrophobic organic contaminants and metals in the estuaries of Ukraine

In this study of Ukrainian estuaries, sediments and tissues from the Dnieper and Boh estuaries and Danube Delta on the mainland, Sevastopol and Balaklava Bays on the Crimean Peninsula, and coastal Black Sea along the Crimean Peninsula were collected in 2006. Contaminant analyses included several metals, the hydrophobic organic chemicals (HOCs) polychlorinated biphenyls, several chlorinated pesticides, and polycyclic aromatic hydrocarbons. When compared to estuarine sediments globally, the Ukrainian sediments were found to be moderately contaminated. However, several metals, especially mercury, were often shown to be elevated in the tissues of the Ukrainian organisms in comparison to organisms from other estuarine locations. Sediment quality guidelines indicate some of the estuarine sediments could be sufficiently contaminated to cause adverse toxicological effects. This investigation represents the first extensive study of HOC and metal baseline concentrations and distributions in Ukrainian estuaries and seeks to characterize exposures to aquatic organisms living in these systems.     

Desorption kinetics of hydrophobic organic contaminants from marine plastic pellets

This study investigated the desorption behavior of polychlorinated biphenyls (PCBs) from marine plastic pellets. Long-term desorption experiments were conducted using field-collected polyethylene (PE) pellets. The results indicate that the desorption kinetics highly depends on the PE-water partition coefficients of PCB congeners. After 128 d of the experiment, the smallest congener considered (CB 8) had desorbed nearly completely (98%), whereas major fractions (90–99%) of highly chlorinated congeners remained in the pellets. An intraparticle diffusion model mostly failed to reproduce the desorption kinetics, whereas an aqueous boundary layer (ABL) diffusion model well approximated the data. The desorption half-lives are estimated to 14 d to 210 years for CB 8 to CB 209 in an actively stirred solution (ABL thickness: 30 μm). Addition of methanol to water enhanced the desorption to a large extent. A need for further work to explore roles of organic matter in facilitating solute transfer is suggested.     

Seasonal and annual loads of hydrophobic organic contaminants from the Susquehanna River basin to the Chesapeake Bay

Water from the Susquehanna River was collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyl (PCB) congeners to estimate seasonal and annual riverine loads to the Chesapeake Bay. Temporal variations in the chemical loads resulted from the large changes in the water flow rates and in the particle-associated contaminant concentrations. Concentrations of PCBs and PAHs in river particles (ng/g) were twice as great as those in the northern Chesapeake Bay, indicating that the Susquehanna River is an important source of these contaminants to the bay. The river carries a majority of its hydrophobic organic contaminants (HOCs) in the particulate phase. During periods of high flow, large amounts of suspended particles in the river result in elevated HOC levels and increased loadings of these contaminants to the bay. From 1997 to 1998, 60% of the total annual HOC loading occurred in the early spring coincident with high river flows. The total PCB and PAH annual loadings from the Susquehanna River to the Chesapeake Bay were 76 and 3160 kg/year, respectively and 75% of the loaded organic contaminants were in the particulate phase. Principal component analysis of PAH and PCB congener patterns in the particles reveals that the river suspended particles were dominated by autochthonous production in the summer and by resuspended sediment and watershed erosion during the winter and early spring.     

Effect of pH on binding of pyrene to hydrophobic fractions of dissolved organic matter(DOM) isolated from lake water

In order to better understand the compositional and structural complexity of dissolved organic matter(DOM) macromolecules and provide mechanistic information on the binding of hydrophobic organic contaminants(HOCs) to DOM, we fractionated large amounts of lake water into three hydrophobic DOM-fractions. The variation of the partitioning coef?cients(K_(DOC)) of pyrene at different p H levels was examined by ?orescence quenching titration. Results show that, relative to the more polar acidic DOM-fractions, the hydrophobic neutral fraction exhibits a higher sorption ability to pyrene. Generally, the sorption of pyrene to the three hydrophobic fractions is strongly pH-dependent. The K_(DOC) values of pyrene generally increase with decreasing p H levels, which is especially obvious in the sorption of pyrene to the fulvic acid fractions, suggesting that the binding is controlled by hydrophobic interactions. The mechanisms underlying the binding of pyrene to the hydrophobic fractions were also discussed. Our data are bene?cial to further understanding the binding of HOCs to DOM and how it has been affected,which may result in more accurate predictions of K_(DOC).     

On the synchronism in the events within the core and on the surface of the earth: the changes in the organic world and in the polarity of the geomagnetic field in the phanerozoic

The data on geomagnetic reversals are compared with the changes in the organic world and with the lower-mantle plumes. The times of the formation of plumes and the times of their appearance on the Earth’s surface relate to the intervals characterized by the different frequencies of geomagnetic reversals, i.e., there is no interrelation between the formation of plumes and the frequency of the changes in the geomagnetic field polarity. At the same time, a certain synchronism is observed between the frequency of the geomagnetic reversals and the boundaries of the biostratigraphic ages, i.e., the changes in the organic world in the long-period range. A hypothesis is proposed, which explains the change in the sign of the geomagnetic field by the combined effect of the irregular rotation of the internal core relative to the mantle and the changes in the slope angle of the axis of the Earth’s rotation, which, in turn, results in synchronous events on the Earth’s surface: the rates of changes in the organic world.     

On the gravimetric undulations of the geoid and the deflections of the vertical

Summary The author mentions the aims of the World-wide gravity project he established in the Ohio State University in Columbus, in 1950. He outlines the practical procedure of the gravimetric computations of the undulationsN and the vertical deflection components and and emphasizes that only by the global international cooperation and additional gravity observations at sea carried out during the last decade it has been possible to gather to Columbus the needed gravity material. Since there exist still large gravimetrically unsurveyed areas it is of vital significance to study what gravity anomalies are best to be used for these regions. The given figures concerning the accuracy of theN, and , estimated theoretically and obtained in practice, indicate that in the gravimetrically well surveyed parts of the world like in Europe and the United States we can get gravimetrically on basis of existing gravity material theN-values with accuracy of about 5–10 meters, and and with the accuracy of about 1. The geoid undulationsN are already computed in Columbus for more than 6000 points of the northern hemisphere. The sample maps show the interesting geoid of Europe and vicinity between the latitudes 60° and 30° and longitude 5° W and 30° E, drafted on basis of more than 1000N-values computed at the corners of 1°×1° squares. It is interesting to realize that the geoid undulations in all this area are positive, the extreme values being between 40 and 50 meters. The geophysical significance of the geoid maps of this kind is pointed out.     

On the maintenance of the axisymmetric part of the flow in the atmosphere

Summary The maintenance of the axisymmetric component of the flow in the atmosphere is investigated by means of a steady-state, quasi-geostrophic formulation of the meteorological equations. It is shown that the meridional variations in the time-averaged axisymmetric variables can be expressed as the sum of three contributions, one being due to the eddy heat transport, another to the eddy momentum transport, and a third to the convective-radiative equilibrium temperature which enters the problem through the specification of a Newtonian form of diabatic heating. The contributions by the large scale eddies are evaluated through the use of observed values for the eddy heat and momentum transports.The contributions from each of the three forcing mechanisms to the temperature and zonal wind fields are invstigated individually and found to be of about equal importance. The sum of the three contributions are also presented for the temperature, the zonal wind, the stream function associated with the mean meridional circulation and the corresponding vertical motion. Although the results fail to reproduce the main observed features of the lower stratosphere, they are found to be in good agreement with observations in the middle latitude troposphere. At any pressure level, for example, the computed mean zonal wind has a jet-like profile and the axis of the jet is found to slope to the south with height, as observed in the atmosphere.Based in part on a thesis submitted by the first author as partial fulfillment of the requirements for the Ph.D. degree at the University of Michigan. — Publication No. 194 from the Department of Meteorology and Oceanography, The University of Michigan.     

太平洋中部地磁台11年周期变化的研究

综合APIA、HONOLULU、PAMATAI 3个地磁台三分量的11年周期变化的形态后,可定性地提出该变化源于内场。如内源为核幔边界的电涡流,则其中心点应位于3台之间。     

Comparison Between the Nutations of the Planet Mars and the Nutations of the Earth

The nutations of the planets Mars andEarth are investigated and compared. Alarge number of interior structureparameters are involved in the nutationcomputations. The comparison between the observations and the computationsprovides several constraints on these parmeters andtherefore allows a better understanding of the physics of the interior of theplanet. For the Earth, the high precision of the observations of the nutationshas led to a very good determination of interior properties of the planet. ForMars, observations of nutations are not yet available, and we review how theamplitude of the Martian nutations depends on the hypotheses consideredfor its interior. Although Mars is very similar to the Earth, its interior is not well known;for example, we don't knowif its core is liquid or solid. Only if the core is liquid,the Free Core Nutation (FCN) normal mode exists and can alter the nutationswhich are close to the resonance. From the observed geoids, it is known thatboth planets are not in hydrostatic equilibrium. The departure is larger forMars than for the Earth, and consequently, the implication of considering a convective mantle instead of a mantle in hydrostatic equilibrium described byClairaut's equation for the initial equilibrium state of the planet is largeron the Martian nutations than on the Earth nutations. The consequences of theuncertainty in the core dimensions are also examined and shown to be of a veryhigh influence for Mars if the core is liquid, due to the potential changes inthe FCN resonance. The influence of the presence of an inner core, which isknown to exist for the Earth, could be more important for Mars than for theEarth if the inner core is large. Due to the presence of Tharsis on Mars, thetriaxiality of this planet has, additionally, larger effects than on Earth.     

Magnetic stratigraphy of the Ordovician in the lower reach of the Kotuy River: the age of the Bysy-Yuryakh stratum and the rate of geomagnetic reversals on the eve of the superchron

Until recently, the existing data prevented the geophysicists from accurately dating the Bysy-Yuryakh stratum, which outcrops in the middle reach of the Kotuy River, constraining the time of its formation to a wide interval from the end of the Late Cambrian to the beginning of the Silurian. The obtained paleomagnetic data unambiguously correlate the Bysy-Yuryakh stratum to the Nyaian regional stage and constrain its formation, at least a considerable part of it, by the Tremadocian. This result perfectly agrees with the data on the Bysy-Yuryakh conodonts studied in this work and yields a spectacular example of the successful application of paleomagnetic studies in solving important tasks of stratigraphy and, correspondingly, petroleum geology. Within the Bysy-Yuryakh stratum, we revealed a large normal-polarity interval corresponding to the long (>1 Ma) period when the geomagnetic reversals were absent. This result, in combination with the data for the Tremadocian and Middle–Upper Cambrian sequences of the other regions, indicates that (1) the rate of occurrence of the geomagnetic reversals on the eve of the Ordovician Moyero superchron of reversed polarity was at most one reversal per Ma; (2) the superchron does not switch on instantaneously but is preceded by a certain gradual change in the operation conditions of the dynamo mechanism which, inter alia, manifests itself by the reduction of the frequency of geomagnetic reversals with the approach of the superchron. This finding supports the views according to which a process preparing the establishment of the superchrons takes place at the core–mantle boundary.     

On the variation in the geomagnetic dipole over the geological history of the Earth

The global database on the paleointensity, containing determinations of the virtual dipole moment (VDM) for a stable (normal) regime of the geomagnetic field in a time interval of up to 3.5 Ga, is supplemented by new VDM determinations and analyzed. The field generation process started no later than 3–3.5 Ga (earlier data are absent) at the stage of the Earth’s core formation. Since that time, the dipole value has differed from its present value by no more than an order of magnitude, and the deviations that have already been detected tend toward smaller values. The distribution of VDM values in the time interval 0–400 Ma is bimodal, which apparently reflects the presence of two different generation levels of the geomagnetic field distinguished by a relatively large value (close to the present field value) and a relatively small value (approximately half as large as the present value). The total duration of decreased VDM values appreciably exceeds that of increased VDM values (179.1 and 28.6 Myr, respectively). On the whole, data on the paleointensity do not contradict the hypothesis about the dipole nature of the field over the last 400 Myr; however, the number of determinations at high paleolatitudes is too small to draw decisive conclusions on the validity (or invalidity) of the dipole field approximation based solely on paleointensity data.     

Structure of the poleward wall of the trough and the inclination of the geomagnetic field above the EISCAT radar

A special high-resolution routine of the EISCAT radar has been used to investigate the structure and development of the poleward wall of a deep trough in electron density. The feature was tracked by the radar during a 7-hour period under very quiet geomagnetic conditions. The field-aligned nature of the structure enabled an estimate to be made of the inclination of the geomagnetic field above EISCAT that was in good agreement with the current model. Observations of narrow field-aligned enhancements in electron temperature demonstrated that the wall of this trough is a dynamic feature, reforming regularly as the electron density responds on a time scale of tens of minutes to energy input from soft-particle precipitation.     

Evolutionary Changes in the Configuration of the Magnetic Field of the Solar Corona in the Epoch of the Minimum

Geomagnetism and Aeronomy - The evolution of the magnetic configuration in the solar corona is studied. The curvature of the K-corona helmets obtained from an analytical approximation of the...