Implementation of Solute Transport in the Vadose Zone into the “HYDRUS Package for MODFLOW”

The “HYDRUS package for MODFLOW” is an existing MODFLOW package that allows MODFLOW to simultaneously evaluate transient water flow in both unsaturated and saturated zones. The package is based on incorporating parts of the HYDRUS-1D model (to simulate unsaturated water flow in the vadose zone) into MODFLOW (to simulate saturated groundwater flow). The coupled model is effective in addressing spatially variable saturated-unsaturated hydrological processes at the regional scale. However, one of the major limitations of this coupled model is that it does not have the capability to simulate solute transport along with water flow and therefore, the model cannot be employed for evaluating groundwater contamination. In this work, a modified unsaturated flow and transport package (modified HYDRUS package for MODFLOW and MT3DMS) has been developed and linked to the three-dimensional (3D) groundwater flow model MODFLOW and the 3D groundwater solute transport model MT3DMS. The new package can simulate, in addition to water flow in the vadose zone, also solute transport involving many biogeochemical processes and reactions, including first-order degradation, volatilization, linear or nonlinear sorption, one-site kinetic sorption, two-site sorption, and two-kinetic sites sorption. Due to complex interactions at the groundwater table, certain modifications of the pressure head (compared to the original coupling) and solute concentration profiles were incorporated into the modified HYDRUS package. The performance of the newly developed model is evaluated using HYDRUS (2D/3D), and the results indicate that the new model is effective in simulating the movement of water and contaminants in the saturated-unsaturated flow domains.     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

The source of sulfur in sulfide deposits in the Siberian Platform traps (from isotope data)

The source of sulfur in giant Norilsk-type sulfide deposits is discussed. A review of the state of the problem and a critical analysis of existing hypotheses are made. The distribution of δ³⁴S in sulfides of ore occurrences and small and large deposits and in normal sedimentary, metamorphogenic, and hypogene sulfates is considered. A large number of new δ³⁴S data for sulfides and sulfates in various deposits, volcanic and terrigenous rocks, coals, graphites, and metasomatites are presented. The main attention is focused on the objects of the Norilsk and Kureika ore districts. The δ³⁴S value varies from -14 to + 22.5‰ in sulfides of rocks and ores and from 15.3 to 33‰ in anhydrites. In sulfide-sulfate intergrowths and assemblages, δ³⁴S is within 4.2-14.6‰ in sulfides and within 15.3-21.3‰ in anhydrites. The most isotopically heavy sulfur was found in pyrrhotite veins in basalts (δ³⁴S = 21.6‰), in sulfate veins cutting dolomites (δ³⁴S = 33‰), and in subsidence caldera sulfates in basalts (δ³⁴S = 23.2-25.2‰). Sulfide ores of the Tsentral’naya Shilki intrusion have a heavy sulfur isotope composition (δ³⁴S = + 17.7‰ (n = 15)). Thermobarogeochemical studies of anhydrites have revealed inclusions of different types with homogenization temperatures ranging from 685 °C to 80 °C. Metamorphogenic and hypogene anhydrites are associated with a carbonaceous substance, and hypogene anhydrites have inclusions of chloride-containing salt melts. We assume that sulfur in the trap sulfide deposits was introduced with sulfates of sedimentary rocks (δ³⁴S = 22-24‰). No assimilation of sulfates by basaltic melt took place. The sedimentary anhydrites were “steamed” by hydrocarbons, which led to sulfate reduction and δ³⁴S fractionation. As a result, isotopically light sulfur accumulated in sulfides and hydrogen sulfide, isotopically heavy sulfur was removed by aqueous calcium sulfate solution, and “residual” metamorphogenic anhydrite acquired a lighter sulfur isotope composition as compared with the sedimentary one. The wide variations in δ³⁴S in sulfides and sulfates are due to changes in the physicochemical parameters of the ore-forming system (first of all, temperature and P_ch4) during the sulfate reduction. The regional hydrocarbon resources were sufficient for large-scale ore formation.     

Late Cainozoic stratigraphy,palaeomagnetic chronology and vegetational history from Lake George,N.S.W.

The sedimentary record from Lake George provides the longest relatively continuous Quaternary continental sequence yet available from Australia, and may record one of the longest Upper Cainozoic lacustrine records in the world.

Palaeomagnetic analysis of a 36 m core from the lake floor identifies a sequence of deposition extending through the Brunhes and Matuyama, to the Gauss magnetic Chron. A longer core from the same site, but with incomplete recovery, extends to 72 m in lacustrine sediment; the age of the base of this core estimated by extrapolation is between 4.2 and 7 Ma. As there are still older and deeper sediments in the basin, extending to an estimated depth of 134 m, the age of the tectonic formation of the Lake George basin must be reckoned as Middle Miocene or older.

The pattern of facies organisation through time demonstrates a phase of deep water deposition extending from the base of the cored sequence (72 m) up to 51.5 m, at which time a major change took place. A disconformity developed at this level, associated with a period of deep weathering and a prolonged phase of slope mantle deposition (from 51.5 to 30.8 m). A gradual return to lacustrine environments, with diminishing proportion of slope wash detritus, resulted in increased rates of deposition coincident with the Jaramillo Subchron at 21.5 m. Thereafter, throughout the Brunhes magnetic Chron, lacustrine conditions dominated, varying from deep to lake dry conditions in a rhythmic fashion, and reflecting the major climatic oscillations of the past 700 000 years, becoming more regular in the past 400 000 years.

The pollen analytical record of the upper 8.6 m, covering the last 350 000 years, provides the main framework for the reconstruction of climatic history. The pollen and algal records indicate a sequence of vegetation and lake level changes, in which four major glacial/interglacial cycles are correlated with stages 1 to 10 of the ¹⁸0 marine record. This provides by far the longest continuous biostratigraphic framework for the Quaternary period in Australia.

Comparison between the palaeoclimatic record and the lake level evidence shows that there is no simple correlation between the lake level fluctuations and the glacial/ interglacial oscillations. In fact, major falls in the lake level occured both at the peak of cold glacials and during the warm interglacials. Though the falls in the lake levels during a warm period (interglacial) can be explained by high rates of evaporation, drying during maximum cold can be explained best in terms of a fall in precipitation. Permanent to deep‐lake conditions generally occurred during intermediate cool periods following warm intervals, when perhaps the seas were still warm and low rates of evaporation on land prevailed. On the other hand, short periods of shallow to deep lake levels also occurred during warm (interglacial) periods, showing that these were associated with reasonably high rates of precipitation.     

Centennial to millennial geomagnetic secular variation

A time-varying spherical harmonic model of the palaeomagnetic field for 0–7 ka is used to investigate large-scale global geomagnetic secular variation on centennial to millennial scales. We study dipole moment evolution over the past 7 kyr, and estimate its rate of change using the Gauss coefficients of degree 1 (dipole coefficients) from the CALS7K.2 field model and by two alternative methods that confirm the robustness of the predicted variations. All methods show substantial dipole moment variation on timescales ranging from centennial to millennial. The dipole moment from CALS7K.2 has the best resolution and is able to resolve the general decrease in dipole moment seen in historical observations since about 1830. The currently observed rate of dipole decay is underestimated by CALS7K.2, but is still not extraordinarily strong in comparison to the rates of change shown by the model over the whole 7 kyr interval. Truly continuous phases of dipole decrease or increase are decadal to centennial in length rather than longer-term features. The general large-scale secular variation shows substantial changes in power in higher spherical harmonic degrees on similar timescales to the dipole. Comparisons are made between statistical variations calculated directly from CALS7K.2 and longer-term palaeosecular variation models: CALS7K.2 has lower overall variance in the dipole and quadrupole terms, but exhibits an imbalance between dispersion in   g ¹₂  and   h ¹₂  , suggestive of long-term non-zonal structure in the secular variations.     

The Locations of Wal-Mart and Kmart Supercenters: Contrasting Corporate Strategies

Wal-Mart and Kmart, the two largest American discount retailers, have begun to utilize a supercenter retailing format that combines a full-service grocery store with a discount department store. Supercenters are expected to be the major format for future expansion of each of these firms. The purpose of this paper is to analyze the spatial expansion strategies of each firm for the locations of its supercenters. Wal-Mart is quickly expanding its number of supercenters in modest-sized communities clustered around its grocery distribution centers, especially in Southern states. Conversely, most Super Kmart Centers are located inthe suburbs of widely scattered major metropolitan markets, and Kmart has yet to develop a grocery distribution network. Kmart currently has major financial problems that severely restrict the expansion of the Super Kmart Center format.     

Heterogenity of planetesimal collisional plume probed by glass inclusions in metal globules of Sierra Gorda 013, an unusual CBa-like chondrite

Metal-rich carbonaceous CB chondrites are generally assumed to be materials accreted from the gas–dust plume formed in catastrophic collisions of planetesimals, at least one of which was differentiated into a metal core and silicate shell. Micron-sized inclusions of siliceous alkali-rich glasses associated with sulfides were found in the metal globules of the Sierra Gorda 013 (SG 013), a CBa-like chondrite. These inclusions are unusual carriers of volatile alkalis which are commonly depleted in CB chondrites. The inclusions are presented by two types: (1) Al-bearing Nb-poor glass associated with daubréelite and (2) Nb-bearing Ca,Al,Mg-poor glass associated with an unknown Na-bearing Cr-sulfide. The glass compositions do not correspond to equilibrium condensation, evaporation, or melting. The Nb-bearing glass has a superchondritic Nb/Ta ratio (31) most likely indicating the fractionation of Nb and Ta in the high-temperature gas–dust impact plume due to condensation from vapor or evaporation of precursor Nb-rich particles. The glasses are interpreted as reaction products between refractory plume condensate particles (or possibly planetary or chondritic solids) with relatively low-temperature K-Na-Si-rich gas in oxidized conditions, possibly in a common plume vapor reservoir. Compositional differences indicate that the glasses and sulfides originated from several different sources under different fO₂, fS₂, and T conditions and were likely combined together and transported to the metal globule formation region by material flows in the heterogeneous impact plume. The glass–sulfide particles were enclosed in the globules aggregated from smaller solid or molten metal grains. The metal globules were further melted during transport to the high-temperature plume region or by plume shockwave heating. Thus, the composition of the glasses, the host metal, and the main mass of SG 013 shows dynamic heterogeneity of physical conditions and impact plume composition after a large-scale planetesimal collision.