Spatio-temporal analysis of recent groundwater-level trends in the Red River Delta, Vietnam

A groundwater-monitoring network has been in operation in the Red River Delta, Vietnam, since 1995. Trends in groundwater level (1995?C2009) in 57 wells in the Holocene unconfined aquifer and 63 wells in the Pleistocene confined aquifer were determined by applying the non-parametric Mann-Kendall trend test and Sen??s slope estimator. At each well, 17 time series (e.g. annual, seasonal, monthly), computed from the original data, were analyzed. Analysis of the annual groundwater-level means revealed that 35?% of the wells in the unconfined aquifer showed downward trends, while about 21?% showed upward trends. On the other hand, confined-aquifer groundwater levels experienced downward trends in almost all locations. Spatial distributions of trends indicated that the strongly declining trends (>0.3?m/year) were mainly found in urban areas around Hanoi where there is intensive abstraction of groundwater. Although the trend results for most of the 17 time series at a given well were quite similar, different trend patterns were detected in several. The findings reflect unsustainable groundwater development and the importance of maintaining groundwater monitoring and a database in the Delta, particularly in urban areas.     

Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

Nuclear field shift in natural environments

The nuclear field shift (NFS) is an isotope shift in atomic energy levels caused by a combination of differences in nuclear size and shape and electron densities at the nucleus. The effect of NFS in isotope fractionation was theoretically established by Bigeleisen in 1996 [Bigeleisen J. (1996) J. Am. Chem. Soc. 118:3676–3680] and has been analytically measured in laboratory chemical exchange reactions. More recently, some isotopic variations of heavy elements (Hg, Tl, U) measured in natural systems as well as isotopic anomalies measured for lower-mass elements in meteorites have been attributed to the NFS effect. These isotopic variations open up new and exciting fields of investigations in Earth sciences. In this paper, we review the different natural systems in which NFS has been proposed to be the origin of isotopic variations.     

Stratigraphy and optically stimulated luminescence (OSL) dating of a Quaternary sequence along the Dong Nai River, southern Vietnam

The pre-Holocene Cenozoic sequence outcrops in the terrestrial part of the eastern margin of the Mekong Basin. However, the stratigraphy of the sequence is still unclear. Its detailed stratigraphy and chronology were therefore studied along the Dong Nai River, southern Vietnam, and the lithofacies and the relations among the formations were investigated from the outcrops. The ages of the deposits were determined by using optically stimulated luminescence (OSL) dating.The Ba Mieu Formation was deposited about 176±52 ka during marine isotope stage (MIS) 7–6. The Thu Duc Formation was deposited about 97±27 ka during MIS 5. Both the Ba Mieu and Thu Duc formations are composed of fluvial and tidally influenced coastal deposits. The newly proposed Nhon Trach Formation was originally an eolian (blanket) deposit, but it has been partly reworked by fluvial processes. The Nhon Trach Formation was deposited about 10.9±4.7 ka, in the last part of the Pleistocene to the beginning of the Holocene. The OSL ages for the Ba Mieu, Thu Duc, and Nhon Trach formations are younger than the ages previously assigned to these formations.     

Theoretical and experimental investigation of nickel isotopic fractionation in species relevant to modern and ancient oceans

Nickel plays a central role as an enzyme co-factor in the metabolism of methanogenic Archaea. Methanogens can fractionate Ni isotopes during assimilation, opening the possibility of using the stable isotopic composition of Ni as a biomarker. However, other sources of Ni isotopic variations need to be evaluated before one can establish Ni isotopes as an unambiguous tracer of methanogenesis in the rock record. Equilibrium exchange of Ni between the different species present in the ocean is a potential source of isotopic fractionation. Through controlled laboratory experiments and theoretical calculations, we quantify equilibrium Ni isotope fractionation between different species relevant to the modern and ancient ocean: Ni(H₂O)₆²⁺, Ni(H₂O)₁₈²⁺, NiOH(H₂O)₅⁺, Ni(OH)₂(H₂O)₄, NiCl(H₂O)₅⁺, cis-NiCl₂(H₂O)₄, trans-NiCl₂(H₂O)₄, NiHS(H₂O)₅⁺, Ni(HS)₂(H₂O)₄, NiSO₄(H₂O)₄, NiHCO₃(H₂O)₄⁺, NiCO₃(H₂O)₄, and organic ligands (crown ether and oxalic acid). The magnitude of ligand-controlled Ni isotopic fractionation, approximately 1.25‰/amu (2.5‰ for the ⁶⁰Ni/⁵⁸Ni ratio), is similar to that previously measured in cultures of methanogenic Archaea.     

Vegetation and climate variability in East Asia driven by low-latitude oceanic forcing during the middle to late Holocene

At centennial to millennial timescales, little is known of C₃ and C₄ plant productivity’s responses to past regional climate changes and the dominant forcing factors during the Holocene, although large-scale changes in glacial-interglacial periods have been attributed to changes in aridity, temperature, and CO₂ concentration. We investigated the δ¹³C of TOC, C/N ratios, and pollen in samples from a wetland on Jeju Island, Korea. The bulk isotopic signal ranging from ?17‰ to ?29‰ was partitioned into C₃ and C₄ plant signals by using a binary mixing model and calculating separate organic carbon-accumulation rates for C₃ and C₄ plants (OCAR₃ and OCAR₄) during the last 6500 years. Pollen data indicated that the temperate deciduous broadleaved trees replaced grassland dominated by Artemisia, dry-tolerant grass, and further expanded in the maar. The long-term decreasing trend of Artemisia-dominated grassland was similar to those of δ¹³C values and OCAR₄. The multi-centennial to millennial variability superimposed on the gradual increasing trend of OCAR₃ was inversely correlated with those of the sea surface temperature (SST) in the western tropical Pacific (WTP) and El Niño-Southern Oscillation (ENSO) activity, suggesting that C₃ plants have stronger sensitivity to regional climate change driven by oceanic forcing. Our data suggest that vegetation changes in a coastal area in East Asia were affected by monsoonal changes coupled with SST in WTP and ENSO activity. The vegetation change on Jeju Island varied quite differently from change in the westerly pathway, suggesting only a weak influence from high-latitude-driven atmospheric circulation changes. We conclude that centennial- to millennial-scale climate changes in coastal regions of East Asia during the mid- to late-Holocene may have been mainly controlled by low-latitudinal oceanic forcing, including forcing by SST and ENSO activity.     

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates,nicotianamine, and phytosiderophore,and new Fe isotopic measurements in higher plants

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ～3‰ (⁵⁶Fe/⁵⁴Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ～1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate₂ and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ⁵⁶Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.     

Short term variability of Particle fluxes and its relation to variability in sea surface temperature and chlorophylla field detected by Ocean Color and Temperature Scanner (OCTS) off Sanriku, northwestern North Pacific in the spring of 1997

A sediment trap experiment was carried out in conjunction with an over flight of Ocean Color Temperature Scanner (OCTS) on board Advanced Earth Observing Satellite (ADEOS) at 40°N, 143°E off Sanriku in April to May 1997. Short term variability of particle fluxes was examined at depths of 450 m and 600 m from April 6 to May 1 with a sampling interval of two days, and at 450 m with one day interval from 2nd to 10th May. Daily averaged mass flux at 450 m and 600 m was 815 mg m⁻²d⁻¹ and 862 mg m⁻²d⁻¹, respectively. A sharp increase in mass flux was observed during the period from April 26 to April 29 with the highest mass flux of 8 g m⁻²d⁻¹. About 85% of the total mass flux for the entire duration (26 days) was collected within these 4 days. Trapped material during the peak flux period was mainly composed of diatoms dominated byThalassiosira spp. and resting spores ofChaetoceros spp. This suggested that the peak flux was the result of (a) diatom bloom(s) in the euphotic column. Current meter records at 420 m showed that on April 26 and 27, the period when the peak flux was observed, the southwestward current had diminished in strength and changed its direction northwestward. Low current speeds appeared to have enhanced trap efficiency to help form the peak flux. A time series of OCTS Intensive-LAC (Local Area Coverage: Region B) images from mid-March to early May was examined todetect phytoplankton bloom(s). In the March 26th Chl image, high concentration region was restricted to the southwest off Cape Erimo, but spread around the warm core ring (WCR) 93A by April 10. East of the WCR93A, high Chl concentration remained steady until May, but to the west of the WCR93A, Chl decreased rapidly before the 19th of April. From this observation we suspect that the peak flux observed at the end of April originated from a bloom, which ceased on the 17th or 18th of April, in the region north of 40°N and west of 143°E. Taking the current meter records into account, the source region for the trapped material is most likely around southwest of the Cape Erimo.     

Seepage and consolidation of bentonite saturated with pure- or salt-water by the method of unified molecular dynamics and homogenization analysis

Bentonite clay is a micro-inhomogeneous material, which consists of clay minerals (mainly montmorillonite), macro-grains (mainly quartz), water, air and others. Properties of the saturated bentonite clay are essentially characterized by the montmorillonite and water (i.e. montmorillonite hydrate). We analyze the molecular behavior of sodium montmorillonite hydrate Na_1/3Al₂[Si_11/3Al_1/3]O₁₀(OH)₂·nH₂O by applying a molecular dynamics (MD) simulation method. And by using the MD results we calculate the swelling property of the montmorillonite hydrate, and compare with an experimental result. Next, by using the same MD procedure we treat a montmorillonite mineral with a large number of external water molecules to check the properties of the water. Here we treat pure- and salt-water. Then we calculate the diffusivity and viscosity of water molecules and Na⁺ and Cl⁻ ions.

For extending the microscopic characteristics of constituent materials to a macroscopic seepage behavior of the micro-inhomogeneous material we apply a homogenization analysis (HA). That is, starting with the Navier–Stokes equation with distributed viscosity that is calculated by the former MD procedure we determine macroscopic permeability characteristics of bentonite for both cases of pure- and salt-water. Then, by using the permeability property we calculate long-term consolidation behavior of buffering clay, which is planed to be used for high-level radioactive waste (HLRW) management. Here the deformation is treated under the well-defined Cam clay model.