Radiation-induced defects in quartz. III. Single-crystal EPR,ENDOR and ESEEM study of a peroxy radical

The X- and W-band single-crystal electron paramagnetic resonance spectra of an electron-irradiated natural quartz permit quantitative analysis of a ²⁹Si hyperfine structure (A ~12.6 MHz) and an ²⁷Al hyperfine structure (A ≤ 0.8 MHz) for a previously reported hole-like center. The ²⁹Si hyperfine structure arises from interaction with two equivalent Si atoms and is characterized by the direction of the unique A axis close to a Si–O bond direction. The ²⁷Al hyperfine structure, confirmed by pulsed electron nuclear double resonance and electron spin echo envelope modulation spectra, is characterized by the unique A axis approximately along a twofold symmetry axis. These ²⁹Si and ²⁷Al hyperfine data, together with published theoretical results on peroxy radicals in SiO₂ as well as our own density functional theory (DFT) calculations on model peroxy centers, suggest this hole-like center to have the unpaired spin on a pair of oxygen atoms linked to two symmetrically equivalent Si atoms and a substitutional Al³⁺ ion across the c-axis channel, a first peroxy radical in quartz. The nuclear quadrupole matrix P also suggests that the Al³⁺ ion corresponds closely to the diamagnetic precursor to the [AlO₄]⁰ center. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The influence of topography and land use on water quality of Xiangxi River in Three Gorges Reservoir region

A self-organizing map (SOM) was used to cluster the water quality data of Xiangxi River in the Three Gorges Reservoir region. The results showed that 81 sampling sites could be divided into several groups representing different land use types. The forest dominated region had low concentrations of most nutrient variables except COD, whereas the agricultural region had high concentrations of NO₃N, TN, Alkalinity, and Hardness. The sites downstream of an urban area were high in NH₃N, NO₂N, PO₄P and TP. Redundancy analysis was used to identify the individual effects of topography and land use on river water quality. The results revealed that the watershed factors accounted for 61.7% variations of water quality in the Xiangxi River. Specifically, topographical characteristics explained 26.0% variations of water quality, land use explained 10.2%, and topography and land use together explained 25.5%. More than 50% of the variation in most water quality variables was explained by watershed characteristics. However, water quality variables which are strongly influenced by urban and industrial point source pollution (NH₃N, NO₂N, PO₄P and TP) were not as well correlated with watershed characteristics.     

Mapping vertical profile of discontinuous permafrost with ground penetrating radar at Nalaikh depression,Mongolia

Ground-penetrating radar (GPR) has become an important geophysical tool which can provide a wealth of interpretive information about the vertical profile of discontinuous permafrost. A GPR investigation was conducted in October 2006 at the Nalaikh site at the southern boundary of the Siberian discontinuous permafrost region in Mongolia. GPR data were collected along four 100-m-long profiles to identify the location of the permafrost body, which included an in situ drilling borehole and analysis of temperature observations and soil water content measurements from boreholes. The GPR interpretation results indicated that the thickness of discontinuous permafrost at the study site was only 1.9–3.0 m and the permafrost is vulnerable to climate change. The soil temperature and soil water content data demonstrate the precision of GPR image interpretation. This case demonstrated that GPR is well suited for mapping the internal structure of discontinuous permafrost with relatively low soil water content.     

Using ocean quahog (<Emphasis Type="Italic">Arctica islandica</Emphasis>) shells to reconstruct palaeoenvironment in Öresund,Kattegat and Skagerrak,Sweden

Shells of Arctica islandica collected between 1884 and 2004 from Öresund, Kattegat and Skagerrak (Swedish West Coast) were used to monitor local climate variations and the influence of human activities on the local environment. For this purpose, we analysed the growth, structure and chemical composition of these shells and compared them with shells collected from Kiel Bay, Norway and Iceland. The growth rate of the studied shells registers an NAO periodicity of ca 8 years. However, the observed signal is weak because of other environmental interferences that are either of natural or anthropogenic origin. For example, the oxygen isotope ratios show temperature fluctuation, but also the influx of low salinity water. Higher contents of S, N, Cu, Zn, As, Cd and P in shell portions formed during the last century are related to human activities such as mining and industrial development. Our study indicates that in order to use Arctica shells as archives of climate change it is necessary to study the full range of environmental data that is recorded in the shells by using a multi element and isotope approach in combination with different analytical techniques including investigation of growth rates and shell structure.     

Dynamics of the soil water and solute in the sodic saline soil in the Songnen Plain,China

According to the field experiment in the sodic saline soil region in the Songnen Plain, the dynamics of the soil water and solute affected by the shallow groundwater were explored during the growing season in 2004. The results presented that, influenced by the strongly evaporative demand, the soil water tended to transport to the upper soil layer with salt. The layered soil water balance model (LSWB model) revealed that the ratio of the water exchange between the groundwater and upper layer of the soil was 11.7:1. The groundwater discharge was 53.86 mm, but the groundwater recharge from the upper layer of soil was only 5.04 mm from 11 July to 06 September, which indicated that the groundwater could discharge to upper layer of soil and influence the soil salinization through capillary rise. The observed values of the salt content from July to mid-October presented that the soil solute was more changeable influenced by the climatic condition at 30 cm depth. As the field saturated hydraulic conductivity was low, the salts mainly accumulated in about 50–70 cm depth soil layer and hardly leached into deeper soil layer. Furthermore, the salt content was mainly controlled by the groundwater in the subsoil below 100 cm depth, the salt content decreased with the groundwater level receding. As influenced by the shallow groundwater and freeze-thaw action, further studies should be performed on the mechanism of soil salinization in the sodic saline soil region in the Songnen Plain of China.     

Water diffusion in Mount Changbai peralkaline rhyolitic melt

Diffusion couple experiments with wet half (up to 4.6 wt%) and dry half were carried out at 789–1,516 K and 0.47–1.42 GPa to investigate water diffusion in a peralkaline rhyolitic melt with major oxide concentrations matching Mount Changbai rhyolite. Combining data from this work and a related study, total water diffusivity in peralkaline rhyolitic melt can be expressed as:

$ D_{{{\text{H}}_{ 2} {\text{O}}_{\text{t}} }} = D_{{{\text{H}}_{ 2} {\text{O}}_{\text{m}} }} \left( {1 - \frac{0.5 - X}{{\sqrt {[4\exp (3110/T - 1.876) - 1](X - X^{2} ) + 0.25} }}} \right), $

$ {\text{with}}\;D_{{{\text{H}}_{ 2} {\text{O}}_{\text{m}} }} = \exp \left[ { - 1 2. 7 8 9- \frac{13939}{T} - 1229.6\frac{P}{T} + ( - 27.867 + \frac{60559}{T})X} \right], $

where D is in m² s^?1, T is the temperature in K, P is the pressure in GPa, and X is the mole fraction of water and calculated as X = (C/18.015)/(C/18.015 + (100 ? C)/33.14), where C is water content in wt%. We recommend this equation in modeling bubble growth and volcanic eruption dynamics in peralkaline rhyolitic eruptions, such as the ~1,000-ad eruption of Mount Changbai in North East China. Water diffusivities in peralkaline and metaluminous rhyolitic melts are comparable within a factor of 2, in contrast with the 1.0–2.6 orders of magnitude difference in viscosities. The decoupling of diffusivity of neutral molecular species from melt viscosity, i.e., the deviation from the inversely proportional relationship predicted by the Stokes–Einstein equation, might be attributed to the small size of H₂O molecules. With distinct viscosities but similar diffusivity, bubble growth controlled by diffusion in peralkaline and metaluminous rhyolitic melts follows similar parabolic curves. However, at low confining pressure or low water content, viscosity plays a larger role and bubble growth rate in peralkaline rhyolitic melt is much faster than that in metaluminous rhyolite.

     

The Air-Coastal Sea Chemical Exchange: A Case Study on the New Jersey Coast

The coastal marine atmosphere adjacent to large urban and industrial centers is in general strongly impacted by pollution emissions, resulting in high loading of pollutants in the ambient air. Among the airborne substances are certain trace elements from a variety of emission sources that can serve as micronutrients to marine organisms in coastal waters. High concentrations of such elements in coastal air can result in enhanced air-to-sea deposition fluxes to coastal waters. They could also be transported over the open ocean, affecting the composition of the remote marine atmosphere and then ocean ecosystems. To provide better understanding of the extent of air-to-sea deposition processes on the New Jersey coast, a heavily polluted coastal region on the US East Coast, a synthesis of observation data was carried out for selected trace elements, including Fe, Cd, Cr and Cu, derived from measurements of both size-segregated and bulk aerosol particles, as well as precipitation around the New Jersey coast. The atmospheric input of Hg was also estimated based on measurement data. Results indicated that the total deposition fluxes of most trace elements were higher in Northern coastal NJ compared to Southern coastal NJ, reflecting the differences in the source strengths of these element emissions between the two coastal regions. Dry deposition processes were more significant for common dust-derived elements, particularly Fe and Al, compared with their wet deposition fluxes. However, the processes of precipitation scavenging appeared to be more important for the elements that were often enriched in fine particles including Zn, Cu, Pb and Ni. The removal of Hg from the ambient air was overwhelmingly dominated by atmospheric wet deposition. In the future, atmospheric measurements at more sites on the NJ coast should be performed simultaneously to reduce the spatial and temporal uncertainties associated with atmospheric deposition fluxes estimated in this study.     

Improvement of saponification extraction method for fatty acids separation from geological samples

The conventional saponification method could result in lower recoveries and artificial changes of long-chain fatty acids. The main reason is the error judgment of the intermediate layer suspended between the aqueous and organic layer during the liquid–liquid extraction process. This study shows that the intermediate layer consists of lots of medium- to long-chain carboxylic salts for their special physical and chemical properties. An improved saponification extraction method is also developed and the results show that the carboxylic salts distributed in the intermediate layer could be obtained completely, which greatly enhances the authenticity and accuracy of fatty acid analysis. Additionally, the possible reasons of formation of the intermediate layer are also discussed.     

Fish,Macroinvertebrate and Epifaunal Communities in Shallow Coastal Lagoons with Varying Seagrass Cover of the Northern Gulf of Mexico

Coastal lagoons are ubiquitous along coastlines worldwide. Here, we compare the abundance of epifauna, seagrass-associated macroinvertebrates, and small fish across a gradient of seagrass cover in shallow coastal lagoons of the northern Gulf of Mexico. Two of the lagoons had little or no seagrass cover (0–18.8 %), and four had high cover (83.8–97.5 %). All of the lagoons were partially covered with fringing marsh. We hypothesized that, due to habitat redundancy between seagrass beds and fringing marshes, seagrass-associated fish and macroinvertebrates would not be largely reduced despite the large differences in seagrass cover among the lagoons. Our results support this hypothesis. For most sampling dates, we did not find significant differences in fish and macroinvertebrate abundance among the lagoons and, when we did, several highly vegetated lagoons did not have larger abundances than sparsely vegetated lagoons. The extreme shallowness of the lagoons studied (<1 m) may also provide further protection from large predatory fishes in the absence of seagrasses. Our results also suggest that marsh detritus, by providing habitat for epifauna and helping maintain prey availability, may further temper reductions in seagrass-associated fishes and macroinvertebrates following seagrass decline. The results highlight the importance of marsh-bordered, shallow lagoons as habitat for small fish and macroinvertebrates regardless of seagrass cover. This study contributes to the characterization of habitat redundancy in coastal ecosystems and pinpoints the importance of considering all habitats in concert for the proper understanding and management of coastal ecosystems.     

Mapping the hydraulic connection between a coalbed and adjacent aquifer: example of the coal-seam gas resource area,north Galilee Basin,Australia

Coal-seam gas production requires groundwater extraction from coal-bearing formations to reduce the hydraulic pressure and improve gas recovery. In layered sedimentary basins, the coalbeds are often separated from freshwater aquifers by low-permeability aquitards. However, hydraulic connection between the coalbed and aquifers is possible due to the heterogeneity in the aquitard such as the existence of conductive faults or sandy channel deposits. For coal-seam gas extraction operations, it is desirable to identify areas in a basin where the probability of hydraulic connection between the coalbed and aquifers is low in order to avoid unnecessary loss of groundwater from aquifers and gas production problems. A connection indicator, the groundwater age indictor (GAI), is proposed, to quantify the degree of hydraulic connection. The spatial distribution of GAI can indicate the optimum positions for gas/water extraction in the coalbed. Depressurizing the coalbed at locations with a low GAI would result in little or no interaction with the aquifer when compared to the other positions. The concept of GAI is validated on synthetic cases and is then applied to the north Galilee Basin, Australia, to assess the degree of hydraulic connection between the Aramac Coal Measure and the water-bearing formations in the Great Artesian Basin, which are separated by an aquitard, the Betts Creek Beds. It is found that the GAI is higher in the western part of the basin, indicating a higher risk to depressurization of the coalbed in this region due to the strong hydraulic connection between the coalbed and the overlying aquifer.