Refined relationship between the position of the fundamental OH stretching and the first overtones for clays

The aim of this paper is to determine a relationship between the wavenumbers of the first OH-stretching overtones (W_2OH) and the wavenumbers of the OH-stretching fundamentals (W_OH) to help to interpret the near-infrared (NIR) spectra. The first overtone (2OH) bands appear at wavenumbers less than twice those of the fundamental bands (OH), due to the anharmonic character of vibrations, X = W_2OH/2 - W_OH, with X being the anharmonicity constant. Talc samples with various crystal chemistries are used to solve the equation and the experimental data are well fitted with X = –85.6 cm^–1. As far as the authors are aware, it is the first time that the anharmonicity constant for the OH-stretching vibrations is determined for phyllosilicates. The anharmonicity constant remains almost unchanged for several types of clay samples. Therefore the relation, established from talc samples because their absorption bands are narrow and their wavenumber range of OH vibrations is wide, can be used for any other clay minerals.     

Dynamics of the radiation belt formed by solar protons during magnetic storms

Experimental proofs of the existence of the formation and destruction mechanisms of solar proton belts in the inner magnetosphere at a rapid change in the penetration boundary of solar protons are presented. An analysis of the measurements of solar protons and alpha-particles on board the Coronas-F low-altitude polar satellite during the magnetic storms in October–November 2003 is performed. During this period, formation and destruction of the belts of solar cosmic rays was observed several times. The compression of the magnetosphere during a storm makes possible the direct penetration of solar protons deep into the inner magnetosphere. The proton trajectories outside the penetration boundary are open, and the preliminary captured particles can easily leave the magnetosphere. During the recovery of the magnetospheric configuration, when the penetration boundary goes away from the Earth, the solar protons and alpha-particles with relatively low velocity of the magnetic drift remain stably captured, whereas the particles of higher energies follow the motion of the penetration boundary. That is why the energy range of the captured protons is limited from above in contrast to the effect of injection during ineffective SC in the low-energy region.     

Natural attenuation, biostimulation and bioaugmentation on biodegradation of polycyclic aromatic hydrocarbons (PAHs) in mangrove sediments

The biodegradability of a mixture of PAHs, namely fluorene (Fl), phenanthrene (Phe) and pyrene (Pyr), in mangrove sediment slurry was investigated. At the end of week 4, natural attenuation based on the presence of autochthonous microorganisms degraded more than 99% Fl and Phe but only around 30% of Pyr were degraded. Biostimulation with addition of mineral salt medium degraded over 97% of all three PAHs, showing that nutrient amendment could enhance Pyr degradation. Bioaugmentation with inoculation of a PAH-degrading bacterial consortium enriched from mangrove sediments did not show any promotion effect and the degradation percentages of three PAHs were similar to that by natural attenuation. Some inhibitory effect was observed in bioaugmentation treatment in week 1 with only 50% Fl and 70% Phe degraded. These results indicate that autochthonous microbes may interact and even compete with the enriched consortium during PAH biodegradation. Natural attenuation appeared to be the most appropriate way to remedy Fl- and Phe-contaminated mangrove sediments while biostimulation was more capable to degrade Pyr-contaminated sediments. The study also shows that although a large portion of the added PAHs (more than 95%) was adsorbed onto the sediments at the beginning of the experiment, most PAHs were degraded in 4 weeks, suggesting that the degraders could utilize the adsorbed PAHs efficiently.     

Fine grain sediment transport and deposition in the Patos Lagoon–Cassino beach sedimentary system

Extensive mud deposits superimposed on the predominantly sandy inner continental shelf adjacent to the Patos Lagoon estuary, indicates that the Lagoon is a potential source of fine sediments to the coastal sedimentary system. The lagoon is large and shallow, and the water movement is mainly controlled by wind-driven set-up and set-down. The mean river inflow is around 2000 m³ s⁻¹, although peak flow rates exceeding 20,000 m³ s⁻¹ have been observed during El Niño periods. Though the tidal elevations are small, tidal velocities in the lagoon's inlet can be significant due to the large extension of the backwaters. Moreover, significant exchange flows can be generated between the estuary and coastal area due to barotropic pressure gradients established as a function of wind and freshwater discharge. The predominant net flow is seawards, but opposite near-bed flows due to pronounced vertical salinity stratification can also be observed. The coastal area is characterized by small tidal effects, large scale ocean circulation, wind-induced residual flows and wave-driven currents, where the waves originate from swell or are locally generated.     

Surveying Upstate NY Well Water for Pesticide Contamination: Cayuga and Orange Counties

Private wells in Cayuga and Orange counties in New York were sampled to determine the occurrence of pesticide contamination of groundwater in areas where significant pesticide use coincides with shallow or otherwise vulnerable groundwater. Well selection was based on local groundwater knowledge, risk modeling, aerial photo assessments, and pesticide application database mapping. Single timepoint samples from 40 wells in each county were subjected to 93‐compound chromatographic scans. All samples were nondetects (reporting limits ≤1 μg/L), thus no wells from either county exceeded any of 15 state groundwater standards or guidance values. More sensitive enzyme‐linked immunosorbent assays (ELISA) found two wells with quantifiable atrazine in each county (0.1–0.3 μg/L), one well with quantifiable diazinon (0.1 μg/L) in Orange County, and one well with quantifiable alachlor (0.2 μg/L) in Cayuga County. Trace detections (<0.1 μg/L) in Cayuga County included atrazine (five wells), metolachlor (six wells), and alachlor (one well), including three wells with multiple detections. All 12 Cayuga County wells with ELISA detections had either corn/grain or corn/forage rotations as primary surrounding land uses (although 20 other wells with the same land uses had no detections) and all quantified detections and most trace detections occurred in wells up to 9‐m deep. Orange County trace (<0.1 μg/L) ELISA detections (atrazine three wells, diazinon one well, and metolachlor five wells) and quantified detections were only generally associated with agricultural land uses. Finding acceptable drinking water quality in areas of vulnerable groundwater suggests that water quality in less vulnerable areas will also be good.     

Representativeness of total ozone trends as derived from satellite BUV and ground-based measurements

The information content of the 7-year BUV data set has been reexamined by a comparison with a fairly large set of ground Dobson and M-83 instruments. The satellite-ground intercomparison of total ozone was done under different types of ground observation techniques (observation code) and different instrument exposure (exposure code) and for various distances of the subsatellite point from the station. Because of the existing latitudinal gradient in total ozone, at a given station the bias ground-BUV tends to be smaller when the subsatellite point is at a latitude higher than the station's latitude. Knowing the total ozone gradient at a given station, the BUV total ozone has been corrected to account for the ozone gradient and the correlation was calculated with the corresponding ground observations. These correlations seem to offer no improvement when compared with the correlations between the ground ozone and the actual BUV ozone at distances of the subsatellite point from the station within 200 km from the station used in previous studies. The seasonal variation of the BUV-ground correlation reveals information on the noise level of the measurements and the geographical distribution of the percentage mean bias: (Ground-BUV)×100/(Ground) is discussed. Both on short and on longer time scales it appears that the BUV derived recommended total ozone data set is reasonably good and possible instrumental drifts are not large. The analysis includes an extension through April 1977 of the BUV and contour-derived total ozone trends byLondon andLing (1980). Over the northern hemisphere both data sets (contour and BUV) show comparable trends over middle and high latitudes which range from –3 D.U./year to –5 D.U./year during the 7-year period April 1970–April 1977. In the southern hemisphere, however, long-term variation in total ozone cannot be determined from ground observations alone. It is concluded that for unknown reasons during the 7-year period of study, total ozone has been decreasing over most of the globe. The negative growth rates at high latitudes of the northern hemisphere are highly significant.     

Monitoring of toxic substances in the Hong Kong marine environment

A long-term programme for monitoring toxic substances in the marine environment was established in Hong Kong in 2004, focusing on chemicals of potential ecological and health concern. The programme ran on 3-year cycles, with the first two years monitoring marine water, sediment, biota, and the third year monitoring pollution sources. Twenty-four priority chemicals were measured, including dioxins/furans, dioxin-like PCBs, total PCBs, PAHs, DDTs, HCHs, TBTs, phenol, nonylphenol (NP), NP ethoxylates, PBDEs and metals. Results from the first three years of monitoring indicate that toxic substances in the Hong Kong marine environment were within the range reported for the coastal waters in China and other regions, but generally lower than in the Pearl River Estuary. The levels met the standards for protecting aquatic life and human consumption. Sewage effluent, stormwater and river water were possible sources of phenolic compounds; whereas air deposition or regional pollution, rather than local discharges, may contribute to the dioxins/furans, PAHs and PCBs found in the marine environment.     

From global to local: Testing the potential of cross-scaling in global data sets

The present study investigates the potential of readily available and easily accessible global data sets to understand regional/local level interactions in wetland systems. The biogeographical zones of India were used a base-frame to select three sites. The study well fits the interests of National Wetland Committee of India to investigate and document fundamental information on wetland extent/distribution. The national partnership with SACON represents this interest. SACON commenced the inland wetland inventory module at national scale using geospatial data, although the provincial scale analysis is underway. In addition, the global irrigated area mapping (GIAM-IWMI) project generated multi-scalar spatial outputs for irrigated/rain-fed areas. With the existing information base, a multi-level geospatial analysis using Arc GIS algorithmic modelling was used to derive comprehensive appraisal of wetland systems complementing the data from GIAM and SACON. It was observed that the overlap between the two layers was 58 percent for Gujarat and 10 percent in Tamil Nadu. In Krishna basin the wetland’s cover 1.04 million hectare excluding the rice agro-ecosystem. The difference in the biogeography of the case sites governs the gradient of information derived from both data layers. Additionally, the global lakes and wetlands database (GLWD) database added thematic information on coastal wetlands. In summary we describe the cross-scaling the global data layers to compliment the regional/national level monitoring assignments.     

Silicate and carbonate weathering in the drainage basins of the Ganga-Ghaghara-Indus head waters: Contributions to major ion and Sr isotope geochemistry

The role of silicate and carbonate weathering in contributing to the major cation and Sr isotope geochemistry of the headwaters of the Ganga-Ghaghara-Indus system is investigated from the available data. The contributions from silicate weathering are determined from the composition of granites/ gneisses, soil profiles developed from them and from the chemistry of rivers flowing predominantly through silicate terrains. The chemistry of Precambrian carbonate outcrops of the Lesser Himalaya provided the data base to assess the supply from carbonate weathering. Mass balance calculations indicate that on an average ∼ 77% (Na + K) and ∼ 17% (Ca + Mg) in these rivers is of silicate origin. The silicate Sr component in these waters average ∼40% and in most cases it exceeds the carbonate Sr. The observations that (i) the⁸⁷Sr/⁸⁶Sr and Sr/Ca in the granites/gneisses bracket the values measured in the head waters; (ii) there is a strong positive correlation between⁸⁷Sr/⁸⁶Sr of the rivers and the silicate derived cations in them, suggest that silicate weathering is a major source for the highly radiogenic Sr isotope composition of these source waters. The generally low⁸⁷Sr/⁸⁶Sr (< 0.720) and Sr/Ca (∼ 0.2 nM/ μM) in the Precambrian carbonate outcrops rules them out as a major source of Sr and⁸⁷Sr/⁸⁶Sr in the headwaters on a basin-wide scale, however, the high⁸⁷Sr/⁸⁶Sr (∼ 0.85) in a few of these carbonates suggests that they can be important for particular streams. The analysis of⁸⁷Sr/⁸⁶Sr and Ca/Sr data of the source waters show that they diverge from a low⁸⁷Sr/⁸⁶Sr and low Ca/Sr end member. The high Ca/Sr of the Precambrian carbonates precludes them from being this end member, other possible candidates being Tethyan carbonates and Sr rich evaporite phases such as gypsum and celestite. The results of this study should find application in estimating the present-day silicate and carbonate weathering rates in the Himalaya and associated CO₂ consumption rates and their global significance.     

Mantle Pb paradoxes: the sulfide solution

There is growing evidence that the budget of Pb in mantle peridotites is largely contained in sulfide, and that Pb partitions strongly into sulfide relative to silicate melt. In addition, there is evidence to suggest that diffusion rates of Pb in sulfide (solid or melt) are very fast. Given the possibility that sulfide melt “wets” sub-solidus mantle silicates, and has very low viscosity, the implications for Pb behavior during mantle melting are profound. There is only sparse experimental data relating to Pb partitioning between sulfide and silicate, and no data on Pb diffusion rates in sulfides. A full understanding of Pb behavior in sulfide may hold the key to several long-standing and important Pb paradoxes and enigmas. The classical Pb isotope paradox arises from the fact that all known mantle reservoirs lie to the right of the Geochron, with no consensus as to the identity of the “balancing” reservoir. We propose that long-term segregation of sulfide (containing Pb) to the core may resolve this paradox. Another Pb paradox arises from the fact that the Ce/Pb ratio of both OIB and MORB is greater than bulk earth, and constant at a value of 25. The constancy of this “canonical ratio” implies similar partition coefficients for Ce and Pb during magmatic processes (Hofmann et al. in Earth Planet Sci Lett 79:33–45, 1986), whereas most experimental studies show that Pb is more incompatible in silicates than Ce. Retention of Pb in residual mantle sulfide during melting has the potential to bring the bulk partitioning of Ce into equality with Pb if the sulfide melt/silicate melt partition coefficient for Pb has a value of ∼ 14. Modeling shows that the Ce/Pb (or Nd/Pb) of such melts will still accurately reflect that of the source, thus enforcing the paradox that OIB and MORB mantles have markedly higher Ce/Pb (and Nd/Pb) than the bulk silicate earth. This implies large deficiencies of Pb in the mantle sources for these basalts. Sulfide may play other important roles during magmagenesis: (1) advective/diffusive sulfide networks may form potent metasomatic agents (in both introducing and obliterating Pb isotopic heterogeneities in the mantle); (2) silicate melt networks may easily exchange Pb with ambient mantle sulfides (by diffusion or assimilation), thus “sampling” Pb in isotopically heterogeneous mantle domains differently from the silicate-controlled isotope tracer systems (Sr, Nd, Hf), with an apparent “de-coupling” of these systems.