Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

Cordierite breakdown under high-pressure hydrous conditions

Green and Vernon (1974) have experimentally determined a divariant field of cordierite-orthoamphibole-kyanite-quartz with a slope of 12±4 bars per °C occurring between 8.0 and 10.4 kbar at 750° C and between 9.5 and 11.3 kbar at 850° C. However, the writers' thermodynamic calculation of the divariant band indicates a more limited range of 0.65 and 0.7 kbar at 750° C and 850° C respectively, with an estimated error of ±0.2 kbar.     

Chemical weathering of carbonates and silicates in the Han River basin,South Korea

A detailed investigation of the fluvial geochemistry of the Han River system allows to estimate the rates of chemical weathering and the consumption of CO₂. The Han River drains approximately 26,000 km² and is the largest river system in South Korea in terms of both water discharge and total river length. It consists of two major tributaries: the North Han River (NHR) and the South Han River (SHR). Distinct differences in basin lithology (silicate vs. carbonate) between the NHR and SHR provide a good natural laboratory in which to examine weathering processes and the influence of basin geology on water quality. The concentrations of major elements and the Sr isotopic compositions were obtained from 58 samples collected in both summer and winter along the Han River system in both 2000 and 2006. The concentrations of dissolved loads differed considerably between the NHR and SHR; compared with the SHR, the NHR had much lower total dissolved solids (TDS), Sr, and major ion concentrations but a higher Si concentration and ⁸⁷Sr/⁸⁶Sr ratio. A forward model showed that the dissolved loads in the NHR came primarily from silicate weathering (55 ± 11%), with a relatively small portion from carbonates (30 ± 14%), whereas the main contribution to the dissolved loads in the SHR was carbonate weathering (82 ± 3%), with only 11 ± 4% from silicates. These results are consistent with the different lithologies of the two drainage basins: silicate rocks in the NHR versus carbonate rocks in the SHR. Sulfuric acid derived from sulfide dissolution in coal-containing sedimentary strata has played an important role in carbonate weathering in the SHR basin, unlike in the NHR basin. The silicate weathering rate (SWR) was similar between the NHR and SHR basins, but the rate of CO₂ consumption in the SHR basin was lower than in the NHR basin due to an important role of sulfuric acid derived from pyrite oxidation.     

Discovery of Pyrrhotite-Chalcopyrite-Bearing Amphibole Megacrysts in Tongling Area, Anhui Province

Some pyrrhotite-chalcopyrite-bearing amphibole megacrysts (including pyroxene megacrysts) were discovered in Mesozoic augite diorite-porphyrite at Caoshan in Tongling area, Anhui Province. The amphibole megacrysts, belonging mainly to pargasite and magnesiohastingsite, are characteristic of the amphibole composition derived from mantle and crystallized in lower crust. In general, the aggregates of pyrrhotite-chalcopyrite take the shapes of cylinder and sphere. Three occurrences have been recognized in the amphibole megacrysts: parallel linear, bunchy and scattered. The unique cylinder-like shape of the aggregates and remarkable Ni-poor sulfides in Caoshan are distinctively different from the spherical Ni-rich sulfides in pyroxene megacrysts and any other kinds of megacrysts. In terms of composition, the amphibole megacrysts and their sulfides in Caoshan are similar to those in the pyroxenite xenoliths in Qilin, Guangdong Province. In terms of origin, the pyrrhotite-chalcopyrites as exsolution products resulted from the subsolidus re-equilibration of sulfide solid solution within amphibole megacrysts.amphibole megacrysts were first discovered inside and outside China. This discovery is important for the study of regional magma evolution and its associated mineralizations and ore sources as well.     

Comparison of the Ordovician-Carboniferous Boundary Between Korea and NE China: Implications for Correlation and Tectonic Evolution

There is a great hiatus between Ordovician and Carboniferous strata in the Northeast China and Korean Peninsula. In order to understand geology and tectonic evolution, and to find out the similarities and differences in both regions, two sections in the Western Hill near Beijing in NE China and several sections in the Korean Peninsula were selected to examine their geologic boundaries between Lower and Upper Paleozoic strata to compare their characteristic features. At four sites in the two sections in the Western Hill near Beijing were examined their contact relations. The Hui Yu section is the same horizon where one site is top of a quarry hill and the other of down hill. Mid-Carboniferous Qingshuijian Formation rests on the Ordovician Majiagou Formation. Limestone beds are more commonly intercalated with shale and sandstone at site 2 of the Hui Yu section, while at site 1, conglomerate beds are dominant. Site 1 of the Se Shu Fen section shows eroded and concealed karst topography and conglomerate beds are intercalated within shale beds. Silurian and Devonian strata are absent in these areas. In the Korean Peninsula, most O-C contacts occur between Ordovician limestone formation and Carboniferous strata, although Silurian strata occur beneath the Carboniferous strata in the Jeongseon area and Pyeongnam Basin. Most contact relations are parallel unconformity and angular unconformity is rarely seen. The O-C relations in both regions are similar to each other, and these indicate that the Korean Peninsula was located near or belonged to the Sino-Korean paraplatform during Paleozoic time.     

Distribution and Removal of Silver and Lead in the Nearshore Waters of Western Taiwan

Concentrations of Al, Mn, Fe, Ag, and Pb in dissolved and particulate phases of the surface water were determined at 15 stations along the coastline off western Taiwan in April of 2007. This study presents the first set of data for Al, Ag, and Pb in the nearshore waters. Latitudinal distribution of these metals showed that high values were present in the regions affected by high fluvial discharge from the Dan-Sui River and the Cho-Sui River. Using the particle fluxes from ²¹⁰Po/²¹⁰Pb disequilibria, the removal fluxes and the residence times of the trace metals were calculated. Based on the K _d values, the sequence of particle affinity of trace metals, Fe ~ Al >> Pb > Mn > Ag, was found. The correlation of the residence times and of the partitioning coefficients of multiple metals in the nearshore waters implies that the affinities to the particles determine the geochemical cycling of metals in the coastal water.     

Preservation of organic matter in mound-forming coral skeletons

This study demonstrates that intracrystalline organic matter in coral skeletons is well preserved over century timescales. The extent of preservation of organic matter in coral skeletons was investigated by measuring total organic carbon (TOC), total hydrolyzable amino acid (THAA), chloropigment, and lipid concentrations in 0-300 year old annual growth bands from Montastraea annularis (Florida Keys) and Porites lutea (Red Sea). Organic matter intrinsic to the calcium carbonate mineral (intracrystalline) was analyzed separately from total skeletal organic matter. The Red Sea coral had less TOC (0.02-0.04 wt%) than the Florida Keys coral (0.04-0.11 wt%), but a higher percent of intracrystalline organic matter in all annual bands measured. Carbon in the form of THAA, most likely from mineral-precipitating proteins, contributed 30-45% of the TOC in both corals. Carbon in lipids represented about 3% of the TOC in the coral skeletons. Chlorophyll-a and b were present in annual bands where endolithic algae were present, but these compounds were minor contributors to TOC. The distribution of specific organic compounds showed that organic matter was well preserved throughout the time period sampled in both the total and intracrystalline pools. Variations in THAA were not correlated with TOC over time, suggesting that organic matter that is involved in biomineralization, like amino acids, may be deposited in response to different environmental factors than are other components of skeletal organic matter. Differences in the quantity and composition of organic matter between the two corals investigated here were assessed using principal components analysis and suggest that location, species and skeletal structure may all influence organic matter content and possibly the degree of physical protection of organic matter by the coral skeleton. Further, our study suggests that intracrystalline organic matter may be better protected from diagenesis than non-intracrystalline organic matter and may therefore be a more reliable source of organic matter for paleoceanographic studies than total skeletal organic matter.     

The imprinting of aridity upon a lateritic landscape: an illustration from southwestern Australia

The southwestern region of Australia contains the Yilgarn Craton that has been exposed to subaerial weathering since mid-Proterozoic. The gently undulating landscape experienced lateritic weathering so that today variably dissected, deep in situ isovolumetrically weathered regolith is widespread. Imposition of a more arid climate since the Miocene with the cessation of effective external drainage has resulted in substantial geochemical modification of the highly porous regolith. This vast pore volume acts as a reservoir for complex solutions that may be highly saline, extremely acid to alkaline and reducing. Diverse precipitates have formed in the regolith including widespread occurrence of silcrete, calcrete, dolocrete, ferricrete and gypcrete together with localised occurrences of pyrite, alunite, jarosite, barite, halite and other salts. Clearing of bush land for agriculture in the 20th century increased recharge so that rising chemically active groundwaters are damaging farmland and infrastructure throughout the region. To cite this article: B. Gilkes et al., C. R. Geoscience 335 (2003).     

Hydrogeochemical characterization of major factors affecting the quality of shallow groundwater in the coastal area at Kimje in South Korea

This study has evaluated the main hydrogeochemical characteristics that affect the quality of shallow groundwater in the coastal area at Kimje in South Korea. In this area, the chemical composition of groundwater is mostly classified into Na⁺?Cl^? and Ca²⁺+Mg²⁺?NO₃^-+Cl^? types. These types are affected by three major factors: seawater intrusion, fertilizers and redox processes. The Na⁺?Cl^? type, which is generally localized in the coastal area, shows typical characteristics of groundwater affected not only by modern seawater but also by old seawater residing in the reclaimed land. In contrast, the Ca²⁺+Mg²⁺?NO₃^-+Cl^? type, which is usually found inland, is very contaminated by fertilizers. As groundwater flows from the inland area to the coast, the redox condition changes from an oxic condition to a suboxic/anoxic condition. In addition, the reclamation has caused a large amount of underlying organic matter. These effects provide optimum conditions for the occurrence of redox processes in the coastal area.     

Evaluation of remedial alternatives for a petroleum contaminated unconfined aquifer with fluctuating groundwater level

This study evaluated remedial alternatives for a petroleum-contaminated site where an unconfined aquifer composed of a sandy layer of about 3–3.5 m thickness is covered by alluvial deposits and reclaimed soil of about 1.5 m thickness. Precambrian gneiss, of low permeability, lies below the sandy layer. The shallow water table is about 3 m below the surface, but shows high fluctuations of up to 1.5 m in response to precipitation events. The unsaturated soil near the water table and the groundwater are highly contaminated with petroleum hydrocarbons, especially toluene, which have apparently leaked from storage tanks. Selection of the remedial alternatives required consideration of the relevant laws on soil and groundwater conservation in Korea, the results of risk analysis and the hydrogeological conditions. The contaminated area has been divided into zones in which different remediation goals are set based on risk analysis and the degree of natural attenuation. It is estimated that the clean-up goal can be achieved in two years by the combined use of a trench drain and well point pumping to collect the contaminated groundwater for treatment, and a dual air injection system for the contaminated soil.