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.     

Kinetics of Cd sorption, desorption and fixation by calcite: A long-term radiotracer study

Time-dependent sorption and desorption of Cd on calcite was studied over 210 days utilizing ¹⁰⁹Cd as a tracer to distinguish between ‘labile’ and ‘non-labile’ forms of sorbed Cd. Stabilizing the calcite suspensions for 12 months under atmospheric P_CO2 and controlled temperature was necessary to reliably follow Cd dynamics following initial sorption. Results revealed time-dependant Cd sorption and marked desorption hysteresis by calcite under environmentally relevant conditions. Data obtained were fitted to a first-order kinetic model and a concentric shell diffusion model. Both models described the progressive transfer of Cd²⁺ to a less reactive form within calcite and subsequent desorption of Cd subject to different initial contact times. The kinetic model provided a better fit to the combined sorption and desorption data (R² = 0.992). It differentiates between two ‘pools’ of sorbed Cd²⁺ on calcite, ‘labile’ and ‘non-labile’, in which labile sorbed Cd is in immediate equilibrium with the free Cd²⁺ ion activity in solution whereas non-labile Cd is kinetically restricted. For the diffusion model (R² = 0.959), the rate constants describing Cd dynamics in calcite produced a half-life for Cd desorption of ∼175 d, for release to a ‘zero-sink’ solution. Results from this study allow comment on the likely mechanisms occurring at the calcite surface following long-term Cd sorption.     

Does continental crust transform during eclogite facies metamorphism?

Eclogites within exhumed continental collision zones indicate regional burial to depths of at least 60 km, and often more than 100 km in the coesite‐stable, ultra‐high pressure (UHP) eclogite facies. Garnet, omphacitic pyroxene, high‐Si mica, kyanite ± coesite should grow at the expense of low‐P minerals in most felsic compositions, if equilibrium obtained at these conditions. The quartzofeldspathic rocks that comprise the bulk of eclogite facies terranes, however, contain mainly amphibolite facies, plagioclase‐bearing assemblages. To what extent these lower‐P minerals persisted metastably during (U)HP metamorphism, or whether they grew afterwards, reflects closely upon crustal parameters such as density, strength and seismic character. The Nordfjord area in western Norway offers a detailed view into a large crustal section that was subducted into the eclogite facies. The degree of transformation in typical pelite, paragneiss, granitic and granodioritic gneiss was assessed by modelling the equilibrium assemblage, comparing it with existing parageneses in these rocks and using U/Th–Pb zircon geochronology from laser ablation ICPMS to establish the history of mineral growth. U–Pb dates define a period of zircon recrystallization and new growth accompanying burial and metamorphism lasting from 430 to 400 Ma. Eclogite facies mafic rock (~2 vol.% of crust) is the most transformed composition and records the ambient peak conditions. Rare garnet‐bearing pelitic rocks (<10 vol.% of crust) preserve a mostly prograde mineral evolution to near‐peak conditions; REE concentrations in zircon indicate that garnet was present after 425 Ma and feldspar broke down after 410 Ma. Felsic gneiss – by far the most abundant rock type – is dominated by quartz + biotite + feldspar, but minor zoisite/epidote, phengitic white mica, garnet and rutile point to a prograde HP overprint. Relict textures indicate that much of the microstructural framework of plagioclase, K‐feldspar, and perhaps biotite, persisted through at least 25 Ma of burial, and ultimately UHP metamorphism. The signature reaction of the eclogite facies in felsic rocks – jadeite/omphacite growth from plagioclase – cannot be deduced from the presence of pyroxene or its breakdown products. We conclude that prograde dehydration in orthogneiss leads to fluid absent conditions, impeding equilibration beyond ~high‐P amphibolite facies.     

Impact of storm runoff from tropical watersheds on coastal water quality and productivity

Storm runoff in the steep watersheds in Hawaii leads to sediment and freshwater pulses to coastal waters that quickly affect nearshore water quality. This is particularly true in semi-enclosed embayments, such as Kaneohe Bay, Oahu, where water has a relatively long residence time compared to more open coastal areas of the islands. In this paper the authors discuss water quality and productivity in Kaneohe Bay after back-to-back rain events in late November and early December 2003, following a particularly dry summer. The short-term biogeochemical response of coastal waters and the ecosystem to runoff and physical forcing was evaluated through a combination of continuous in situ measurements and adaptive synoptic sampling carried out on a variety of temporal and spatial scales.     

Bias in hydraulic head measurements from multilevel vibrating-wire piezometers with excessively permeable backfill

Hydrogeology Journal - An extensive network of multilevel vibrating-wire piezometers (VWP) was recently created to monitor the spatial and temporal variation of pore pressure (and hydraulic head)...     

Sequential extraction and leaching characteristics of heavy metals in abandoned tungsten mine tailings sediments

The chemical speciation of potentially toxic elements (As, Cd, Cu, Pb, and Zn) in the contaminated soils and sulfides-rich tailings sediments of an abandoned tungsten mine in Korea was evaluated by conducting modified BCR sequential extraction tests. Kinetic and static batch leaching tests were also conducted to evaluate the potential release of As and other heavy metals by acidic rain water and the leaching behaviors of these heavy metals. The major sources of the elements were As-, Zn- and Pb-bearing sulfides, Pb carbonates (i.e., cerussite), and Pb sulfates (i.e., anglesite). The biggest pollutant fraction in these soil and tailing samples consists of metals bound to the oxidizable host phase, which can be released into the environment if conditions become oxidative, and/or to residual fractions. No significant difference in total element concentrations was observed between the tailings sediments and contaminated soils. For both sample types, almost no changes occurred in the mobility of As and the other heavy metals at 7 days, but the mobility increased afterwards until the end of the tests at 30 days, regardless of the initial pH. However, the mobility was approximately 5–10 times higher at initial pH 1.0 than at initial pHs of 3.0 and 5.0. The leached amounts of all the heavy metal contents were higher from tailings sediments than from contaminated soils at pH > 3.0, but were lower at pH < 3.0 except for As. Results of this study suggest that further dissolution of heavy metals from soil and tailing samples may occur during extended rainfall, resulting in a serious threat to surface and groundwater in the mine area.     

Structural similarity and variety at the tips in a wide range of strike–slip faults: a review

Strike–slip faults are often accompanied by a variety of structures, particularly at their tips. The zones of additional fracturing are classified as tip‐damage zones. These zones can be subdivided into several different damage patterns based on the nature and orientation of faults and fractures developed. Damage zones at the ends of small strike–slip faults (mode II tips) develop wing cracks, horsetail splays, antithetic faults, synthetic branch faults and solution surfaces. Similar tip‐damage patterns are also commonly observed at larger (regional) scales, but with a dominance of faulting over tensile cracks and solution surfaces. Wing cracks and horsetail splays developed at small‐scale faults are replaced by normal faults in large‐scale faults. Antithetic faults and synthetic branch faults are observed at small and large scales. Thrust faults are developed at large scales, in a similar pattern to solution surfaces at a small scale. All these structures may show slightly different angular relationships to the master fault at small and large scale, but develop in response similar stress distribution and mechanics around the fault. Thus, mode II tip‐damage zones show similar patterns over a wide range of fault scales.     

Effects of biochar, cow bone, and eggshell on Pb availability to maize in contaminated soil irrigated with saline water

Toxicity of heavy metals adversely affects environment and human health. Organic materials derived from natural matters or wastes have been applied to soils to reduce the mobility of contaminants such as heavy metals. However, the application of cow bone powder (CB), biochar (BC), and eggshell powder (ES) is rarely investigated for the reduction of Pb bioavailability in soils irrigated with saline water. The objective of this study was to assess the effectiveness of CB, BC, and ES additions as immobilizing substances on Pb bioavailability in shooting range soil irrigated with deionized and saline water. Each additive of CB, BC, and ES at 5 % (w/w) was mixed with soils and then the deionized and saline water were irrigated for 21 days. With deionized water irrigation, the soils treated with CB, BC, and ES exhibited higher pH when compared with saline water irrigation. With saline water irrigation, the electrical conductivity, water-soluble anions, and cations were significantly increased in soils treated with CB, BC, and ES. The water-soluble Pb in soils treated with CB, BC, and ES was significantly decreased with saline water irrigation. On the other hand, the water-soluble Pb in soil treated with CB was increased with deionized water irrigation. Only BC with saline water irrigation decreased the Pb concentration in maize shoots.