Seasonal effects of natural attenuation on drainage contamination from artisanal gold mining, Cambodia: Implication for passive treatment.

In Mondulkiri province, Cambodia, artisanal gold miners dump tailings and wastewater from gold processing into a tributary of the Prek Te River. In the rainy season, heavy metal concentrations in the tributary decrease below the WHO drinking water standard levels through natural attenuation; however, this does not occur in the dry season. To further understand the natural attenuation mechanism, detailed analyses of the wastewater from tailing and tributary water, tributary sediments, waste rock, and ore minerals were undertaken in both seasons. The high concentration of dissolved Fe in the contaminated tributary plays a significant role in As removal during the rainy season, whereas other elements such as Ni, Se, and Cu concentration decrease due to dilution. Schwertmannite formation, controlled by iron-oxidizing bacteria, was only found at the bottom of the tributary during the rainy season. In the dry season, As, Ni, Se, and Cu concentrations remained at their original levels because there was no formation of schwertmannite or dilution by rainwater. The existing schwertmannite also starts to dissolve as the pH decreases. Seasonal dynamics cause the failure of natural attenuation; thus, methods for maintaining its effectiveness in the dry season are needed. In addition, geochemical modeling was conducted to determine the significant roles of schwertmannite formation and dilution of rainwater in the tributary. Schwertmannite is a potential adsorbent for As removal from drainage. However, dilution provided indirect and direct impacts on the tributary, such as increasing the pH and diluting the concentration of toxic elements.

Subseafloor sulphide deposit formed by pumice replacement mineralisation.

Seafloor massive sulphide (SMS) deposits, modern analogues of volcanogenic massive sulphide (VMS) deposits on land, represent future resources of base and precious metals. Studies of VMS deposits have proposed two emplacement mechanisms for SMS deposits: exhalative deposition on the seafloor and mineral and void space replacement beneath the seafloor. The details of the latter mechanism are poorly characterised in detail, despite its potentially significant role in global metal cycling throughout Earth's history, because in-situ studies require costly drilling campaigns to sample SMS deposits. Here, we interpret petrographic, geochemical and geophysical data from drill holes in a modern SMS deposit and demonstrate that it formed via subseafloor replacement of pumice. Samples from the sulphide body and overlying sediment at the Hakurei Site, Izena Hole, middle Okinawa Trough indicate that sulphides initially formed as aggregates of framboidal pyrite and matured into colloform and euhedral pyrite, which were replaced by chalcopyrite, sphalerite and galena. The initial framboidal pyrite is closely associated with altered material derived from pumice, and alternating layers of pumiceous and hemipelagic sediments functioned as a factory of sulphide mineralisation. We infer that anhydrite-rich layers within the hemipelagic sediment forced hydrothermal fluids to flow laterally, controlling precipitation of a sulphide body extending hundreds of meters.

Geochemical behaviour of heavy metals in sludge effluents and solid deposits on the Zambian Copperbelt: Implication for effluent treatment and sludge reuse.

Sludge effluents and solid deposits generated from the conventional lime treatment processes on the Zambian Copperbelt have led to reports of copper (Cu) and cobalt (Co) contamination into the nearby water bodies. To better understand the behaviour of the metals; partitioning, adsorption and their specific binding forms were studied through sequential extraction, batch adsorption experiments and surface complexation modeling (SCM). Results of mineral composition analyses indicated that micas, kaolinite, quartz and feldspar are abundant with hydrous ferric oxide (HFO) precipitates that formed as a result of the weathering of biotite grains existing as grain surface coating. Sequential extractionrevealed that Cu and Co metals are partitioned in the order of: exchangeable (F1: 600-1500 mg/kg Cu; 100-200 mg/kg Co), acid-soluble (F2: 2200-5500 mg/kg Cu; 190-220 mg/kg Co) and reducible fraction (F3: 2200-5500 mg/kg Cu; 260-300 mg/kg Co). Metals in F1 are hosted by kaolinite, F2 by both kaolinite and HFO whereas in F3 by dominantly HFO. Equal Cu concentration between F2 and F3 is due to both the limited amount of HFO (i.e. 5-10 g/kg) and desorption of loosely adsorbed Cu and Co metals to HFO surfaces. Batch adsorption experiments revealed adsorption as the dominant metal retention mechanism. According to modeling predictions, HFO sites are the dominant metal adsorption sites. At HFO site; >(s)FeOCo+, Co showed adsorption decrease from 40% in single system to 25% in binary system between pH 7 - 7.5 due to metal competition for adsorption sites. The high Cu concentration (i.e. 0.5-1.1% Cu) displaced low Co (i.e. 0.03-0.07% Co) concentration from the adsorption sites present in sludge, thus rendering Co mobile into the environment. To keep the adsorbed metals stable from release, optimal pH of 7.5 is suggested during treatment with lime. At this optimal pH, metals are decreased to below the regulation standard values and with less generation of voluminous sludge. Adsorbed Cu and Co can be recoverable from sludge through acid treatment at pH <3 based on sequential extraction results. The resultant metal-free sludge material has potential of been used as aggregate in construction.

Effect of Soil Organic Matters in Dredged Soils to Utilization of their Mixtures Made with a Steel Slag.

Dredged soils have been used as construction materials by alkaline activation with steel slag (steel slag-dredged soil mixtures) at harbors. Such mixtures develop strength chiefly by calcium silicate hydrate (C-S-H) formation by the pozzolanic reaction. However, the strength of such mixtures is unpredictable, and in some cases, mixtures have been too soft for the intended engineering application. An identification of strength development indicators would accelerate evaluation processes for strength development to facilitate and promote the utilization of such materials. This paper focuses on the relationship between the characteristics of soil organic matters in dredged soils and the strength development of the mixtures by a comparison of eight dredged soils collected from eight different Japanese harbors. The characteristics of the soil organic matters were identified to determine as indicators of mixtures with weak strength development, i.e., enriched sulfur content in extracted soil organic matter (humic acid) fraction, and the N/C ratio of humic acid similar to land humic acid standards. Increases in the validated fraction of dredged soils and steel slag by replacing fractions disadvantageous to construction resources would contribute to reduce waste production, which would lower the environmental impact of the use, aiming to achieve sustainable utilization of such materials.

Mechanisms of Se(IV) Co-precipitation with Ferrihydrite at Acidic and Alkaline Conditions and Its Behavior during Aging.

Understanding the form of Se(IV) co-precipitated with ferrihydrite and its subsequent behavior during phase transformation is critical to predicting its long-term fate in a range of natural and engineered settings. In this work, Se(IV)-ferrihydrite co-precipitates formed at different pH were characterized with chemical extraction, transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS) to determine how Se(IV) is associated with ferrihydrite. Results show that despite efficient removal, the mode and stability of Se(IV) retention in the co-precipitates varied with pH. At pH 5, Se(IV) was removed dominantly as a ferric selenite-like phase intimately associated with ferrihydrite, while at pH 10, it was mostly present as a surface species on ferrihydrite. Similarly, the behavior of Se(IV) and the extent of its retention during phase transformation varied with pH. At pH 5, Se(IV) remained completely associated with the solid phase despite the phase change, whereas it was partially released back into solution at pH 10. Regardless of this difference in behavior, TEM and XAS results show that Se(IV) was retained within the crystalline post-aging products and possibly occluded in nanopore and defect structures. These results demonstrate a potential long-term immobilization pathway for Se(IV) even after phase transformation. This work presents one of the first direct insights on Se(IV) co-precipitation and its behavior in response to iron phase transformations.

A novel method for remediation of nickel containing wastewater at neutral conditions.

Heavy metals contained in wastewater are generally removed by adding antalkaline to increase the pH, and Ni is commonly precipitated as Ni-hydroxides at pH 10. However, a more sustainable remediation method of treatment at neutral conditions would be attractive due to the high cost of chemical reagents and inefficient treatment at present. Based on natural attenuation, the method of adding Al ions has been used in wastewater treatment to precipitate layered double hydroxides (LDH). Here, we investigated the use of Al ion addition in the Ni containing wastewater treatment, experimentally and thermodynamically. By co-precipitation experiments adding Al ions to Ni-containing water, Ni was selectively incorporated into the structure of LDH, and the removal efficiency of Ni was close to 100% even in pH 7 and 8 samples (lower pH than conventional methods) with initial Ni concentrations of 200-10,000mg/L. Geochemical modeling results replicate the experimental results well when the Al/Ni ratio of LDH is assumed to be 0.33. This model makes it possible to estimate the amount of Al ions and additive agents necessary for use in treatment of wastewater containing different Ni concentrations.

Effects of Glycine, Water, Ammonia, and Ammonium Bicarbonate on the Oligomerization of Methionine.

The abiotic oligomerization of amino acids may have created primordial, protein-like biological catalysts on the early Earth. Previous studies have proposed and evaluated the potential of diagenesis for the amino acid oligomerization, simulating the formation of peptides that include glycine, alanine, and valine, separately. However, whether such conditions can promote the formation of peptides composed of multiple amino acids remains unclear. Furthermore, the chemistry of pore water in sediments should affect the oligomerization and degradation of amino acids and oligomers, but these effects have not been studied extensively. In this study, we investigated the effects of water, ammonia, ammonium bicarbonate, pH, and glycine on the oligomerization and degradation of methionine under high pressure (150 MPa) and high temperature conditions (175 °C) for 96 h. Methionine is more difficult to oligomerize than glycine and methionine dimer was formed in the incubation of dry powder of methionine. Methionine oligomers as long as trimers, as well as methionylglycine and glycylmethionine, were formed under every condition with these additional compounds. Among the compounds tested, the oligomerization reaction rate was accelerated by the presence of water and by an increase in pH. Ammonia also increased the oligomerization rate but consumed methionine by side reactions and resulted in the rapid degradation of methionine and its peptides. Similarly, glycine accelerated the oligomerization rate of methionine and the degradation of methionine, producing water, ammonia, and bicarbonate through its decomposition. With Gly, heterogeneous dimers (methionylglycine and glycylmethionine) were formed in greater amounts than with other additional compounds although smaller amount of these heterogeneous dimers were formed with other additional compounds. These results suggest that accelerated reaction rates induced by water and co-existing reactive compounds promote the oligomerization of less reactive amino acids during diagenesis and enhance the formation of peptides composed of multiple amino acids.

Abiotic formation of valine peptides under conditions of high temperature and high pressure.

We investigated the oligomerization of solid valine and the stabilities of valine and valine peptides under conditions of high temperature (150-200 °C) and high pressure (50-150 MPa). Experiments were performed under non-aqueous condition in order to promote dehydration reaction. After prolonged exposure of monomeric valine to elevated temperatures and pressures, the products were analyzed by liquid chromatography mass spectrometry comparing their retention times and masses. We identified linear peptides that ranged in size from dimer to hexamer, as well as a cyclic dimer. Previous studies that attempted abiotic oligomerization of valine in the absence of a catalyst have never reported valine peptides larger than a dimer. Increased reaction temperature increased the dissociative decomposition of valine and valine peptides to products such as glycine, ß-alanine, ammonia, and amines by processes such as deamination, decarboxylation, and cracking. The amount of residual valine and peptide yields was greater at higher pressures at a given temperature, pressure, and reaction time. This suggests that dissociative decomposition of valine and valine peptides is reduced by pressure. Our findings are relevant to the investigation of diagenetic processes in prebiotic marine sediments where similar pressures occur under water-poor conditions. These findings also suggest that amino acids, such as valine, could have been polymerized to peptides in deep prebiotic marine sediments within a few hundred million years.

Stability of amino acids and their oligomerization under high-pressure conditions: implications for prebiotic chemistry.

The polymerization of amino acids leading to the formation of peptides and proteins is a significant problem for the origin of life. This problem stems from the instability of amino acids and the difficulty of their oligomerization in aqueous environments, such as seafloor hydrothermal systems. We investigated the stability of amino acids and their oligomerization reactions under high-temperature (180-400°C) and high-pressure (1.0-5.5 GPa) conditions, based on the hypothesis that the polymerization of amino acids occurred in marine sediments during diagenesis and metamorphism, at convergent margins on early Earth. Our results show that the amino acids glycine and alanine are stabilized by high pressure. Oligomers up to pentamers were formed, which has never been reported for alanine in the absence of a catalyst. The yields of peptides at a given temperature and reaction time were higher under higher-pressure conditions. Elemental, infrared, and isotopic analyses of the reaction products indicated that deamination is a key degradation process for amino acids and peptides under high-pressure conditions. A possible NH(3)-rich environment in marine sediments on early Earth may have further stabilized amino acids and peptides by inhibiting their deamination.