A single column separation method for barium isotope analysis of geologic and hydrologic materials with complex matrices

The increasing significance of barium (Ba) in environmental and geologic research in recent years has led to interest in the application of the Ba isotopic composition as a tracer for natural materials with complex matrices. Most Ba isotope measurement techniques require separation of Ba from the rest of sample prior to analysis. This paper presents a method using readily available materials and disposable columns that effectively separates Ba from a range of geologic and hydrologic materials, including carbonate minerals, silicate rocks, barite, river water, and fluids with high total dissolved solids and organic content such as oil and gas brines, rapidly and without need for an additional cleanup column. The technique involves off-the-shelf columns and cation exchange resin and a two-reagent elution that uses 2.5 N HCl followed by addition of 2.0 N HNO3. We present data to show that major matrix elements from almost any natural material are separated from Ba in a single column pass, and that the method also effectively reduces or eliminates isobaric interferences from lanthanum and cerium.

A density functional theory study of Fe(II)/Fe(III) distribution in single layer green rust: a cluster approach

Green rust (GR) is a potentially important compound for the reduction of heavy metal and organic pollutants in subsurface environment because of its high Fe(II) content, but many details of the actual reaction mechanism are lacking. The reductive capacity distribution within GR is a key to understand how and where the redox reaction occurs and computational chemistry can provide more details about the electronic properties of green rust. We constructed three sizes of cluster models of single layer GR (i.e., without interlayer molecules or ions) and calculated the charge distribution of these structures using density functional theory. We found that the Fe(II) and Fe(III) are distributed unevenly in the single layer GR. Within a certain range of Fe(II)/Fe(III) ratios, the outer iron atoms behave more like Fe(III) and the inner iron atoms behave more like Fe(II). These findings indicate that the interior of GR is more reductive than the outer parts and will provide new information to understand the GR redox interactions.

Influences on tidal channel and aquaculture shrimp pond water chemical composition in Southwest Bangladesh

Detailed geochemical studies of both major and minor elements in Bangladesh surface waters are sparse, particularly in shrimp aquaculture pond environments. Therefore, water samples from shrimp aquaculture ponds and tidal channels were collected in high precipitation (July) and low precipitation (May) months from 2018–2019 in Southwest Bangladesh and analyzed for complete water chemistry. Selenium (Se) and arsenic (As) were elevated above WHO guidelines in 50% and ~ 87% of samples, respectively, but do not show any recognizable spatial patterns. Shrimp pond and tidal channel water compositions in the dry season (May) are similar, illustrating their connectivity and minimal endogenous effects within shrimp ponds. Tidal channels are less saline in July than shrimp ponds still irrigated by tidal channels, suggesting that either farmers limit irrigation to continue farming saltwater shrimp, or the irrigation flux is low and leads to a lag in aquaculture-tidal channel compositional homogenization. δ18O and δ2H isotopic compositions from samples in May of 2019 reveal tidal channel samples are closer to the local meteoric water line (LMWL) than shrimp pond samples, because of less evaporation. However, evaporation in May shrimp ponds has a minimal effect on water composition, likely because of regular drainage/exchange of pond waters. Dissolved organic carbon (DOC) is positively correlated with both δ18O and δ2H in shrimp ponds, suggesting that as evaporation increases, DOC becomes enriched. Multiple linear regression reveals that As and Se can be moderately predicted (adjusted R2 values between 0.4 and 0.7, p < 0.01) in surface waters of our study with only 3–4 independent predictor variables (e.g., Ni, V and DOC for Se prediction; Cu, V, Ni and P for As prediction). Thus, this general approach should be followed in other regions throughout the world when measurements for certain hazardous trace elements such as Se and As may be lacking in several samples from a dataset.

Dissolution and solubility of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] at 25 °C

A complete series of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] are prepared, and their dissolution processes in various water samples are experimentally investigated. The crystal morphologies of the solid solutions vary from blocky spherical crystal aggregates to smaller spheres with an increasing incorporation of Mn in the solids. Regarding dissolution in N2-degassed water, air-saturated water and CO2-saturated water at 25 °C, the aqueous Ca and Mn concentrations reach their highest values after 1240–2400 h, 6–12 h and < 1 h, respectively, and then decrease gradually to a steady state; additionally, the ion activity products (log_IAP) at the final steady state (≈ solubility products in log_Ksp) are estimated to be − 8.46 ± 0.06, − 8.44 ± 0.10 and − 8.59 ± 0.10 for calcite [CaCO3], respectively, and − 10.25 ± 0.08, − 10.26 ± 0.10 and − 10.28 ± 0.03, for rhodochrosite [MnCO3], respectively. As XMn increases, the log_IAP values decrease from − 8.44 ~ − 8.59 for calcite to − 10.25 ~ − 10.28 for rhodochrosite. The aqueous Mn concentrations increase with an increasing Mn/(Ca + Mn) molar ratio (XMn) of the (Ca1-xMnx)CO3 solid solutions, while the aqueous Ca concentrations show the highest values at XMn = 0.53–0.63. In the constructed Lippmann diagram of subregular (Ca1-xMnx)CO3 solid solutions, the solids dissolve incongruently, and the data points of the aqueous solutions move progressively up to the Lippmann solutus curve and then along the solutus curve or saturation curve of pure MnCO3 to the Mn-poor side. The microcrystalline cores of the spherical crystal aggregates are preferentially dissolved to form core hollows while simultaneously precipitating Mn-rich hexagonal prisms.