Controlling factors of groundwater chemistry and statistical analysis of the samples related to ophiolite of Nourabad-Harsin, West of Iran.

Recognizing controlling factors of groundwater chemistry in the ophiolite region of the southeastern area of Kermanshah is the aim of this study. The findings reveal that some samples' calcium, magnesium, and sodium absorption risk is higher than the standard range. Besides, statistical relationships of the data were investigated to recognize the key factors controlling water chemistry. Pearson's correlation was used to determine the elements with the same source. Saturation index (SI) and water-rock interaction helped us find the important minerals in reaction with water. Besides, the map of the spatial distribution of heavy elements was applied to prove the elements with a common source. According to these ties, the important factors controlling groundwater chemistry of the region are dissolution of gypsum as the common source of Ca, Sr, and S; dissolution and weathering of Cr-spinel mineral in peridotites as the common source of Si, Mg, and Cr; dissolution of existing Fe-Mg olivine and pyroxene in peridotite silicates as the common source of Mg and Ni, and dissolution of chalcedony, barite, and calcite as three minerals with the highest dissolution in water-rock interaction of groundwater samples.

Surface clay formation during short-term warmer and wetter conditions on a largely cold ancient Mars.

The ancient rock record for Mars has long been at odds with climate modelling. The presence of valley networks, dendritic channels and deltas on ancient terrains points towards running water and fluvial erosion on early Mars1, but climate modelling indicates that long-term warm conditions were not sustainable2. Widespread phyllosilicates and other aqueous minerals on the Martian surface3-6 provide additional evidence that an early wet Martian climate resulted in surface weathering. Some of these phyllosilicates formed in subsurface crustal environments5, with no association with the Martian climate, while other phyllosilicate-rich outcrops exhibit layered morphologies and broad stratigraphies7 consistent with surface formation. Here, we develop a new geochemical model for early Mars to explain the formation of these clay-bearing rocks in warm and wet surface locations. We propose that sporadic, short-term warm and wet environments during a generally cold early Mars enabled phyllosilicate formation without requiring long-term warm and wet conditions. We conclude that Mg-rich clay-bearing rocks with lateral variations in mixed Fe/Mg smectite, chlorite, talc, serpentine and zeolite occurrences formed in subsurface hydrothermal environments, whereas dioctahedral (Al/Fe3+-rich) smectite and widespread vertical horizonation of Fe/Mg smectites, clay assemblages and sulphates formed in variable aqueous environments on the surface of Mars. Our model for aluminosilicate formation on Mars is consistent with the observed geological features, diversity of aqueous mineralogies in ancient surface rocks and state-of-the-art palaeoclimate scenarios.

Inhibition of phosphorus sorption on calcite by dairy manure-sourced DOC.

In confined animal feeding operations, such as dairies, manure is amended to soils at high rates leading to increases in P and organic matter in the soils. Phosphorus reacts with soil-Ca to form Ca-P minerals, which controls P availability for leaching and transport through the watershed. In this research, the effects of manure sourced dissolved organic matter (DOM) on P sorption on calcite were measured at different reaction times and concentrations. Reactions were monitored in 1% and 10% manure-to-water extract solutions spiked with P. When manure-DOM was present, a significant reduction in P sorption occurred (2-90% absolute decrease) compared to samples without manure-DOM. The greatest decrease occurred in the samples reacted in the 10% manure solution. XANES spectroscopic analysis showed that at 1% manure solution, a Ca-P phase similar to hydroxyapatite formed. In the calcite samples reacted in the 10% manure solution, K-edge XANES spectroscopy revealed that P occurred as a Ca-Mg-P phase instead of the less soluble hydroxyapatite-like phase. Results from this study suggest that in manure-amended calcareous soils, increased DOM from manure will decrease P sorption capacity and increase the overall P concentration in solution, which will increase the mobility of P and subsequently pose greater risks for impairment of surface water quality.

Biochar Soil Amendment Effects on Arsenic Availability to Mountain Brome ().

Biochar is a renewable energy byproduct that shows promise for remediating contaminated mine sites. A common contaminant at mine sites is arsenic (As). In this study, the effects of biochar amendments to a mine-contaminated soil on As concentrations in mountain brome ( Nees ex Steud.) were investigated. In the biochar-amended soil, mountain brome had greater root biomass and decreased root and shoot As concentrations. X-ray absorption near-edge structure spectroscopy results showed that arsenate [As(V)] is the predominant species in both the nonamended and biochar-amended soils. Soil extraction tests that measure phosphate and arsenate availability to plants failed to accurately predict plant tissue As concentrations, suggesting the arsenate bioavailability behavior in the soils is distinct from phosphate. Results from this study indicate that biochar will be a beneficial amendment to As-contaminated mine sites for remediation.

Lead immobilization and phosphorus availability in phosphate-amended, mine-contaminated soils.

Over a century of mining activities in the Coeur d'Alene mining district in Idaho have contaminated soils of the downstream basin with lead, arsenic, zinc, and cadmium. Elevated soil-Pb levels are a significant hazard to the health of humans and wildlife in the region. One in situ treatment approach for remediating Pb-contaminated soils is application of phosphorus to promote the formation of lead phosphate minerals that have low solubility. However, this remediation strategy may result in excess P runoff to surface waters, which can lead to eutrophication, particularly when used in riparian areas. Research presented in this paper describes experiments in which monopotassium phosphate (KHPO) solution was applied to two Pb-contaminated soils from the Coeur d'Alene River valley to determine how P loading rates affect both Pb immobilization and P mobility and to determine if an optimal P amendment rate can be predicted. Toxicity characteristic leaching procedure extractions were used to assess changes in Pb availability for uptake by an organism or mobilization through the soil, and Bray extractions were used to assess P availability for leaching out of the soil system. For the two soils tested, increasing phosphate amendment caused decreasing Pb extractability. Phosphorus amendment rates above approximately 70 mg kg, however, did not provide any additional Pb immobilization. Phosphorus availability increased with increasing phosphate application rate. An empirical relationship is presented that predicts extractable Pb as a function of extractable P. This relationship allows for prediction of the amount of Pb that can be immobilized at specified P leaching amounts, such as regulatory levels that have been established to minimize risks for surface water degradation. Results suggest that phosphate can be used to immobilize Pb in contaminated wetland or riparian areas without posing risks of P loading to surface waters.

Metal content of charcoal in mining-impacted wetland sediments.

Charcoal is well known to accumulate contaminants, but its association with metals and other toxic elements in natural settings has not been well studied. Association of contaminants with charcoal in soil and sediment may affect their mobility, bioavailability, and fate in the environment. In this paper, natural wildfire charcoal samples collected from a wetland site that has been heavily contaminated by mine waste were analyzed for elemental contents and compared to the surrounding soil. Results showed that the charcoal particles were enriched over the host soils by factors of two to 40 times in all contaminant elements analyzed. Principal component analysis was carried out on the data to determine whether element enrichment patterns in the soil profile charcoal are related to those in the soils. The results suggest that manganese and zinc concentrations in charcoal are controlled by geochemical processes in the surrounding soil, whereas the concentrations of arsenic, lead, zinc, iron, phosphorus, and sulfur in charcoal are unrelated to those in the surrounding soil. This study shows evidence that charcoal in soils can have a distinct and important role in controlling contaminant speciation and fate in the environment.

Chemical Extractability of Pb in Field-Contaminated Soils: Implications for Estimating Total Pb.

Lead (Pb) is frequently present in urban soils at concentrations of concern for human health. Regulations for this metal are based on total soil concentrations as determined by acid digestion, but a less expensive screening test for Pb would be useful in facilitating more thorough soil testing of urban areas if it could be shown to correlate strongly to total soil Pb. In this study, three extractants (0.1 M citrate, Modified Morgan, 1 M nitric acid) were evaluated for their ability to estimate the total Pb in contaminated soils. Nitric acid not only extracted a greater fraction of total soil Pb, but also produced the strongest correlation to total Pb and is concluded to be the superior extractant for a soil Pb screening test. As the spatial distribution of Pb was observed in selected soils to be highly heterogeneous on the micron scale, thorough soil homogenization prior to testing is recommended.

Molecular characterization of copper in soils using X-ray absorption spectroscopy.

Bioavailability of Cu in the soil is a function of its speciation. In this paper we investigated Cu speciation in six soils using X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and synchrotron-based micro X-ray fluorescence (mu-XRF). The XANES and EXAFS spectra in all of the soils were the same. mu-XRF results indicated that the majority of the Cu particles in the soils were not associated with calcium carbonates, Fe oxides, or Cu sulfates. Principal component analysis and target transform of the XANES and EXAFS spectra suggested that Cu adsorbed on humic acid (HA) was an acceptable match. Thus it appears that Cu in all of the soils is primarily associated with soil organic matter (SOM). Theoretical fitting of the molecular structure in the soil EXAFS spectra revealed that the Cu in the soils existed as Cu atoms bound in a bidentate complex to O or N functional groups.

Speciation of Cu in a contaminated agricultural soil measured by XAFS, micro-XAFS, and micro-XRF.

Contamination of agricultural soils with Cu as a result of fungicide application and spills threatens environmental quality and reduces soil quality for crop growth. In this paper advanced spectroscopic and microscopic methods were used to elucidate the Cu speciation in a calcareous soil contaminated since the 1940s. Microscopically focused synchrotron-based XRF (micro-SXRF) was used to map the elemental distribution in the soils. Results indicated that most of the Cu was not associated with metal oxides, silicates, phosphates, or carbonates. Bulk and microscopically focused X-absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra indicated thatthe Cu in the soil was predominantly Cu adsorbed on soil organic matter (SOM). Interpretation of the fitting results suggests that the Cu is complexed to SOM via bidentate inner-sphere coordination with carboxyl or amine ligands. Results presented in this paper provide detailed information on the molecular coordination of Cu in a contaminated soil. Such information is critical for understanding the long-term fate and best management practices for Cu in the environment.