Iron Oxyhydroxide Transformation in a Flooded Rice Paddy Field and the Effect of Adsorbed Phosphate.

The mobility and bioavailability of phosphate in paddy soils are closely coupled to redox-driven Fe-mineral dynamics. However, the role of phosphate during Fe-mineral dissolution and transformations in soils remains unclear. Here, we investigated the transformations of ferrihydrite and lepidocrocite and the effects of phosphate pre-adsorbed to ferrihydrite during a 16-week field incubation in a flooded sandy rice paddy soil in Thailand. For the deployment of the synthetic Fe-minerals in the soil, the minerals were contained in mesh bags either in pure form or after mixing with soil material. In the latter case, the Fe-minerals were labeled with 57Fe to allow the tracing of minerals in the soil matrix with 57Fe Mössbauer spectroscopy. Porewater geochemical conditions were monitored, and changes in the Fe-mineral composition were analyzed using 57Fe Mössbauer spectroscopy and/or X-ray diffraction analysis. Reductive dissolution of ferrihydrite and lepidocrocite played a minor role in the pure mineral mesh bags, while in the 57Fe-mineral-soil mixes more than half of the minerals was dissolved. The pure ferrihydrite was transformed largely to goethite (82-85%), while ferrihydrite mixed with soil only resulted in 32% of all remaining 57Fe present as goethite after 16 weeks. In contrast, lepidocrocite was only transformed to 12% goethite when not mixed with soil, but 31% of all remaining 57Fe was found in goethite when it was mixed with soil. Adsorbed phosphate strongly hindered ferrihydrite transformation to other minerals, regardless of whether it was mixed with soil. Our results clearly demonstrate the influence of the complex soil matrix on Fe-mineral transformations in soils under field conditions and how phosphate can impact Fe oxyhydroxide dynamics under Fe reducing soil conditions.

Solid Phase Speciation and Solubility of Vanadium in Highly Weathered Soils.

Vanadium (V) is increasingly recognized both as a medical trace element with essential biological functions and as a potentially toxic environmental pollutant, yet the current knowledge on V speciation in soils is limited. Here, we investigated the chemical speciation and extractability of V in highly weathered tropical soils, which are often rich in V compared to soils of temperate climatic regions. Vanadium K-edge X-ray absorption near edge structure (XANES) spectra of soil samples, along with a range of reference compounds differing in V-oxidation state and coordination chemistry, revealed the predominance of V4+/5+ in a primarily octahedral or tetrahedral coordination. The soil spectra were best fitted with linear combinations of reference spectra of V4+ in the structure of kaolinite, V5+ adsorbed to kaolinite, and other V5+-sorbed solids. Vanadate adsorbed to goethite, ferrihydrite, gibbsite, and/or Fe(III)-natural organic matter complexes and V4+ in the structure of goethite may be present, but cannot unequivocally be distinguished from each other by XANES spectroscopy. Sequential and single chemical extractions provided complementary information on the solubility of V under various conditions. The most labile V fractions, interpreted as weakly and strongly adsorbed V5+, are the most relevant to V mobility and bioavailability in the environment, and accounted for only ∼2% of total soil V. Our results demonstrate that kaolinite and Fe oxides can effectively sequester V in highly weathered soils by mechanisms of adsorption and structural incorporation and are relevant to other Fe-oxide-rich environments under acidic and oxic conditions.

Culture-independent study of bacterial communities in tropical river sediment.

Ubiquitous microbial communities in river sediments actively govern organic matter decomposition, nutrient recycling, and remediation of toxic compounds. In this study, prokaryotic diversity in two major rivers in central Thailand, the Chao Phraya (CP) and the Tha Chin (TC) distributary was investigated. Significant differences in sediment physicochemical properties, particularly silt content, were noted between the two rivers. Tagged 16S rRNA sequencing on a 454 platform showed that the sediment microbiomes were dominated by Gammaproteobacteria and sulfur/sulfate reducing Deltaproteobacteria, represented by orders Desulfobacteriales and Desulfluromonadales together with organic degraders Betaproteobacteria (orders Burkholderiales and Rhodocyclales) together with the co-existence of Bacteroidetes predominated by Sphingobacteriales. Enrichment of specific bacterial orders was found in the clayey CP and silt-rich TC sediments, including various genera with known metabolic capability on decomposition of organic matter and xenobiotic compounds. The data represent one of the pioneered works revealing heterogeneity of bacteria in river sediments in the tropics.

Cadmium toxicity to and accumulation in a soil collembolan (Folsomia candida): major factors and prediction using a back-propagation neural network model.

Accurate prediction of cadmium (Cd) ecotoxicity to and accumulation in soil biota is important in soil health. However, very limited information on Cd ecotoxicity on naturally contaminated soils. Herein, we investigated soil Cd ecotoxicity using Folsomia candida, a standard single-species test animal, in 28 naturally Cd-contaminated soils, and the back-propagation neural network (BPNN) model was used to predict Cd ecotoxicity to and accumulation in F. candida. Soil total Cd and pH were the primary soil properties affecting Cd toxicity. However, soil pH was the main factor when the total Cd concentration was < 3 mg kg-1. Interestingly, correlation analysis and the K-spiked test confirmed nutrient potassium (K) was essential for Cd accumulation, highlighting the significance of studying K in Cd accumulation. The BPNN model showed greater prediction accuracy of collembolan survival rate (R2 = 0.797), reproduction inhibitory rate (R2 = 0.827), body Cd concentration (R2 = 0.961), and Cd bioaccumulation factor (R2 = 0.964) than multiple linear regression models. Then the developed BPNN model was used to predict Cd ecological risks in 57 soils in southern China. Compared to multiple linear regression models, the BPNN models can better identify high-risk regions. This study highlights the potential of BPNN as a novel and rapid tool for the evaluation and monitoring of Cd ecotoxicity in naturally contaminated soils.

Temporal development of arsenic speciation and extractability in acidified and non-acidified paddy soil amended with silicon-rich fly ash and manganese- or zinc-oxides under flooded and drainage conditions.

Oxides of silicon (Si), manganese (Mn), and zinc (Zn) have been used as soil amendments to reduce As mobility and uptake in paddy soil systems. However, these amendments are hypothesized to be affected differently depending on the soil pH and their effect on As speciation in rice paddy systems is not fully understood. Herein, we used a microcosm experiment to investigate the effects of natural Si-rich fly ash and synthetic Mn and Zn oxides on the temporal development of porewater chemistry, including aqueous As speciation (As(III), As(V), MMA, DMA, and DMMTA) and solid-phase As solubility, in a naturally calcareous soil with or without soil acidification (with sulfuric acid) during 28 days of flooding and subsequent 14 days of drainage. We found that soil acidification to pH 4.5 considerably increased the solubility of Si, Fe, Mn, and Zn compared to the non-acidified soil. Additions of Mn and Zn oxides decreased the concentrations of dissolved arsenite and arsenate in the non-acidified soil whereas additions of Zn oxide and combined Si-Zn oxides increased them in the acidified soil. The Si-rich fly ash did not increase dissolved Si and As in the acidified and non-acidified soils. Dimethylated monothioarsenate (DMMTA) was mainly observed in the acidified soil during the later stage of soil flooding. The initial 28 days of soil flooding decreased the levels of soluble and exchangeable As and increased As associated with Mn oxides, whereas the subsequent 14 days of soil drainage reversed the trend. This study highlighted that soil acidification considerably controlled the solubilization of Ca and Fe, thus influencing the soil pH-Eh buffering capacity, the solubility of Si, Mn, and Zn oxides, and the mobility of different As species in carbonate-rich and acidic soils under redox fluctuations.

Contact with soil impacts ferrihydrite and lepidocrocite transformations during redox cycling in a paddy soil.

Iron (Fe) oxyhydroxides can be reductively dissolved or transformed under Fe reducing conditions, affecting mineral crystallinity and the sorption capacity for other elements. However, the pathways and rates at which these processes occur under natural soil conditions are still poorly understood. Here, we studied Fe oxyhydroxide transformations during reduction-oxidation cycles by incubating mesh bags containing ferrihydrite or lepidocrocite in paddy soil mesocosms for up to 12 weeks. To investigate the influence of close contact with the soil matrix, mesh bags were either filled with pure Fe minerals or with soil mixed with 57Fe-labeled Fe minerals. Three cycles of flooding (3 weeks) and drainage (1 week) were applied to induce soil redox cycles. The Fe mineral composition was analyzed with Fe K-edge X-ray absorption fine structure spectroscopy, X-ray diffraction analysis and/or 57Fe Mössbauer spectroscopy. Ferrihydrite and lepidocrocite in mesh bags without soil transformed to magnetite and/or goethite, likely catalyzed by Fe(II) released to the pore water by microbial Fe reduction in the surrounding soil. In contrast, 57Fe-ferrihydrite in mineral-soil mixes transformed to a highly disordered mixed-valence Fe(II)-Fe(III) phase, suggesting hindered transformation to crystalline Fe minerals. The 57Fe-lepidocrocite transformed to goethite and small amounts of the highly disordered Fe phase. The extent of reductive dissolution of minerals in 57Fe-mineral-soil mixes during anoxic periods increased with every redox cycle, while ferrihydrite and lepidocrocite precipitated during oxic periods. The results demonstrate that the soil matrix strongly impacts Fe oxyhydroxide transformations when minerals are in close spatial association or direct contact with other soil components. This can lead to highly disordered and reactive Fe phases from ferrihydrite rather than crystalline mineral products and promoted goethite formation from lepidocrocite.

Sulfur amendments to soil decrease inorganic arsenic accumulation in rice grain under flooded and nonflooded conditions: Insights from temporal dynamics of porewater chemistry and solid-phase arsenic solubility.

Rice cultivation under flooded conditions enhances arsenic (As) solubility and favors As accumulation in rice grain that poses an indisputable threat to human health worldwide. The reduction of sulfur may induce processes that decrease As solubility, but its impact on rice grain As species remains unresolved. Herein, we investigated the influence of sulfur (S)-containing materials, including chicken manure and elemental sulfur powder on As accumulation and speciation in rice grain as well as the dynamics of the porewater chemistry and solid-phase As solubility throughout the entire growth stage under continuous flooding and intermittent flooding conditions in pot experiments. The S amendments (200 mg S kg-1) to the soil significantly decreased inorganic As in rice grain under continuous flooding (~65% decrease) as well as under intermittent flooding (~70% decrease). The chicken manure amendment promoted sulfur reduction and enhanced dissolvable Mn, Fe, and As at an earlier growth stage. The sequential extraction results corroborated a decrease in the soluble and exchangeable As (F1) and an increase in residual As (F5) fractions in the S-amended treatments. Solubility data suggested that As adsorption onto Fe oxides was the primary mechanism controlling As solubility rather than the formation of AsFe sulfides. Porewater As, considered to represent the most bioavailable As fraction, failed to explain the grain As accumulation. The time-averaged concentration of oxalate-extractable As explained grain arsenite best, suggesting that poorly crystalline Fe oxides may be the primary dissolvable reactive phases that control As bioavailability in the soil-rice system. Our results suggest that the application of S-containing soil amendments can effectively decrease inorganic As accumulation in rice grains grown under the flooded conditions, which are most widely applied in paddy rice production.

Feasibility assessment of bentonite drilling mud to improve the physical quality of loamy sand soil and water deficit of forest plant seedlings.

Spent drilling mud (DM), a co-product during horizontal directional drilling operations, needs proper disposal to comply with social and environmental sustainability awareness, with one option being its cost-effective reuse as a soil amendment. The possibility was investigated of DM applications to improve the physical quality of loamy sand soil. The soil was treated with increasing DM contents in a laboratory at volumetric DM-to-soil ratios of 0:100 (DM0, no DM), 25:75 (DM25), 50:50 (DM50), 75:25 (DM75), and 100:0 (DM100, no soil). The mixtures were analyzed for water retention, available water capacity, water storage capacity, S-index, soil aggregate stability (SAS), and chemical quality based on pH, effective electrical conductivity (ECe), sodium adsorption ratio (SAR), and exchangeable sodium percentage (ESP). The optimal ratio of DM and the control (DM0) in the batch experiment were selected for application to three species of forest plant seedlings in the field. The results showed that DM positively influenced soil physical qualities. The water retention increased (from 10 to 67%) with increasing DM, but the most suitable ratio was DM25, considering its water storage capacity deviated the least (1.4%) from the optimal value. DM25 also produced the highest S-index (0.081). The SAR data increased with the drilling mud application rate (1.1 to 10.9). However, the DM25 pH remained at 7.7, with an ECe of 2.5 dS m-1, a SAR of 7.0, and an ESP of 9.2, which were still favorable regarding soil structure, as indicated by no decrease in SAS with added drilling mud. In the field experiment, DM25 also decreased the water deficit of the three species of forest plant seedlings, suggesting a positive attribution to other relevant soil-plant systems. DM could be a feasible option to improve soil physical quality, but further long-term experiments are necessary before applying it as a soil amendment in real situations.Implications: With the demand in energy-driven economics, establishing national energy security nationwide in Thailand requires the installation capacity, transmission, and distribution pipelines. Horizontal directional drilling (HDD) operations are generally used to install underground pipelines, generating large amounts of drilling mud rich in sodium bentonite as a co-product. At present, drilling mud is becoming a more serious solid waste and has been raised in proper management. The best management practices are expected to reuse as a soil amendment, a cost-effective approach, for coarse-textured soils. Before any drilling mud application can be introduced to agriculture and the environment, we must clarify the optimal rate of drilling mud. This rate has to significantly improve soil physical quality associated with air-water capacity balance while minimizing the adverse effect of residual sodium to favor soil structure and sensitive plants.

The Distribution of Trace Metals in Roadside Agricultural Soils, Thailand.

Vehicle emissions have been known to cause trace metal contamination in soils. The extent of such contaminations in soils, and of the effects of traffic density and distance from highways on the concentration of trace metals in roadside agricultural soils is largely unknown. This study examined the total concentrations of common trace metals (Cd, Co, Cr, Cu, Ni, Pb, V, and Zn) in roadside agricultural soils from Thailand with diverse traffic densities (approximately 30⁻200 million vehicles/kilometer/year), roadside distances (0, 10, 20, 50, and 100 m from the road edge), and crops (rice, maize, and sugarcane). Cadmium, Cu, Pb, and Zn concentrations significantly decreased with increasing distance away from the roads (p < 0.05). However, the concentrations of these metals were not correlated with traffic density, probably due to extensive road maintenance and expansion. The contamination factor demonstrated that the road edge soils were moderately- to highly-polluted with Cd, Cu, Pb, and Zn. The safest distance to minimize metal pollution for agricultural production is proposed to be greater than 10 m away from the road edge.

Biochar and ash derived from silicon-rich rice husk decrease inorganic arsenic species in rice grain.

Exposure to arsenic (As) through rice consumption potentially threatens millions of people worldwide. Understanding is still lacking the recycling impacts of rice residues on As phytoavailability in paddy soils and is of indisputable importance in providing a sustainable and effective measure to decrease As accumulation in rice grain. Herein, we examined the effects of rice husk biochar (RHB) and rice husk ash (RHA) on As grain speciation, and As dynamics in the soil porewater and solid-phase fractions. The results corroborated that both the RHB and RHA (0.64% w/w) treatments significantly (p < 0.05) decreased inorganic As accumulation in rice grain to 0.27-0.29 mg kg-1, which was below the maximum inorganic As level in husked rice (0.35 mg kg-1) established by the Codex. The residual phase (F6 = 90% of total soil As) as quantified by the sequential extraction was the dominant As pool; the fractions were subsequently transformed into several As pools associated with soluble and exchangeable (F1), organically bound (F2), Mn oxides (F3), poorly crystalline (F4) and crystalline (F5) Fe oxides during the rice growing periods. The Si-rich amendments enhanced the residual phase formation upon soil flooding, which decreased the As availability to rice plant. The inorganic grain-As concentrations were well explained by the soil-extractable As concentrations in the F2, F3, F5, and F6 fractions. The pore-water analysis indicated that Mn oxides were important sources and sinks for As released to the soil solution. Our findings shed light on the beneficial role of RHB and RHA in alleviating inorganic As uptake in paddy rice.

Solid-Phase Speciation and Solubility of Phosphorus in an Acid Sulfate Paddy Soil during Soil Reduction and Reoxidation as Affected by Oil Palm Ash and Biochar.

Understanding phosphorus (P) speciation and how redox conditions control P solubility in acid sulfate paddy soils with limited P availability is crucial for improving soil P availability. We examined P speciation and extractability in an acid sulfate paddy soil incorporated with oil palm ash (OPA) and biochar (OPB) during soil reduction and subsequent oxidation. Phosphorus K-edge X-ray absorption near edge structure (XANES) spectra of the soil samples revealed that P in the soil mainly occurred as P adsorbed to ferrihydrite and P adsorbed to gibbsite. During soil reduction, gibbsite-bound P was transformed into variscite, which was back-transformed to gibbsite-bound P during soil reoxidation. Sequential extraction results confirmed the dominance of Fe/Al (hydr)oxides-bound P (average 72%) in the soils. The OPA incorporation increased the exchangeable P pool concurring with the decrease in gibbsite-bound P. The OPB incorporation enhanced the dissolved P from the residual pool presumably due to electron shuttling of biochar with Fe(III) minerals during soil reduction. Our results highlight P dynamics in paddy soils, which are of immense importance for effective P-management strategies in rice cultivation.