Tomoyuki Makino

Remediation of heavy metal(loid)s contaminated soils - To mobilize or to immobilize?

Unlike organic contaminants, metal(loid)s do not undergo microbial or chemical degradation and persist for a long time after their introduction. Bioavailability of metal(loid)s plays a vital role in the remediation of contaminated soils. In this review, the remediation of heavy metal(loid) contaminated soils through manipulating their bioavailability using a range of soil amendments will be presented. Mobilizing amendments such as chelating and desorbing agents increase the bioavailability and mobility of metal(loid)s. Immobilizing amendments such of precipitating agents and sorbent materials decrease the bioavailabilty and mobility of metal(loid)s. Mobilizing agents can be used to enhance the removal of heavy metal(loid)s though plant uptake and soil washing. Immobilizing agents can be used to reduce the transfer to metal(loid)s to food chain via plant uptake and leaching to groundwater. One of the major limitations of mobilizing technique is susceptibility to leaching of the mobilized heavy metal(loid)s in the absence of active plant uptake. Similarly, in the case of the immobilization technique the long-term stability of the immobilized heavy metal(loid)s needs to be monitored.

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) (R(L/S)) increased with pH due to the flooded incubation. The R(L/S) for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.

Heavy metal contamination of agricultural soil and countermeasures in Japan

Many heavy metals exist in minute amounts in natural agricultural soil. However, when their amounts exceed a certain level due to pollutants brought from outside, soil contamination occurs and agricultural products become contaminated. There have been many cases in Japan of heavy metal contamination originating from old mines and smelters, and soil contamination of agricultural land has become a social issue. In particular, cadmium (Cd) is one of the most harmful heavy metals. If agricultural products absorb an excessive amount of Cd, they may adversely affect people’s health, and therefore allowable concentrations are regulated by law. If agricultural land has become contaminated with Cd, measures for minimizing the absorption of Cd by agricultural crops are necessary; these include: (1) soil dressing, (2) water management (paddy field), (3) chemical cleaning of soil, (4) phytoextraction, and (5) use of different varieties and rootstock. Other heavy metals such as arsenic, lead, copper, zinc, and mercury also sometimes cause contamination of agricultural soil.

Arsenic Dissolution from Japanese Paddy Soil by a Dissimilatory Arsenate-Reducing Bacterium Geobacter sp. OR-1

Dissimilatory As(V) (arsenate)-reducing bacteria may play an important role in arsenic release from anoxic sediments in the form of As(III) (arsenite). Although respiratory arsenate reductase genes (arrA) closely related to Geobacter species have been frequently detected in arsenic-rich sediments, it is still unclear whether they directly participate in arsenic release, mainly due to lack of pure cultures capable of arsenate reduction. In this study, we isolated a novel dissimilatory arsenate-reducing bacterium, strain OR-1, from Japanese paddy soil, and found that it was phylogenetically closely related to Geobacter pelophilus. OR-1 also utilized soluble Fe(III), ferrihydrite, nitrate, and fumarate as electron acceptors. OR-1 catalyzed dissolution of arsenic from arsenate-adsorbed ferrihydrite, while Geobacter metallireducens GS-15 did not. Furthermore, inoculation of washed cells of OR-1 into sterilized paddy soil successfully restored arsenic release. Arsenic K-edge X-ray absorption near-edge structure analysis revealed that strain OR-1 reduced arsenate directly on the soil solid phase. Analysis of putative ArrA sequences from paddy soils suggested that Geobacter-related bacteria, including those closely related to OR-1, play an important role in arsenic release from paddy soils. Our results provide direct evidence for arsenic dissolution by Geobacter species and support the hypothesis that Geobacter species play a significant role in reduction and mobilization of arsenic in flooded soils and anoxic sediments.

Optimal Soil Eh, pH, and Water Management for Simultaneously Minimizing Arsenic and Cadmium Concentrations in Rice Grains

Arsenic (As) and cadmium (Cd) concentrations in rice grains are a human health concern. We conducted field experiments to investigate optimal conditions of Eh and pH in soil for simultaneously decreasing As and Cd accumulation in rice. Water managements in the experiments, which included continuous flooding and intermittent irrigation with different intervals after midseason drainage, exerted striking effects on the dissolved As and Cd concentrations in soil through changes in Eh, pH, and dissolved Fe(II) concentrations in the soil. Intermittent irrigation with three-day flooding and five-day drainage was found to be effective for simultaneously decreasing the accumulation of As and Cd in grain. The grain As and Cd concentrations were, respectively, linearly related to the average dissolved As and Cd concentrations during the 3 weeks after heading. We propose a new indicator for expressing the degree to which a decrease in the dissolved As or Cd concentration is compromised by the increase in the other. For minimizing the trade-off relationship between As and Cd in rice grains in the field investigated, water management strategies should target the realization of optimal soil Eh of -73 mV and pH of 6.2 during the 3 weeks after heading.

Chapter Four - Cadmium Contamination and Its Risk Management in Rice Ecosystems

Cadmium (Cd) has been identified as one of the major heavy metals reaching the food chain through various geogenic and anthropogenic activities. In many East and South Asian countries including Japan, Bangladesh, Indonesia, and Korea, Cd accumulation in rice (Oryza sativa L.) ecosystems and its subsequent transfer to the human food chain is a major environmental issue. Rice soils in these countries have been affected by Cd accumulation derived from fertilizer and manure application, mine tailings, and refining plants. Excessive intake of Cd into the human body is detrimental to human health, causing serious illnesses such as itai-itai disease. To ensure the safety of foods, the concentrations of Cd in staple crops should be below a standard value; this applies particularly to rice because 34–50% of the Cd intake by people in many Asian countries has been derived from rice. Therefore, development of remediation methods for Cd-contaminated rice soils has become an urgent task to ensure food safety. This chapter provides an overview of the various sources of Cd in rice ecosystems and the biogeochemical processes that regulate Cd bioavailability to organisms, including microbes, plants, animals, and humans. Because of the complexity involved in dealing with Cd in rice ecosystems, exacerbated by the Cd source, site characteristics, and the nature of water management strategies, we have attempted to describe an “integrated” approach that employs a combination of remediation technologies, with the aim of securing methods that are economically and technologically viable.

Release of Arsenic from Soil by a Novel Dissimilatory Arsenate- Reducing Bacterium, Anaeromyxobacter sp. Strain PSR-1

ABSTRACT A novel arsenate-reducing bacterium, designated strain PSR-1, was isolated from arsenic-contaminated soil. Strain PSR-1 was phylogenetically closely related to Anaeromyxobacter dehalogenans 2CP-1T with 16S rRNA gene similarity of 99.7% and coupled the oxidation of acetate with the reduction of arsenate. Arsenate reduction was inhibited almost completely by respiratory inhibitors such as dicumarol and 2-heptyl-4-hydroxyquinoline N-oxide. Strain PSR-1 also utilized soluble Fe(III), ferrihydrite, nitrate, oxygen, and fumarate as electron acceptors. Strain PSR-1 catalyzed the release of arsenic from arsenate-adsorbed ferrihydrite. In addition, inoculation of washed cells of strain PSR-1 into sterilized soil successfully reproduced arsenic release. Arsenic K-edge X-ray absorption near-edge structure (XANES) analysis revealed that the proportion of arsenite in the soil solid phase actually increased from 20% to 50% during incubation with washed cells of strain PSR-1. These results suggest that strain PSR-1 is capable of reducing not only dissolved arsenate but also arsenate adsorbed on the soil mineral phase. Arsenate reduction by strain PSR-1 expands the metabolic versatility of Anaeromyxobacter dehalogenans. Considering its distribution throughout diverse soils and anoxic sediments, Anaeromyxobacter dehalogenans may play a role in arsenic release from these environments.

Influence of Soil Chemical Properties on Adsorption and Oxidation of Phenolic Acids in Soil Suspension

Abstract Relationships between abiotic oxidation and adsorption of phenolic acids added to soils and soil chemical properties were investigated by using 32 soil samples and ferulic, vanillic, and p-hydroxybenzoic acids. Soil properties studied were as follows: (as adsorption factors) contents of acid oxalate extractable Al (Alo), Fe (Feo), dithionite-citrate-bicarbonate (DCB) extractable Fe (Fed), total carbon and clay, and (as oxidation factors) level of soil oxidative activity (Cr oxidation) determined by the amount of Cr(VI) converted from Cr(III) added to soils. Soil samples were divided into 3 types based on chemical properties: Andosols A (A horizon of Andosols), Andosols B (B horizon of Andosols and light-colored Andosols), and non-Andosols. The recovery of all phenolic acids (RPA) was negatively correlated with the total carbon and Feo contents in Andosols A and B, respectively, which suggested adsorption onto soil organic matter in Andosols A and onto Feo in Andosols B. It was considered that alm...

The heavy metal partition in size-fractions of the fine particles in agricultural soils contaminated by waste water and smelter dust

The partitioning of pollutant in the size-fractions of fine particles is particularly important to its migration and bioavailability in soil environment. However, the impact of pollution sources on the partitioning was seldom addressed in the previous studies. In this study, the method of continuous flow ultra-centrifugation was developed to separate three size fractions (<1 μm, <0.6 μm and <0.2 μm) of the submicron particles from the soil polluted by wastewater and smelter dust respectively. The mineralogy and physicochemical properties of each size-fraction were characterized by X-ray diffraction, transmission electron microscope etc. Total content of the polluted metals and their chemical speciation were measured. A higher enrichment factor of the metals in the fractions of <1 μm or less were observed in the soil contaminated by wastewater than by smelter dust. The organic substance in the wastewater and calcite from lime application were assumed to play an important role in the metal accumulation in the fine particles of the wastewater polluted soil. While the metal accumulation in the fine particles of the smelter dust polluted soil is mainly associated with Mn oxides. Cadmium speciation in both soils is dominated by dilute acid soluble form and lead speciation in the smelter dust polluted soil is dominated by reducible form in all particles. This implied that the polluted soils might be a high risk to human health and ecosystem due to the high bioaccessibility of the metals as well as the mobility of the fine particles in soil.

Influence of soil-drying under field conditions on exchangeable manganese, cobalt, and copper contents

Abstract The changes in the exchangeable Mn (Ex-Mn), exchangeable Co (Ex-Co), and exchangeable Cu (Ex-Cu) contents by air-drying of soils were reported in our previous paper. The drying effect, however, was not analyzed in the field. The objective of this study was to investigate the influence of soil-drying under field conditions on Ex-Mn, Ex-Co, and Ex-Cu levels. Two paddy soils (Tsukuba and Yawara) were collected at four different soil depths (0∓1, 1∓5, 5∓10, and 10∓20 cm) under three different soil moisture conditions i.e., after harvest, after successive sunny days and after rainy days. After sunny days, Ex-Mn and Ex-Co contents in the surface soil layer markedly increased and drastically decreased after rainfall, while they remained almost unchanged in the lower soil layers. Ex-Cu contents slightly increased in the surface soil layer after sunny days. A similar tendency was observed in soil column experiments. The contents of Ex-Mn, Ex-Co, and Ex-Cu increased 12, 12, and 2 times in the upper layer of soil columns that had been sampled from the Yawara field and stored in a dark room for 8 d. The increase of the Ex-Mn and Ex-Co contents in the upper layer could not be explained by the capillary rise of soil water from the lower layers of the columns. In a soil-drying experiment under laboratory conditions, Ex-Mn and Ex-Co contents began to increase when the water content of the Yawara soil was lower than 0.09∓0.13 kg kg−1. The water content of the surface soil of the Yawara field after sunny days was 0.08 kg kg−1. Ex-Cu content did not change apprecially with the water content. It is concluded that the increase of the Ex-Mn and Ex-Co levels in field surface soils after sunny days can be ascribed to soil-drying. Some of the excess Ex-Mn and Ex-Co is expected to leach down into lower layers due to rain, which may contribute to plant uptake of Mn and Co.