Chemical Extraction Tests Research Articles

Cadmium isotope fractionation during sorption to soil minerals: Lab evidence and field implication

Stable isotope is a potent geochemical tracer unveiling the dynamic sources of cadmium (Cd) in the environment. However, the sorption process of aqueous Cd onto solid surfaces (e.g., soil) fractionates isotopic signatures, which makes it difficult to interpret its sources and migration processes. Understanding how Cd fractionates during sorption to soil minerals, therefore, provides necessary data to open the isotope fractionation black box of liquid-solid phase partition of Cd. In this study, we explored isotopic fractionation characteristics during Cd sorption to typical soil minerals. Distinct Cd isotope fractionation was observed during sorption, including goethite (∆114/110Cdsolid−solution=−0.51∼−0.47‰), montmorillonite (−0.34∼−0.32‰), quartz (−0.34∼−0.30‰), gibbsite (−0.29∼−0.25‰), and kaolinite (−0.09∼−0.07‰), where lighter isotopes tended to be preferentially sorbed to the solid phase in a reversible manner. We've also conducted a field survey in a historical flooding-affected region to explore Cd isotopic compositions of soil samples adjacent to a polluted creek. Distinct isotopic signatures for surficial soils and deep soils were observed, which was depicted by a binary mixing mode. Leaching of Cd from mine tailings to the creek, as well as its re-adsorption to soil during historical flooding events both led to preferential enrichment of light isotopes in the solid phase, which was consistent with findings from lab sorption experiments. Mineralogical analyses including EPMA, TOF-SIMS, Mössbauer spectra, XRD, and chemical extraction tests, were applied to unveil how Cd was bound to soil minerals at field. Possible linkage between lab and field data were discussed on the basis of these findings. Results from this study are encouraging for future application of Cd isotopes for source tracing.

The Effect of Physical Separation and Calcination on Enrichment and Recovery of Critical Elements from Coal Gangue

Critical metallic elements in coal gangue have great utilization potential, especially due to the current shortage of these metals. This paper focused on examining the feasibility of physical separation (screening and float-sink tests) and calcination treatment for the enrichment of critical elements (Li, Ga, and rare earth elements plus yttrium (REY)) from coal gangue. The impacts of these enrichment methods on the acid leaching recovery of these elements were then studied. Screening tests indicated that Li and Ga were enriched in >0.125 mm size fraction and the content of REY was highest in <75 μm size fraction. Float-sink tests showed that high-density fractions were enriched in Li and Ga, and low-density fractions were enriched in REY. Physical separation cannot significantly improve the leaching rate of Li, Ga, and REY. Notably, Li, Ga, and REY were enriched significantly, and their acid leaching recoveries were increased by 54~68% after calcination under 400 °C. Sequential chemical extraction tests showed that the majority of insoluble Li, Ga, and REY was converted into soluble forms at the above temperature, which is attributed to the formation of amorphous metakaolinite and the decomposition of organic matter. Based on the results, a conceptually combined flowsheet was proposed for the extraction of Li and Ga from coal gangue.

Effects of calcination temperature on the occurrence modes of rare earth elements in coal

Prior research confirmed that acid leaching recovery of rare earth elements (REEs) from coal was significantly enhanced by calcination pretreatment. To better understand the positive effect, sequential chemical extraction tests were performed in this study on raw and calcined coals of the Western Kentucky No. 13 and Fire Clay seams. The effects of calcination temperature on the occurrence modes of REEs and other selected elements in the calcination products were evaluated. Correlations between distributions of the REEs and major elements in different occurrence modes were established. Experimental results indicated that reactions such as organic matter oxidization, clay dehydration, phosphate mineral decomposition, aluminum silicate fusion, and iron oxide aggregation occurred during the calcination process and collectively determined the occurrence modes of REEs. Findings from the study will contribute to REE recovery and comprehensive utilization of coal.

Enhanced leaching recovery of rare earth elements from a phosphatic waste clay through calcination pretreatment

Phosphatic clay is a waste material produced during the beneficiation of phosphate ore, which likely poses severe environmental problems. In this study, a phosphatic clay containing 258 ppm of total rare earth elements (REEs) was used as a feedstock for REE recovery. By reacting with 0.1 M HCl at 75 °C for 3 h, around 36 % of light REEs and 65 % of heavy REEs were extracted from the raw material. However, after calcination pretreatment at 600 °C for 2 h, the recovery was increased to 73 % and 81 %, respectively, which are close to the recoveries obtained from the raw material using a much higher acid concentration of 1.2 M. Based on the findings from sequential chemical extraction tests and scanning electron microscopy analysis, the positive impact was explained by the decomposition and conversion of REE-bearing minerals into more leachable species. Using a higher calcination temperature of 900 °C, recovery of both the light and heavy REEs was largely reduced relative to the raw material. Mineralogical analyses showed that the dominant minerals existing in the material, such as muscovite, were fused and sintered during the calcination at 900 °C. These reactions likely caused the decreases in the recovery. The results and findings from this study will contribute to the beneficial uses of phosphatic clay and the production of REEs.

Characterization and recovery of rare earth elements and other critical metals (Co, Cr, Li, Mn, Sr, and V) from the calcination products of a coal refuse sample

The impacts of calcination on the leaching recovery of rare earth elements (REEs) and other critical metals from a Baker seam coal refuse material were investigated in this study. Acid leaching test results showed that leaching recovery of the REEs, especially the light REEs, was increased significantly from around 24% to 80–90% after calcination under 600–750 °C for two hours. By considering the major element leaching kinetics and the mineralogical changes of the dominant minerals caused by calcination, two mechanisms were proposed for the improved leaching performance: (1) decomposition of difficult-to-dissolve REE-bearing minerals into soluble forms; and (2) liberation of REE-bearing minerals encapsulated in clays after calcination due to the dehydration and disintegration of the layered clay structure. Sequential chemical extraction tests showed that a significant fraction (around 75%) of the REEs in the raw material were present in an insoluble form. After calcination under proper temperatures (600–800 °C), the majority of the insoluble light REEs (LREEs) were converted into soluble forms. Changes in the modes of occurrence of the LREEs and phosphorous based on leaching rate and sequential leaching correlated well as a function of the calcination temperature. This finding in addition to SEM-EDX results tends to indicate the potential that the LREEs occur primarily as rare earth phosphates such as monazite in the untreated coal refuse material. The acid leaching and sequential chemical extraction results show that co-extraction of REEs and other critical metals such as Co, Mn, and Li is possible using a calcination-acid leaching procedure.

Combining diffusive gradients in thin films (DGT) and spectroscopic techniques for the determination of phosphorus species in soils

A wide range of methods are used to estimate the plant-availability of soil phosphorus (P). Published research has shown that the diffusive gradients in thin films (DGT) technique has a superior correlation to plant-available P in soils compared to standard chemical extraction tests. In order to identify the plant-available soil P species, we combined DGT with infrared and P K- and L2,3-edge X-ray adsorption near-edge structure (XANES) spectroscopy. This was achieved by spectroscopically investigating the dried binding layer of DGT devices after soil deployment. All three spectroscopic methods were able to distinguish between different kinds of phosphates (poly-, trimeta-, pyro- and orthophosphate) on the DGT binding layer. However, infrared spectroscopy was most sensitive to distinguish between different types of adsorbed inorganic and organic phosphates. Furthermore, intermediates of the time-resolved hydrolysis of trimetaphosphate in soil could be analyzed.

Phosphorus availability of sewage sludge‐based fertilizers determined by the diffusive gradients in thin films (DGT) technique

AbstractThe plant‐availability of phosphorus (P) in fertilizers and soil can strongly influence the yield of agricultural crops. However, there are no methods to efficiently and satisfactorily analyze the plant‐availability of P in sewage sludge‐based P fertilizers except by undertaking time‐consuming and complex pot or field experiments. We employed the diffusive gradients in thin films (DGT) technique to quantify the plant P availability of various types of P fertilizers with a novel focus on sewage sludge‐based P fertilizers. Mixtures of fertilizer and soil were incubated for 3 weeks at 60% water holding capacity. DGT devices were deployed at the beginning of the incubation and again after 1, 2, and 3 weeks. Two weeks of incubation were sufficient for the formation of plant‐available P in the fertilizer/soil mixtures. In a pot experiment, the DGT technique predicted maize (Zea mays L.) biomass yield and P uptake significantly more accurately than standard chemical extraction tests for P fertilizers (e.g., water, citric acid, and neutral ammonium citrate). Therefore, the DGT technique can be recommended as a reliable and robust method to screen the performance of different types of sewage sludge‐based P fertilizers for maize cultivation minimizing the need for time‐consuming and costly pot or field experiments.

Advantages and limitations of chemical extraction tests to predict mercury soil-plant transfer in soil risk evaluations.

In this study, we compared the size of the mobile Hg pool in soil to those obtained by extractions using 2M HNO3, 5M HNO3, and 2M HCl. This was done to evaluate their suitability to be used as proxies in view of Hg uptake by ryegrass. Total levels of Hg in soil ranged from 0.66 to 70mgkg(-1) (median 17mgkg(-1)), and concentrations of Hg extracted increased in the order: mobile Hg < 2M HNO3 < 5M HNO3 < 2M HCl. The percentage of Hg extracted relative to total Hg in soil varied from 0.13 to 0.79% (for the mobile pool) to 4.8-82% (for 2M HCl). Levels of Hg in ryegrass ranged from 0.060 to 36mgkg(-1) (median 0.65mgkg(-1), in roots) and from 0.040 to 5.4mgkg(-1) (median 0.34mgkg(-1), in shoots). Although results from the 2M HNO3 extraction appeared to the most comparable to the actual total Hg levels measured in plants, the 2M HCl extraction better expressed the variation in plant pools. In general, soil tests explained between 66 and 86% of the variability of Hg contents in ryegrass shoots. Results indicated that all methods tested here can be used to estimate the plant total Hg pool at contaminated areas and can be used in first tier soil risk evaluations. This study also indicates that a relevant part of Hg in plants is from deposition of soil particles and that splashing of soil can be more significant for plant contamination than actual uptake processes. Graphical Abstract Illustration of potential mercury soil-plant transfer routes.

Comparing Traditional Soil Extraction With Ion Exchange Resin Capsules for Determining Sulfur Bioavailability in Semiarid Low-Fertility Soils

AbstractSulfur (S) is an essential plant nutrient found in most soils primarily in the organic matter phase; consequently, predicting bioavailability is difficult. Ion exchange resin capsules provide a viable alternative to soil chemical extraction tests in evaluating the S status of fertilized soil

Assessing Environmental Risks Associated with Ultrafine Coal Wastes Using Laboratory-Scale Tests

Characterisation of the risk of acid rock drainage is typically achieved through the quantification of acid-generating and acid-consuming components present within a sample using initial laboratory-scale, chemical static tests. Such tests, however, consider ARD generation under chemical conditions and do not account for the role of micro-organisms. Their focus is exclusively on the net potential for acid generation, with no account of metal deportment or the relative rate of acid generation and consumption. The present study investigates the ARD potential of two ultrafine coal wastes samples using the standard static tests as well as the UCT biokinetic test to account for microbial ARD generation. The deportment of metal species under each test condition was also considered. The UCT biokinetic test results supported the static test classification, adding provided preliminary kinetic data on the ARD generation. Sequential chemical extraction tests allowed for differentiation of the host minerals according to their leaching potentials, providing supporting evidence for the deportment of metal species under the characterisation tests, thereby improving the knowledge base on which to classify coal wastes as benign or otherwise.

Chemical characterization and mobility of metal species in fly ash–water system

The present investigation was conducted to study the leaching characteristics, speciation and fractionation of trace and major elements from fly ash. Five liquid-to-solid ratios (L/S) were selected, ranging from 0.5 to 1. The releasing of trace and major elements from fly ash increased as L/S ratios increased or over time (at pH = 2.88). γ-Al(OH)3, Cd3(PO4)2, azurite, jarosite, MnCO3, Pb(OH)2, quartz (SiO2) and ZnCO3 are the solid phases that control Al, Cd, Cu, Fe, Mn, Pb, Si and Zn activities in fly ash leachates. The sequential chemical extraction tests showed that Al, Cd, Cu, Fe, Mn, Pb, Si and Zn were mainly present in the last three fractions, which were Fe–Mn oxides, organics and residual fractions and their leachability could be well-controlled in common natural environment. According to risk assessment code (RAC); Cd, Cu, Mn and Pb show a medium risk, while Zn and Fe shows low risk level, but Al and Si are considered safe to our environment.

Influence of compost addition on lead and arsenic bioavailability in reclaimed orchard soil assessed using Porcellio scaber bioaccumulation test

Long-term application of lead arsenate in orchards has led to a significant accumulation of Pb and As in the topsoil. Reclamation of old orchards for agricultural purposes entails the exposure of humans to Pb and As, which can be reduced by adequate remediation actions. In this study, we assessed the remediation efficiency of compost addition, commonly used as a sustainable agricultural practice, in decreasing the human exposure Pb and As by direct ingestion. The remediation was evaluated based on Pb and As bioavailability, assessed by means of a selective non-exhaustive chemical extraction (modified Morgan extraction, MME), with a physiologically based extraction test (PBET) for the assessment of Pb and As bioavailability in ingested soils and with a novel in vivo bioaccumulation test with isopods (Porcellio scaber). All the tests showed that compost addition consistently reduced Pb, but increased As potential bioavailability. The bioaccumulation test with P. scaber was sensitive to changes in Pb and As bioavailability in test soils. However, the results indicate that the bioavailability of As could be under- or overestimated using solely chemical extraction tests. Indirect assessment of trace metal bioavailability with bioaccumulation in isopods can be used as complementary source of data to the existing in vitro chemical extraction test approach for the estimation of human exposure to trace elements in polluted and remediated soil. This is the first report on the use of As accumulation in P. scaber as a tool for the assessment of As bioavailability in contaminated orchard soil.

Eisenia fetida avoidance behavior as a tool for assessing the efficiency of remediation of Pb, Zn and Cd polluted soil

Remediation by means of soil leaching with ethylenediaminetetraacetic acid (EDTA) is capable of extracting the most labile soil fractions, leaving the residual metals in biologically non-available forms. We evaluated the feasibility of the standardized earthworm ( Eisenia fetida) avoidance test for assessing the efficiency of soil remediation of Pb, Zn and Cd polluted soil. Chemical extraction tests (six-step sequential extraction, toxicity characteristic leaching procedure, physiologically based extraction test, diethylenediaminepentaacetic acid extraction) indicated that the mobility, oral bioaccessibility and phytoavailability of Pb, Zn and Cd were consistently reduced. However, the avoidance test showed no significant avoidance of polluted soil in favor of that which had been remediated. Pb, Zn and Cd accumulation in E. fetida mirrored the decreasing pattern of metal potential bioavailability gained by leaching the soil with increasing EDTA concentrations. The calculated bioaccumulation factors indicated the possibility of underestimating the metal bioavailability in soil using chemical extraction tests.

Development of a simulated earthworm gut for determining bioaccessible arsenic, copper, and zinc from soil

Soil physicochemical characteristics and contamination levels alter the bioavailability of metals to terrestrial invertebrates. Current laboratory-derived benchmark concentrations used to estimate risk do not take into account site-specific conditions, such as contaminant sequestration, and site-specific risk assessment requires a battery of time-consuming and costly toxicity tests. The development of an in vitro simulator for earthworm bioaccessibility would significantly shorten analytical time and enable site managers to focus on areas of greatest concern. The simulated earthworm gut (SEG) was developed to measure the bioaccessibility of metals in soil to earthworms by mimicking the gastrointestinal fluid composition of earthworms. Three formulations of the SEG (enzymes, microbial culture, enzymes and microbial culture) were developed and used to digest field soils from a former industrial site with varying physicochemical characteristics and contamination levels. Formulations containing enzymes released between two to 10 times more arsenic, copper, and zinc from contaminated soils compared with control and 0.01 M CaCl2 extractions. Metal concentrations in extracts from SEG formulation with microbial culture alone were not different from values for chemical extractions. The mechanism for greater bioaccessible metal concentrations from enzyme-treated soils is uncertain, but it is postulated that enzymatic digestion of soil organic matter might release sequestered metal. The relevance of these SEG results will need validation through further comparison and correlation with bioaccumulation tests, alternative chemical extraction tests, and a battery of chronic toxicity tests with invertebrates and plants.

Liming to remediate Ni contaminated soils with diverse properties and a wide range of Ni concentration

Historic emissions from a Ni refinery at Port Colborne, Ontario, caused Ni contamination of regional soils and raised concerns about potential Ni phytotoxicity. Previous tests revealed that if these soils were made alkaline and fertilized with Mn and other common nutrients as needed to maintain fertility of such alkaline soils, full remediation (prevention of Ni phytotoxicity) would be obtained. This experiment was conducted to test this method of remediation on diverse soils from Port Colborne, and to evaluate chemical extraction tests which would be predictive of plant uptake and potential for Ni phytotoxicity in Ni-contaminated soils. Ten soils with varied levels of Ni contamination and varied soil properties were amended with limestone or nitric acid to raise or lower pH so that a wide pH range could be examined for the soils. For lower Ni organic and mineral soils near the Ontario remediation limit (200 mg/kg), neither crop suffered Ni phytotoxicity at any pH tested. Only when more highly contaminated soils were strongly acidic did Ni phytotoxicity occur. Phytotoxic soils were fully remediated by making soils alkaline even for these Ni-sensitive crop species. Only the most contaminated organic soil remained slightly toxic – but this soil was remarkably contaminated (over 1.1% of Ni). The Sr nitrate extraction method was much more effective in predicting plant Ni concentrations than the DTPA method. This test provides an inexpensive soil extraction result highly predictive of potential for Ni phytotoxicity across soils.

Structural proteins associated with ribosomal cistrons in Xenopus laevis chromosomes

The N banding technique to define the location of nucleolus organiser in mammalian and marsupial chromosomes was applied to the Xenopus laevis chromosomes. Results obtained are: 1. The N bands coincide with the location of all the clustered ribosomal cistrons including the 18S + 28S RNA genes as well as the 5S RNA genes. 2. The N bands are consistently detected in both metabolically active (interphase) and metabolically inactive (metaphase) nuclei. 3. Cytochemical and chemical extraction tests indicate that the N bands show typical biochemical properties requested for non-histone (residual) chromosomal proteins. 4. Proteins associated with the 5S RNA genes differ, in their acid-solubility, from those for the 18S+28S RNA genes. 5. The N banding proteins comprise a small portion of a total nuclear protein. These findings strongly suggest the existence of ribosomal gene-specific non-histone proteins which probably represent the structural chromatin element rather than the primary gene product. The possible role of N banding proteins in eukaryotes is discussed.

Low-temperature calcination of “C”-grade phosphate from christmas island

Christmas Island in the Indian Ocean possesses large reserves of a “C”-grade phosphate ore which is unsuitable for normal fertiliser production on account of its extremely high iron and aluminium content. The phosphate of this material occurs in the form of crandallite and millisite, rather than apatite. Although this ore is of little agronomic value in its raw state, low-temperature calcination at approximately 450°c results in degradation of the mineral lattice with enhanced solubility of the phosphate content. Chemical extraction tests and pasture growth trials on Papatoetoe silt loam have shown that the calcined product compares favourably to superphosphate as a source of fertiliser phosphorus.