Sorption of cadmium by complexes of kaolinite with humic acid

Abstract

Levels of cadmium (Cd) in New Zealand pastoral soils have increased due to Cd impurities in applied fertilisers. As there is little information on the interaction of Cd with soil mineral‐organic matter complexes, the sorption of Cd by complexes of kaolinite with humic acid has been investigated. Sorption was measured at pH and ionic strength values typically found for solutions of pastoral soils in New Zealand. Sorption increased with the content of humic acid in the complex, and as the pH of the medium was raised from 4.2 to 6.3. Sorption was also influenced by the ionic strength of the ambient solution, notably by the nature of the cation in the added electrolyte. The experimental data were interpreted in terms of the effect of solution pH and ionic composition on the charge characteristics of kaolinite and humic acid. These factors, in turn, influence clay particle association as well as the clay‐humic and metal‐humic interaction.     

The sorption of Cd and Zn by different soils in the presence of dissolved organic matter from sludge

Dissolved organic matter (DOM) is one of the important factors affecting metal mobility and phytotoxicity in the soils receiving sewage sludge. The aim of this study was to investigate the effects of DOM from anaerobically digested dewatered sludge on Cd and Zn sorption by three different soil types (calcareous clay loam, calcareous sandy loam and acidic sandy loam) of different physico-chemical properties through batch studies. The addition of DOM significantly reduced the Cd and Zn sorption capacity by a factor of 2.1–5.7 for Cd and 2.3–13.7 for Zn for these three soils as seen by their K values in the Freundlich equation compared to the control receiving no DOM, suggesting that DOM had a stronger inhibitory effect on Zn sorption than that of Cd. The reduction in metal sorption caused by DOM was very apparent in the pH range of 5 to 8, with a maximum inhibition on metal sorption occurring at pH 7–7.5 especially for Zn but the effect was minimal at lower pH. At a DOM concentration of < 200 mg C l^− 1, Cd and Zn sorption by all the three soils decreased with an increase in DOM concentration. At each given DOM concentration, the inhibition of metal sorption of the different soil types increased in the following order: acidic sandy loam < calcareous sandy loam < calcareous clay loam. DOM derived from sludge would significantly reduce metal sorption and increase its mobility through the formation of soluble DOM–metal complexes and poses risk of metal leaching and phytotoxicty in near-neutral and alkaline soils.     

Soil slaking sensitivity as influenced by soil properties in alluvial and residual humid tropical soils

Purpose

In the humid Caribbean region characterized by high-intensity tropical rainfall, soil aggregate breakdown and pore blocking due to slaking pressures are major land degradation mechanisms. In this research, we investigated the susceptibility of soils to slaking pressures under rapid wetting as influenced by soil properties and the depositional origin from which the soil is formed using water-stable aggregates (WSAr) and percolation stability (PSc) as indices of the strength of aggregate inter-particle cohesion.

Materials and methods

Wet sieving and percolation stability analyses were employed to investigate WSAr and pore blocking, respectively. The combined effect of soil properties of clay, organic matter (OM), cation exchange capacity (CEC), and exchangeable sodium percentage (ESP) was used to determine the slaking sensitivity score (SSc) of 14 physiogeographically important soils in Trinidad, comprising of nine alluvial and five residual soils.

Results and discussion

Results showed that irrespective of alluvial or residual depositional nature of the parent material, samples had high SSc with an average WSAr of 37.8% and PSc of 6.0 mm/10 min. The linear relationships between SSc with WSAr (r²?=???0.12) and SSc with PSc (r²?=???0.012) of all the 14 soils although negative were weak. Clay content accounted for 94.0% of the variation in CEC in alluvial soils and had strong negative relationships with WSAr (r²?=???0.74) and PSc (r²?=???0.79) in residual soils. Additionally, OM with WSAr (r²?=?0.52) and PSc (r²?=?0.24), and CEC with WSAr (r²?=?0.46) and PSc (r²?=?0.39) showed significant positive linear relationships in residual soil.

Conclusions

The predominantly micaceous and kaolinitic clay mineralogy of these soils, coupled with the low OM contents, increases the proneness of the soils to slaking. This suggests that clay mineralogy is responsible for the high slaking sensitivity rather than clay content or just the depositional origin of the soils. As CEC increases, an accompanying increase in OM is required to increase inter-particle cohesion and to impart partial hydrophobicity, which in turn decreases mineralogically induced susceptibility of individual aggregates to slaking.

     

Cleaning heavy metal contaminated soil with soluble humic substances instead of synthetic polycarboxylic acids

Abstract

Soils contaminated with heavy metals constitute a serious and widespread ecological problem but to clean such soils requires strong chemicals such as polycarboxylates; frequently ethylenediaminetetraacetic acid and nitrilotriacetic acid are used. However, these compounds are synthetic and toxic and their replacement by natural products such as soluble humic substances as washing agents for cleaning heavy metal polluted soils would be environmentally very attractive. In fact, such a replacement seems possible at least on cadmium and copper contaminated soil inasmuch as humic substances, depending on the concentration, were found to extract up to 45% and 54% of total cadmium and copper from a highly contaminated calcareous soil. Even though higher amounts of the two metals were extracted by ethylenediaminetetraacetic acid and nitrilotriacetic acid, the humic substances undoubtedly extracted the most reactive fractions. However, the humic substances extracted only 4% of total lead and 17% of total nickel, whereas the percentages for the synthetic polycarboxylates were about 30% for nickel and lead. Ethylenediaminetetraacetic acid and nitrilotriacetic acid may therefore be replaced by humic substances as washing agents for cadmium, copper and maybe nickel contaminated soils, whereas they seem unsuited for cleaning lead contaminated soils, at least if the soils are as calcareous as the soil tested.     

Effects of water and organic manure coupling on the immobilization of cadmium by sepiolite

Purpose

Natural sepiolite (SP) has proven effective on the in-situ immobilization remediation of Cd-contaminated soils. But the practical remediation effect may largely influenced by water management and the application of organic manure. The effects of chicken manure (CM) on SP-amended soils were investigated under normal and saturated water conditions using a pot experiment with Brassica campestris L.

Materials and methods

Cd-contaminated paddy soils were amended with CM, SP, and CM?+?SP with no amendment as control. The amount of sepiolite was 0.5% (w/w, the same below) either in SP or CM?+?SP amended soils, while the amount of CM was 0.5, 1.0, and 2.0% in CM and CM?+?SP-amended soils. The plant metal contents, fresh weight, and soluble sugar content of plant edible parts were measured on harvest. Soil Cd was extracted by diethylenetriaminepentaacetic acid (DTPA) and HCl to estimate the mobility of heavy metal. Soil pH and dissolved organic matter (DOM) of rhizosphere soil were determined. The electronegative charges of soils were also measured using the zeta potential.

Results and discussion

The application of CM and increasing soil moisture on SP-amended soil increased plant growth to a greater extent than the application of SP alone. The application of CM along with the increase of soil moisture decreased Cd uptake and translocation in plants grown on SP-amended soil compared to the application of SP alone. Cd content of edible plant parts reached a minimum of 0.24 mg kg^?1 with the application of 2.0% CM on SP-amended soils under water-saturated conditions, which was approximately 50% lower than the Cd concentration found when applying SP alone.

Conclusions

The results of this study suggest that the application of sepiolite on Cd contaminated soil can effectively reduce Cd uptake by B. campestris L., and the addition of CM combined with effective water management also appears to further reduce Cd absorption and accumulation.

     

Two-year fluctuation of Cd bioavailability in a remediated rice field under different water managements

Purpose

Based on two consecutive years of field-scale trials, under different water managements, we illustrated the persistence of remediation effect of palygorskite on a Cd-polluted rice field.

Materials and methods

The Cd uptake by a plant, pH and Cd chemical extractability, available P/K, and extractable Zn/Cu in paddy soils were used to evaluate the influence of palygorskite on Cd immobilization and soil fertility index.

Results and discussion

In contrast to the 1st year, at 0–1.5% palygorskite applied dose in soils, 0.025 M HCl–extractable Cd in continuous flooding reduced by 12.1–19.0%, and that in wetting irrigation increased by 10.9–18.9% in the 2nd year (p?<?0.05). The toxicity characteristic leaching procedure Cd reduction of 3.0–11.4% and increase of 8.9–12.0% were obtained under above-mentioned water managements (p?<?0.05). Compared with the 1st year, at different clay additional concentrations, grain Cd in continuous flooding reduced by 7.0–11.3%, and that in wetting irrigation increased by 6.5–10.8% in the 2nd year (p?<?0.05). Although trace elements in clay treated soils declined, they had no influence on the grain yield due to a minimum value higher than the critical value of 1.5 mg kg^?1 for Zn and 2.0 mg kg^?1 for Cu. The available P in continuous flooding took on a maximum increase of 8.2% in the 2nd year (p?<?0.05).

Conclusions

Two consecutive years of field-scale in situ demonstration tests revealed that continuous flooding was a preferable water management regime for Cd immobilization using palygorskite in the rice field. There were no remarkable differences in extractable Zn/Cu between 2 years.

     

Soil organic carbon storage and quality are impacted by corn cob biochar application on a tropical sandy loam

Purpose

Humic substances, which are integral components of total organic carbon (TOC), influence soil quality. The study aimed to investigate whether humic and non-humic fractions exhibit early, consistent, and measurable changes and affect TOC sensitivity and storage in a tropical sandy loam soils amended with corn cob biochar.

Materials and methods

There were four treatments with four replicates established in a randomized complete block design. Composite soil samples were taken from plots without biochar (CT), from plots incorporated with 15 t biochar ha^?1 (BC-15), and 30 t biochar ha^?1 without or with phosphate fertilizer (BC-30 and BC-30+P). The TOC, and humin, humic acid (HA), and fulvic acid (HA) fractions of soil organic carbon were determined for each treatment. The optical densities (400–700 nm) were measured on the soil-free extracts by spectrophotometry; the densities measured at 465 and 665 nm were used to calculate the E₄₆₅/E₆₆₅ ratios.

Results and discussion

The BC-30 and BC-30+P plots recorded the highest TOC, humin, humic acid (HA), and fulvic acid (FA) contents with respect to the lowest in the CT. The total exchangeable carbon stratification was significantly higher in all the biochar-treated plots relative to the CT. Spectral analysis showed higher values of E₄₆₅/E₆₆₅ (5.02 and 5.15) in the CT and BC-15-treated soils, respectively, compared with the BC-30 and BC-30+P-amended soils with E₄₆₅/E₆₆₅ ratios of 2.76 and 2.98, respectively.

Conclusions

Corn cob biochar applied to a tropical sandy loam:

? increased the concentrations of HA and FA and led to increased stratification of TOC, with a stronger effect on HA compared with FA;

? significantly lowered E₄₆₅/E₆₆₅ at the high biochar application rate of 30 t ha^?1, implying the dominance of high molecular weight humic acid-like substances, and increased degree of aromaticity of the TOC.

     

Cadmium speciation as influenced by soil water content and zinc and the studies of kinetic modeling in two soils textural classes

Background and aimsSince few studies have existed in the literature about the effect of zinc (Zn) on cadmium (Cd) chemical forms in soils. Therefore, this study has been performed to determine the impact of Zn on cadmium Cd chemical forms in two soil textural classes in Fars province-Iran at two soil water content (SWC) (flooded soil water content (FSWC) and field capacity soil water content (FCSWC)) and study the kinetic modeling of Cd.Methods and materialsVariables were three levels of Cd (0, 30 and 60 mg kg^-1 of soil as CdSO₄·8H₂O), three levels of Zn (0, 5 and 10 mg kg^-1 of soil as Zn-EDTA) three level Incubation times (2, 4 and eight weeks), two soil textural classes (clay and sandy clay loam) and two SWC. The randomized completed block design (RCBD) was used for this experiment. The Tessier sequential extraction method was used to determine the Cd concentration in (WsEx), (Fe-MnOx), (Car), (Om) and (Res) chemical forms.ResultsIn the FSWC, Zn reduced the Cd concentration in Fe-MnOx, Car and Om forms and increased the WsEx but had no significant effect on the Res form. Changes in the Cd chemical forms under the influence of Zn in both soils followed a similar trend. In the FCSWC, Zn reduced the Cd concentration Car and Om forms and increased the Cd concentration in the Fe-MnOx and WsEx forms while had no significant effect on Res form in the sandy clay loam soil. In the clay soil adding Zn reduced the Cd concentration in Car and Om fractions and increased the Fe-MnOx and Res forms while has no significant effect on WsEx form. The competitive transport and adsorption Interactions between these two ions caused the changing in the Cd concentration in its chemical forms. Zn reduces the Cd concentration in the forms which are easily released into the soil solution from where they can be absorbed by plants. The power function kinetic mode is the best fitted model which can describe the Cd adsorption in our soil samples. The clay and organic compounds control the Cd adsorption in soils. The higher rate of Cd adsorption in almost all shaking times shows that Cd has more ability to occupy the adsorption sites in soils.     

Chemical and physical characteristics of humic substances extracted from greek soils varying in classification order and natural drainage

Abstract

Humic and fulvic acids were extracted from the surface horizons of Alfisols, Vertisols, and Entisols with good and impeded natural drainage. These profiles are located in the temperate subhumid zone. The extracted humic substances were characterized by elementary and functional group analyses, IR‐spectroscopy, differential thermal analysis (DTA) and electron spin resonance spectroscopy (ESR). Some differences in the humic substances seem to be associated with differences in the natural drainage of the soils. When data from samples of the same soil order are compared, indicate that humic (HAs) and fulvic acids (FAs) extracted from soils with impeded drainage, have higher contents of carbon and spin concentration, but less total acidity and fewer carboxylic groups (COOH), than the respective humic substances extracted from well drained soils. The IR‐spectra of the HAs extracted from soils with impeded drainage showed more aliphatic groups than those of the well drained soils. No essential differences, which could be related to the drainage conditions of the studied soils, were observed in the IR‐spectra of FAs. DTA‐diagrams shows that the thermal stability of the HAs and the FAs are related to their carbon and ash contents. Iron was the dominant element in the ash of the humic acids, aluminum and silicon were the most abundant elements in the ash of the fulvic acids.     

Distinguishing black carbon from biogenic humic substances in soil clay fractions

Most models of soil humic substances include a substantial component of aromatic C either as the backbone of humic heteropolymers or as a significant component of supramolecular aggregates of degraded biopolymers. We physically separated coarse (0.2–2.0 μm e.s.d.), medium (0.02–0.2 μm e.s.d.), and fine (> 0.02 μm e.s.d.) clay subfractions from three Midwestern soils and characterized the organic material associated with these subfractions using ¹³C-CPMAS-NMR, DTG, SEM-EDX, incubations, and radiocarbon age. Most of the C in the coarse clay subfraction was present as discrete particles (0.2–5 μm as seen in SEM images) of black carbon (BC) and consisted of approximately 60% aromatic C, with the remainder being a mixture of aliphatic, anomeric and carboxylic C. We hypothesize that BC particles were originally charcoal formed during prairie fires. As the BC particles aged in soil their surfaces were oxidized to form carboxylic groups and anomeric and aliphatic C accumulated in the BC particles either by adsorption of dissolved biogenic compounds from the soil solution or by direct deposition of biogenic materials from microbes living within the BC particles. The biogenic soil organic matter was physically separated with the medium and fine clay subfractions and was dominated by aliphatic, anomeric, and carboxylic C. The results indicate that the biogenic humic materials in our soils have little aromatic C, which is inconsistent with the traditional heteropolymer model of humic substances.     

Characterization by isoelectric focusing of the organic matter of a regenerated soil

Abstract

Regeneration of a soil with a high degree of desertification was conducted by the addition of different doses of municipal solid waste organic matter (MSW). Five years after this treatment, humic substances were extracted from these soils and characterized by spectroscopy and isoelectric focusing. No significant differences between E4/E6 ratio and ?log K (Log A400 nm‐log A600 nm) were observed for humic substances extracted from treated and untreated soils. However, the isoelectric focusing (IEF) technique established differences between the humic substances from control and treated soils. The focusing pattern of the former showed a well defined band at pH 9.1 which nearly disappeared in the soils with high doses of MSW (1–2 %). However the organic matter which focused at pH 5.8 was present in all soils.     

土壤主要理化性质对湘粤污染农田镉稳定效果的影响

利用盆栽试验研究了稳定剂(石灰、海泡石联合施用)对湖南、广东两省区不同性质土壤上生长的小青菜(Brassica chinensis L.)生物量、重金属吸收以及土壤pH和重金属提取态含量的影响,探讨了影响镉(Cd)稳定修复效果的土壤性质参数。结果表明:施加稳定剂对增加酸性土壤上小青菜生物量效果显著,土壤pH、有机质(OM)、全量Cd和黏粒是影响小青菜生物量变化的主要因素;土壤pH、阳离子交换量(CEC)、OM、黏粒是影响小青菜Cd含量变化的主要因素;土壤pH、CEC、全量Cd和黏粒是影响土壤提取态Cd含量变化的主要因素。     

Underlying dynamics and effects of humic acid on selenium and cadmium uptake in rice seedlings

Purpose

Natural organic acids, such as humic acid (HA), play crucial roles in biogeochemistry of anions and cations in soil due to their numerous functional groups on their surfaces. Selenium (Se) and cadmium (Cd) could bind strongly to HA; nevertheless, it is still unclear as to the effects of HA on Se and Cd uptake in rice which will be focused on in this paper.

Materials and methods

Pot experiments were carried out at Huazhong Agricultural University, Wuhan City, Hubei Province, China. Agricultural soils were treated with different concentrations of HA (0, 4, and 8 g kg^?1 soil) and Se (Se^IV or Se^VI) (0 and 2 mg kg^?1 soil) as well as with base fertilizer 3 days prior to planting. For Cd treatment, experimental soils were treated with Cd (0 and 2 mg kg^?1 soil) 1 month before sowing. For element determination, root (after DCB extraction) and shoot samples were digested with a mixed solution of HNO₃-HClO₄, and the Se and Cd in digest solution were measured by HG-AFS and ICP-MS, respectively. Fe, Se, and Cd in iron plaque were extracted by DCB extraction and measured by AAS, HG-AFS, and ICP-MS, respectively.

Results and discussion

HA reduced Se (or Cd)-induced growth stimulation and Se and Cd uptake in rice seedlings, whereas iron plaque formation varied little with different treatments. HA inhibited Se^IV (or Se^VI) uptake in rice seedlings by reducing Se translocations from soil to iron plaque (or by increasing Se adsorption capacity of iron plaque and decreasing Se transport from iron plaque to root). HA reduced Cd uptake in rice seedlings by reducing Cd transport from soil to iron plaque and from iron plaque to root. Compared with single addition of Se^IV or Se^VI or HA, adding HA combined with Se^IV or Se^VI could further reduce Cd uptake in rice seedlings, whereas Se contents of aerial tissues did not change obviously.

Conclusions

HA inhibited the accumulation of Se (Se^IV or Se^VI) and Cd in rice seedlings; nevertheless, the mechanism was different. Compared with adding Se (or HA) alone, application of Se mixed with HA might be a more effective way to produce Se-enriched and Cd-deficient crop in Cd-contaminated soil.

     

Biological activity of humic substances extracted from soils under different vegetation cover

Abstract

Comparisons were made between the chemical compositions of humic substances extracted from three soils covered by different vegetation and their biological activities assayed using 15‐ and 30‐day‐old seedlings of Pinus sylvestris and Picea abies. The growth, “α‐amylase and invertase activity were affected by humic fractions and by gibberellic acid (GA), indicating that humic matter had a gibberellin‐like activity. The isoenzymatic polymorphism in the electrophoretic patterns of esterase was influenced in a similar way by all humic fractions and by indoleacetic acid (IAA), which also suggested that the humic fractions exhibited an auxin‐like activity. The humic fractions extracted from the grassland, exhibiting higher amounts of phenolic and a considerable amount of carboxyl carbon, showed the best metabolic effect. The forest humic fractions, characterized by lower phenolic carbon content, appeared less effective in influencing plant metabolism, whereas the grassland‐forest humic substances proved to be even more less effective. The auxin‐ and the gibberellin‐like activities were related to a high content of phenolic and carboxylic groups. These results presented evidence that the biological activity of the humic substances was attributed to their chemical structure and to their functional groups, which could interact with hormone‐binding proteins in the membrane systems, evoking a hormone‐like response.     

Composition of organic C fractions in soils of different texture affected by sugarcane monoculture

ABSTRACT

Sugarcane is a strategic commodity in Indonesia. It is usually raised in a monoculture system. There is a lack of information about the effects of extended sugarcane monoculture on the soil carbon fraction. The aim of this study was to determine the relative changes in the soil organic C fractions in response to the duration of sugarcane monoculture on Entisols, Inceptisols, and Vertisols. The measured variables were the percentages of sand, silt, and clay, organic matter (OM), total nitrogen (TN), pH (H₂O), cation exchange capacity (CEC), NH₄ ⁺, NO₃ ^-, labile carbon fraction (soil carbon mineralization (C-Min), soil microbial carbon (C-Mic), and carbon particulate organic matter (C-POM)), and stable carbon fraction (humic and fulvic acids). Soil type with sugarcane monoculture period had significant influences on the percentages of clay, sand, silt, CEC, and pH (H₂O). Soil type and sugarcane monoculture period had no apparent significant effect on C-Min or C-POM but did significantly influence C-Mic. The humic and fulvic acid levels in all three soil types were affected by the duration of sugarcane monoculture. To establish the impact of long-term sugarcane monoculture on the physicochemical properties of soils with various textures, it is more appropriate to measure the soil stable carbon fractions such as humic and fulvic acid rather than the soil labile carbon fractions such as C-Min, C-POM, or C-Mic.     

The effect of water and acid‐washing soil treatment on the measurement of pH,delta pH and zero point of charge in some variable charge soils

Abstract

This study was undertaken to determine the effect of previous water and acid‐washing soil treatment on soil pH, Delta pH and Zero Point of Charge of soil surface samples of three Hawaii soils, Molokai (Typic Torrox), Wahiawa (Tropeptic Eutrustox), and Hilo (Typic Hydrandept).

The acid‐washing treatment lowered the soil pH and shifted the Zero Point of Charge to lower pH values. The effect was greater in the Wahiawa and Molokai soils that are dominated by oxidic materials. Whereas the acid‐washing treatment did not change the magnitude of the negative charge in the Wahiawa and Molokai soils, it overestimated the magnitude of the positive charge in the Hilo soil. This phenomena probably was enhanced by the dominance of variable charge clay minerals in the Hilo soil. The results indicated that the acid‐washing treatment changed the nature of the charge characteristics of the soils, hence it should not be recommended in the characterization of the net charge in variable charge soils.     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

The geochemistry of black water in selected coastal streams of the Southeastern United States

Abstract

An investigation was conducted in a watershed formed by the tributaries of the Little River in South Georgia to study the nature of the humic and inorganic fractions of black water, and their influence on stream water quality. Large amounts of black colored water were sampled during 1983 to 1984 according to streamflow pattern in December, March, June and September. Measurements of air and water temperature and dissolved oxygen were made at the gaging sites, whereas water analysis for conductivity, Cl, NO₃‐N, NH₄‐N, P, total N, and other macro‐ and microelements were conducted in the laboratory. Fulvic (FA) and humic acid (HA) were isolated from the water samples, and analyzed by infrared and ¹³C NMR spectroscopy. Suspended clay from the water samples were collected and determined by x‐ray diffraction analysis. The results showed that black water was characterized by low conductivity and low ion concentrations indicating satisfactory chemical quality. The Na content was half the amount of other rivers in the Southeastern United States, whereas the ? content was similar to the world average. A seasonal fluctuation was noticed for Ca and Mg concentration. The increase of these ions during high streamflow in spring and summer was attributed to agricultural practices in the surrounding lands. Dissolved organic matter (DOM) concentration was highest in December during low streamflow. As DOM content decreased during high streamflow, water pH increased. A large part of the humified DOM was composed of fulvic acid, which was more aromatic in nature than soil‐fulvic acid as determined by ¹³C NMR. The suspended clay had a composition reflecting the clay mineralogy of Tifton soils in the surrounding uplands. It is believed that the Tifton soil, with its low activity clay and hence low CEC, may not be able to buffer the effect of acid leaching of black water.     

Effect of Organic Matter and Salinity on Ethylenediaminetetraacetic Acid–Extractable and Solution Species of Cadmium and Lead in Three Agricultural Soils

Abstract

A study was conducted to investigate the chemical speciation of added cadmium (Cd) and lead (Pb) and their availability as influenced by fresh organic matter (OM) and sodium chloride (NaCl) in three agricultural soils. The soils were treated with 20 mg Cd/kg as cadmium nitrate [Cd(NO₃)₂ · 4H₂O], 150 mg Pb/kg as lead nitrate [Pb(NO₃)₂], 20 g/kg alfalfa powder, and 50 mmol/kg of NaCl and then incubated for 3 months at 60% water‐holding capacity (WHC) and constant temperature (25 °C). Subsamples were taken after 1, 3, 6, and 12 weeks of incubation, and electrical conductivity (EC), pH, dissolved organic carbon (DOC), and concentrations of cations and anions were determined in the 1:2.5 soil/water extract. Available Cd and Pb were determined in 0.05 M ethylenediaminetetraacetic acid (EDTA) extract. Concentrations of organic and inorganic species of Cd and Pb in soil solution were also predicted using Visual Minteq speciation program. The most prevalent species of dissolved Pb and Cd in the soils were Pb‐DOC and Cd²⁺ species, respectively. Salinity application increased the available and soluble Cd significantly in the acid and calcareous soils. It, however, had little effect on soluble Pb and no effect on available Pb. Organic‐matter application decreased availability of added Pb significantly in all soils. In contrast, it raised soluble Pb in all soils except for the acid one and approximated gradually to the added Pb with time. Impact of OM on available Cd was somewhat similar to that of Pb. Soluble Cd increased by OM application in the calcareous soil, whereas it decreased initially and then increased with time in the other soils.     

Effect of organic amendment on amount and chemical characteristics of humic acids in upland field soils

To assess the effect of continuous organic material (OM) application on soil humic acids, the amount and chemical characteristics of humic acids in various types of soils (n = 10) were compared between plots treated with farmyard manure (FYM) or rice straw compost (RSC) plus chemical fertilizer (CF) and plots treated with CF alone. The degree of humification (degree of darkening), molecular size distribution and ¹³C cross polarization/magic angle spinning nuclear magnetic resonance spectra of humic acids from CF‐treated soils showed wide variation among the soils. Humic acid content was generally larger in OM + CF soils than in corresponding CF soils, and the stable C isotopic ratio suggested partial replacement of indigenous humic acids with OM‐derived ones even where no apparent increase in humic acid content was observed. The rate of OM application and the indigenous humic acid content were related positively and negatively, respectively, to the apparent accumulation rate of humic acids among soils. The degree of humification of humic acids was generally smaller in OM + CF soils than in CF soils. Humic acids extracted from FYM and RSC exhibited chemical characteristics typical of humic acids having a smaller degree of humification, which suggested the contribution of OM‐derived humic acids to the differences between OM + CF and CF soil humic acids, such as larger average molecular sizes and smaller and larger proportions of aromatic C and O‐alkyl C, respectively, relative to total C in the OM + CF soil humic acids. Little change was observed in the chemical characteristics of humic acids when the degree of humification of indigenous humic acids was small. The effect of OM application on the chemical characteristics of humic acids was most conspicuous in soils containing humic acids having an intermediate degree of humification, possibly resulting from the combination of accelerated degradation of indigenous humic acids and the accumulation of OM‐derived humic acids.