DNAPL TCE Oxidation with Permanganate: Influence of the Phase Transfer Catalyst Pentyltriphenylphosphonium

Dense nonaqueous phase (DNAPL) trichloroethylene (TCE) degradation by potassium permanganate (KMnO₄) was investigated in the presence of the cationic surfactant pentyltriphenylphosphonium (PTPP) bromide, acting as a phase transfer catalyst. Series of batch tests were performed in 5.0-mL conical vials containing Milli-Q water and 1.0 mM DNAPL TCE with initial permanganate concentrations ([MnO₄ ^?]₀) of 1.0, 2.0, 3.0, and 5.0 mM, adding PTPP (0, 10, and 20 mol% of permanganate, respectively). Chloride ion (Cl^?) and MnO₄ ^? in water samples were analyzed to observe MnO₄ ^? consumption and TCE degradation over the elapsed time (0 to 90 min). The calculated values of pseudo first-order rate constants for MnO₄ ^? consumption indicated that the rate of MnO₄ ^? depletion increased with higher mole percent PTPP. At experimental conditions of 1.0 and 2.0 mM [MnO₄ ^?]₀, analyses of Cl^? concentration showed that higher mole percent of PTPP induced greater Cl^? release, indicating faster TCE oxidation. On the other hand, for 3.0 and 5.0 mM [MnO₄ ^?]₀, the concentration of Cl^? was lower with the presence of PTPP. This result indicated that MnO₄ ^? had migrated further into the inner space of DNAPL, and consequently, the Cl^? took a longer time to diffuse from DNAPL to an aqueous phase.     

Influences of water pH,alkalinity and acid additions on growth and nutrient relationships in chrysanthemum morifolium ’bright golden anne‘ 1

Growth of Chrysanthemum morifolium ‘Bright Golden Anne’ was assessed after application of irrigation water containing five alkalinity levels (0, 100, 250, 500, 1000 mg/liter bicarbonate) in a greenhouse study. Irrigation water having alkalinity levels exceeding 500 (week 12)or 1000 (week 6) mg/liter bicarbonate affected plant height and fresh and dry weights. High levels of irrigation water alkalinity altered nutrient availability in the growing medium and plant tissue nutrient content. This was attributed to a rise in growing medium pH. Between 6 and 12 weeks, the critical level of alkalinity in water that altered growing medium nutrient availability and plant growth decreased from 1000 to 500 mg/liter bicarbonate. Acid additions improved plant growth for the water treatment containing 500 mg/liter bicarbonate. Sulfuric acid was the most effective acid treatment.     

Effect of Groundwater Inorganics on the Reductive Dechlorination of TCE by Zero-Valent Iron

Although permeable reactive barriers (PRB) technology appears to be a very suitable and cost effective option, the extent to which remediation results will be realized, greatly depends on the long-term integrity of the system. The formation of mineral precipitates is possibly a major factor in the long-term performance of PRB. Precipitates may passivate reactive surfaces by blocking electron-transfer sites, and thereby reduce the long-term reactivity of the granular iron to degrade groundwater contaminants. To evaluate the potential passivation impacts of inorganic groundwater chemistry, column experiments containing zero-valent iron (Fe⁰) were performed under anoxic conditions to treat two contrasting Danish groundwater types spiked with trichloroethylene (TCE). For most of the experiments using Danish groundwater types, a soft low alkalinity groundwater produced slightly higher TCE dechlorination rate than did a hard high alkalinity groundwater. Compared to a soft low alkalinity baseline groundwater, it was also found the dechlorination of TCE in the column was enhanced in the presence of 1 mM CaCO₃ and 1 mM NaHCO₃. The dechlorination of TCE in the presence of 1 mM KNO₃ and 1 mM Na₂SiO₃ was found to decrease considerably compared with the baseline solution. The results suggest that the composition of field groundwater is likely to strongly affect the ability of Fe⁰ barriers to degrade TCE.     

Surfactant-Enhanced Permanganate Oxidation on Mass-Flux Reduction and Mass Removal (MFR-MR) Relationship for Pool-Dominated TCE Source Zones in Heterogeneous Porous Media

Chlorinated solvents generally enter the subsurface as dense nonaqueous phase liquids (DNAPL) and accumulation mostly occurs in aquifers as pool-dominated zones that can cause long-term aqueous phase groundwater contamination. In situ remediation of DNAPL source zones in such systems is crucial for protecting and/or restoring groundwater quality in these aquifer systems having significant groundwater potential. The objective of the project was to investigate the surfactant-enhanced permanganate oxidation efficacy for pool-dominated DNAPL source zones in heterogeneous aquifer media. A complementary objective of this study was to investigate the impact of nonuniform distribution of DNAPL source zones, surfactant-enhanced dissolution and surfactant-enhanced permanganate oxidation conditions on mass-flux reduction/mass-removal behavior relationships. A series of 2-D flow-cell tank experiments using various grain sizes silica sand and natural soil were conducted as part of this study. DNAPL trichloroethene (TCE) was used as a chlorinated solvent, and SDS (sodium dodecyl sulfate) and KMnO₄ (potassium permanganate) were used as anionic surfactant and oxidant (remediation agents), respectively. The results were compared with a water-flooding experiment to test the remediation effort. Although, high fractions of TCE source zones in the heterogeneous porous media were removed by sodium dodecyl sulfate (SDS)-enhanced flushing, TCE removal in this system exhibited an extended multi-step concentration elution behavior. This nonideal behavior was observed for both the water-flood and SDS-flushing experiments. The results emphasized that in the early stage, some portion of the organic liquid is hydraulically accessible (matrix) whereas the later stage of mass removal was controlled by the more poorly accessible mass (pool) associated with higher saturation zones. Our results also showed that the distribution and the emplacement of organic liquid and flow-field heterogeneity had a significant influence on remediation and removal for both flushing solution (SDS and water). It was postulated that when SDS/MnO₄ was applied with sufficient dosage and provided enough contact time, pool-dominated source zones could be remediated more efficiently compared to surfactant flushing alone. As a result, the performance of technology depends on the site characteristics which are critical to characterize effective DNAPL remediation strategies for contaminated sites.     

Occurrence of acidic groundwater in precambrian crystalline bedrock aquifers,Southwestern Sweden

The pH and alkalinity of groundwater from 7651 wells drilled in the Precambrian crystalline bedrock of southwestern Sweden has been evaluated. The wells are generally less than 100 m deep. Analytical results were collected from different laboratories and authorities in the region. In areas with thin soil cover or coarse-grained deposits overlying the bedrock, alkalinity is normally less than 100 mg HCO₃ L^?1. Below the marine limit, where clayey sediments predominate, alkalinity sometimes even exceeds 200 mg HCO₃ L^?1. When comparing pH and alkalinity of groundwaters from Quaternary deposits with bedrock groundwaters, the latter always have higher pH and alkalinity values. The most acidic bedrock groundwaters are found in small areas close to the city of Göteborg due to additional factors of high acid loadings, high groundwater discharge and thin soil layers. A study of data from 1949 to 1985 in the province of Värmland suggests that no regional acidification of importance is in progress. However, results from public water supplies support the hypothesis that the groundwaters which are most sensitive to acidification are those where discharge from wells in small bedrock aquifers induces rapid groundwater recharge of acidic surficial water.     

Organic Acids in the Atmosphere and Bulk Deposition of Hong Kong

Results from the first study in Hong Kong, Southern China, to investigate the concentrations of organic acids in bulk deposition, aerosol and gas phase samples are presented. 57 daily bulk deposition samples were collected in central Kowloonand analyzed by ion chromatography, from May 1999 to May 2000. The volume-weighted (vw) mean concentrations for formate, acetate, propanoate and oxalate were 6.1, 4.5, 0.4 and 1.4 μeq dm^-3, respectively, with vw mean pH being 4.65.The maximum acidity contributions by formic and acetic acidsfor bulk deposition samples collected on a daily basis, withpH < 5.0, were 17 and 14%, respectively. The concentrationsof these acids were significantly correlated with each other, butnot with pH. Higher organic acid concentrations were foundin the dry, winter season, and for the synoptic weather systemtypes: approaching cyclone and cold front. Oxalate levels weregenerally higher in bulk deposition samples for north/northeasterly air masses, higher surface windspeeds, and low rainfall amounts. Formic and acetic acids were present at higher concentrations in the gas phase (mean concentrations at two sites were in the range from 3.2 to 6.5 μg m^-3, with formate usually < acetate), than in aerosols (mean concentration of formate, acetate or oxalate ≤2.2 μg m^-3). Higher levels of organic acids both in aerosols and in the gas phase were found at a busy roadside site than at a residential site. Deposition fluxes for formic and acetic acidsare reported.     

Mineral-catalyzed peroxidation of tetrachloroethylene

The treatment of perchloroethylene (PCE) was investigated by the promotion of Fenton-like reactions using the iron oxyhydroxide goethite (α-FeOOH) as the sole source of the iron catalyst. A silica sand-goethite matrix was contaminated with 5 mg L^?1 PCE and the oxidative treatments were conducted with 0.15 mM, 2 mM, 5mM, 10mM, 20mM, and 30mM H₂O₂. Perchloroethylene was effectively degraded within 96 hr and the most efficient treatment stoichiometry was observed using 0.15 mM H₂O₂ at pH 3. The degree of heterogeneous catalysis was evaluated by conducting oxidation reactions in parellel systems with an equivalent concentration of soluble iron. The results showed that, within the first 24 hr, up to 94% of the PCE degradation was attributed to heterogeneous catalysis. This modified Fenton's process, when used to treat 5 mg L^?1 PCE in natural subsurface materials with 2 mM H₂O₂ at pH 3, resulted in a residual of 0.20 mg L^?1 PCE after 96 hr.     

Effects of liming on water chemistry in shallow acidified pools in the netherlands: Enclosure experiments

Enclosure experiments have been carried out in two shallow acidified moorland pools in order to study the effects of liming on the water chemistry. The addition of buffering substances (sodium bicarbonate and calcium chloride or powdered marlstone) to enclosures in the Ven bij Schaijk, an oligotrophic acidified moorland pool with a mineral sediment, did not demonstrate internal eutrophication. After addition of NaHCO₃ and CaCl₂ the pH and alkalinity increased and all macronutrient concentrations, such as that of phosphate, remained low. After treatment with powdered marlstone, there was only a slight increase of pH and alkalinity, due to the slow weathering of marlstone. The alkalinity in this moorland pool remained more stable on a mineral sandy substrate than on an organic substrate, probably as a result of a higher acid release from the organic sediment. In enclosures in the Padvindersven, an eutrophied, acidified moorland pool with an organic gyttja-type of sediment, internal eutrophication took place after adding buffering substances. The phosphate concentration and turbidity of the water increased significantly after treatments with NaHCO₃ and CaCl₂ as well as with powdered marlstone. The acid release was even higher than from the organic sediment from the Ven bij Schaijk. It was concluded from these experiments that in case of the Ven bij Schaijk, liming with marlstone would be a sufficient way to restore the original water chemistry. In the Padvindersven, however, recovery of the non acidified poorly buffered conditions is only possible by liming in combination with the removal of the organic top layer of the sediment.     

Infiltration and Distribution of Elemental Mercury DNAPL in Water-Saturated Porous Media: Experimental and Numerical Investigation

Liquid elemental mercury occurrence in the subsurface as dense non-aqueous phase liquid (DNAPL) is reported worldwide in proximity of several industrial facilities, such as chlor-alkali plants. Insight into Hg⁰ DNAPL infiltration behavior is lacking and, to date, there are no experimental observations of its infiltration and distribution in water-saturated porous media, except for capillary pressure-saturation column experiments. To better understand the processes governing elemental mercury DNAPL flow behavior, a series of flow container experiments were performed using mercury DNAPL (in sands and glass beads) and tetrachloroethylene (PCE) (in sands). While liquid Hg⁰ was not able to infiltrate in the sand-filled container due to an overall lower permeability of the sample and a defect of the setup, in the glass beads experiment mercury DNAPL infiltration occurred. Dual gamma ray measurements showed that, in glass beads, liquid Hg⁰ preferentially migrated towards higher porosity zones. As for PCE, infiltration and distribution of Hg⁰ DNAPL are strongly affected by the heterogeneities within the porous formation. However, compared to other DNAPLs, liquid Hg⁰ shows a strong attenuation potential of gamma rays. Finally, numerical simulations of the glass beads experiment showed an overall good agreement with the experimental results, highlighting that, among the factors influencing the prediction of liquid Hg⁰ migration in water-saturated porous media, the most critical are (i) the knowledge of the inflow rate, (ii) the reliable estimation of the porous formation permeability, and (iii) the accurate representation of the correlation between retention properties and intrinsic permeability.     

The Combined Toxic and Genotoxic Effects of Chromium and Volatile Organic Contaminants to Pseudokirchneriella subcapitata

In this report, the toxic effect of TCE (trichloroethylene), PCE (tetrachloroethylene), and potassium dichromate on P. subcapitata was investigated. The test was conducted at different concentrations of pollutants, starting from the European Community limit values defined for each analysed contaminant. Mixtures of pollutants were also tested to verify the combined effect of algae cells. Results suggest that both TCE and PCE were able to reduce P. subcapitata growth and metabolism starting from 0.05 and 0.02 mg L^?1 of contaminant, respectively. PCE seems to be substantially more toxic than TCE. Chromium produces a clear effect on algae growth and esterase activity only starting from 1 mg L^?1 of potassium dichromate; this result confirms the suitability of EU limit value. AFLP analysis showed that all tested pollutants produce DNA mutations probably due to oxygen radicals. Generally, chromium, at high concentrations, is more toxic and genotoxic that TCE or PCE. Test performed with a mixture of pollutants showed a synergic effect of chromium and organic compounds suggesting that the membrane damage induced from organic substances should increase the chromium cellular access.     

Effects of Grafting on Alkali Stress in Tomato Plants: Datura Rootstock Improve Alkalinity Tolerance of Tomato Plants

Plant growth, nutritional status, and proline content were investigated in non-grafted and grafted greenhouse tomato plants onto five rootstocks of eggplant, datura, orange nightshade, local Iranian tobacco, and field tomato, exposed to 0, 5, and 10 mM sodium bicarbonate (NaHCO₃) to determine whether grafting could improve alkalinity tolerance of tomato. The leaf fresh mass of ungrafted and grafted tomato plants decreased significantly as NaHCO₃ levels increased. Despite other rootstocks and ungrafted plants, alkalinity had no significant effect on stem and root fresh mass and shoot phosphorus (P), potassium (K) and magnesium (Mg) concentrations of datura grafted plants. The lowest solution pH and electrical conductivity (EC) values and the highest leaf proline content were observed in the plants grafted onto datura rootstock. Moreover, sodium (Na) concentration in shoots was lower in plants grafted onto datura rootstock than in other plants especially under high NaHCO₃ levels. Overall, using datura rootstock improved alkalinity tolerance of tomato plants under NaHCO₃ stress.     

Acid neutralizing capacity of solutions containing organic acids isolated from Finnish lakes

Organic vs. bicarbonate contribution to Gran alkalinity was studied using empirical measurements. Distilled water with various amounts of bicarbonate and organic acids was equilibrated with synthetic air during Gran titrations. Natural organic acids isolated from Finnish lakes were used as a carbon source for these solutions. The experimental design corresponded to computer simulations made by Cantrell et al. (1990). The results indicate that the discrepancy between the Gran ANC and the ANC calculated from anion deficit can be explained partly by the organic acids, which remain unprotonated in the titration. The unprotonated fraction of organic acids was on average 5.5 and 6.2 eq per mg of dissolved organic carbon (DOC), when pH ranges of 3.0–4.0 and 3.5–4.5 for Gran plot regression were used, respectively. The acid neutralizing capacity provided by organic acids varied from 18 to 75 eq/L, depending on the initial pH and DOC concentration and the pH range of the Gran plot regression. The results of empirical Gran titrations agree with the theoretical calculations made by Cantrell et al. (1990).     

Model organic compounds differ in priming effects on alkalinity release in soils through carbon and nitrogen mineralisation

The influence of organic matter and its cycling on soil pH change is still unclear. This study investigated the effect of organic compounds on carbon and nitrogen dynamics and their relationship with pH changes in two soils differing in initial soil pH (Podosol of pH 4.5 and Tenosol of pH 6.2). Seven organic compounds representing common compounds in decomposing plant residues or root exudates were added to the soils and incubated for 60 d. The largest cumulative soil respiration occurred when glucose, malic acid and citric acid were added. In addition, the Tenosol had the greater respiration compared to the Podosol. The addition of organic acids (acetic, malic, citric, ferulic and benzoic acid) instantly decreased soil pH due to the dissociation of H⁺ from the acids. The pH of both soils was then restored over time, which was positively correlated with decomposition % of these compounds. The pH of the Tenosol amended with all the organic acids and of the Podosol with malic acid exceeded that of the control, and net alkalization occurred, with the degree of alkalization being greater with malic and citric acid. Adding organic acids to the Tenosol generally increased NH₄ concentrations but decreased NO₃ concentrations. The addition of glucose decreased pH in Podosol but slightly increased it in the Tenosol. The addition of glucosamine hydrochloride decreased pH due to significant nitrification. The results suggest that the addition of organic acids stimulates microbial NO₃ uptake, and ammonification and decomposition of indigenous soil organic matter, resulting in a priming effect on alkalinity release, and that the degree of the priming effect is influenced by the type of organic acid and initial soil pH.     

Effects of sulfate amendments on mineralization and phosphorus release from South Florida (USA) wetland soils under anaerobic conditions

We investigated the potential effects of elevated water-column sulfate (SO₄) levels on heterotrophic microbial respiration and net phosphorus (P) release for soils collected from impacted and unimpacted Everglades wetlands in south Florida. Soils from three sites, ranging from low P and low SO₄ to high P and high SO₄ environments, were examined under controlled laboratory conditions. The soils were subjected to anaerobic incubations to evaluate net P release and organic matter decomposition in response to SO₄ amendments of 32 or 96 mg l⁻¹ (0.33 and 1.0 mM).Three processes have been described in the literature to explain why SO₄ enrichment may lead to P release from soils under anaerobic conditions. First, alkalinization can lead to a more favorable pH environment for decomposition. For the soils examined here, alkalinization due to the hydrogen ion-consuming reaction of SO₄ reduction was not a prominent mechanism. We found that pH decreased in the incubation vessels, and that increases in alkalinity were more likely attributable to calcium carbonate dissolution than SO₄ reduction. Moreover, all the soils exhibited near circum-neutral pH levels, with moderate to high concentrations of native alkalinity.Second, formation of iron sulfide (FeS_x) compounds has been shown to mobilize iron (Fe)-associated P. Soils from only one of the study sites had Fe concentrations that would be expected to be high enough to influence P mobility. Relatively high porewater Fe:soluble reactive P (SRP) ratios (>83:1) were observed at this site, which suggests that Fe could theoretically exert control over the release of P from the soil. However, soil P levels at this site were too low to measure any substantial influence of Fe on net P mobilization.Finally, availability of electron acceptors such as SO₄ is a major determinant of decomposition rate, and thus rate of organic P release. Amending the soils with SO₄ did not result in either more heterotrophic microbial respiration as measured by carbon dioxide (CO₂) and methane (CH₄) production, or increased net P mobilization. In two of the SO₄-amended soils where post-incubation total sulfide concentrations were as high as 23.4 mg l⁻¹, SO₄ addition reduced production of respiratory carbon end products, suggesting hydrogen sulfide inhibition. Moreover, limitations imposed by substrate quality and low P contributed to the lack of meaningful enhanced decomposition of organic matter with the addition of 32 or 96 mg SO₄ l⁻¹ to the oligotrophic wetland soils. Even though P release did occur under anaerobic conditions for the more enriched site, addition of SO₄ did not enhance P release.     

Contribution of soluble and insoluble fractions of agricultural residues to short‐term pH changes

The retention of agricultural residues in cropping systems to maintain soil fertility is also important for the redistribution of alkalinity. In systems that adopt minimum or no‐tillage practices residue incorporation into the soil may occur slowly and the contribution of soluble and insoluble residue fractions to pH change may vary temporally and spatially. In this study we examined the contribution of whole, water soluble (70°C for 1 hour for two cycles) and insoluble fractions of canola, chickpea and wheat residues (added at 10 g kg^?1 soil) to pH change in a Podosol (Podzol; initial pH 4.5) and a Tenosol (Cambisol; initial pH 6.2) over a 59‐day incubation period. Whole residues increased pH in both soils, with the magnitude of the pH increase (chickpea > canola > wheat) being related to alkalinity content (concentration of excess cations) of the residue. Temporal release of alkalinity was only observed for the larger alkalinity content canola and chickpea residues and the change in pH was greater than during the initial period (approximately 4 hours; T0). Increases in pH were attributed to the decarboxylation of organic anions and the association of H⁺ with organic anions and other negatively charged chemical functional groups. The relative contribution of these processes depended on the residue and the initial soil pH. Our results show that 40–62% of the alkalinity of canola and chickpea residues resided in the soluble fraction. Furthermore, pH increases caused by soluble fractions may be transient if these contain large N concentrations. Soil properties that influence inorganic N dynamics such as inhibition of nitrification at acid pH will be important in determining the subsequent direction and magnitude of pH change.     

Enhancement of alkalinity tolerance in two cucumber genotypes inoculated with an arbuscular mycorrhizal biofertilizer containing Glomus intraradices

The aim of the present study was to determine whether arbuscular mycorrhizal (AM) inoculation with a biofertilizer containing clays as granular carriers, leek root pieces and Glomus intraradices spores could improve alkalinity tolerance of two cucumber genotypes, and to study the changes induced by AM at agronomical and physiological level. A greenhouse experiment was carried out to determine yield, growth, fruit quality, net photosynthesis (A_CO2), electrolyte leakage, and mineral composition of two cucumber (Cucumis sativus L.) genotypes (hybrid “Ekron” or open-pollinated variety “Marketmore”) with inoculated and noninoculated arbuscular mycorrhizal biofertilizer. Plants were supplied with nutrient solutions at two pH values (6.0 or 8.1). The high pH nutrient solution had the same basic composition with an additional 10 mM NaHCO₃ and 0.5 g l⁻¹ CaCO₃. The percentage root colonization was higher in “Marketmore” (21.8%) than “Ekron” (12.7%). Total and marketable yield and total biomass were significantly higher by 189%, 213%, and 77%, respectively, with Ekron in comparison to those recorded with Marketmore. The highest crop performance with Ekron in comparison to Marketmore was due to the improved nutritional status (higher N, P, K, Ca, Mg, Fe, Mn, and B), higher leaf area, and net photosynthesis. Increasing the concentration of NaHCO₃ from 0 to 10 mM in the nutrient solution significantly decreased yield, plant growth, A_CO2, N, P, Fe, Cu, Zn, Mn, and B concentration in leaf tissue, whereas the electrolyte leakage increased. The inoculated plants under alkaline conditions had higher total, marketable yield, and total biomass than noninoculated plant. Mycorrhizal cucumber plants grown under alkaline conditions had a higher macronutrient concentration in leaf tissue compared to noninoculated plants. The highest yield and biomass production in inoculated plants seems to be related to the capacity of maintaining higher net A_CO2 and to a better nutritional status (high P, K, Mg, Fe, Zn, and Mn and low Na accumulation) in response to bicarbonate stress with respect to −AM plants.     

Screening Soybean Cultivars for Resistance to Iron-Deficiency Chlorosis in Culture Solutions Containing Magnesium or Sodium Bicarbonate

ABSTRACT

Hydroponic culture solutions containing bicarbonate (HCO₃ ^?) may be used to screen crops such as soybeans (Glycine max) for resistance to iron (Fe) deficiency or chlorosis. Some successful methods use sodium bicarbonate (NaHCO₃) in combination with elevated partial pressures of carbon dioxide (CO₂) to buffer pH and elevate bicarbonate. Replacing NaHCO₃ with magnesium bicarbonate [Mg(HCO₃)₂] as the form of bicarbonate alkalinity has the potential to produce culture solutions that simulate soil solutions more closely and eliminate any potential for specific sodium (Na) toxicities in sensitive plants. A modified screening solution based on Mg(HCO₃)₂-CO₂ was tested against the successful NaHCO₃-CO₂ method, using three soybean varieties of known resistance to Fe-deficiency chlorosis. Alkalinity was 10 mM [added as NaHCO₃ or Mg(HCO₃)₂], solutions were aerated with 3% CO₂, and Fe was provided as FeDTPA (diethylenetriamine-pentaacetic acid) at 15 μM (low Fe) or 60 μM (adequate Fe). Leaf chlorophyll, visual chlorosis index, and leaf Fe concentration were closely related. Solutions based on NaHCO₃ or Mg(HCO₃)₂ provided identical chlorosis-susceptibility rankings for the three cultivars.     

Relationship between rhizosphere acidification and phytoremediation in two acacia species

Purpose

Phytoremediation is the most sustainable and economical strategy for reclamation of the salt-affected soils. In order to investigate the relationship between phytoremediation and rhizosphere acidification, two experiments (greenhouse and field) were conducted using two acacia species viz. Acacia ampliceps and Acacia nilotica.

Materials and methods

In greenhouse experiment, both the species were exposed to 100 and 200 mM NaCl concentrations in solution culture. The release of organic acids from plant roots was determined after 14 and 28 days of the salt treatment. Shoot and root ash alkalinity was determined after harvesting the plants. In field experiment, both the species were grown on a saline sodic soil for 2 years. After every 6 months, plant growth data were recorded and soil samples were collected from different soil depths for physicochemical analyses.

Results and discussion

The results of greenhouse study indicated higher rhizosphere acidification by A. ampliceps than A. nilotica in terms of release of citric acid, malic acid, and tartaric acid along with ash alkalinity. The comparison of both the species in the field indicated higher amelioration in the soil properties like pH_s, EC_e, SAR, bulk density, and infiltration rate by A. ampliceps than A. nilotica.

Conclusions

It is concluded from these studies that A. ampliceps is more suitable species than A. nilotica for the phytoremediation of the salt-affected soils due to its higher rhizosphere acidification potential.

     

SOIL ALKALINITY. I. EQUILIBRIA AND ALKALINITY DEVELOPMENT

Theoretical relationships between pH, CO₂ partial pressure and alkalinity (bicarbonate + carbonate concentrations) have been shown to apply to solutions and calcite and soil suspensions. The exchange of Na onto three Ca clays shows that Ca is preferred but with negative free energies of exchange. With decreasing total electrolyte concentration, the preference for Ca increases, so that only when the concentration is above 10^-3M will significant amounts of exchangeable Na be found in soils. The preference for Ca is illite > montmorillonite > vermiculite. Dilution of the mixed Na-Ca clay suspensions causes exchange, desorption of Na and. in some cases Ca. This desorbed or ‘alkaline’ Na (and Ca) is replaced by H some of which attacks the clays. The apparent hydrolysis coefficient, KG = H adsorbed (Na)/Na adsorbed (H), varies between 5 and 9 × 10⁵, increases with increase in electrolyte concentration and varies in the order vermiculite > illite > montmorillonite. The concentration of alkaline Na + Ca increases with increasing ESP, and with clay type in the same order as the KG values. The pH calculated from the alkaline Na + Ca, assumed equal to the alkalinity was equal to measured values except for montmorillonite where the calculated values were low. Magnesium release by acid attack of the montmorillonite may explain the differences. Vermiculite rich soils will be most likely to accept exchangeable Na and to hydrolyse and develop alkalinity.     

Effect of crop residue biochar on soil acidity amelioration in strongly acidic tea garden soils

Strongly acidic soil (e.g. pH < 5.0) is detrimental to tea productivity and quality. Wheat, rice and peanut biochar produced at low temperature (max 300 °C) and differing in alkalinity content were incorporated into Xuan‐cheng (Ultisol; initial pH_{soil/water = 1/2.5} 4.12) and Ying‐tan soil (Ultisol; initial pH _{soil/water = 1/2.5} 4.75) at 10 and 20 g/kg (w/w) to quantify their liming effect and evaluate their effectiveness for acidity amelioration of tea garden soils. After a 65‐day incubation at 25 °C, biochar application significantly (P < 0.05) increased soil pH and exchangeable cations and reduced Al saturation of both tea soils. Association of H⁺ ions with biochar and decarboxylation processes was likely to be the main factor neutralizing soil acidity. Further, biochar application reduced acidity production from the N cycle. Significant (P < 0.05) increases in exchangeable cations and reductions in exchangeable acidity and Al saturation were observed as the rate of biochar increased, but there were no further effects on soil pH. The lack of change in soil pH at the higher biochar rate may be due to the displacement of exchangeable acidity and the high buffering capacity of biochar, thereby retarding a further liming effect. Hence, a significant linear correlation between reduced exchangeable acidity and alkalinity balance was found in biochar‐amended soils (P < 0.05). Low‐temperature biochar of crop residues is suggested as a potential amendment to ameliorate acidic tea garden soils.