Sequencing Zerovalent Iron Treatment with Carbon Amendments to Remediate Agrichemical-Contaminated Soil

Agrichemical spills and discharges to soil can cause point-source contamination of surface and ground waters. When high contaminant concentrations inhibit natural attenuation in soils, chemical treatments can be used to promote degradation and allow application of treated soils to agricultural lands. This approach was used to remediate soil containing >650 mg atrazine, >170 mg metolachlor and >18,000 mg nitrate kg^?1. Results indicated a decrease in metolachlor concentration to <1 mg kg^?1 within 95 days of chemical treatment with zerovalent iron (Fe⁰, 5% w/w) and aluminum sulfate (Al₂(SO₄)₃, 2% w/w) but after one year >150 mg atrazine and >7000 mg nitrate kg^?1 remained. Laboratory experiments confirmed that subsequent additions of sucrose (table sugar) to the chemically pretreated soil promoted further reductions in atrazine and nitrate concentrations. Field-scale results showed that adding 5% (w/w) sucrose to windrowed and pretreated soil significantly reduced atrazine (<38 mg kg^?1) and nitrate (<2,100 mg kg^?1) concentrations and allowed for land application of the treated soil. These results provide evidence that zerovalent iron in combination with Al₂(SO₄)₃ and sucrose can be used for on-site, field-scale treatment of pesticide- and nitrate-contaminated soil.     

Organic matter bound to mineral surfaces: Resistance to chemical and biological oxidation

Understanding the turnover of organic matter (OM) in soils necessitates information on biological stability and ecological functions. For easy characterization of slowly cycling OM, treatments using oxidants such as sodium hypochlorite (NaOCl) have been applied. The rationale for that approach is, however, questionable and concerns exist to which extent abiotic oxidation can mimic biological mineralization. Here we compare biological mineralization of mineral-bound OM to its resistance to chemical oxidation by 6 mass% NaOCl. Water-extractable OM, sorbed to goethite, vermiculite, and pyrophyllite at pH 4.0 and in different background electrolytes (CaCl₂, NaCl, NaCl-NaH₂PO₄) to favor or exclude certain binding mechanisms, was subsequently subjected to NaOCl treatment (pH 7, either for 18 or 6 × 6 h). Irrespective of mineral surface properties and mechanisms involved in OM sorption, NaOCl removed a constant portion of the sorbed OC. More OC survived when bound to goethite than to vermiculite, thus confirming previous results on the increase of oxidation-resistant OC with increasing Fe and Al (hydr)oxide contents in different soils. Mineralizable OC (within 90 days) was much smaller than the NaOCl-removable OC and both fractions were negatively correlated (r² = 0.90 for the 18 h treatment; r² = 0.86 for the 6 × 6 h treatment), suggesting that chemically oxidizable OM does not represent the portion of sorbed OM available to biological consumption.     

Chemistry of Lowland Rice Soils and Nutrient Availability

Rice is the staple food crop for about 50% of the world's population. It is grown mainly under two ecosystems, known as upland and lowland. Lowland rice contributes about 76% of the global rice production. The anaerobic soil environment created by flood irrigation of lowland rice brings several chemical changes in the rice rhizosphere that may influence growth and development and consequently yield. The main changes that occur in flooded or waterlogged rice soils are decreases in oxidation–reduction or redox potential and increases in iron (Fe²⁺) and manganese (Mn²⁺) concentrations because of the reductions of Fe³⁺ to Fe²⁺ and Mn⁴⁺ to Mn²⁺. The pH of acidic soils increased and alkaline soils decreased because of flooding. Other results are the reduction of nitrate (NO₃ ^?) and nitrogen dioxide (NO₂ ^?) to dinitrogen (N₂) and nitrous oxide (N₂O); reduction of sulfate (SO₄ ^2?) to sulfide (S^2?); reduction of carbon dioxide (CO₂) to methane (CH₄); improvement in the concentration and availability of phosphorus (P), calcium (Ca), magnesium (Mg), Fe, Mn, molybdenum (Mo), and silicon (Si); and decrease in concentration and availability of zinc (Zn), copper (Cu), and sulfur (S). Uptake of nitrogen (N) may increase if properly managed or applied in the reduced soil layer. The chemical changes occur because of physical reactions between the soil and water and also because of biological activities of anaerobic microorganisms. The magnitude of these chemical changes is determined by soil type, soil organic-matter content, soil fertility, cultivars, and microbial activities. The exclusion of oxygen (O₂) from the flooded soils is accompanied by an increase of other gases (CO₂, CH₄, and H₂), produced largely through processes of microbial respiration. The knowledge of the chemistry of lowland rice soils is important for fertility management and maximizing rice yield. This review discusses physical, biological, and chemical changes in flooded or lowland rice soils.     

Organic manure input and straw cover improved the community structure of nitrogen cycle function microorganism driven by water erosion

Water erosion process induces differences to the nitrogen (N) functional microbial community structure, which is the driving force to key N processes at soil-water interface. However, how the soil N transformations associated with water erosion is affected by microorganisms, and how the microbial respond, are still unclear. The objective of this study is to investigate the changes of microbial diversity and community structure of the N-cycle function microorganisms as affected by water erosion under application of organic manure and straw cover. On the basis of iso-nitrogen substitution, four treatments were set up: 1) only chemical fertilizer with N 150 kg ha^?1, P₂O₅ 60 kg ha^?1 and K₂O 90 kg ha^?1 (CK); the N was substituted 20% by 2) organic manure (OM); 3) straw (SW); and 4) organic manure + straw (1:1) (OMSW). The results showed that applying organic manure and straw to sloping farmland can increase soil N contents, but reduce runoff depth, K_w, sediment yield and N loss, especially in the OMSW. Straw cover and straw + organic manure increased the diversity (Chao1) of nitrifier (AOB), and both diversity and uniformity (Shannon) of denitrifier (nirK/S) were increased in the OMSW. All erosion control measures reduced N-fixing bacteria diversity and increased their uniformity, and the combined application of organic manure and straw cover was a better erosion control measure than the single application of them. Improved soil chemistry and erodibility were the main drives for the changes of N-functional microbial community structure and the appearance of dominant bacteria with different organic materials.     

Comparison of Various Phosphate Stabilisation Agents for the Immobilisation of Ni and Zn in Sewage Sludge

This paper reports the results of the treatment of polychlorinatedbiphenyl (PCB) contaminated sandy soils (100 mg kg^-1 Aroclor 1242) with the Fenton advanced oxidation process (AOP). The results obtained in the various assays permitted the optimization of conditions as follows: 5% H₂O₂; 100 ppm of Fe³⁺; and a ratio of sandy soil mass/volume of oxidizing solution (m/V) of 1/3 g mL^-1. In addition, these tests established the need for agitation and dispensed with the need for heat. The results obtained confirm that the oxidation process occurs in solid phase (on the PCBs adsorbed to soil particles), producing 98% elimination of the original PCB structure and 82% dechlorination, all within a reaction time of 72 hr. The degree of elimination was found to be dependent on the level of congener chlorination and the process displays a pseudo first order kinetics. In addition, the Fenton chemical oxidation process may be complemented by subsequent aerobic biological degradation which, after 15 days, produces 72% mineralization of the products generated during the chemical oxidation process.     

Is CO2 evolution in saline soils affected by an osmotic effect and calcium carbonate?

Salt-affected soils are widespread, particularly in arid climates, but information on nutrient dynamics and carbon dioxide (CO₂) efflux from salt-affected soils is scarce. Four laboratory incubation experiments were conducted with three soils. To determine the influence of calcium carbonate (CaCO₃) on respiration in saline and non-saline soils, a loamy sand (6.3% clay) was left unamended or amended with NaCl to obtain an electrical conductivity (EC) of 1.0 dS?m^?1 in a 1:5 soil/water extract. Powdered CaCO₃ at rates of 0%, 0.5%, 1.0%, 2.5%, 5.0% and 10.0% (w/w) and 0.25-2 mm mature wheat residue at 0% and 2% (w/w) were then added. Cumulative CO₂-C emission from the salt amended and unamended soils was not affected by CaCO₃ addition. To investigate the effect of EC on microbial activity, soil respiration was measured after amending a sandy loam (18.8% clay) and a silt loam (22.5% clay) with varying amount of NaCl to obtain an EC_1:5 of 1.0–8.0 dS?m^?1 and 2.5 g glucose C?kg^?1 soil. Soil respiration was reduced by more than 50% at EC_1:5?≥?5.0 dS?m^?1. In a further experiment, salinity up to an EC_1:5 of 5.0 dS?m^?1 was developed in the silt loam with NaCl or CaCl₂. No differences in respiration at a given EC were obtained between the two salts, indicating that Na and Ca did not differ in toxicity to microbial activity. The effect of different addition rates (0.25–2.0%) of mature wheat residue on the response of respiration to salinity was investigated by adding NaCl to the silt loam to obtain an EC_1:5 of 2.0 and 4.0 dS?m^?1. The clearest difference between salinity levels was with 2% residue rate. At a given salinity level, the modelled decomposition constant ‘k’ increased with increasing residue addition rate up to 1% and then remained constant. Particulate organic carbon left after decomposition from the added wheat residues was negatively correlated with cumulative respiration but positively correlated with EC. Inorganic N (NH ₄ ⁺ -N and NO ₃ ^? -N) and resin P significantly decreased with increasing salinity. Resin P was significantly decreased by addition of CaCl₂ and CaCO₃.     

Oxygen Transfer and Industrial Wastewater Treatment Efficiency of a Vertically Moving Biofilm System

A vertically moving biofilm system (VMBS) was developed to treat wastewater. In this system, the biofilm grows on a biofilm module consisting of plastic media that is vertically and repeatedly moved up into the air and down into the water. The objectives of this study were to investigate the oxygen transfer efficiency and industrial wastewater treatment performance of the VMBS. The oxygen transfer coefficient (K _L a) depended on the movement frequency (n) of the biofilm module and was proportional to n ^1.67. K _L a values measured were within the range of 0.0001 to 0.0027 s^-1. The VMBS exhibited good carbonaceous removal when treating industrial wastewater produced in a factory manufacturing synthetic fibres. Removal efficiency of filtered chemical oxygen demand (COD) and biological oxygen demand (BOD₅) was up to 93.2 and 97.9%, respectively. The volumetric removal rates of filtered COD and BOD₅ reached 1320 g COD m^-3 day^-1 and 700 g BOD₅ m^-3 day^-1. The areal organic removal rates, based on the surface area of the biofilm substrata, were 16 g BOD₅ m^-2 day^-1 and 39 g COD m^-2 day^-1. No clogging occurred during the experiment. The mean areal biofilm mass increased with increasing the mean areal BOD₅ removal rate. The new biofilm process has such advantages as high carbonaceous oxidation, energy saving, simpleconstruction and easy operation for industrial wastewater treatment.     

Remediation of Atrazine-contaminated Soil and Water by Nano Zerovalent Iron

Atrazine-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of nano zerovalent iron (nano ZVI) to dechlorinate atrazine (2-chloro-4ethylamino-6-iso-propylamino-1,3,5-triazine) in contaminated water and soil. This study determined the effects of iron sources, solution pH, Pd catalyst and presence of Fe or Al sulfate salts on the destruction of atrazine in water and soil. Our results indicate nano ZVI can be successfully used to remediate atrazine in water and soil. Aqueous solution of atrazine (30 mg l^?1) was treated with 2% (w/v) of nano ZVI and 5% (w/v) of commercial ZVI. Although, iron dose in nano ZVI treatment was less than that in commercial ZVI treatment, atrazine destruction kinetic rate (k _obs) of nano ZVI treatment (1.39 days^?1) was around seven times higher than that of commercial ZVI treatment (0.18 days^?1). Reductive dechlorination was the major process in destruction of atrazine by nano ZVI. The dechlorination product was 2-ethyl-amino-4-isopropylamino-1,3,5-triazine. Lowering the pH from 9 to 4 increased the destruction kinetic rates of atrazine by nano ZVI. Moreover, nano ZVI/Pd enhanced destruction kinetic rates of atrazine (3.36 day^?1). Pd played the important role as a catalyst during treatment of atrazine by nano ZVI. Atrazine destruction kinetic rates were greatly enhanced in both contaminated water and soil treatments by nano ZVI when sulfate salts of Fe(II), Fe(III) or Al(III) was add with the following order of removal rates: Al (III) (2.23 day^?1) > Fe (III) (2.04 day^?1) > Fe(II) (1.79 day^?1). The same results were found in atrazine-nano ZVI-soil incubation experiments.     

Alkalinity generation by Fe(III) reduction versus sulfate reduction in wetlands constructed for acid mine drainage treatment

Despite the widespread use of wetlands for acid mine drainage (AMD) treatment, alkalinity generating mechanisms in wetlands and their abiotic and biotic controls are poorly understood. While both dissimilatory sulfate reduction and Fe(III) reduction are alkalinity-generating mechanisms, only the former has been considered as important in wetlands constructed for AMD treatment. This study was conducted to determine the extent to which Fe(III) reduction occurs and the extent to which sulfate reduction versus Fe(III) reduction contributes to alkalinity generation in 5 wetlands constructed with different organic substrates (Sphagnum peat with limestone and fertilizer, Sphagnum peat, sawdust, straw/ manure, mushroom compost) that had been exposed to the same quality and quantity of AMD for 18–22 months. These substrates had Fe oxyhydroxide concentrations of 250–810 μmol Fe g^?1 dry substrate. Flasks containing 100 g of wet substrate along with either 150 mL of wetland water or 130 mL of wetland water and 20 mL of 37 % formalin were incubated at 4 °C in January and 25 °C in May. On days 0, 2, 4, 8, 12 and 16, the slurry mixtures were analyzed for concentrations of H⁺, Fe²⁺ and SO₄ ^2?. The bulk of the evidence indicates that for all except the mushroom compost wetland, especially at 25 °C, biologically-mediated Fe(II) reduction occurred and generated alkalinity. However, in none of the wetlands, regardless of incubation temperature, was there evidence to support net biological sulfate reduction or its attendant alkalinity generation. Sulfate reduction and concurrent Fe(III) oxyhydroxide accumulation may be important in the initial stages of wetland treatment of AMD, both contributing to effective Fe retention. However, as Fe(III) oxyhydroxides accumulate over time, Fe(III) reduction could lead not only to decreased Fe retention, but also to the potential net release of Fe from the wetland.     

Yield,Nutrient Uptake,and Changes in Soil Chemical Properties as Influenced by Liming and Iron Application in Common Bean in a No-Tillage System

Soil acidity is the principal limiting factor in crop production in Oxisols, and deficiency of micronutrients has increased in recent years because of intensive cropping. A field experiment was conducted over three consecutive years to assess response of common bean (Phaseolus vulgaris L.) to lime and iron (Fe) applications on an Oxisol in a no-tillage system. Changes in selected soil chemical properties in the soil profile (0- to 10- and 10- to 20-cm depths) with liming were also determined. Lime rates used were 0, 12, and 24 Mg ha^–1, and Fe application rates were 0, 50, 100, 150 200, and 400 kg ha^–1. Both lime and Fe were applied as broadcast and incorporated in the soil. Grain yields of common bean were significantly increased with the application of lime. Iron application, however, did not influence bean yield. There were significant changes in soil profile (0- to 10-cm and 10- to 20-cm depths) in pH, calcium (Ca²⁺), magnesium (Mg²⁺), hydrogen + aluminum (H⁺ + Al³⁺), base saturation, acidity saturation, cation exchange capacity (CEC), Ca²⁺ saturation, Mg²⁺ saturation, potassium (K⁺) saturation, and ratios of Ca/Mg, Ca/K, and Mg/K. These soil chemical properties had significant positive association with common bean grain yield. Averaged across two depths and three crops, common bean produced maximum grain yield at pH_w 6.3, Ca²⁺ 3.8 cmol_c kg^–1, Mg²⁺ 1.1 cmol_c kg^–1, 3.5 H⁺ + Al³⁺ cmol_c kg^–1, acidity saturation 41.8%, CEC 7.5 cmol_c kg^–1, base saturation 57.4%, Ca saturation 45.2%, Mg saturation 14.2%, K saturation 9.1%, Ca/Mg ratio 3.1, Ca/K ratio 22.6, and Mg/K ratio 6.7.     

Ion input/output budgets for five wetlands constructed for acid coal mine drainage treatment

Five wetlands, each 6 m wide and 30 m long and containing 30 cm of an organic substrate (Sphagnum peat to which limestone and fertilizer were surface-applied on a quarterly basis, Sphagnum peat, sawdust, straw/manure, spent mushroom compost), were exposed to controlled inputs of acid coal mine drainage (AMD; pH 2.89, soluble Fe, Mn, and SO₄ ^2? concentrations of 119, 19, and 3132 mg L^?1, respectively) at a mean flow rate of 8513 L da^?1 for 111 weeks, beginning in July of 1989. All wetlands were net sources, rather than sinks, for base cations (Ca²⁺, Mg²⁺, Na⁺, K⁺). The Sphagnum peat wetland was the least effective in treating the AMD, retaining 35% of the soluble Fe influx, but not retaining substantial H⁺, soluble Mn, soluble Al, SO₄ ^2?, or acidity. The straw/manure and mushroom compost wetlands were the most effective in treating the AMD, retaining 53 and 67% of the H⁺ influx, 80 and 78% of the soluble Fe influx, 7 and 20% of the soluble Mn influx, 54 and 53% of the soluble Al influx, 15 and 11% of the SO₄ ^2? influx, and 57 and 63% of the acidity influx. For these two wetlands especially, treatment effectiveness was substantially diminished during the cold winter months of January through March. Moreover, from March through July of the final year of the study, treatment effectiveness was minimal with outflow pH and concentrations of soluble Fe, Mn, Al, SO₄ ^2? and acidity that were similar to inflow values. Decreases in treatment effectiveness over time appeared to be related to a decrease in the ability to counter the substantial acid load entering the wetlands in the AMD. Lime or limestone dissolution and bacterial dissimilatory sulfate reduction may have contributed substantially to pH improvement and acidity consumption in the straw/manure and mushroom compost wetlands, but after 2 years the cumulative input of acidity apparently had overwhelmed biotic and abiotic alkalinity generating mechanisms, as reflected in a progressive decrease in both substrate pH and abiotic acid neutralization capacity (ANC) over time, especially in the surface substrates. Also over time, effluent H⁺ and acidity concentrations became more like influent and H⁺ and acidity concentrations. Although samples of wetland interstitial water were not collected for chemical analysis, as substrate pH and ANC decreased and as influent and effluent water chemistry became more similar, it is likely that wetland interstitial water became progressively more acidic, potentially inhibiting bacterial processes that could contribute to effective treatment, favoring dissolution rather than formation of insoluble metal precipitates, and thereby contributing to the eventual failure of the wetlands to effectively treat the AMD. In general, when constructed wetlands are used to treat particularly acidic (pH<4) AMD, if abiotic and biotic alkalinity generation cannot balance the influent acid load, long-term effective treatment will not be achieved.     

Biogeochemistry of a Hyperacidic and Ultraconcentrated Pyrite Leachate in San Telmo mine (Iberian Pyrite Belt, Spain)

This work describes recent research carried out in an extremely acidic (pH 0.61–0.82) and hypersaline (e.g., 134 g/L SO₄ ^2-, 74 g/L Fe, 7.5 g/L Al, 3 g/L Mg, 2 g/L Cu, 1 g/L Zn) leachate which seeps from a pyrite pile in San Telmo mine (Huelva, SW Spain) and forms evaporative pools of ultra-concentrated water in which attractive crystals of Zn-rich melanterite (Fe^IISO₄ 7H₂O) are formed. Geochemical modeling with the Pitzer method indicates that the acidic brine was near saturation with respect to melanterite (SI_Mel?=?0?±?0.2). The microbiological investigation has revealed a surprisingly high biomass (1.4?×?10⁶ cells mL^?1) and an exotic ecosystem composed of acidophilic, Fe-oxidizing archaea (mainly Ferroplasma spp., representing 52% of the microbial population), and minor numbers of acidophilic bacteria (including Leptospirillum spp. (3.2%), Acidithiobacillus spp. (1.6%), and Alphaproteobacteria (2.8%)). The microbial production of Fe^III allows the oxidative dissolution of pyrite and other sulphides, which results in additional inputs of Fe^II, SO₄ ^2- and acidity to the system. The surfaces of the pyrite crystals show a typical etch-pitted texture, as well as blobs of elemental sulphur, which are both compatible with this indirect, microbially mediated oxidation mechanism. The composition of the acidic leachate seems to result from the combination of several processes which include: (1) formation of melanterite within the pile during relatively dry seasons, (2) subsequent dissolution of melanterite during rainy episodes, (3) microbial oxidation of Fe^II, (4) sulphide oxidation mediated by Fe^III, (5) dissolution of chlorite and other aluminosilicates present in the pile, and (6) cooling and/or evaporation of seepage from the pile and consequent melanterite precipitation.     

A study on the improvement iron nutrition of peanut intercropping with maize on nitrogen fixation at early stages of growth of peanut on a calcareous soil

Abstract

A glasshouse study employing a split-root technique was conducted to investigate the influence of intercropping with maize (Zea mays L.) in a calcareous soil on N₂ fixation by peanut (Arachis hypogaea L.) at early stages of growth. In this intercropping system, competitive interactions between maize and peanut for N and improvement of Fe uptake were likely to be important factors affecting N₂ fixation of peanut. The experiment was comprised of three treatments which included treatment I: peanut monocropping; treatment II: maize/peanut intercropping (the major and the minor compartments with low N, 50 mg kg^?1); treatment III: maize/peanut intercropping (the major compartment with low N, 50 mg kg^?1 and the minor compartment with high, N 200 mg kg^?1). The minor compartment of treatment III was fertilized with 200 mg kg^?1 N for reducing or eliminating the competition of N coming from intercropping maize. Intercropping with maize corrected Fe chlorosis of peanut by significantly increasing plant Fe concentration and uptake. Compared with the monocropping treatment, iron uptake increased from intercropping treatment II and III by 22 and 24% per plant, 30 and 29% shoots, 38 and 60% nodules. Iron uptake by the root nodules was especially enhanced in the intercropping system. In contrast, intercropping with maize had little effect on NO₃ ^?1-N concentrations in the soil rhizosphere of peanut or on N concentrations and uptake by peanut compared with plants in monoculture. The results indicate that the improvement in Fe nutrition was an important factor promoting N₂ fixation by peanut in the intercropping system at the flowering stage of peanut growth, and that competition for N by intercropped maize had little effect on N₂ fixation by peanut under the experimental conditions.     

Laboratory mesocosm studies of Fe,Al, Mn,Ca, and Mg dynamics in wetlands exposed to synthetic acid coal mine drainage

To evaluate the potential for constructed wetlands to treat acid coal mine drainage, six model wetland mesocosms (each 2.4 m × 15 cm) were filled with Sphagnum peat (15 cm deep), planted either with cattails (Typha latifolia) and living Sphagnum, living Sphagnum only, or left as bare peat (2 mesocosms per treatment). The model wetlands were exposed to synthetic acid coal mine drainage (pH 3.5, concentrations of Fe²⁺, Al³⁺, Mn^2*, Ca²⁺, and Mg²⁺ of 78.8, 10.0, 5.2, 12.0, and 4.5 mg L^?1, respectively) at a rate of 90 mL min^?1, 6 hr d^?1, 5 d wk^?1, over a 16 week period. Chemical analysis of peat at periodic intervals indicated that the model wetlands were net sources of Al³⁺, Mn²⁺ Ca²⁺ and Mg²⁺, but net sinks for Fe²⁺. Type of vegetation had no significant effect on Fe²⁺ retention; of the 204 g of Fe²⁺ added to the model wetland systems, 162 g were retained. Formation of Fe oxides accounted for 73 to 86% of the Fee' retention, with exchangeable Fe contributing 0.2 to 1.2%, organically bound Fe contributing 4 to 19%, and residual Fe contributing 7 to 15% of total Fee' retention. Fe retention was greatest at the inflow ends of the model wetlands where Fe retention appeared to reach saturation at a final Fe concentration in the peat of 235 mg g^?1. At the rate of application of the synthetic acid mine drainage, we estimated that the model wetland systems would have reached complete Fe saturation after 157 days. We suggest that the mesocosm approach could be useful in generating site-specific data that can be applied to the formulation of cost-benefit analyses that can compare a proposed wetland treatment system with alternative conventional chemical methods for treating acid mine drainage.     

Characterization of E1 Kraft Mill Effluent by Toxicity Identification Evaluation Methodology

In order to recover and reuse water in the Kraft mill process, evaluation of separate streams is required to identify toxic compounds or microcontaminants. The stage E1 Kraft effluent, corresponding to the first extraction step of the bleaching Kraft mill process, provides the main toxic compounds found in the final process effluent. This paper uses the toxicity identification evaluation (TIE) procedure for the physicochemical and ecotoxicological characterization of the E1 Kraft effluent. To distinguish the most important toxic compounds, a physicochemical characterization and Phase I of the TIE procedure were performed. The acute toxic effect of the E1 Kraft effluent and treated fraction was performed on Daphnia magna. Results show that untreated E1 Kraft effluent exerts an acute toxic effect on D. magna (24 h LC₅₀?=?27.6%), where the E1 Kraft effluent is characterized by pH 10.5, chemical organic demand (COD) 1,348.8 mg/l, and biological organic demand (BOD₅) 397.5 mg/l, while total phenolic compounds and color are 853.7 mg/l and 0.204 1?×?1 cm, respectively. Additionally, Cu⁺² (0.51 mg/l) and Fe⁺² (0.64 mg/l) were detected. With respect to different treatments, our results indicate that activated carbon, anionic and cationic exchange treatments were able to reduce more that 45% of E1 Kraft effluent’s acute toxicity and that the ethylenediaminetetraacetic acid treatment was able to reduce the E1 Kraft effluent’s acute toxicity to around 75% and the Cu⁺² concentration to 0.019 mg/l. Moreover, specific analysis of heavy metals and organic compounds by GC-MS show that the main compound responsible for the toxicity was Cu⁺², whose tolerance level on D. magna of the 0.12 mg/l.     

Recycling gamma irradiated sewage sludge as fertilizer: A case study using onion (Alium cepa)

Recycling sewage sludge into fertilizer for agricultural purposes may improve soil fertility by influencing the physical, chemical, and biological properties of the land. However, there is concern regarding elevated levels of heavy metals and pathogenic microorganisms, which may result from the use of untreated sewage sludge. Gamma radiation is found to be an efficient tool in the hygienization of municipal sewage sludge. In order to evaluate the agricultural potential of gamma irradiated sewage sludge and to assess the safety of this fertilizer, field experiments were performed in a root crop, onion (Alium cepa), during the 2003–2004 and 2004–2005 winter months. The influence over major nutrients, metallic micronutrients, and heavy metals in soil and crop plant were key factors to be analyzed. Treatments consisted of three source of fertilizers {S₁: farmyard manure (FYM); S₂: gamma irradiated sewage sludge (GISS); and S₃: non-irradiated sewage sludge (NISS)}, each at three separate levels (L₁: 5 t ha^?1; L₂: 10 t ha^?1; and L₃: 15 t ha^?1), which were evaluated and compared. The growth parameters and onion yield were not significantly influenced by the different sources of fertilizer, or the different application levels. Values of pH, organic carbon, organic N, available P and K, metallic micronutrients (Zn, Mn, Fe, Cu) and heavy metals (Ni, Cd, Pb, Co) indicate no negative effects on either soil or plant properties. Concentrations of heavy metals in soil and plant were slightly higher in NISS treatment in compare to GISS; however, the concentrations did remain within the prescribed limit, and no significant increase was consistently noted. The results prove that the gamma irradiated sludge material was of equal quality compared to the conventional FYM.     

连续翻压紫云英对福建单季稻产量与化肥氮素吸收、分配及残留的影响

【目的】紫云英翻压后在一定程度上可改善土壤理化性状,并提高后作水稻的产量,但是该机理是由于紫云英翻压矿化后提供的氮素还是由于与翻压紫云英后化肥氮素利用率的提高有关尚不清楚,因此,本项目通过连续4年紫云英翻压还田的定位试验与原状土柱模拟及15N示踪,研究了福建单季稻区紫云英压青回田对水稻产量与化肥15N吸收、 分配及残留的影响。【方法】采用单季稻田间定位试验,设5个处理: 1）对照,不翻压紫云英,不施化肥（CK）;2）不翻压紫云英,常规化肥施用量（100%H）;3）紫云英＋常规化肥用量（Z+100%H）;4）紫云英＋60%的常规化肥（Z+60%H）;5）只翻压紫云英,不施化肥（Z）。常规化肥用量（100%H）为施氮量N 135 kg/hm2,N∶P2O5∶K2O=1∶0.4∶0.7,每年紫云英翻压量为18000 kg/hm2。每个处理3次重复,小区面积15 m2,种植水稻为每小区2015丛。于定位试验的第4年,在田间定位试验小区中,采用15N-尿素（丰度10%）示踪法与原状土柱模拟水稻植株的氮素吸收及分配情况。PVC管直径25 cm,长35 cm,其中压入田面下20 cm,每小区埋两个土柱,每个土柱中种植两株水稻。【结果】紫云英年翻压18000 kg/hm2并结合施用100%化肥（Z+100%H）,水稻子粒4年平均产量比单施100%化肥（100%H）增产6.5%,同时在18000 kg/hm2 的紫云英翻压量下,主作物水稻化肥减量40%（Z+60%H）的产量与100%H的处理基本相当。Z+100%H处理对提高水稻分蘖期植株氮含量最为明显,尤其是茎叶氮含量较100%H提高7.0%,差异显著。虽然不同施肥处理水稻生育期的化肥氮素利用率无明显变化,但Z+100%H处理分蘖期与成熟期植株氮素吸收量分别较100%H提高23.0%与18.0%,说明绿肥与化肥配施有利于水稻植株吸收外源氮素,且植株吸收氮的差异主要来自于紫云英矿化的氮源。Z+60%H 与100%H处理的分蘖期与成熟期植株氮素吸收量则基本相当。不同施肥处理均有提高土壤全氮含量的趋势;Z+60%H 处理的耕层土壤化肥氮素的残留率最高,并显著高于Z+100%H处理。【结论】连续4年翻压紫云英明显提高了福建单季稻区黄泥田的农田生产力,在减少40%常规化肥用量的情况下仍可维持产量稳定。翻压绿肥减肥增效的主要机制之一是紫云英矿化的养分替代了化肥。     

Adsorption of Heavy Metals on Mixed Fe-Al Oxides in the Absence or Presence of Organic Ligands

A study was carried out on the adsorption of Co²⁺, Cu²⁺, Pb²⁺, and Zn²⁺ ions on mixed Fe-Al oxides inthe absence or presence of increasing concentrations of oxalate or tartrate. Mixed Fe-Al oxides were prepared by precipitating at pH 5.5 mixtures of Fe and Al ions at initial Fe/Al molar ratios (R) of 0, 1, 2, 4, 10 and ∞ (R0, R1, R2, R4, R10 and R∞).The oxides aged 7 days at 20 °C or 30 days at 50 °C showed different chemical composition and physico-chemical and mineralogical properties. All the mixed Fe-Al oxides showed presence of poorly crystalline materials (ferrihydrite) even after prolonged aging. The heavy metals wereselectively adsorbed on the oxides. For all the precipitates aged7 days at 20 °C, the selectivity sequence wasPb²⁺> Cu²⁺ > Zn²⁺ > Co²⁺, but the pH at which 50% ofeach cation was adsorbed (pH₅₀) was different from sample tosample. It was found that usually the greater the amounts of Fe in Fe-Al gels the lower the pH₅₀ for each metal, but the adsorption of a heavy metal was not linearly related to Fe content. The pH₅₀ usually did not change significantly when the oxides were aged 30 days at 50 °C. Competitive adsorption of Cu and Zn on ferrihydrite (R∞) showed thatCu strongly prevented Zn adsorption even at an initial Zn/Cu molar ratio of 8, whereas Cu sorption was not inhibited. In thepresence of oxalate (OX) or tartrate (TR) (organic ligand/Pb molar ratio (r_L) from 0 to 7) the quantities of Pb adsorbedon the Fe-Al oxides usually increased with increasing r_L. The adsorption increase of Pb was particularly high on the oxidesricher in Fe (R4-R∞), but a significant increase was also observed on R0-R2 samples. The adsorption of Pb on the oxides hasbeen influenced not only by the presence and concentration of organic ligands but also by the sequence of addition of Pb and tartrate on the sorbents. It has been ascertained that on each oxide the greater amounts of Pb were adsorbed when tartrate wasadded before Pb and usually according to the following sequence: Tr before Pb > Pb before Tr > Pb + Tr > Pb.     

TDR estimation of electrical conductivity and saline solute concentration in a volcanic soil

Relative to montmorillonitic or kaolinitic soils, volcanic soils have atypical dielectric characteristics that interfere with the applicability of the Time Domain Reflectometry (TDR) technique for soil moisture (θ) determination when common, empirical calibration equations are used. This particular dielectric response affects estimation of salinity in volcanic soils. Six TDR-based methods to estimate bulk electrical conductivity (σ_a) on a range of KCl saline reference solutions were compared, with Nadler's method giving the best results (R_1:1²=0.988). Three models (linear, non-linear and empirical) for predicting soil solution electrical conductivity (σ_w) based on σ_a and θ, were experimentally tested on 24 hand-packed soil columns varying in salinity (Br⁻) from 0.2 to 4.0 dS m⁻¹, each in four θ levels (36–58%). Rhoades' linear model performed better, especially for large water contents, than the other two (R_1:1²=0.986 vs. 0.976 and 0.983, respectively). An interpretation in terms of mobile vs. immobile volumetric fractions of water present in volcanic soils is suggested as a possible explanation for these results. The empirical model resulted over-parameterized and an alternative equation with fewer non-correlated parameters, σ_a=(aθ²+bθ)σ_w+cθ², is proposed and tested with good results in volcanic soils from the Canary Islands and New Zealand. The equation encompasses both the relative dielectric dominance of the mobile water fraction at high water content typical of volcanic soils, and of the immobile fraction at low water contents. Simultaneous measurements made with a standard four-electrode probe and TDR gave good correlation (R²=0.964). A good linear correlation was also found between tracer concentration in the soil solution and σ_w (R²=0.960). Nadler's and the new empirical model also tested with good results under dynamic (flow) conditions during a miscible displacement experiment in a large monolith using bromide as a tracer. The method reveals itself as a robust tool for solute transport studies under controlled salinity conditions in a volcanic soil.     

Yield enhancement and biofortification of chickpea (Cicer arietinum L.) grain with iron and zinc through foliar application of ferrous sulfate and urea

Abstract

This study investigated effects of iron (Fe) and nitrogen (N) foliar application on Fe and zinc (Zn) content in chickpea grain, grain yield, and protein content. Application of FeSO₄ at 0.5% at flowering?+?pod formation stages resulted in the highest Fe (73.50 and 75.34?mg Fe kg^?1 grain in first and second year) and Zn (35.08 and 34.21?mg Zn kg^?1 grain) content in grain followed by the application of FeSO₄ at 0.5% at flowering stage alone (68.27 and 69.97?mg Fe kg^?1 grain and 32.44 and 32.27?mg Zn kg^?1 grain) and control (54.63 and 55.69?mg Fe kg^?1 grain and 29.48 and 29.07?mg Zn kg^?1 grain). Urea spray at 2% at flowering as well as at flowering?+?pod formation stages also improved the Zn and Fe content in the grain. Combined use of Fe and urea improved the grain Fe and Zn content over sole application of Fe.