Effect of Humic Acid on the Nitrate Removal by Strong Base Anion Exchanger Supported Nanoscale Zero-valent Iron Composite

To probe the effect of common coexist substances on the nitrate removal by polymeric resin supported nanoscale zero-valent iron composite (D201-nZVI), humic acid (HA) was added into the nitrate removal system to elaborate the different interactions between each two and among all in the system including HA, nitrate, and D201-nZVI. The results showed that the effect of HA on the reduction of nitrate by D201-nZVI was concentration-dependent. At low HA concentration (<?5 mg/L), HA coating formed by the HA adsorption on the surface of the nZVI particles enhanced the dispersion of the particles, which led to a more evenly distribution of nZVI particles in the solution, and thus a higher nitrate reduction activity. When HA concentration was increased to 5 mg/L or more, the competitive adsorption of HA and NO₃^? on the surfaces of the D201-nZVI dominated, and the nitrate removal rate and ammonia nitrogen production were decreased. When the HA concentration reached to a further high level (>?20 mg/L), HA acted as an electron shuttle to accelerate the reduction of Fe(III) to Fe(II) in the D201-nZVI, and thus the nitrate reduction rate was accordingly enhanced. The ammonia production increased by 24.8% at HA concentration of 40 mg/L as compared with that of the control (without addition of HA). This research elucidated the interaction of HA within different HA concentration in the complicate system of anions removal by organic support-nanoscale metal particle composite, which may shade some new light on the potential application of nanoscale zero-valent materials in the practical remediation of natural water.     

Ammonia,Nitrous Oxide,Carbon Dioxide and Methane Emissions from Commercial Broiler Houses in Mediterranean Portugal

Limited data are available on ammonia (NH₃), nitrous oxide (N₂O), carbon dioxide (CO₂) and methane (CH₄) emissions from poultry housing in Mediterranean countries. The aim of the present study was to assess the NH₃, N₂O, CO₂ and CH₄ emission rates from commercial breeding hen and broiler houses under Mediterranean climate conditions. Research was conducted at one commercial breeding hen house and in two commercial broiler houses located in central Portugal. The environmental conditions, gas concentrations and ventilation rates were measured in the cold (8.0?±?2.1 °C) and hot (20.7?±?1.9 °C) season for the breeding hen house, whereas for the two broiler houses, measurements were made during one fattening cycle in the fall (17.3?±?1.7 °C) season. Results showed that the annual average emission rates for breeding hen and broiler houses were 0.52?±?0.27 and 0.06?±?0.01 for NH₃, 0.030?±?0.042 and 0.006?±?0.001 for N₂O, 169.6?±?56.2 and 58.0?±?15.1 for CO₂ and 0.092?±?0.131 and 0.0113?±?0.0002 g day^?1 bird^?1 for CH₄, respectively. The N₂O emission rates observed in breeding hen houses may have been overestimated, being higher than previously reported for Mediterranean countries.     

Peroxicoagulation and Solar Peroxicoagulation for Landfill Leachate Treatment Using a Cu–Fe System

Leachates, particularly those from mature landfills, are difficult to treat by biological processes because of their high toxicity and low biodegradability. Therefore, the development of new treatment technology is necessary. The treatment of landfill leachate by peroxicoagulation and solar peroxicoagulation using a batch electrolytic reactor with a Fe cathode and a Cu anode is proposed. The tested operational variables included pH (2.8 and 8.2), current density (11 and 16 mA cm^?2), treatment time (5, 10, 15, 20, 25, and 30 min), and presence of solar ultraviolet (UV) light and were collected using a compound parabolic collector. The optimum conditions were a pH, current density, and treatment time of 2.8, 16 mA cm^?2, and 10 min, respectively. The presence of UV did not have a significant effect. The chemical oxygen demand and biochemical oxygen demand removed were 62.3% and 55.5%, respectively. The results of UV-visible absorption, fluorescence, and Fourier transform infrared spectroscopy measurements confirm the oxidation process.     

Slow nitrogen release from humic substances modified with aminoorganosilanes

Purpose

The purpose of the present study is to evaluate slow-release nitrogen capabilities of soil amendments obtained by modification of humic materials from peat and lignite with alkoxyorganosilanes carrying different amine substituents.

Materials and methods

The humates from lignite and peat were modified using (3-aminopropyltriethoxy)-silane (APTES) and (1-aminohexamethylenene, 6-aminomethylene)-triethoxysilane (AHATES). The obtained derivatives were characterized using elemental analysis and Fourier transform infrared spectroscopy. Nitrogen release in the form of ammonia or nitrate was evaluated using dissolution tests under sterile aqueous conditions as well as long-term soil experiments. Ammonium and nitrate were determined using ion-selective electrodes. Activity index (AI) was calculated from the dissolution tests. For soil trials, arable Retisol was sampled from 0- to 5-cm layer in Yaroslavl region (Russia). The soil experiments were conducted over 78 days using (NH₄)₂SO₄ as an activator of nitrification and 3-amino-1,2,4-triazole as an inhibitor of autotrophic nitrifying bacteria.

Results and discussion

Modification of lignite and peat humates leads to an increase in nitrogen content up to 2 and 4.3 %, respectively, in case of APTES, and up to 3 and 6 %, respectively, in case of AHATES. All humic derivatives gradually released N upon dissolution in water over 6 days up to 51 % of the total N. The AI values ranged from 4 to 13 %. Amendment of soil with the modified humic materials induced an increase in nitrate content resulting from nitrification of released ammonia by soil microflora. This was confirmed by aminotriasole experiments. The nitrogen release occurred slowly: over the first week of incubation, it did not exceed 36–69 % of the total N content. The higher release rate of ammonium nitrogen was observed for CHS-AHATES versus CHS-APTES derivative, whereas no difference was seen between the two peat derivatives, which showed release rate on the level of CHS-AHATES derivative. Positive effect of all modified humic materials lasted over 78 days.

Conclusions

Modification of lignite and peat humates with two aminoorganosilanes carrying one and two nitrogen atoms in the amine substituent brought about twofold to threefold enrichment of the parent humic materials with nitrogen, which was capable of slow release upon incubation in soils. It was released in the form of ammonia and transformed to nitrates by autotrophic nitrifying soil microflora. There was no clear relationship established between structure of amine substituent of organosilane and slow-release properties of the corresponding humic derivatives. The conclusion was met that principal application of aminoorganosilane derivatives of humic substances (HS) is soil structuring, whereas nitrogen-fertilizing capabilities might be considered as beneficial added-value feature of these humic products.

     

Relationships between soil macroaggregation and humic carbon in a sandy loam soil following conservation tillage

Purpose

Humic substances are recalcitrant and might act as persistent binding agents to form macroaggregates. The focus of this study is in investigating the contribution of humic carbon (HC) to soil aggregation in response to various tillage and residue managements.

Materials and methods

Arable soils following 8-year contrasting managements were collected to determine aggregate size distribution and stability and HC fractions including humic acid (HA) and fulvic acid (FA). The contribution of HC to aggregation was divided into three special effects including positive effect (PE), negative effect (NE), and combined effect (CE), and these effects were measured using aggregate fractionation techniques.

Results and discussion

As well as to promote structural stability, HC bounds predominantly with the silt + clay fraction and secondarily with microaggregates to form larger aggregates. The PE increased with increasing aggregate size, whereas the NE followed the opposite pattern. A positive CE was observed for large and small macroaggregates, whereas the CE for microaggregates and the silt + clay fraction was negative. Compared to continuous tillage, reduced- and no-tillage decreased the PE for large and small macroaggregates by 1.58–30.98% at the 0–20 cm depth, and straw returning also slightly decreased the corresponding PE relative to straw removing. By contrast, a significantly higher NE for small macroaggregates at the 0–10 cm depth while 6.33–81.11% decreases in CE for large and small macroaggregates at the 0–10 cm depth as well as for large macroaggregates at the 10–20 cm depth, were observed under reduced- and no-tillage. The extraction of HC significantly reduced the aggregate stability and reduced- and no-tillage effectively limited its decrease magnitude. Small macroaggregates and microaggregates made larger contributions to soil HC accumulation than did other fractions. An averagely increased contribution from large or small macroaggregates was observed under both reduced-/no-tillage and straw returning at the 0–20 cm depth. A significant and positive relationship was found between the mass proportion of macroaggregates and the HC accumulation in 0–20 cm soil. Large macroaggregates had significantly higher HA/FA ratios than small macroaggregates, and reduced- and no-tillage significantly increased these ratios both in large and in small macroaggregates. The CE for large or small macroaggregates was also significantly negatively correlated with their HA/FA ratios.

Conclusions

Overall, the HC accumulation in soil is likely to play a key role in macroaggregation, but conservation tillage might decrease the contribution magnitude of HC to large or small macroaggregation through increasing the corresponding HA/FA ratios.

     

Using humic products as amendments to restore Zn and Pb polluted soil: a case study using rapid screening phytotest endpoint

Purpose

Heavy metal contamination is a priority issue affecting millions of hectares of soil throughout the world. One of the most promising, environmentally friendly, and cost-effective approaches to restore polluted soils could be applying organic amendments. We investigated the remediation potential of three types of humic products with regard to their effect on the bioavailability of Pb and Zn, content of nutrients, and the ability to mitigate acute phytotoxicity in contaminated soil.

Materials and methods

Spodosol samples were spiked with Pb (550 mg kg^?1) and Zn (880 mg kg^?1). Then, two different commercial humic products (from peat and lignosulfonate) and natural humic acids (from brown oxidized coal) were added in two doses to reach an equal content of carbon: a 10% increment and a 30% increment of the initial total organic carbon in the soil. After 30 days, the content of metals and nutrients (S, K, Na, Ca, Mn, P) was determined by the sequential extraction (i?H₂O, ii?NH₄COOH pH 4.8, iii–CH₃COOH). The effect of humic products on heavy metals bioavailability was evaluated using the calculated partition indexes. Seed germination and root elongation of Sinapis alba were also determined. Chemical and biochemical variables were aggregated by the principal component analysis.

Results and discussion

Humic products reduced the amount of bioavailable fractions of Pb and Zn in soils. The partition index, which quantitatively describes bioavailable fractions of the Zn and Pb in the soil, was 28–49% lower than in the spiked (Pb+Zn) control. The inhibition of root elongation and seed germination of mustard by Zn and Pb was significantly mitigated by humic products; in the soil test, the root length and seed germination were up to 36–87% higher than those of the Pb+Zn control and did not differ from those in the non-amended treatments. This effect may have been associated with the structural differences (H/C and O/C ratio) and content of nutrients (Na and K) in humic products.

Conclusions

Commercial humic products used in poor multi-contaminated soils can maintain plant growth by improving nutrient status due to heavy metals immobilization and can be a promising approach to remediate the soil contaminated with heavy metals at extremely high concentrations.

     

Responses of soil microbial community to nitrogen fertilizer and precipitation regimes in a semi-arid steppe

Purpose

Changes of nitrogen (N) cycle caused by N fertilization and precipitation regimes have affected the key ecosystem structure and functions in temperate steppe, which may modify the structure of soil microbial communities involved in N transformation. This paper was designated to examine the response of soil ammonia oxidizers and denitrifiers to the N fertilization and precipitation regimes in a semi-arid steppe where N and water contents are major limiting factors of the grassland productivity.

Materials and methods

This study was based on a long-term N fertilization and precipitation regimes experiment in Inner Mongolia (116° 17′ 20″ E, 42° 2′ 29″ N). The treatments including CK (control), R (reduced precipitation), W (30% increase in precipitation), N (10 g N m^?2 y^?1), RN (reduced precipitation and 10 g N m^?2 y^?1), and WN (30% increase in precipitation and 10 g N m^?2 y^?1). Soil basic chemical properties and microbial activities were analyzed. Molecular methods were applied to determine the abundance, structure and diversity of ammonia oxidizers and denitrifiers. Statistical analysis detected the main and interactive effect of treatments on soil microbial communities and revealed the relationship between soil microbial community structures and environmental factors.

Results and discussion

N fertilization significantly increased ammonia-oxidizing bacteria (AOB) abundance. Ammonia-oxidizing archaea (AOA) community structure was markedly changed in N fertilizer treatment and strongly affected by soil pH, while soil nitrate and water content correlated with AOB community structure. Soil nitrate was the key factor influencing nirK gene community structure, while soil pH and water content explained much of the variations of nosZ gene community. AOB-amoA and nosZ gene community diversities were influenced by precipitation regimes and interaction of N fertilization and precipitation regimes, respectively.

Conclusions

N fertilization and precipitation regimes had significant influences on the changes of soil properties and microbial functional communities. Soil nitrification was mainly driven by AOB in the semi-arid grassland. Changes of substrate content and soil pH were the key factors in shifting functional microbial communities. The non-synergistic effects of N fertilization and precipitation regimes on the microbial functional groups indicated that the negative effect of lower pH induced by N fertilization would be alleviated by precipitation regimes, which should be well considered in grassland restoration.

     

Changes in forest soil organic matter quality affected by windstorm and wildfire

Purpose

Windthrows and fires are major natural disturbances in forest ecosystems, which can affect organic matter in the surface and the mineral layer of forest soil. The main aim of this study was to evaluate the changes occurring in the structure and properties of humic acid (HA) in the lands where windthrows and wildfires occurred.

Materials and methods

In November 2004, the forest in the area of 12,000 ha in the Tatra National Park, Slovakia, was seriously damaged by northern wind gusts exceeding 200 km/h. In July 2005, a wildfire broke out in a 220 ha of wind-damaged area. The HAs have been isolated from four research plots: (a) the area where the fallen trees were removed (EXT); (b) an area after windstorm covered by wood from struck trees (NEX), left for spontaneous succession; (c) an area after extracted timber, damaged by the surface wildfire (FIR); and (d) a reference intact spruce forest area (REF). Changes in the chemical structure of the HAs isolated from the research plots were determined on the basis of elemental analysis and UV-Vis, EPR, IR, and ¹³C NMR spectroscopy.

Results and discussion

All used analytical methods showed a decrease in the humification degree of the humic acids extracted from the soils where the spruce forest has been affected by a wildfire and a windthrow. In the case of the control sample HA (REF), the calculated atomic H/C and O/C ratios and the degree of aromaticity (α) calculated from the ¹³C NMR spectra were higher, indicating higher aromaticity of HA from the REF area. The more complex and developed structure of REF HA was confirmed by the higher value of E^1%₆ and the lower E4/E6 ratio obtained using UV-Vis spectroscopy. Also, the higher g-parameters determined from the EPR spectra of the stable radicals present in HA confirmed the lower aromaticity on the plots that have been subjected to the calamities. The ¹³C NMR spectra and the elemental analysis show that the structure of the HA extracted from the NEX plot is the closest to the REF.

Conclusions

The results of the systematic research showed significant changes in the structure of HA taken from spruce forest soils that were subjected to windstorms and fires. An enrichment of the HAs in aliphatic carbon and so a lower humification degree of the organic matter in the areas calamity-affected were observed. The results clearly indicate that the HAs extracted from the disturbed plots of the spruce forest are not as stable as those extracted taken from the control plot.

     

Effectiveness of crop straws,and swine manure in ameliorating acidic red soils: a laboratory study

Purpose

Crop straws and animal manure have the potential to ameliorate acidic soils, but their effectiveness and the mechanisms involved are not fully understood. The aim of this study was to evaluate the effectiveness of two crop (maize and soybean) straws, swine manure, and their application rates on acidity changes in acidic red soils (Ferralic Cambisol) differing in initial pH.

Materials and methods

Two red soils were collected after 21 years of the (1) no fertilization history (CK soil, pH 5.46) and (2) receiving annual chemical nitrogen (N) fertilization (N soil, pH 4.18). The soils were incubated for 105 days at 25 °C after amending the crop straws or manure at 0, 5, 10, 20, and 40 g kg^?1 (w/w), and examined for changes in pH, exchangeable acidity, N mineralization, and speciation in 2 M KCl extract as ammonium (NH₄⁺) and nitrate plus nitrite (NO₃^??+?NO₂^?).

Results and discussion

All three organic materials significantly decreased soil acidity (dominated by aluminum) as the application rate increased. Soybean straw was as effective (sometimes more effective) as swine manure in raising pH in both soils. Soybean straw and swine manure both significantly reduced exchangeable acidity at amendment rate as low as 10 g kg^?1 in the highly acidic N soil, but swine manure was more effective in reducing the total acidity especially exchangeable aluminum (e.g., in the N soil from initial 5.79 to 0.50 cmol₍₊₎ kg^?1 compared to 2.82 and 4.19 cmol₍₊₎ kg^?1 by soybean straw and maize straw, respectively). Maize straw was less effective than soybean straw in affecting soil pH and the acidity. The exchangeable aluminum decreased at a rate of 4.48 cmol₍₊₎ kg^?1 per pH unit increase for both straws compared to 6.25 cmol₍₊₎ kg^?1 per pH unit from the manure. The NO₃^??+?NO₂^? concentration in soil increased significantly for swine manure amendment, but decreased markedly for straw treatments. The high C/N ratio in the straws led to N immobilization and pH increase.

Conclusions

While swine manure continues to be effective for ameliorating soil acidity, crop straw amendment has also shown a good potential to ameliorate the acidity of the red soil. Thus, after harvest, straws should preferably not be removed from the field, but mixed with the soil to decelerate acidification. The long-term effect of straw return on soil acidity management warrants further determination under field conditions.