Chromatographic behavior of humic materials extracted from Barberton sludge

Humic and fulvic acids extracted from alkali treated municipal sludge contain more higher molecular weight materials than from secondary wastewater effluents. This suggests that higher molecular weight materials (greater than 30 000)' are more easily entrapped on the proteinaceous surface of the biomass. About 28% of the sludge COD is humic material. The humic acid fraction is of a higher molecular weight than the fulvic acid fraction. The value of theE ₄:E ₆ ratio indicates that humic materials of raw sludges are of recent origin.     

Adsorption of cadmium to kaolinite in the presence of organic material

Kaolinite was equilibrated with Cd and with varying amounts of the individual compounds: EDTA, NTA, alginic acid, and humic acid. In experiments in which the Cd and kaolinite concentrations were held constant, and the ligand concentration allowed to vary, conditions under which ligand enhanced and inhibited Cd association with the solid phase were noted. Further experiments at constant Cd: ligand confirmed that, for alginic acid and humic acid, enhancement of uptake occurred, while EDTA diminished uptake. These results were compared with the adsorption of ligand by clay in the absence of organic, and it is suggested that the enhancement of uptake is due to the formation of an adsorbed organic layer on the clay serving as a solid phase ligand.     

Some considerations on the sorption and desorption phenomena of iodide and iodate on soil

Radiotracer experiments on the sorption of I^? (iodide) and IO _inf ^{3 p?} (iodate) from water by soils such as field soil, rice paddy soil and sandy soil, as well as by some soil components, have been carried out with special reference to the effects of heating and gamma-irradiating the soil. Desorption phenomena of I from soil to various solutions were also studied. The sorption of I^? by soil was markedly reduced through treatments of air-drying and heating the soil prior to its equilibration with water. The results indicated that I^? sorption was by the soil fraction which was unstable at about 150 °C, while IO _inf ^{3 p?} sorption was by the soil fraction which was relatively stable to heating. Gamma-irradiation at 27 kGy affected the sorption to a smaller extent than heating at 150 °C. A very high sorption (or soil-water distribution coefficient, Kd) was found in untreated field soil (andosol) with a low organic C (humus) content, while the sorption by sandy soil was considerably smaller than the other soils. Neither I^? or IO _inf ^{3 p?} were well sorbed by clay minerals, Al₂O₃ and quartz sand, while the sorption by Fe₂O₃ was IO _inf ^{3 p?} were desorbed by 1N NaOH solution. By acidifying this solution, only a part of the desorbed I was re-precipitated with humic acid. The desorption by solutions containing K₂SO₃ or KI was also high, while that by solutions containing HCI, CH₃COONH₄ or chemical fertilizer was considerably lower. These findings suggested the possibility that I was not directly associated with humic acid itself.     

Evaluation of different fractions of the organic matter of peat on tetracycline retention in environmental conditions: in vitro studies

Purpose

Due to the modernization of the agro-industrial sector, compounds with different toxicity and effects on human health and animal have been used and consequently affecting the environment. Among them, tetracycline (TC) stands out as one of the antibiotics most commonly used worldwide. This study evaluated the TC interaction with different fractions of peat in natura and humic substances, humic acid, fulvic acid, and humin.

Materials and methods

The different fractions of the organic matter were characterized by organic matter content, elemental analysis, spectroscopic analysis (E₄/E₆), and nuclear magnetic resonance of carbon 13 (NMR ¹³C), and the interaction between TC and different fractions of organic matter was made by fluorescence spectrometry. We used the tangential ultra-filtration system for determining the complexation capability of humic substances (HSs), fulvic acids (FA), humic acids (HA), and humin (HUM) from peat with TC. Finally, we evaluated sorption kinetic experiments between TC and peat in natura.

Results and discussion

The peat samples, humic substances, FAs, HAs, and HUM were characterized by organic matter (OM), atomic ratio (H/C and C/O) calculated from elemental analysis data, functional groups quantified by NMR ¹³C data, and E₄/E₆ ratio, and the results show significant differences in the structural characteristics of the fractions of OM influenced by the type of microorganisms and environmental factors associated with this decomposition. Data analysis revealed the strongest interaction between HUM and TC (59.19 mg g^?1), followed by interaction between HS and TC (43.36 mg g^?1 HS). In the sorption studies, these conditions showed the best model to describe the system under consideration using the Freundlich model.

Conclusions

The results showed that the different fractions of the OM extracted from peat show different contributions that affect the bioavailability of contaminants to the environment.

     

The influence of soil organic matter fractions on aggregates stabilization in agricultural and forest soils of selected Slovak and Czech hilly lands

Purpose

Because the stability of soil aggregates is affected by many factors, we studied aggregates formed in forest and agricultural soils in different soil types (Cambisols, Luvisols, Chernozems). We evaluated: (1) the differences in water-stable aggregates (WSA) as related to soil type and land management and (2) the relationships between quantitative and qualitative parameters of soil organic matter (SOM), particle-size distribution and individual size classes of WSA.

Materials and methods

Soil samples were taken from three localities (Sobě?ice, Báb, Vieska nad ?itavou). Each study locality included both a forest and an agricultural soil-sampling area.

Results and discussion

We found that in forest soils, the proportion of water-stable macroaggregates (WSA_ma) relative to water-stable microaggregates (WSA_mi) was greater than in agricultural soils. When all soils were assessed together, positive statistically significant correlations were observed between the size classes WSA_ma > 1 mm and organic carbon (C_org) content; however, the WSA_mi content was negatively correlated with C_org content. Favorable humus quality positively influenced the stabilization of WSA_ma > 5 mm; however, we found it had a negative statistically significant effect on stabilization of WSA_ma 1–0.25 mm. In agricultural soils, the stabilization of WSA_ma was associated with humified, i.e., stable SOM. The WSA_ma content was highly positively influenced mainly by fulvic acids bound with clay and sesquioxides; therefore, we consider this humus fraction to be a key to macroaggregate stability in the studied agricultural soils. On the other side, all fractions of humic and fulvic acids participated on the formation of WSA_ma in forest soil, which is a major difference in organic stabilization agents of macroaggregates between studied forest and agricultural soils. Another considerable difference is that WSA_mi in agricultural soils were stabilized primarily with humic acids and in forest soils by fulvic acids. Moreover, in forest soils, a higher content of labile carbon in WSA had a positive effect on formation of WSA_mi.

Conclusions

The observed changes in individual size classes of WSA and interactions between SOM, particle-size distribution, and WSA have a negative impact on soil fertility and thereby endanger agricultural sustainability.

     

Study of the antimony species distribution in industrially contaminated soils

Purpose

The purpose of the present study was to investigate the distribution of antimony (Sb) and its species in soil fractions in order to understand better the real risk associated with Sb in the environment.

Materials and methods

Nine surface soil samples contaminated from lead/zinc and iron smelting operations and coal fired power plants were examined using: (1) four-step sequential extraction procedure (BCR); (2) two-step sequential extraction including ethylenediaminetetraacetic acid (EDTA), sodium hydroxide (NaOH) and NH₄F; and (3) single extraction with EDTA and NaOH. Liquid phase extraction was used for redox speciation of Sb. The distribution of Sb between soil fulvic and humic acids was determined after their chemical separation. The concentrations of Sb were measured by electrothermal atomic absorption spectrometry.

Results and discussion

The main part of total Sb (2.5–105 mg?kg^?1) was associated with the residual fraction in all soils. The exchangeable/carbonate-bound concentrations were 0.83–4.7 % of total Sb. Up to 6.8 % was in the reducible and up to 1.4 % was in the oxidizable fraction. EDTA removed 7.2–11.4 % of total content. Sb(V) was the predominant form in acetic acid and EDTA extracts. Single extraction with 0.1 mol?l^?1 NaOH released up to 13.7 % of soil antimony. The main part of Sb was complexed to the higher molecular weight fraction of soil-derived humic substances.

Conclusions

For highly contaminated soils, 4 % solubility in acetic acid could represent risk of contamination of ground water under specific conditions. Also, the relatively high phytoavailable Sb (7–11 %) can represent a significant proportion in highly polluted soils. Pentavalent antimony was the main antimony species extracted from soils. The main part of the organically antimony was found to be present as complexes with higher molecular weight humic acids fraction.     

Irreversible sorption of humic substances causes a decrease in wettability of clay surfaces as measured by a sessile drop contact angle method

Purpose

The objective of the study was to obtain quantitative assessments of the hydrophobic impact of irreversible sorption of humic substances (HSs) onto clay mineral surfaces using a sessile drop contact angle method.

Materials and methods

Two clays (kaolin and montmorillonite) were modified with four humic materials: (1) sod podzolic soil, (2) chernozem, (3) peat, and (4) coal (leonardite). The humic materials were characterized using elemental analysis, size exclusion chromatography, and ¹³C NMR spectroscopy. Both clay samples were saturated with Ca²⁺ prior to modification with HS using a sorption isotherm technique. Contact angles (CAs) of the obtained HS-clay complexes were determined using a static sessile drop method after drying the obtained HS-clay complexes in the form of a thin film.

Results and discussion

HS modification rendered both clays under study—kaolin and montmorillonite—more hydrophobic. In case of Ca-kaolin, the CA values increased from 27° (Ca-kaolin) up to 31°–32° (all HS-kaolin complexes) with no significant difference among the HS types used for modification. In the case of Ca-montmorillonite, the CA values increased from 41° (Ca-montmorillonite) up to 51°–83° with the following ascending trend for the humic types investigated: chernozem HS < coal HS < peat HS < sod-podzolic HS. This trend is in reverse to the degree of aromaticity of the HS, expressed as the content of aromatic carbon, and it is directly proportional to the molecular weight of each HS.

Conclusions

Application of a sessile drop method showed increased surface hydrophobicity of HS-modified clays. Much more substantial hydrophobization was observed for montmorillonite as compared to kaolin, which was explained by the differences in the sorption mechanism.

     

Humic substances and aggregate stability in rhizospheric and non-rhizospheric soil

Purpose

The paper describes rhizospheric (Rs) and non-rhizospheric (nRs) soil to demonstrate the zone of the plant root impact on physical and chemical properties of the soil. The effects of the process accompanying the transformations of organic matter into humic substances in the rhizosphere of “common dandelion” Taraxacum officinale have been determined, and the properties of humic acids (HAs) were described. The importance of iron and clay minerals for the formation of a stable and water-resistant soil structure has been emphasized.

Materials and methods

The laboratory analysis involved determination of basic physical and chemical soil properties: texture, pH, cation exchange capacity (CEC), electrical conductivity, and content of total organic carbon (TOC) and dissolved organic carbon (DOC) and quality of humic substances: optical properties of HAs and its separation into hydrophilic (HIL) and hydrophobic (HOB) fractions, speciation of iron, glomalin operationally described as an easily extractable glomalin-related soil protein (EE-GRSP), and soil aggregate stability (SAS) of six size classes of soil aggregates.

Results and discussion

The Rs was reported with a higher TOC and DOC content (measured in the CaCl₂ extracts), however not significantly. The HAs isolated from Rs revealed a significantly higher content of humic substances at its initial decomposition stage, as compared with nRs. A significantly higher concentration of EE-GRSP was noted in the aggregates of the rhizospheric zone (mean 1.14 g kg^?1) than in the aggregates collected from root-free soil (mean 0.94 g kg^?1). There was noted the highest mean share of 1–3 mm soil aggregates in Rs as well as in nRs, respectively 44.4 and 38.3%. The soil material both in Rs and in nRs contained high amounts of exchangeable Ca²⁺, and smectite is the predominant clay mineral. It was favorable for the accumulation of organic carbon and for the formation of good soil physical condition (tilth). Higher but insignificant SAS values were observed for Rs (mean SAS?=?95.6%) than for nRs (mean SAS?=?93.9%).

Conclusions

The studies confirm the role of common dandelion roots in the process of organic carbon accumulation in rhizospheric zone and a favorable effect on the mechanism of the formation of water-resistant aggregates. Higher values of SAS for the Rs were affected by the content of TOC, DOC, exchangeable Ca²⁺ and the concentration of EE-GRSP, and, less considerably, the content of Fe and clay minerals.

     

The response of soil organic matter to manure amendments in a long-term experiment at Ultuna, Sweden

In a long-term field experiment started in 1956 on a clay loam soil at Uppsala, Sweden, changes of organic carbon in the topsoils receiving various organic amendments at the rate of 200 kg C ha^'1 year^'1 were studied to determine soil organic matter characteristics, variations of δ¹³C in the soil and to estimate a carbon balance. Fallow and mineral fertilizer without N led to a significant decrease of soil organic matter (SOM) in the soil, green manure maintained the SOM content, and animal manure and peat increased the SOM content significantly. The stable portion of the added organic materials after 37 years of continuous input was 12·8, 27·3, and 56·7%, for green manure, animal manure and peat, respectively. This was reflected by half-lives of organic carbon originating from the amendments between 3·0 (green manure) and 14·6 years (peat). The isotopic composition of SOM changed both due to mineralization (continuous fallow) and the addition of amendments is topically different from soil humus (green manure, animal manure). The isotopic effect was used to calculate the percentage of carbon derived from animal manure present for the year 1993. This value (55·4%) was larger than that derived from the carbon balance, which indicated a priming effect of the animal manure on the initial soil humus. Mineralization of microbially available organic substances led to an increase in the degree of humification on plots not receiving organic amendments. Adding peat and animal manure resulted in a decrease of the humification index due to the continuous input of poorly humified material. The extinction ratio (E₄/E₆) and ratio of fulvic acid to humic acid changed considerably in the peat treated plots. Fourier transform infrared (FTIR)-measurements of the extracts showed that peat characteristics can be detected in peat treated soils. The other amendments did not alter the characteristics of the extractable humic substances.     

Soil porosity in physically separated fractions and its role in SOC protection

Purpose

Processes that lead to soil organic carbon (SOC) protection depend on both soil porosity and structure organization, as well as chemical and biological properties. In particular, the soil micro-nano porosity (<30 μm) regulates microorganism accessibility to the soil pore system and offers surfaces for organic carbon adsorption and intercalation into soil minerals. The aim of this work was to investigate how pore size distribution can selectively protect specific carbon pools in different aggregate size fractions, by considering the effects of long-term application of farmyard manure (FYM) and mineral (Min) fertilization.

Materials and methods

Macroaggregates (250–2000 μm), microaggregates (53–250 μm), and silt–clay (<53 μm) fractions of three different soils (clayey, peaty, and sandy) were separated by wet sieving technique and then subjected to chemical and physical analysis. Sample porosity and pore size distribution were analyzed using mercury intrusion porosimetry (MIP), while SOC chemical structure was characterized by means of nuclear magnetic resonance (¹³C cross-polarization–magic angle spinning nuclear magnetic resonance (CP MAS ¹³C NMR)) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopies.

Results and discussion

Results showed that FYM increased organic (OC) and humic carbon (HC) content compared to the Min fertilization and unfertilized soils. However, it caused a gradual decrease in O,N-alkyl C, and alkyl C of humic C from macroaggregate to silt–clay fractions, suggesting an advanced state of humic component degradation as revealed by CP MAS ¹³C NMR, DRIFT analyses. MIP analysis showed a clear increase of micropores (5–30 μm) and cryptopores (0.0035–0.1 μm) from macroaggregate to silt–clay fractions, while minor differences were observed among the treatments. The application of principal component analysis to mineral soil fractions identified the formation of three main clusters, where (i) macroaggregates of clayey soil were mainly associated to cryptopores and OC and (ii) microaggregates and silt–clay fraction were mainly isolated by carbonyl C, ultramicropores, and total porosity. The third cluster was associated with medium and fine sand of the sand soil fraction as coupled with O,N-alkyl C, anomeric C, mesopores, and HC/OC ratio.

Conclusions

Overall, this study indicates that pore size distribution may be a valuable indicator of soil capacity to sequester carbon, due to its direct influence on SOC linkages with soil aggregates and the positive effects against SOC decomposition phenomena. In this context, micropore- to nanopore-dominated structures (e.g., clayey soil) were able to protect OC compounds by interacting with mineral surfaces and intercalation with phyllosilicates, while meso/macropore-dominated structures (i.e., sandy soil) exhibited their low ability to protect the organic components.

     

Quantitative and qualitative characterisation of humic products with spectral parameters

Purpose

The application of different humic products for the treatment of soils and plants has increased in recent years. The characteristics of humic products, such as the content and composition of organic carbon and the maturity, provide valuable information which is essential for an adequate application. Such information is crucial for manufacturers, business consultants and users involved in the production, distribution and implementation of humic products. This article presents the correlation between the quantitative indicators of commercial humic products and their spectral characteristics via measurements in the ultraviolet spectrum at 300 nm, in the visible area at 445 and 665 nm and in the near-infrared spectrum at 850 nm.

Materials and methods

We evaluated humic products (liquid and solid) of different origins. Via wet combustion, the content of total organic carbon in humic products can be determined. The precipitation of humic acids from the starting solution determines the composition of the humic products in terms of humic acids (HAs) and fulvic acids (FAs). The dissolution of HAs determines their concentration by titration, while the specific extinction can be assessed via spectrophotometry via measuring the absorption of HAs spectra at the following wavelengths: 300, 465, 665 and 850 nm. The degree of aromaticity and condensation of humic products determines the optical density of the HAs via the E₄/E₆ ratio.

Results and discussion

The content of total organic carbon varied widely from 0.55 to 37.5% across all groups. The content of carbon in HAs, as a percentage of the total carbon in fulvic-type humic products, ranged from 1.29 to 16.00%, while in humic-type products, it ranged from 51.43 to 91.92%. The minimum value of the E₄/E₆ ratio was 2.97, while the maximum value was 6.35. We observed a direct relationship between the dominant type of acids in humic products and the E₄/E₆ ratio.

Conclusions

The optical density of HAs indicates their quality characteristics. The presented optical characteristics for humic products show that there is a direct relationship, especially between HAs/FAs and E₄/E₆ ratios. Measurement at 300 nm (E₃₀₀) in the near-ultraviolet area and at 850 nm (E₈₅₀) in the near-infrared area can increase the range of the spectral study.

     

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.

     

Biosorption of lead and uranium by Streptomyces sp.

Both Pb(II) and UO₂ ²⁺ were abstracted from aqueous solution by both living and dead biomasses of Streptomyces sp. The organisms were particularly effective in taking up UO₂ ²⁺ ions. Optimum pH for both metals was pH 5 to 6. For a UO₂ ²⁺ concentrations of 1 mmol L^?1 and a dead biomass concentration of 1 g L^?1, 60% of the UO₂ ²⁺ was removed from solution. If cell wall material of the organism was prepared from a killed biomass an equal weight of the material removed 90% of the UO₂ ²⁺ from solution. in this case accumulated U in the biomass was 0.9 mmol g^?1 of dry biomass. Electron micrographs showed clearly that the Pb abstracted was only in the microorganisms cell surface, but UO₂ ²⁺ uptake was also intracellular.     

Effects of in-situ straw decomposition on composition of humus and structure of humic acid at different soil depths

Purpose

Returning straw to soil improved soil carbon sequestration capacity and increase soil organic matter. However, in different soil depth, especially in subsoil, there were few studies on the effects of straw decomposition on soil carbon sequestration and the properties of humic substances. Therefore, an in-situ incubation study, with six different straw rates and three different soil depths, was carried out to explore the effects of straw decomposition on soil organic carbon and humic substance composition at different soil depths.

Materials and methods

The experiment was composed of six straw rates: 0, 0.44, 0.88, 1.32, 2.64, and 5.28% of soil dry mass. The maize straw was proportionately mixed with soil and put into nylon bags. Then, the nylon bags were buried in soil at three depths (15, 30, and 45 cm) and the straw decomposition trial lasted for 17 consecutive months in-situ. Soil samples were collected after completion of the field trial. Humic substances were quantitatively and qualitatively analyzed using the modification method of humus composition and the methods specified by the International Humus Association. Fourier transform infrared spectroscopy and fluorescence spectroscopy were used in this study.

Results and discussion

Results indicated that CO₂ concentration increased with increase in soil depth. Compared with the “zero” straw control, soil organic carbon contents in the treatments amended with 1.32, 2.64, and 5.28% maize straw increased significantly, and most accumulations were at 30–45 cm depths. FTIR and fluorescence emission spectra analyses indicated that the addition of straw enhanced the aliphatic structure and decreased the aromaticity of humic acid (HA), that was to say that HA molecular structure approaches to the development of simplification and younger. The maximum change in HA molecular structure was under the 5.28% treatment in the 30–45 cm depth.

Conclusions

Returning maize straw to the subsoil layers is more conducive to the accumulation of soil organic carbon and improvement of the quality and activity of HA and the organic carbon in the subsoil can be renewed.

     

Temperature-dependent oxide removal from manganese- and iron oxide-coated soil redox bars

Purpose

Soil temperature is a fundamental parameter affecting not only microbial activity but also manganese (Mn^III,IV) and iron (Fe^III) oxide reduction rates. The relationship between Mn^III,IV oxide removal from oxide-coated redox bars is missing at present. This study investigated the effect of variable soil temperatures on oxide removal by Mn^III,IV and Fe^III oxide-coated redox bars in water-saturated soil columns in the laboratory.

Materials and methods

The Mn coatings contained the mineral birnessite, whereas the Fe coatings contained a mixture of ferrihydrite and goethite. Additionally, platinum (Pt) electrodes designed to measure the redox potential (E_H) were installed in the soil columns, which were filled with either a humic topsoil with an organic carbon (C_org) content of 85 g kg^?1 (pH 5.8) or a subsoil containing 2 g C_org kg^?1 (pH 7.5). Experiments were performed at 5, 15, and 25 °C.

Results and discussion

Although elevated soil temperatures accelerated the decrease in E_H after water saturation in the topsoil, no E_H decreases regardless of soil temperature occurred in the subsoil. Besides soil temperature, the importance of soil organic matter as an electron donor is highlighted in this case. Complete removal of the Mn^III,IV oxide coating was observed after 28, 14, and 7 days in the soil columns filled with topsoil at 5, 15, and 25 °C, respectively. Along the Fe redox bars, Fe^III reducing conditions first appeared at 15 °C and oxide removal was enhanced at 25 °C because of lower E_H, with the preferential dissolution of ferrihydrite over goethite as revealed by visual differences in the Fe^III oxide coating. Oxide removal along redox bars followed the thermodynamics of the applied minerals in the order birnessite > ferrihydrite > goethite.

Conclusions

In line with Van’t Hoff’s rule, turnover rates of Mn^III,IV and Fe^III oxide reduction increased as a result of increased soil temperatures. Taking into account the stability lines of the designated minerals, E_H-pH conditions were in accordance with oxide removal. Soil temperature must therefore be considered a master variable when evaluating the oxide removal of redox bars employed for the monitoring of soil redox status.

     

Kinetics of the reaction between the hydroxyl radical and organic matter standards from the International Humic Substance Society

Purpose

The objective of this study was to evaluate the effect of the physicochemical properties of five dissolved organic matter (DOM) isolates on their reactivity with the hydroxyl radical (HO·) in water.

Materials and methods

Five DOM isolates were purchased from the International Humic Substance Society (IHSS). Weight average molecular weight (M _W) of these samples was quantified using size exclusion chromatography based on polyethylene glycols as reference standards. Functional group and elemental composition of the DOM samples were available from the IHSS website. Room temperature rate constants were measured using electron pulse radiolysis.

Results and discussion

Five IHSS standards were examined in this study: two soil organic and three aquatic organic matters. The composition varied from samples that had primarily aliphatic carbon (Pony Lake fulvic acid) to mostly aromatic carbon moieties (Elliot Soil humic acid). The M _W values of the five samples ranged from 2,400 to 4,100 Da, with an average value of 3,060 Da. Second-order reaction rate constants between DOM and HO· (k _DOM-HO·) were measured using thiocyanate competition kinetics, giving values ranging from 1.21 to 10.36?×?10⁸ M_C ^?1?s^?1. The k _DOM-HO· values were not found to correlate with either M _W or the aliphatic-aromatic carbon ratio, which is consistent with previous reports looking at natural organic matter (NOM), but is different to reports on size-fractionated (ultrafiltration through 15–1 kDa membranes) effluent organic matter (EfOM). We attribute this difference to the larger molecular weight distributions in size-fractionated EfOM compared to NOM.

Conclusions

The k _DOM-HO· values in this study ranged over a factor of 10, suggesting that hydroxyl radical reactivity does depend on the sample composition; however, no major correlation was found between the measured reactivity and bulk physicochemical properties of DOM.     

Titanium oxide nanoparticle effects on composition of soil microbial communities and plant performance

We examined the effect of TiO₂ nanoparticles (NPs) on the growth of maize and soybean plants and associated soil microbial communities. Plants were grown in a greenhouse, and low levels of undoped or nitrogen-doped TiO₂ NPs were applied. Plant growth and nutrient content were determined, and effects of NPs on composition of soil microbial communities were examined using terminal restriction fragment length polymorphism analysis (TRFLP) of rDNA. We found no significant effects of TiO₂ NPs on plant growth, nutrient content, or the composition of bacterial communities within the rhizosphere. However, arbuscular mycorrhizal fungal communities were affected by application of undoped and nitrogen-doped TiO₂ NPs. This observation may be partially attributed to the small but significant TiO₂ NP uptake levels in the root tissues of both plants. Our results suggest that even low concentrations of TiO₂ NPs may influence some important groups of soil microbes, such as mycorrhizal fungi, but changes in the composition of microbial communities may not affect plant growth under conditions of adequate moisture and nutrients.     

Mercury volatilization from a floodplain soil during a simulated flooding event

Purpose

Middle-European floodplain soils are often contaminated with mercury (Hg) and periodically flooded. In this study, the influence of a flooding event and subsequent dewatering on the volatilization of elemental Hg and methylated species was investigated in a laboratory experiment.

Material and methods

Undisturbed soil cores were taken from a topsoil (12.1?±?0.75 mg kg^?1 Hg) at the Elbe River in Lower Saxony, Germany. Soil columns were incubated at 20 °C with varying soil moisture (water-saturated for 2 weeks, 95 and 90 % water content for 1 week each), and the redox potential (E_H) was recorded. The gaseous Hg that accumulated in the headspace of the flux chamber of the columns was pumped over cooled traps filled with adsorber material and analyzed by gas chromatography/inductively coupled plasma mass spectrometry for the various Hg species.

Results and discussion

The watering of the soil resulted in a rapid decrease in the E_H and the achievement of strongly reducing conditions (E_H??1 Hg at the beginning to 5.78 μg L^?1 Hg at the end of the experiment. Species analyses revealed that exclusively elemental Hg volatilized. The volatilization rate was between 1.73 and 824 ng m^?2 h^?1 Hg, which is consistent with other studies at the Elbe River.

Conclusions

Even when flooded for a longer period of time, floodplain soils should show neither emission of methylated Hg nor exceptionally high volatilization of elemental Hg.     

Effects of temperature on soil organic carbon fractions contents,aggregate stability and structural characteristics of humic substances in a Mollisol

Purpose

Under a global warming scenario, understanding the response of soil organic carbon fractions and aggregate stability to temperature increases is important not only for better understanding and maintaining relevant ecosystem services like soil fertility and crop productivity, but also for understanding key environmental processes intimately related with the maintenance of other regulatory ecosystem services like global climate change mitigation through carbon sequestration. An increase in temperature would accelerate the mineralization of soil organic carbon. However, the properties of organic carbon remained in soil after mineralization is not well known.

Materials and methods

Mollisol was collected at 0–20-cm depth from maize (Zea mays L.) field in Northeast China. A 180-day incubation experiment was conducted at three different temperatures (10, 30, and 50 °C) under constant soil moisture (60 % water holding capacity). Soil samples were assayed for total organic carbon (TOC), water-soluble organic carbon (WSOC), easily oxidizable organic carbon (EOC), humic fractions carbon, aggregate-associated carbon, and water stability of aggregates. Elemental analysis and solid-state ¹³C nuclear magnetic resonance spectroscopy were used to characterize humic acid and humin fractions.

Results and discussion

The contents of soil TOC, EOC, humic fractions carbon, and aggregate-associated carbon decreased with the increase in temperature. The proportion of 2–0.25-mm macroaggregate and the mean weight diameter (MWD) of aggregates also decreased. The C, H, N, S, alkyl C, and O-alkyl C contents of humic acid and humin decreased, whereas the O, aromatic C, and carbonyl C contents increased. The H/C, aliphatic C/aromatic C, and O-alkyl C/aromatic C ratios in humic acid and humin fractions decreased.

Conclusions

The increase in temperature has a negative impact on soil organic carbon content, soil aggregation, and aggregate stability. Moreover, humic acid and humin molecules become less aliphatic and more decomposed with the increase in temperature.