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.

Purpose

The traditional method to determine humic content (humic and fulvic acids) in commercial fertilizers, biostimulants, and organic materials is based on the oxidation of the organic carbon contained in the basic-soluble but acid-insoluble fraction (humic acids) and the basic-acid soluble fraction (fulvic acids) of their alkaline water extracts. This methodology, merely operational, makes it impossible to distinguish if the quantified carbon corresponds to substances with “humic” chemical nature or to non-humic organic matter but with similar solubility properties to those of humic matter. The aim of this work is to develop a new methodology that not only quantifies the humic content in commercial products (and raw materials) but also assesses the humic quality of the quantified organic matter.

Materials and methods

To this end, humic and fulvic (-like) fractions have been isolated/purified from several humic and non-humic materials and characterized by means of elemental analysis and UV-visible, fluorescence, and infrared spectroscopies, and these data have been used to perform a discriminant analysis (DA).

Results and discussion

The model obtained from the DA is able to discriminate humic and fulvic fractions from apparently humic or fulvic ones and provides discriminant classification functions that have proven to successfully predict the “humic quality” of the fractions isolated from commercial products, after their elemental and spectroscopic characterization.

Conclusions

Therefore, the combination of the fractionation, characterization, and evaluation by the DA is proposed as an effective methodology for quantifying and assessing the quality of the humic content claimed in the labels of commercial products.

Purpose

Aquatic macrophytes are an important source of autochthonous dissolved organic carbon in aquatic ecosystems. Yield and mass loss of aquatic humic substances released from macrophytes decomposition could be affected by the plant species and oxygen availability. Our aim was to describe the kinetics of dissolved fulvic and humic acids formed from decomposition of four aquatic macrophytes under aerobic and anaerobic conditions.

Materials and methods

Samples of Eichhornia azurea (Sw.) Kunth, Egeria najas Planch, Oxycaryum cubense (Poepp. and Kunth), and Salvinia molesta (Mitchell) were incubated under aerobic and anaerobic conditions. On sampling days, the remaining particulate detritus were weighted and were measured for the pH, the electrical conductivity, and the organic carbon in the dissolved fraction. Humic substances were extracted from the dissolved fraction, separated into fulvic and humic acids, and then quantified. The mass loss of particulate and dissolved fractions were fitted to first order kinetic models.

Results and discussion

Aerobic environment favored mineralization of aquatic macrophyte detritus and humification of organic dissolved carbon. Incubations under aerobic conditions formed 3.6 times more humic acid than incubations under anaerobic conditions. However, incubations in an anaerobic environment formed 1.84 times more fulvic acid. The dissolved humic compounds presented low mineralization rates probably due to the presence of the macrophyte detritus in the incubation representing a more attractive source of resource for microorganisms.

Conclusions

In many cases, the mineralization of HS was not noticed, leading to an increase in humic and fulvic acid concentration in the water. O. cubense detritus presented the highest carbon concentration, were related to refractory features, and generated the highest amounts of dissolved HA (mainly under aerobic condition). Egeria najas detritus presented the lowest carbon concentration, were related to labile features, and generated the highest amounts of dissolved FA (mainly under anaerobic condition). Besides that, high humic substance concentrations in the dissolved organic carbon were related to low mineralization of this fraction.

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.

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.

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.

Purpose

The aims of this paper were to review tools and methods for qualitative and quantitative evaluation of soil organic matter (SOM) coming from diverse egzogenic sources for effective soil management, and to introduce a new approach to predict dynamics of SOM transformations, especially humification, as a key process in the formation of humic substances (HSs).

Materials and methods

A review of existing literature is presented on tools and methods for qualitative and quantitative assessment of organic matter in soil originating from various sources for reasonable soil management, attempting to provide a better understanding of the advances in organic matter transformations and new research directions for modeling. Diverse tools and methods for qualitative and quantitative evaluation of organic matter in soil coming from diverse sources have been adopted so far to express transformation processes.

Results and discussion

For the qualitative analysis of SOM and humic acids (HAs), the analytical techniques are applied, e.g., HPSEC, NMR, and ESI-FTICRMS. The quantitative analysis is done through the following parameters: humification index (HI), humification degree (HD), and humification rate (HR). These analyses indicated that because of lack of reliable data from sufficiently long-term experiments, mathematical modeling may be applied as a numerical tool for quantitative estimation and prediction of humification of SOM. The effective soil management should include soil properties as well as different functions: food production, nutrient and water cycling, storage, filtrating, buffering, biological habitat, gene pool, source of raw materials, climate regulations, heritage, platform for man-made structure. The soil utility value should be evaluated through the SOM qualitative and quantitative analysis of organic carbon and total nitrogen. Knowledge about dynamics of SOM transformations is essential, particularly in the context of stability and efficiency of different sources of organic matter applied into soil. A qualitative understanding of SOM dynamics transformations along with modeling for quantitative assessment of HS formation should be used to develop sustainable soil management. The modeling may be considered as a tool for predicting SOM humification dynamics and consequently the formation of HSs from the diverse sources. The existing archival data from a long-term experiment may be used to build and calibrate the reliable mathematical model of SOM humification.

Conclusions

Managing of SOM remains a sound basis for maintaining soil in a good condition for optimizing productivity. The development of land management strategies to optimize both the increase of soil organic carbon levels and the recycling of nutrients from SOM needs to be a priority. This should include policy makers and other users as well.

Purpose

Detonation synthesis nanodiamonds (ND) are among the most widely applied nanoparticles due to their low cost of production and broad scope of applications. However, the fate and behavior of NDs in the environment are largely unknown. The behavior of NDs is greatly affected by humic substances (HSs), which comprise 50 to 80 % of natural organic matter in water and soil ecosystems. The uptake of detonation NDs by wheat seedlings and its toxicity were evaluated in the presence of seven HSs of different origins, including humic acids (HA, HS fraction soluble in alkali and insoluble in acid) and fulvic acids (FA, soluble in both alkali and acid).

Materials and methods

To monitor the uptake of NDs by plants, tritium-labeled NDs were produced. Liquid scintillation spectrometry and autoradiography were used to determine the amount of NDs absorbed by plants. The photosynthetic activity of the plants was measured using light response curves.

Results and discussion

After a 24-h exposure period, the ND content in the plant roots was 1720 μg g^?1. The introduction of HSs decreased the ND contents in the plant roots to 680–1570 μg g^?1 (except for peat FA, for which the ND content did not differ from the blank value). The observed phenomenon was probably related mainly to the influence of HSs on the zeta potential of the NDs, which shifted from positive to negative. Based on chlorophyll fluorescence evaluation, the toxicity of NDs did not inhibit photosynthesis during illumination in the physiological range. However, NDs were slightly toxic to wheat plants under excessive light, likely due to the inhibition of electron transport between Q _A and Q _B and the disruption of the formation of a thylakoid transmembrane potential.

Conclusions

The introduction of HA in a suspension of NDs obviously reduced the inhibiting effect of the NDs; however, the mitigating activities of FA were not so apparent. Our results demonstrate the urgent need for further studies of the influences of NDs on plant growth and development.

Purpose

This study aims to investigate the response of a high biomass producer non-hyperaccumulator legume plant species, Dolichos lablab L., to cadmium (Cd) stress for phytoremediation process.

Materials and methods

Three individual experiments were carried out to assess physiological and biochemical parameters to support the use of this plant species as a phytoremediator. The first experiment was carried out in Cd-contaminated soil while the second and third experiments were conducted in sand in which Cd was applied to study biochemical responses. Analysis of mineral nutrition, phytoremediation parameters, antioxidant response, and protein identification by gel-based proteomics were performed.

Results and discussion

Good tolerance to Cd under moderate level of contamination was observed. Mineral nutrition was little affected, and phytoremediation index was satisfactory. Additionally, biochemical responses based on antioxidant enzyme analysis were well responsive in roots, reflecting the capacity of Cd stress attenuation in this organ. A proteomic analysis revealed positive regulation of root proteins involved in carbohydrate, amino acids, nitrogen metabolism, and abiotic/biotic stress response, which together may contribute to create a scenario to overcome Cd-induced stress.

Conclusions

Based on the physiological and biochemical results, we concluded that D. lablab L. is suitable for phytoremediation/phytostabilization purposes.

Purpose

The use of composted sewage sludge and limestone outcrop residue in land rehabilitation, soil improvement, and technosol making can influence the mobility of nitrogen compounds in groundwater.

Materials and methods

This experiment analyzed this source of possible pollution under an experimental design based on the use of columns (0–30 cm) formed by both wastes and a heavy irrigation regime. Two waters of different quality (saline and non-saline) were used for irrigation. The presence of nitrate, nitrite, and ammonium in the leachates was checked.

Results and discussion

The environmental risk due to the presence of nitrogen species associated with the use of these materials was very low in general, although nitrate was the most important compound affected by the use of sewage sludge compost and saline water.

Conclusions

The combination of saline water for irrigation with the compost has to be seriously considered as a source of pollution for surface and ground waters, and the use of both resources may be a key factor to be studied (low-quality water and sewage sludge compost).

Purpose

Soil organic matter (SOM) plays an important role in terrestrial ecosystems and agroecosystems. Changes in the agricultural sector in the Czech Republic within the past 25 years have had a negative impact on SOM content and contribute to gradual soil degradation. The aim of this study is to estimate the effect of long-term application of different mineral fertilizers (NPK) and organic manures (manure, cattle slurry) on soil chemical properties (quality of humus, available nutrients, and soil reaction).

Materials and methods

Soil samples were collected from Luvisol during two selected periods 1994–2003 and 2014–2016 from long-term field experiment carried out in Prague-Ruzyně (Czech Republic). Average annual temperature is 8.5 °C, and annual precipitations are 485 mm. Different fertilization regimes have been applied for 62 years. The crop rotation was as follows: cereals (45%), root crops (33%) and legumes (22%). Soil analysis—soil organic carbon (SOC) was determined by oxidimetric titration method. Short fractionation method for evaluation of humic substance (HS), humic acid (HA) and fulvic acid (FA) content was used. Absorbance of HS in UV-VIS spectral range was measured by Varian Carry 50 Probe UV-VIS spectrometer. Degree of humification (DH) and color index (Q_4/6) were calculated from fractional composition data. Soil reaction was measured by potentiometric method. Available nutrients (phosphorus, potassium, magnesium, calcium) were determined by Mehlich II and Mehlich I methods and by ICP-OES. For data analysis, the following are used: exploratory data analysis, ANOVA, and principal component analysis (PCA).

Results and discussion

PCA analysis differentiated fertilizers into two categories: (1) variant NPK (lower quality of humus)—higher acidity, lower SOC and HS content, predomination of FA, higher DH and lower content of available nutrients; (2) variants with organic manures (higher quality of humus)—lower acidity, higher SOC and HS content, predomination of HA, middle DH, and high content of available nutrients. The main result of presented study is to give a synthesis of effect of different type of fertilizers on a sustainable organic matter management in arable soils, with respect to yields, food security and adaptation to predict climate changes.

Conclusions

Long-term application of mineral fertilizers (NPK) without organic matter input can accelerate humus mineralization and soil quality degradation with all negative consequences such as (nitrogen leaching, higher availability of toxic element for plants, slow energy for soil microorganisms etc.). Application of organic fertilizers (manure and cattle slurry) helps to achieve the long-term stable yields while maintaining soil at optimum quality (long-term sustainable management with SOM). Principal component analysis is a useful tool for evaluation of soil quality changes.

Purpose

The phosphate adsorption on natural adsorbents is of particular importance in regulating the transport and bioavailability of phosphates in environmental system. In soils, oxides are often associated with organic matter and form mineral-organic complexes. The aim of the present paper was to investigate the mechanisms of phosphate adsorption on these complexes.

Materials and methods

Phosphate adsorption on uncoated and humic acid (HA)-coated iron oxide complexes was investigated at different ionic strengths and pH by isotherm experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy.

Results and discussion

Results showed that HA-coated iron oxide complexes caused a decrease in the specific surface area (SSA) and the isoelectric point (IEP) of oxides. Phosphate adsorption on iron oxides was insensitive to changes of ionic strength, while it increased on the complexes with increasing ionic strength. The presence of HA decreased the maximum adsorption and the affinity of phosphate on the complexes. The zeta potential of phosphate-bound iron oxides linearly reduced with the increment of phosphate surface coverage, while the zeta potential of complexes with adsorbed phosphate kept at the same level. ATR-FTIR analysis suggested the formation of phosphate-metal complexation. The presence of HA promotes the formation of the monodentate phosphate complexes at pH 4.5 and significantly influenced phosphate species at pH 8.5.

Conclusions

The amount of phosphate adsorbed was reduced, and the phosphate speciation was also influenced when phosphate was adsorbed on HA-coated iron oxide complexes compared with phosphate adsorption on pure goethite and hematite.

Purpose

The interaction of mercury with organic matter was studied on three soils with distinct physical-chemical compositions (Fluvisol, Luvisol, and Chernozem) and three vermicomposts based on various bio-waste materials (digestate, kitchen waste with woodchips, and garden bio-waste).

Materials and methods

Laboratory batch experiments, in which organic matter composition was modeled by adding graded doses of vermicompost to individual soils, were carried out. The composition of organic matter in these vermicomposts was assessed via fractionation of humic acids, fulvic acids, hydrophilic compounds, and possible hydrophobic neutral organic matter. Furthermore, the samples were artificially contaminated with inorganic and organic mercury. Prepared samples were stored under constant temperature of 25 °C. The incubation experiments lasted for 56 days, in which the samples were taken ten times. During the experiments, the changes in mercury mobile phase amount were observed, and the influence of the source of contamination was evaluated.

Results and discussion

The amount of mobile mercury increased and then decreased during the time. In most of the soils and vermicompost combinations, the content of mercury bound to the soil was stable after 21 days. The effects of the mercury source on the exchangeable portion of Hg in the soils were most obvious in samples without added vermicompost. Nevertheless, differences between mobile inorganic and organic forms of Hg were lower in the case of Fluvisol compared to other soils. Moreover, in this soil, the content of available mercury was higher than from others.

Conclusions

In general, the smallest differences between mobile inorganic and organic forms of Hg were observed in the case of soil with the highest content of organic matter. Also higher doses of vermicomposts decreased the amount of mercury mobile phase available. Additionally, the largest positive influence of vermicompost dose on Hg mobility was measured in soils combined with vermicompost with the highest portion of humic acids.

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.

Purpose

The use of humic substances (HS) in agriculture is beneficial and has positive environmental impacts. However, to optimize the use of HS possible links between their structural characteristics and bioactivity must be shown. The goal of this study is to evaluate the bioactivity of different humic fractions extracted from vermicompost (VC) in rice plants and to shed light to possible structure-function relationships.

Materials and methods

Humic-like fractions were obtained from cattle manure vermicompost processed by African nightcrawlers (Eudrilus eugeniae spp.). Humic-like acid fraction using only water as extractor (HLAw), HLA fraction extracted following the International Humic Substances Society (IHSS) recommended method, and the solid residue (humified residual (HR)) after extraction of HLA were characterized using complementary chemical, physic, and spectroscopic technics (elemental composition, UV-Vis and Fourier transform infrared spectroscopy (FTIR) spectroscopies, ¹³C-CP MAS NMR, and MEV). Biological activity of the three HS was conducted in growth chambers and measured in roots using WinRhizo Arabidopsis software. Principal component analysis (PCA) was used to find a grouping pattern between the structural variables evaluated and the obtained root parameters.

Results and discussion

Differences were found in elemental composition among HS with larger C/N ratio in HR than in HLA and HLAw. HLA and HLAw FTIR spectra showed carboxyl band at 1714.66 cm^?1 better resolved than in HR. Bands at 1642 cm^?1 (amide I) and 1510 cm^?1 (lignin), were better resolved in HLA. ¹³C-NMR showed the following order of aromaticity: HLA > HLAw > HR. For HLAw bioactivity, the structures C_Alkyl-H,R, C_C=O, and C_COO-H,R correlated with the number and growth of smaller root. The aromatic C_Ar-H,R, C_Ar-O,N, and aliphatic C_Alkyl-O,N, C_Alkyl-O, and C_Alkyl-di-O structures in HLA, correlated with larger roots growth. HR also stimulated root growth and development in rice plants.

Conclusions

Aliphatic and oxygenated structures in HLAw showed a relation with induction of initial root emissions, whereas the presence of aromatic compounds in HLA was related with root growth stimulation activity. Higher concentration of HLAw was necessary to produce an equivalent stimulus compared with HLA; it could indicate that, although both fractions showed similar types of structures in their composition, differences in the predominant structures may be determining different effects on the root.

Purpose

The scope of this article was to investigate the spatial and temporal variability of enantiomeric fractions (EFs) of persistent organic pollutants (POPs) in soil compared to the uncertainty of the analytical data.

Materials and methods

Soil samples were taken with high spatial resolution at two sites in Czech Republic in 2008 to investigate variability on a small spatial scale. In addition, composite soil samples were taken from ten sites in 2005 and 2008 to investigate temporal variations. All samples were analysed for a suite of soil properties as well as concentrations and EFs of polychlorinated biphenyl (PCB) -95, PCB-132 and PCB-149; α-hexachlorocyclohexane (HCH); o,p′-dichlorodiphenyltrichloroethane (DDT); and o,p′-dichlorodiphenyldichloroethane (DDD).

Results and discussion

Median EFs of PCB-95 and PCB-149, α-HCH, o,p′-DDT and o,p′-DDD did not change significantly on the sites sampled in 2005 and again in 2008, while PCB-132 changed from EF?=?0.38 to EF?=?0.53. The sampling methodology is therefore very important, and composite samples will not be the best option if enantioselective degradation processes are investigated. Non-racemic EFs of POPs in the subsampled sites in 2008 were correlated to soil parameters, such as total organic carbon (TOC), total nitrogen and humic acids. These parameters are site specific and might vary on a small scale. This can explain why certain soil parameters are reported as significantly correlated with non-racemic EFs of chiral POPs in some studies, but not always in other similar studies.

Conclusions

While composite samples may still represent the overall prevailing EF range, they are not ideally suited to study enantiomeric degradation processes, which are taking place at a relative small scale, depending on the heterogeneity of soil parameters such as TOC, total organic nitrogen (TON) and humic acids.

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.

Purpose

The study aimed at comparing organic matter decomposition in two semi-natural agrobiocenozes, namely fallows and meadows, with similar plant biomass but differing in plant community composition and diversity and in succession stage.

Materials and methods

The decomposition rate of a standard material (cellulose) was measured in soils from six fallows and six meadows spanning a few kilometres apart. The mathematical model was fitted to the data.

Results and discussion

The model showed a significantly longer lag-time in cellulose decomposition in the meadows. Despite the delayed start of decomposition in the meadows, the estimated decomposition rates were similar in both ecosystem types, once the decay started.

Conclusions

The faster start of decomposition in fallows seems to be promoted by higher contents of nitrates and phosphates in the fallow soils. The fallows, as younger ecosystems, may have faster C turnover than older grasslands due to remains of fertilisers on these ex-arable fields.

Purpose

Sulfonamides are widely used for the prevention and treatment of bacterial infections, hard-degraded contaminants distributed in the environment if they are discharged into the soil and water. Biochar could probably influence the geochemical behavior of ionized antibiotics in the soils.

Materials and methods

To determine the sorption/desorption of three representative sulfonamides (SAs) in soils amended with biochar, we investigated the effects of water pH, Cu²⁺, and dissolved humic acid on the sorption of sulfamethoxazole (SMX), sulfamethazine (SMZ), and sulfadiazine (SD) onto two different soil samples (S1 pH?=?5.13 and S2 pH?=?7.33) amended with wheat straw-derived biochar (size 0.5～0.6 mm).

Results and discussion

Batch experiments showed that the sorption/desorption isotherms of SAs on soil with/without biochar followed the Freundlich model. The biochar had a strong adsorption potential for SMX, SMZ, and SD both in S1 and S2 at low water pH. Except for SMX, the presence of Cu²⁺ inhibited the sorption of SMZ and SD through competing hydrophobic adsorption region in soils. HA suppressed the sorption of three sulfonamides in soil S2 by electrostatic repulsion under alkaline condition. The soil leaching column experiments showed the SA transport in soils, and S1 and S2 amended with biochar (0.5 and 1.0 wt%) brought about 12–20 % increase in SMX, SMZ, and SD retention compared to the untreated soil.

Conclusions

The results indicated that the presence of biochar effectively mitigated the mobility of ionized antibiotics such as SMX, SMZ, and SD in soils, which helps us reconsider the potential risk of antibiotics in the environment.

Purpose

We evaluated the decay of humic (HA) and fulvic acids (FA) in order to discuss the contribution of these substances as a sink and source of carbon in a tropical lagoon.

Materials and methods

Experiments were conducted under aerobic and anaerobic conditions using FA and HA isolated from decomposition of Oxycaryum cubense submitted to 10 and 60 days of degradation. HA and FA were added to water samples from a tropical floodplain oxbow system, the Infernão Lagoon. The mineralization chambers were incubated in the dark at 21.0 °C. The carbon balance, electrical conductivity, pH, and optical density were measured over 95 days.

Results and discussion

The results from the carbon budget were fitted with a first-order kinetics model. The mineralization of refractory fractions predominated for both FA and HA. Overall, although the mineralization pathway yields varied according to the type of resource and oxygen availability, the mineralization half-lives were quite similar (49 to 64 days), suggesting a similar microbial catabolism efficiency during the decay of humic substances. The short-term routes are represented by biochemical oxidations, and the immobilization and labile fractions (varying from 0 to 30%) of FA and HA supported these processes. A yield varying from 61.0 to 91.3% represents a carbon source degradation in the middle term (ca. 2 months) considering the ecosystem.

Conclusions

In tropical floodplain lagoons, there are three carbon routes: (i) the IN₁, representing a short-term pathway (hours to days) in the carbon transformation and (ii) IN₃, a middle-term carbon source from HA and FA mineralization to the water column and subsequently to the atmosphere. A third route (IN₂) supported the heterotrophic metabolism of the lagoon acting as a transitory sink of carbon.