Valorization of Organic Wastes to Reduce the Movement of Priority Substances Through a Semiarid Soil

In this work, we examined the effect of two different organic wastes, composted sheep manure and coir, on the sorption, persistence, and mobility of three pesticides (alachlor, chlorfenvinphos, and chlorpyrifos) included as priority substances in European Directive 2013/39/EU. With this aim, leaching studies were conducted using disturbed soil columns filled with a typical agricultural soil (hipercalcic calcisol) from a semiarid area (southeastern Spain) to determine their potential for groundwater pollution. The three compounds were found in leachates of unamended soil although in different proportions: 53% (alachlor), 9% (chlorfenvinphos), and 6% (chlorpiryfos). The addition of organic wastes significantly increased the sorption of the studied pesticides. As a consequence, the half-lives of the studied pesticides were higher in amended than in unamended soils. A marked reduction of the amount recovered in leachates was observed in the amended soils, except for chlorpiryfos, whose recoveries barely changed. According to their potential groundwater pollution calculated as the groundwater ubiquity score (GUS) index, alachlor and chlorfenvinphos show medium leachability while chlorpiryfos is unlikely to leach.     

Effect of soil pollution with polycyclic aromatic hydrocarbons on the properties of humic acids

Purpose

Interestingly, soil is the component of the natural environment in which most hydrophobic organic pollution including polycyclic aromatic hydrocarbons (PAHs) gets accumulated. The aim of the present paper was to determine the effect of soil pollution with PAHs on the elemental composition, spectral properties, and hydrophobic and hydrophilic properties of humic acids. The research was performed on different types of soil samples that were artificially polluted with selected PAHs (anthracene, pyrene, fluorene and chrysene).

Materials and methods

The soil samples were polluted with selected PAHs in an amount corresponding to 10 mg PAHs kg^?1. The PAHs-polluted soil samples were incubated for 180 and 360 days at a temperature of 20–25 °C and fixed moisture (50 % of field water capacity). Humic acids (HAs) were extracted from the soil samples prior to the incubation (additionally, soils not polluted with PAHs) and after 180 and 360 days of incubation. For isolated HAs, the following analyses were performed: elemental composition, UV–Vis and IR spectra, susceptibility to oxidation, and hydrophilic (HIL) and hydrophobic (HOB) properties were determined using high-performance liquid chromatography.

Results and discussion

The research demonstrated that introducing anthracene, fluorene, pyrene and chrysene to soil samples resulted in a change in some of the quality parameters of humic acids. However, the intensity and the direction of those changes were determined by soil properties. The changes of the parameters, once PAHs were introduced, that did not depend on the soil properties were ΔA _665u and ΔA _465u (susceptibility to oxidation at wavelengths of 465 and 665 nm) as well as HIL/ΣHOB. The same tendency in changes in the structure of humic acids, once PAHs were introduced, was also observed based on the Fourier transform infrared spectra pattern.

Conclusions

A single pollution of soils with PAHs that leads to changes in the quality parameters of humic acids shows that, as for the soils permanently exposed to pollution with those compounds, significant changes can occur in the properties of humic acids. As a result, it can lead to a change in the functions played by humic acids in the environment.     

Humic Substance Fractions and Attributes of Histosols and Related High‐Organic‐Matter Soils from Brazil

Abstract

Knowledge of the distribution of soil organic matter (SOM) fractions is important in managing soils toward a sustainable agricultural system in a tropical environment. However, data on Histosols is limited. This study developed 19 profiles of Histosols and soils with high organic-matter content from different regions of Brazil. Soil organic matter was fractionated into fulvic acids (FAF), humic acids (HAF), and humin (HUM). The ratios HAF/FAF and AE (alkaline extract)/HUM were calculated. The objectives were to evaluate the method for SOM fractionating in Histosols and related soils and to correlate the distribution of organic fractions with other soil attributes. The humic fractions presented significant correlations with other soil attributes, the best being the correlation between FAF and nutrient level. The HAF and HUM presented high correlation with cationic exchange capacity, active acidity (H⁺) and pH. Humin and the alkaline extract absorbance measured at 380 nm and 465 nm and presented good correlation with total organic carbon.     

Pesticide sorption on soils treated with evergreen oak biomass at different humification stages

Abstract

The sorption of twelve pesticides (alachlor, atrazine, carbofuran, 2,4—D, 2,4—DB, methyl parathion, metoxuron, monuron, prometryne, propanil, silvex and spergon) was studied on two soil samples with a different carbonate content and treated with evergreen oak (Quercus ilex L. subsp. ballota) biomass at successive humification stages. The direct interaction between the above pesticides and lignocellulosic materials was also assayed independently. After the samples were suspended in 25 ppm pesticide solutions for 12 h, the concentrations in the supernatants were measured by derivatographic UV spectroscopy. The major fixations on the biomass of evergreen oak were found for spergon, prometryne and propanil. Except for atrazine, carbofuran, prometryne and silvex, composting the forest residue for 87 weeks significantly increased pesticide sorption. No correlations were found between the sorption values measured directly in the lignocellulosic materials and those in the soils amended with the latter, indicating the conspicuous influence of organo‐mineral interactions in the soil. Calcium carbonate played an important role in pesticide sorption: the lowest pesticide retentions were observed for the samples of the soil with the highest pH, where the addition of organic matter led to the greatest enhancements. The fixation of silvex and carbofuran increased considerably when the organic matter was added to the soil with the lowest pH, whereas in the calcic soil samples the major fixation corresponded to chlorinated phenoxy acids. Possible mechanisms involved in pesticide sorption in the systems studied are discussed.     

化肥配施不同剂量有机肥对黑土团聚体中有机碳与腐殖酸分布的影响

【目的】 团聚体的形成为土壤有机碳的稳定提供了重要的物理保护,施用有机肥影响着土壤团聚体的形成,量化有机肥施用剂量与团聚体有机碳稳定性之间的关系对于阐明农田土壤有机碳的固碳机制具有重要意义。 【方法】 以黑龙江省海伦市国家野外科学观测研究站为平台,选择连续10年进行化肥配施不同剂量有机肥处理[0、7.5、15、22.5 t/(hm2·a)]的黑土为研究对象,将团聚体分组与腐殖酸提取相结合,分析了不同粒径团聚体中有机碳和腐殖酸的含量与光学特性。 【结果】 1)与单施化肥相比,化肥配施有机肥增加了大团聚体( > 0.25 mm)的分配比例与团聚体的平均重量直径,二者均随着有机肥剂量的增加而逐渐升高,回归拟合分析表明,团聚体的平均重量直径与有机肥剂量之间呈现显著的正相关关系(P=0.03)。2) 2~0.25 mm团聚体是黑土有机碳的主要贮存场所,约占有机碳总量的64.8%~68.8%,大团聚体中有机碳的含量与储量均随着有机肥剂量的增加而逐渐升高, < 0.053 mm团聚体中有机碳含量与储量则维持在较稳定的水平。3)各粒级团聚体中腐殖酸碳含量以0.25~0.053 mm团聚体最高,各粒级团聚体中腐殖酸碳占有机碳百分比之间的差异不显著。化肥配施有机肥提高了各粒级团聚体中腐殖酸碳的含量,使团聚体对有机碳的固持能力增加,且各粒级团聚体中腐殖酸碳的含量随着有机肥剂量的增加逐渐升高。4)化肥配施有机肥增加了各粒级团聚体中腐殖酸的E4/E6比值,表明其分子结构简单化,且以 > 2 mm和0.25~0.053 mm团聚体中腐殖酸E4/E6比值的增加最显著。 【结论】 在黑土中,长期连续进行化肥配施有机肥,促进了团聚体的形成,改善了耕层土壤结构,增加了团聚体中有机碳的积累与固持能力,并使各粒级团聚体中腐殖酸的结构“年轻化”,这种促进作用在高剂量有机肥施用下更为显著。实际生产中,在短期内可通过适当提高有机肥的施用量以提高黑土肥力及其固碳能力。     

Sorptive interactions of pesticides in soils treated with modified humic acids

Different structural changes in peat humic acid (HA) were induced through treatments leading to chemical derivatization and/or the removal of functional groups. Eleven humic products were obtained after acetylation, amidation, ammonia fixation, methylation, nitration, oximation, sulphonation, selective degradations and ‘fixation’ of stearic acid. The sorption of 12 pesticides (alachlor, atrazine, carbofuran, 2,4-D, 2,4-DB, methyl parathion, metoxuron, monouron, prometryne, propanil, fenoprop and chloranil) on the above products was determined by ultraviolet derivatographic spectroscopy. In addition, pesticide sorption was evaluated on samples from neutral and calcic soils treated with the corresponding potassium humates. The most intense interactions occurred in samples from the neutral plot, whereas the greatest effect of the humic matter in enhancing pesticide sorption was found with the calcic soil. As expected, the sorption patterns in HA-pesticide systems were poorly correlated with those in soil-HA-pesticide systems. In the former case, the sorption performance was influenced mainly by hydrophobic interactions, whereas in the latter it depended on the participation of multiple parameters suggesting that the molecular volume and the van der Waals energy of the pesticide molecule play a chief role. The HA characteristics most frequently correlated with pesticide sorption were those connected with the aromatic/aliphatic ratio and the particle size. In the calcic-soil-HA-pesticide systems, the base saturation of the exchange complex correlated negatively with pesticide sorption.     

长期施用有机肥和磷肥对潮褐土土壤有机质及腐殖质组成的影响

采用长期肥料定位试验,研究了施用有机肥和磷肥对土壤有机质、腐殖质含量与组成的影响。结果表明:与本试验布置时的基础土样相比,连续10年隔年施用有机肥、有机肥和磷肥配施使土壤有机质增加了8.4%~17.3%,单施磷肥土壤有机质下降了7.8%~10.7%,其差异均达显著水平;与P0M0相比,单施磷肥、有机肥、有机肥和磷肥配施处理的土壤中有机质分别增加了2.9%~6.2%、24.8%~29.8%、25.2%~35.1%;土壤腐植酸总量及胡敏酸含量与土壤有机质含量呈显著正相关关系;施用磷肥利于土壤富里酸的积累,并影响土壤胡富比。     

Fe2+与胡敏酸的络合特征及其抗氧化性和生物有效性研究

在研究不同来源胡敏酸性质的基础上,研究了Fe2+与胡敏酸的络合特征以及络合态Fe2+的抗氧化性和生物有效性。结果表明,来源于土的胡敏酸属于A型,而来源于腐解秸秆、粪肥的胡敏酸属于RP型。A型胡敏酸与Fe2+络合能力大于RP型。HA-Fe2+络合物的络合稳定常数越大,络合物中Fe2+抗氧化性越强,玉米叶片中全铁含量也越高,但存在活性铁含量和全铁含量不一致现象。     

Response of sorption processes of MCPA to the amount and origin of organic matter in a long-term field experiment

Changes in farming practices over long times can affect the sorption behaviour of MCPA ((4‐chloro‐2‐methylphenoxy)acetic acid). We studied the adsorption–desorption mechanisms of MCPA on soil with varied amounts and origins of soil organic matter obtained from a long‐term field experiment with various organic amendments. The origin of the soil organic matter seems to be crucial for the sorption behaviour of MCPA. Samples of soil amended with sewage sludge sorbed MCPA more strongly than the soil under any other treatment. Peat‐amended soil was second followed by soil receiving animal manure, green manure, mineral fertilizer without N and the fallowed soil. Both the carbon content and the origin of the organic matter are important for the sorption. A decrease of carbon content of a soil does not necessarily imply a reduction of sorption capacity for polar organic acids such as MCPA. Nevertheless, our adsorption–desorption experiments suggest that with decreasing carbon content the role of mineral sorption mechanisms could become more pronounced. Our results showed that interactions of soil organic matter and soil minerals distinctly influence adsorption properties for MCPA.     

Competitive sorption between imidacloprid and imidacloprid-urea on soil clay minerals and humic acids

Soil organic matter and clay minerals are responsible for the adsorption of many pesticides. Adsorption and competitive sorption of imidacloprid on clay minerals and humic acids (HA) were determined using the batch equilibration method. The sorption coefficient of imidacloprid on humic acids was significantly higher than that on Ca-clay minerals, indicating that soil organic matter content was a more important property in influencing the adsorption of imidacloprid. Competitive sorption was investigated between imidacloprid and its main metabolite imidacloprid-urea on HA and Ca-clay minerals. The results showed that the sorption capacity of imidacloprid on clay minerals and HA was reduced in the presence of the metabolite, implying that imidacloprid-urea could occupy or block adsorption sites of imidacloprid on soil, potentially affecting the fate, transport, and bioavailability of imidacloprid in the environment. The interactions between a Ca-clay or HA-clay mixture and adsorption of imidacloprid and imidacloprid-urea were studied using IR differential spectra on thin films made of the adsorbent. The possible mechanisms were discussed from the shift of characteristic IR absorption bands of imidacloprid and imidacloprid-urea after sorption.     

Sorption of 2,4,6-trichlorophenol in model humic acid-clay systems

Humic acids and clays are important soil components that influence the sorption and desorption of organic contaminants; however, it is unclear how humic acids influence the sorption of organic contaminants onto clays and their subsequent desorption. Sorption and desorption of 2,4,6-trichlorophenol (2,4,6-TCP) by and from humic acid-modified K(+)- and Ca(2+)-montmorillonite and -illite were compared with unmodified clays using batch equilibration methods. Commercial humic acid and the humic acid extracted from forest soil were employed in this experiment. The adsorbed amount of 2,4,6-TCP by commercial humic acid was almost twice as large as that adsorbed by the extracted soil humic acid. More 2,4,6-TCP was sorbed onto K(+)- and Ca(2+)-illite than onto K(+)- and Ca(2+)-montmorillonite. K(+) clays were more effective in adsorbing 2,4,6-TCP than Ca(2+) clays. Sorption of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-montmorillonite and -illite increased as compared with unmodified clays. The sorption nonlinearity of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-illite increased remarkably as compared with the unmodified clays. The sorption nonlinearity of 2,4,6-TCP on humic acid-modified Ca(2+)- and K(+)-montmorillonite increased slightly in contrast to unmodified montmorillonites. By comparing sorption and desorption results, we observed hysteresis for all sorbents including humic acids, clays, and humic acid-modified clays. Sorption nonlinearity and hysteresis were dependent on the structure of humic acids. Higher aromaticity of humic acids resulted in greater sorption nonlinearity and desorption hysteresis. In addition, sorption capacity (K(f)') was positively correlated with the humic acid content of the sorbents. These results show that modification of humic acids on clays can not only increase the adsorption ability of clays but also affect the sorption nonlinearity of 2,4,6-TCP, and the desorption hysteresis was probably due to the structural characteristics of humic acids.     

Soil organic matter and sorption capacity under different soil management practices in a productive vineyard

The effect of soil organic matter (SOM) on sorptive parameters under different soil management practices in Rendzic Leptosol was studied. In 2006, an experiment of different management practices in a productive vineyard was established in the locality of Nitra-Dra?ovce (Slovakia). The following treatments were established: (1) control (grass without fertilization), (2) T (tillage), (3) T + FYM (tillage + farmyard manure), (4) G + NPK3 (grass + 3rd intensity of fertilization for vineyards), (5) G + NPK1 (grass + 1st intensity of fertilization for vineyards). Soil samples were collected every month during the year 2010. Obtained results showed increased hydrolytic acidity (by 23%), sum of basic cations (by 37%) and decreased total cation exchange capacity (CEC) (by 36%) with higher doses of fertilization in comparison to control. Application of farmyard manure had a positive effect on the increase in the SOM cation sorption capacity. Positive correlations between pH and sum of basic cations (SBC) (r = 0.493, p ≤ 0.001), CEC (r = 0.498, p ≤ 0.001) and cation sorption capacity of SOM (r = 0.391, p ≤ 0.01) were observed. Higher values of labile carbon:potentially mineralizable nitrogen (C_L:N_pot) ratio corresponded with lesser CEC, SBC and base saturation values in the soil. With increased humus quality (higher values of humic acid:fulvic acid (C_HA:C_FA) ratio), cation sorption capacity of SOM significantly increased (r = 0.329, p ≤ 0.01). The results of this study proved that the application of farmyard manure had a positive effect on the increase of SOM sorption capacity, but higher doses of mineral fertilizers added to soil had a negative effect.     

Dissolved organic matter sorption on sub soils and minerals studied by 13C-NMR and DRIFT spectroscopy

Sorption on the mineral matrix is an important process restricting the movement of dissolved organic matter (DOM) in soils. In this study, we aimed to identify the chemical structures responsible for the retention of DOM by sorption experiments with total DOM and acidic humic substances (AHS), containing humic and fulvic acids, on soil samples and minerals (goethite, ferrihydrite, and amorphous Al(OH)₃). The AHS remaining in solution after sorption were studied by ¹³C nuclear magnetic resonance (NMR) analysis, and total DOM and AHS for bed on the surfaces of minerals by diffuse reflectance Fourier-transform infrared (DRIFT) spectroscopy. The soil samples were taken from strongly sorbing Bw horizons of two Inceptisols rich in pedogenetic Fe (29 and 35 g kg ^?1) and containing little C (7 and 22 g kg^?1). The ¹³C-NMR spectra showed that sorption causes a preferential removal of aromatic and carboxyl C from the solution, whereas alkyl-C accumulates in the solution. No change was observed for O-alkyl C. The DRIFT spectra of sorbed total DOM and AHS showed a relative increase of the band intensity of carboxyl groups compared to DOM in the initial solution, confirming the importance of those groups for the sorption to mineral surfaces. The spectra also indicated reactions of carboxyl groups with metals at the mineral surfaces. The extent to which the carboxyl groups are bound depended on the surface coverage with DOM and the type of mineral.     

Land use effects on the composition of organic matter in soil particle size separates. III. Analytical pyrolysis

Soil samples from the A horizon of an Eutrochrept under spruce forest and permanent grass were fractionated into clay-, silt- and sand-size separates. Humic acids extracted from each fraction were analysed by pyrolysis-gas chromatography-mass spectrometry. Protection of functional groups by simultaneous pyrolysis and methylation yielded pyrolysates in which methyl esters of fatty acids, aliphatic dicarboxylic acids, abietic acids, phenolic acids and benzenecarboxylic acids were represented. However, methylation was not complete, and unmethylated compounds were also present. Spectra showed differences in humic acid composition between size separates as well as across land use regimes. The abundance of lignin-derived pyrolysis products increased with decreasing particle size, and was greater in soil under spruce than in soil under grass. Also, the lipid components differed, with hexadecanoic and docosanoic acid methyl esters being the dominant compounds in humic acids from soil under spruce and hexadecanoic and octadecanoic acid methyl esters in the humic acids from grassland. A good correlation was found between previous ¹³CNMR and wet chemical data and pyrolysis data, indicating that pyrolysis-methylation can be used for fast detailed chemical characterization of humic acids extracted from size separates.     

不同施肥措施对白土腐殖质组成的影响

以白土稻区4年大田定位试验为基础,设置2种翻耕深度(10 cm、20 cm,分别标记为T10、T20)和4种施肥措施(单施化肥、化肥+畜禽粪肥、化肥+秸秆还田、化肥+绿肥,分别标记为F、F+M、F+S、F+G),通过腐殖质组成修改法分别提取表层土壤水溶性物质、胡敏酸、富里酸和胡敏素,研究不同施肥措施对白土腐殖质各组分碳含量的影响。结果表明:单施化肥措施下,翻耕20 cm处理(T20+F)土壤总有机碳和腐殖质各组分碳含量均低于翻耕10 cm处理(T10+F),但差异未达显著水平。在翻耕20 cm的基础上增施有机肥能显著提高土壤总有机碳和腐殖质各组分碳含量,增施畜禽粪(T20+F+M)、秸秆还田(T20+F+S)和增施绿肥(T20+F+G)3处理的土壤总有机碳、胡敏酸、富里酸和水溶性物质碳含量较T20+F处理分别提高14.57%~30.64%、10.36%~30.57%、0.74%~12.31%和14.25%~26.80%。增施有机肥显著提高胡敏素碳含量,T20+F+M、T20+F+S和T20+F+G处理较T20+F处理提高18.87%~35.78%。4年不同翻耕与施肥措施对白土腐殖质性质未产生显著影响。增施有机肥能一定程度上提高土壤PQ值、胡富比、E4/E6值和色调系数。相关性分析表明,胡敏素、胡敏酸、富里酸碳含量与总有机碳含量间均存在显著或极显著正相关,与水溶性物质碳含量间无明显相关性。     

Characterization of fresh and decomposed dissolved organic matter using excitation-emission matrix fluorescence spectroscopy and multiway analysis

Fresh and decomposed dissolved organic matter (DOM) derived from 13 plant biomass and animal manure sources was characterized using multidimensional fluorescence spectroscopy with parallel factor analysis (PARAFAC), high-performance size-exclusion chromatography, and UV-vis spectroscopy. The PARAFAC analysis modeled seven fluorescence components: tryptophan-like, tyrosine-like, and five humic substance-like components. For most of the plant-derived DOM solutions, decomposition significantly affected the concentration of three humic substance-like-associated components, increasing two and decreasing one. The effect of decomposition upon DOM derived from animal manures was dependent on the manure source. For a majority of the DOM extracts, the ratio of fluorescence intensity to absorptivity at 254 nm increased following decomposition, indicating that fluorescing DOM compounds were generally more resistant to biodegradation than nonfluorescing UV-absorbing compounds. Molar absorptivity, humification index (HIX), and apparent molecular weight (MWAP) increased by 38.0, 38.8, and 370%, respectively, following decomposition. Spearman correlation analysis showed a strong positive relationship between the humic substance-like components and the DOM MWAP, absorptivity, and HIX. The results of this study support the use of multidimensional fluorescence spectroscopy with PARAFAC as a method to monitor the decomposition of carbon-rich soil amendments such as crop residues, green manures, and animal manures.     

Structural influences in relative sorptivity of chloroacetanilide herbicides on soil

Adsorption of the chloroacetanilide herbicides acetochlor, alachlor, metolachlor, and propachlor was determined on soils and soil components, and their structural differences were used to explain their sorptivity orders. On all soils and soil humic acids, adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca(2+)-saturated montmorillonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR differential spectra of herbicide-clay or herbicide-humic acid-clay showed possible formation of hydrogen bonds and charge-transfer bonds between herbicides and adsorbents. The different substitutions and their spatial arrangement in the herbicide molecule were found to affect the relative sorptivity of these herbicides by influencing the reactivity of functional groups participating in these bond interactions. It was further suggested that structural characteristics of pesticides from the same class could be used to improve prediction of pesticide adsorption on soil.     

Degradation of alachlor in natural and sludge-amended soils, studied by gas and liquid chromatography coupled to mass spectrometry (GC-MS and HPLC-MS)

Alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide] is an herbicide used worldwide. The relative rates of disappearance of alachlor, the formation kinetics of alachlor ethane sulfonic acid (ESA), and the formation of other degradation products in two different soils (a soil with natural organic matter and a sludge-amended soil) has been studied. For such a purpose, soil samples were spiked with alachlor at 2.5 mg kg(-1), concentration generally applied in agricultural soils, and were submitted to sunlight, simulating natural field conditions. Extracts were analyzed by GC-MS and HPLC-MS in scan mode. A good correlation was observed between both techniques, and HPLC-MS allowed the determination of two eluting peaks corresponding to the two stereoisomeric forms of alachlor ESA. Degradation of alachlor in the two soils followed first-order kinetics. Half-life in the natural soil was 4.2 +/- 0.1 days, and half-life in the sludge-amended soil was 5.8 +/- 0.8 days. The higher half-life observed in the sludge-amended soil was attributed to the higher sorption of alachlor to this soil compared to the natural soil. The degradation of alachlor in both soils gave rise to the production of alachlor ESA. Its concentration increased during the incubation period, and after 27 days, its concentration was about 0.59 mg kg(-1) in the natural soil and 0.37 mg kg(-1) in the sludge-amended soil. The other two alachlor transformation products were identified using GC-MS, and the abundance of these degradation products increased while alachlor was degraded.     

Assessment of biogeochemical trends in soil organic matter sequestration in Mediterranean calcimorphic mountain soils (Almería, Southern Spain)

Total soil organic matter levels and humic acid formation processes in mountain calcimorphic soils from Sierra María-Los Vélez Natural Park (Almería, Southern Spain) were found to differ depending on soil use (pine and oak forests, and cleared areas either cultivated or affected by bush encroachment). Biogeochemical indicators such as the concentration of exchangeable cations, or the concentration of the different types of humic substances were neither influenced by the type of vegetation nor soil use. In fact, multidimensional scaling and multiple correlations suggest that soil carbon sequestration processes are controlled by small-scale topographical features and their impact on water holding capacity. From a qualitative viewpoint, there were two more or less defined sets of soils: one set consisted of soils with humic acids with marked aliphatic character, displayed intense 2920 cm⁻¹ infrared band, and had low optical density. The resolution-enhanced infrared spectra suggested typical lignin patterns and well-defined amide bands, which point to a selective preservation of comparatively young organic matter. This situation contrasts with that in other set of soils with low C levels (<20 g kg⁻¹) where humic acids with featureless infrared spectra showed high aromaticity and were associated with perylenequinonic chromophors of fungal origin: this is considered the consequence of overlapping biogeochemical mechanisms involving both microbial synthesis and condensation processes. The results from visible and infrared derivative spectroscopies suggest that the reliability of statistically assessing the biogeochemical performance of the different uses on the site studied in terms of the intensity of the prevailing humic acid formation mechanisms, i.e., accumulation of inherited macromolecular substances in the former set, vs. microbial synthesis including the condensation of precursors of low molecular weight substances in the latter.     

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.