Humic Substances Fractions Research Articles

Spectral characterization of the fluorescent components present in humic substances, fulvic acid and humic acid mixed with pure benzo(a)pyrene solution

The fate of benzo(a)pyrene (BaP), a ubiquitous contaminant reported to be persistent in the environment, is largely controlled by its interactions with the soil organic matter. In the present study, the spectral characteristics of fluorophores present in the physical fractions of the soil organic matter were investigated in the presence of pure BaP solution. After extraction of humic substances (HSs), and their fractionation into fluvic acid (FA) and humic acid (HA), two fluorescent compounds (C1 and C2) were identified and characterized in each physical soil fraction, by means of fluorescence excitation-emission matrices (FEEMs) and Parallel Factor Analysis (PARAFAC). Then, to each type of fraction having similar DOC content, was added an increasing volume of pure BaP solution in attempt to assess the behavior of BaP with the fluorophores present in each one. The application of FEEMs-PARAFAC method validated a three-component model that consisted of the two resulted fluorophores from HSs, FA and HA (C1 and C2) and a BaP-like fluorophore (C3). Spectral modifications were noted for components C2HSs (C2 in humic substances fraction) (λex/λem: 420/490–520 nm), C2FA (C2 in fulvic acid fraction) (λex/λem: 400/487(517) nm) and C1HA (C1 in humic acid fraction) (λex/λem: 350/452(520) nm). We explored the impact of increasing the volume of the added pure BaP solution on the scores of the fluorophores present in the soil fractions. It was found that the scores of C2HSs, C2FA, and C1HA increased when the volume of the added pure BaP solution increased. Superposition of the excitation spectra of these fluorophores with the emission spectrum of BaP showed significant overlaps that might explain the observed interactions between BaP and the fluorescent compounds present in SOM physical fractions.

Relationship between Molecular Components and Reducing Capacities of Humic Substances

Humic substances (HSs) are collections of diverse organic compounds with broad redox capacities, which directly or indirectly affect the biogeochemical behaviors and fates of almost all the pollutants in the environment. The present study investigates the relationships between the molecular characteristics of HSs and their reducing capacities or electron-donating capacities (EDCs) by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), total phenolic assay, and mediated electrochemical oxidation analysis. For decreasing the molecular heterogeneity of bulk HSs, HSs were first separated into three fractions according to their polarities. The results demonstrated that compounds in HS fractions with moderate polarity possessed a high content of total phenols and consistently had high EDCs. A strong linear correlation (R2 = 0.97) existed between EDCs and the total phenolic content, which confirmed that phenols contributed to the EDCs of HSs. Further anal...

Optical and molecular characterization of dissolved organic matter (DOM) in the Arctic ice core and the underlying seawater (Cambridge Bay, Canada): Implication for increased autochthonous DOM during ice melting

Sea ice contains a large amount of dissolved organic matter (DOM), which can be released into the ocean once it melts. In this study, Arctic sea ice DOM was characterized for its optical (fluorescence) properties as well as the molecular sizes and composition via size exclusion chromatography and Fourier transformation ion cyclotron resonance mass spectrometry (FT-ICR MS). Ice cores were collected along with the underlying seawater samples in Cambridge Bay, an Arctic area experiencing seasonal ice formation. The ice core samples revealed a marked enrichment of dissolved organic carbon (DOC) compared to the seawater counterparts (up to 6.2 times greater). The accumulation can be attributed to in situ production by the autotrophic and heterotrophic communities. Fluorescence excitation emission matrices (EEMs) elaborated with parallel factor analysis (PARAFAC) evidenced the prevalence of protein-like substances in the ice cores, which likely results from in situ production followed by accumulation in the ice. Size exclusion chromatography further revealed the in situ production of all DOM size fractions, with the exception of the humic substance fraction. The majority of DOM in both the ice and seawater consists of low molecular weight compounds (<350 Da) probably derived by the microbial degradation/transformation of freshly produced DOM. Molecular characterization also supported the in situ production of DOM and highlighted the marked difference in molecular composition between sea ice and seawater. This study provides new insights into the possible role of sea ice DOM in the Arctic carbon cycle under climate change.

Zinc and lead detoxifying abilities of humic substances relevant to environmental bacterial species

The effect of humic substances (HS) and their different fractions (humic acids (HA) and hymatomelanic acids (HMA)) on the toxicity of zinc and lead to different strains of bacteria was studied. All tested bacteria demonstrated a lower resistance to zinc than lead showing minimum inhibitory concentrations of 0.1 − 0.3mM and 0.3–0.5mM, respectively. The highest resistance to lead was characteristic of Pseudomonas chlororaphis PCL1391 and Rhodococcus RS67, while Pseudomonas chlororaphis PCL1391 showed the greatest resistance to zinc. The combined fractions of HS and HA alone reduced zinc toxicity at all added concentrations of the organic substances (50 – 200mgL−1) to all microorganisms, while hymatomelanic acids reduced zinc toxicity to Pseudomonas chlororaphis PCL1391 at 200mgL−1 organic concentration only. The HS fractions imparted similar effects on lead toxicity also. This study demonstrated that heavy metal toxicity to bacteria could be reduced through complexation with HS and their fractions. This was particularly true when the metal-organic complexes held a high stability, and low solubility and bioavailability.

Water-extractable humic substances speed up transcriptional response of maize roots to nitrate

Humic substances are known to positively influence plant growth and nutrition. In particular, the water-extractable fraction of humic substances (WEHS) has been shown to enhance nitrate acquisition, increasing the activity of high affinity nitrate uptake system. However, molecular bases of this physiological response are not clarified so far.Thus, in the present work, the physiological effect of WEHS on nitrate acquisition in maize roots was correlated with changes in the root transcriptomic profile.Results confirmed that WEHS caused a faster induction of a higher capacity to take up nitrate in maize roots. Comparing the root transcriptomic profile of Nitrate- and Nitrate + WEHS-treated plants with Control (-N) ones, more than 2000 transcripts appeared to be modulated only in the presence of WEHS. Among these, genes involved in nitrate transport and assimilation (NRT1s, NRT2s, NAR2.1, NR, GS, GOGAT, CNX, UPM) were strongly modulated by WEHS. Furthermore, also some genes known to be linked to the nitrogen limitation responses were affected by WEHS, as transcripts coding for transcription factors (as LBD37, NIN-like protein, NFY-A, GRF5) and enzymes of hormones’ metabolism. The modulation of these transcripts might play a crucial role in coordinating the induction to nitrate, favouring its uptake and assimilation in WEHS-treated plants. The overexpression of nitrogen assimilatory genes by WEHS might led to an early feedback regulation of the high affinity nitrate transport system, as being operated by N-metabolites.Results of the present work shed further light on the contribution of the organic soil component to the nitrogen use efficiency in crops.

Quantification of the Carbon Content of the Fractions of Humic Substances and Total Organic Carbon in Different Production Systems

Soil organic matter is degraded and easily altered by the type of management. The objective of this work is to determine the total organic carbon and humic substance fractions in the organic matter of the soil with different management types and depths in the western region of Paraná, Brazil. The work was carried out in the Experimental Farm “Professor Antônio Carlos dos Santos Pessoa”, belonging to the State University of the West of Paraná. Five soil management systems were evaluated: one area with corn cultivation for silage (CS); other area with succession of crops, with soybean in summer and corn in winter (SC); the next area also with succession of crops, with soy in the summer and oat in the winter (SO); the following area with permanent pasture with Tifton (PP); and the last area with crop-livestock integration (ILC). For each management system, four plots were randomly selected, in each plot three simple samples were collected in a diagonal direction to form a composite sample for the depth of 0.00-0.05 m, 0.05-0.10 m and 0.10-0.15 m. Total organic carbon, fractionation of the humic substances and the AH/AF and EA/HUM ratios were calculated. For most of the analyzed variables, it was verified that there were significant differences (P &lt; 0.05) between the systems evaluated in the studied depths. In the evaluated areas, the PP, SO and ILC systems presented the highest carbon content for all attributes analyzed.

Influence of humic substances and iron and aluminum ions on the sorption of acetamiprid to an arable soil

Humic substances (HS) in soil and sediments, and surface water influence the behavior of organic xenobiotics in the environment. However, our knowledge of the effects of specific HS fractions, i.e., humic acids (HAs), fulvic acids (FAs), and humin (HM), on the sorption of organic xenobiotics is limited. The neonicotinoid insecticide acetamiprid is thought to contribute to the collapse of honeybee colonies. To understand the role that soil organic matter plays in the fate of acetamiprid, interactions between acetamiprid and the above HS fractions were examined. Batch experiments were conducted using various combinations of a field soil sample and the above 3 HS fractions prepared from the same soil, and differences in isotherm values for acetamiprid sorption were investigated based on the structural differences among the HS fractions. The sorption of acetamiprid to soil minerals associated with HM (MHM) (Freundlich isotherm constant, Kf: 6.100) was reduced when HAs or FAs were added (Kf: 4.179 and 4.756, respectively). This can be attributed to hydrophobic interactions between HM and HAs or FAs in which their dissociated carboxyl and phenolic groups become oriented to face the soil solution. The amount of acetamiprid that was adsorbed to (MHM+HA) or (MHM+FA) increased when aluminum ions were added (Kf: 6.933 and 10.48, respectively), or iron ions were added (Kf: 7.303 and 11.29, respectively). Since acetamiprid has no affinity for inorganic components in soil, the formation of HS–metal complexes by cation bridging may have oriented the hydrophobic moieties in the HAs or FAs to face the soil solution and may also have resulted in the formation of dense structures, resulting in an increase in the amount of acetamiprid that becomes adsorbed to these structures. These results highlight the importance of interactions among soil components in the pedospheric diffusion of acetamiprid.

Carbon fractions and soil fertility affected by tillage and sugarcane residue management an Xanthic Udult

The gradual change in management practices in sugarcane (Saccharum spp.) production from burning straw to a green harvesting system, as well as the use of minimum soil tillage during field renovation, may affect soil fertility and soil organic matter (SOM) contents. The objectives of this work were to investigate the influence of sugar cane production systems on: (1) soil fertility parameters; (2) on physical carbon fractions; (3) and on humic substance fractions, in a long-term experiment, comparing two soil tillage and two residue management systems an Xanthic Udult, in the coastal tableland region of Espírito Santo State, Brazil. The treatments consisted of plots (conventional tillage (CT) or minimum tillage (MT)) and subplots (residue burned or unburned at harvesting), with five replicates The highest values of Ca2+ + Mg2+ and total organic carbon (TOC) were observed in the MT system in all soil layers, while high values of K+ were observed in the 0.1-0.2 m layer. The CT associated with the burned residue management negatively influenced the TOC values, especially in the 0.1-0.2 and 0.2-0.4 m layers. The carbon in the humin fraction and organic matter associated with minerals were significantly different among the tillage systems; the MT showed higher values than the CT. However, there were no significant differences between the sugarcane residue management treatments. Overall, fractioning the SOM allowed for a better understanding of tillage and residue management systems effects on the soil properties.

我が国の腐植物質研究とその展望 2. 腐植物質の抽出および分画

我が国の腐植物質研究とその展望 2. 腐植物質の抽出および分画

Soil organic matter pools under management systems in Quilombola Territory in Brazilian Cerrado

ABSTRACT The aim of this study was to evaluate the stable and labile fractions of soil organic matter and carbon (C) management index in cultivated areas with conservation and conventional management used by Quilombola farmers in the Goiás state, Brazil. The management systems were studied in the areas of Cerradão: Native Cerrado; Pasture; Conventional grain cultivation; Conservation cultivation of perennial crop; and in the sensu stricto Cerrado: Native Cerrado; Natural pasture; Conventional grain cultivation; Conventional cultivation of perennial crop. The study was considered as observational, with five replicates. Total organic C, fractions of humic substances, labile C and C management index were determined. The Cerradão phytophysiognomy had the highest total organic C values and stable soil organic matter fractions. The native areas had low levels of labile C. The conservation cultivation of perennial crop showed the largest accumulation of total organic C in the different fractions of soil organic matter and the highest rates of C management index.

Effects of Biochar Pyrolyzed at Varying Temperatures on Soil Organic Carbon and Its Components: Influence on the Composition and Properties of Humic Substances

Application of biochar (BC) is an important way to increase soil organic carbon sequestration. At the same time, the effect of BC on fractions and properties of soil humic substances is concerned. A laboratory experiment was conducted to study the influences of BC pyrolyzed at different temperatures on the composition and properties of humic substances. The modified method for the extraction and fractionation of humic substances was adopted in this work. The carbon (C) contents of Humin (Hu), Humic acids (HA), Fulvic acids (FA) were analyzed by the thermal oxidation of K2Cr2O7 and TOC analyzer, and the optical properties of HA and FA were measured by using spectrophotometer. The results showed that the increasing temperature (from 300 to 600℃) decreased like-humic substances (LHS) from 10.93 g·kg-1 to 0.26 g·kg-1, while the structure of theLHS tended to be complicated. Compared with control treatment (CK), the addition of BC produced under 400℃ increased the contents of HA and FA (after 240 d incubation a lower FA content was found in treatments) and increased as BC application rate increased, after 360 d of incubation, BC300 and BC400 significantly increased by 69.93% and 48.75% for HA (P<0.05), while decreased by 1.35% and 5.19% for FA. Higher contents of HA and FA were found in soil samples amended with BC prepared at above 400℃ only during the initial period of 3-10 d of incubation and increased as BC application rate increased, at the end of the incubation, the contents of HA and FA significantly decreased by 34.38%, 44.48% in BC500 treatments and 42.84%, 49.27% in the BC600 treatments (P<0.05). During the incubation, the addition of BC significantly increased the contents of Hu (P<0.05), and the treatments amended with BC500 were the highest. The addition of BC decreased the relative contents of HA and FA, while increased the relative content of Hu, indicating that the proportion of relatively stable organic carbon in the soil was increased. The ratio of HA/FA (H/F) varied between 0.88 and 2.52 and increased with decreasing pyrolysis temperature and increasing BC application. A significantly lower color tonal coefficient (ΔlgK) and E4/E6 values in treatments amended with BC produced at temperatures above 400℃, indicating that higher temperatures derived BC complicated the structure of soil humic substance, while an opposite rend was observed in treatments amended with BC produced at temperatures under 400℃. Considering the improvement of the stability of organic carbon, when the BC products were applied to the Loutu soil, 500℃ was the optimal temperature for preparing apple-derived BC not only because it could significantly increase the content of inert soil organic carbon, but also improve the quality of the soil as a result of enhancing the degree of soil humification.

Enumeration of carboxyl groups carried on individual components of humic systems using deuteromethylation and Fourier transform mass spectrometry.

Here, we report a novel approach to enumeration of carboxylic groups carried by individual molecules of humic substances using selective chemical modification and isotopic labeling (deuteromethylation) and high-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR MS). Esterification was conducted with a use of thionyl chloride-deuteromethanol reagent under mild conditions to avoid transesterification. The deuteromethylated products were subjected to solid phase extraction using PPL Bond Elute cartridges prior to FTICR MS analysis. An amount of carboxyl groups in the individual molecular component was estimated from the length of identified deuteromethylation series. The method allowed for discerning between compounds with close elemental compositions possessing different protolytic properties. We found that different carboxylic moieties occupy distinct regions in molecular space of humic substances (HS) projected onto Van Krevelen diagram. These locations do not depend on the source of the humic material and can be assigned to carboxyl-rich alicyclic molecules (5 to 6 COOH), hydrolyzable tannins (3-4 COOH), lignins (1 to 2 COOH), condensed tannins and lignans (0 to 1 COOH), and carbohydrates (0 COOH). At the same time, the alignment pattern of these carboxylated species along the structural evolution lines in Van Krevelen diagrams was characteristic to the specific transformation processes undergone by the humic materials in the different environments. The obtained data enable mapping of molecular ensemble of HS with regards to their specific acidic compartments and might be used for directed fractionation of HS. Graphical abstract Selective isotopic labeling followed by FTICR MS enables discerning between humic molecules with close elemental compositions carrying different numbers of carboxylic groups.

Changes in soil organic matter pools and fractionation of humic substances in soils of long-term nutrient management

Changes in soil organic matter pools and fractionation of humic substances in soils of long-term nutrient management

Análise de metodologias de quantificação de substâncias húmicas em lixiviados de aterros de resíduos sólidos

Substâncias Húmicas (SH) são definidas como polímeros amorfos, de massa molar elevada, estruturas complexas e heterogêneas, que alteram com frequência as suas conformações em função das interações que ocorrem entre os grupos funcionais presentes na sua estrutura. A presença dessas substâncias principalmente nos lixiviados de aterros de resíduos sólidos e, em maior quantidade, em lixiviados de aterros antigos, dificulta o tratamento dos lixiviados, devido ao alto grau de recalcitrância de tal matéria orgânica. Nesse estudo, dois métodos de quantificação de SH foram testados em dois lixiviados gerados em aterros do Estado do Rio de Janeiro, oriundos do Aterro Controlado de Gericinó (ACG) e o Aterro Metropolitano de Gramacho (AMG), assim como o seu fracionamento nas frações Ácidos Húmicos (AH) e Ácidos Fúlvicos (AF). Os resultados de SH foram, respectivamente, 616 e 608 mg L-1 para o lixiviado proveniente do ACG e 1182 e 1191 mg L-1 para o lixiviado proveniente do AMG. O lixiviado oriundo do ACG apresentou 33% (201 mg L-1) de AH e 67% (411 mg L-1) de AF e o de AMG apresentou 37% (437 mg L-1) de AH e 63% (741 mg L 1) de AF.

Гумусовий стан чорноземів типових терсових місцевостей Західного Бугу та Стиру

Volyn Upland Haplic Chernozems are distributed mainly on the terrace landscapes of the Western Bug and the Styr and their tributaries (Chornohuzka, Luha, Lypa). Most of these soils are old ploughlands that have experienced various types of degradation. Haplic Chernozems are low-humus soils and they have low storages of humus substance in the 20 cm arable layer and middle storages of humus in 100 cm soil thickness. There is correlation of C humic acids to C fulvic acids within 1.2–3.3 in the humus profile. Among the various fractions of humic substances the 2nd fraction associated to Calcium dominates. A content of “free” humic acids (1rst fraction) is very low and the amount of humin is low. The optical density of humic acids ( 0,001% НА Е1 cm, 465 nm ) are high and very high. The organic matter of Volyn Upland Haplic Chernozems has some regional peculiarities. First, it caused by topographical conditions of its formation and evolution in the Holocene. Chernozems of the 1st terrace of the River Western Bug are extremely deep. They have progressive-accumulative type of humus distribution in profile, humate type of humus in upper 100 cm layer, a very high degree of organic matter humification and the same content of humic fraction associated to Calcium and lowmiddle content of 3rd fraction associated to clay minerals. The molecules of humic acids in the humus horizon of Chernozems of the 1rst terrace are better structured that indicates the older age of humus in these soils. Chernozems of the 2nd terrace above the floodplain of the River Styr are middle-deep soils. They are characterised by the regressive-accumulative type of humus distribution in profile, humate-fulvate type of humus and very high degree of organic matter humification only in 25–50 cm layer. The content of fractions associated to Calcium and clay minerals is predominantly high. Key words: Haplic Chernozems, humus, humic acids, fulvic acids, optical density, humus condition.

Phototransformation of iodate by UV irradiation: Kinetics and iodinated trihalomethane formation during subsequent chlor(am)ination

The photodegradation of IO3− at 254nm and the formation of iodinated trihalomethanes (I-THMs) during subsequent chlorination or chloramination in the presence of natural organic matter (NOM) were investigated in this study. The thermodynamically stable IO3− can be degraded by UV irradiation with pseudo-first order kinetics and the quantum yield was calculated as 0.0591moleinstein−1. Solution pH posed no remarkable influence on the photolysis rate of IO3−. The UV phototransformation of IO3− was evidenced by the determination of iodide (I−) and hypoiodous acid (HOI) in solution. NOM sources not only enhanced the photodegradation rate of IO3− by photoejecting solvated electrons, but also greatly influenced the production I-THMs in subsequent chlor(am)ination processes. In UV irradiation and sequential oxidation processes by chlorine or chloramine, the I-THMs formation was susceptible to NOM sources, especially the two major fractions of aqueous humic substances (humic acid and fulvic acid). The toxicity of disinfected waters greatly increased in chloramination over chlorination of the UV photodecomposed IO3−, as far more I-THMs especially CHI3, were formed. As “the fourth iodine source” of iodinated disinfection by-products, the occurrence, transportation and fate of IO3− in aquatic environment should be of concern instead of being considered a desired iodine sink.

Accumulation of humic-like and proteinaceous dissolved organic matter in zero-discharge aquaculture systems as revealed by fluorescence EEM spectroscopy

Recirculating aquaculture systems (RAS), offering many economic and fish husbandry benefits, are characterized by an accumulation of dissolved organic matter (DOM) and, specifically, humic substances (HS). As reported in a number of studies, HS may affect biological activity in both invertebrates and vertebrates. Given the accumulation of HS in RAS, it is therefore of great interest to characterize DOM and, specifically, its HS fraction in the RAS. The present study was aimed at characterizing long-term changes in fluorescent DOM composition in the culture water of RAS systems, which were operated in a novel, zero water exchange mode. Two such zero-discharge recirculating systems (ZDS) were examined: a freshwater system, stocked with hybrid tilapia (Oreochromis aureus x Oreochromis niloticus) and a marine system, stocked with gilthead seabream (Sparus aurata). Excitation-emission matrices (EEMs) of fluorescence, coupled with parallel factor analysis (PARAFAC), were used to characterize and quantify the different DOM components in the ZDS. In the culture water, one tryptophan-like and four HS-like components were identified. The fluorescence intensities of three of the HS-like components as well as the tryptophan-like component increased at comparable rates during ZDS operation while a much slower accumulation of these compounds was observed in a parallel operated, flow-through, freshwater aquarium. The ZDS examined in this study comprised a sludge digestion stage where a considerable accumulation of all fluorescent components was detected. A HS-like components and a tryptophan-like component in blood of tilapia from the freshwater ZDS were similar to components found in the culture water. Blood levels of both components were higher in fish cultured in the DOM-rich ZDS than in fish raised in the control, flow-through freshwater aquarium. Fluorescence of the HS-like component found in the fish blood increased also with time of ZDS operation. The finding that fish blood contains a HS-like fluorescent component may have important implications for the understanding of the physiological effects of HS in fish and the possible benefits of these substances in aquaculture.

Reducing Capacities and Distribution of Redox-Active Functional Groups in Low Molecular Weight Fractions of Humic Acids.

Humic substances (HS) are redox-active organic compounds with a broad spectrum of molecular sizes and reducing capacities, that is, number of electrons donated or accepted. However, it is unknown which role the distribution of redox-active functional groups in different molecule sizes plays for HS redox reactions in varying pore sizes microenvironments. We used dialysis experiments to separate bulk humic acids (HA) into low molecular weight fractions (LMWF) and retentate, for example, the remaining HA in the dialysis bag. LMWF accounted for only 2% of the total organic carbon content of the HA. However, their reducing capacities per gram of carbon were up to 33 times greater than either those of the bulk HA or the retentate. For a structural/mechanistic understanding of the high reducing capacity of the LMWF, we used fluorescence spectroscopy. We found that the LWMF showed significant fluorescence intensities for quinone-like functional groups, as indicated by the quinoid π-π* transition, that are probably responsible for the high reducing capacities. Therefore, the small-sized HS fraction can play a major role for redox transformation of metals or pollutants trapped in soil micropores (<2.5 nm diameter).

Fouling behaviors correlating to water characteristics during the ultrafiltration of micro-polluted water with and without the addition of powdered activated carbon

The aim of this paper was to investigate the effects of powdered activated carbon (PAC) pretreatment on the fouling behavior of an ultrafiltration (UF) membrane during micro-polluted water treatment. The results of this study demonstrated that PAC had a positive influence on fouling mitigation. Specifically, PAC-pretreated water had lower fouling resistances (FRs) and fouling indexes (FIs) than raw water. Liquid chromatography combined with peak-fitting analyses of raw water with and without PAC pretreatment suggested that PAC adsorption was much effective in reducing the contents of the low molecular weight acids and building blocks (LMWA&BB) and the humic substance (HS) fractions in raw water. Principal component analysis (PCA) was also used to identify the fouling behaviors associated with the characteristics of the water samples. Significant correlations (r2) of LMWA&BB with hydraulic reversible resistance (Rre), hydraulic irreversible resistance (Rir), total fouling index (TFI) and the hydraulically irreversible index (HIFI) were found (0.7534, 0.8430, 0.6297 and 0.7015, respectively), indicating that LMWA&BB contributed more significantly than biopolymers(BP) and HS to membrane fouling. The likely mechanism by which the PAC alleviated fouling was the reduction of the LMWA&BB fraction’s presence at the membrane surface and pores. These results suggest that the application of the PAC pretreatment preceding passage through the UF membrane is a promising approach for membrane fouling mitigation.

Humic substances alter the uptake and toxicity of nanodiamonds in wheat seedlings

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). 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. 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. 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.