Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectrosc...Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectroscopic techniques. After 23 HA extractions the residue was separated into high and low organic carbon humin fractions. HA yield was the highest for the first extraction and then gradually decreased with further extractions. Organic carbon (OC) of the humin fractions accounted for 58% of total OC …展开更多
The humic acids (HAs) isolated from the sediments of the various rivers,lakes,and reservoirs in China were studied using elemental analyzer,fourier transform infrared (FT-IR),and CP/MAS 13C nuclear magnetic resonance ...The humic acids (HAs) isolated from the sediments of the various rivers,lakes,and reservoirs in China were studied using elemental analyzer,fourier transform infrared (FT-IR),and CP/MAS 13C nuclear magnetic resonance (NMR) spectroscopy.The results showed that the HAs were characterized by some common chemical and physicochemical properties,but they also pose some differences in the C-containing functional groups.The C/N,C/H,O/C,and O/H ratios differ widely for the various HAs,showing that the elemental comp...展开更多
Revegetation is a traditional practice widely used for soil protection. We evaluated the effect of natural revegetation succession on soil chemical properties and carbon fractions （particulate organic carbon （POC）,...Revegetation is a traditional practice widely used for soil protection. We evaluated the effect of natural revegetation succession on soil chemical properties and carbon fractions （particulate organic carbon （POC）, humus carbon （HS-C）, humic acid carbon （HA-C） and fulvic acid carbon （FA-C）） on the Loess Plateau of China. The vegetation types, in order from the shortest to the longest enclosure duration, were： （a） abandoned overgrazed grassland （AbG3; 3 years）; （b） Hierochloe odorata Beauv. （HiO7; 7 years）; （c） Thymus mongoficus Ronnm （ThM15; 15 years）; （d） Artemisia sacrorum Ledeb （AtS25; 25 years）; （e） Stipa bungeana Trin Ledeb （StB36; 36 years） and （f） Stipa grandis P. Smirn （StG56; 56 years）. The results showed that the concentrations of soil organic carbon, total nitrogen and available phosphorus increased with the increase of restoration time except for ThM15. The concen- tration of NH4-N increased in the medium stage （for ThM15 and AtS25） and decreased in the later stage （for StB36 and StG56） of vegetation restoration. However, NO3-N concentration significantly increased in the later stage （for StB36 and StG56）. Carbon fractions had a similar increasing trend during natural vegetation restoration. The con- centrations of POC, HS-C, FA-C and HA-C accounted for 24.5%-49.1%, 10.6%-15.2%, 5.8%-9.1% and 4.6%-6.1% of total carbon, respectively. For AbG3, the relative changes of POC, HS-C and FA-C were significantly higher than that of total carbon during the process of revegetation restoration. The higher relative increases in POC, HS-C and FA-C confirmed that soil carbon induced by vegetation restoration was sequestrated by higher physical and chemical protection. The increases of soil C fractions could also result in higher ecological function in semiarid grassland ecosystems.展开更多
Six hydrophobic and hydrophilic fractions were isolated using XAD-8 and XAD-4 resins, and were extensively characterized. Partition coefficients of perylene, pbenanthrene and anthracene binding to the six fractions we...Six hydrophobic and hydrophilic fractions were isolated using XAD-8 and XAD-4 resins, and were extensively characterized. Partition coefficients of perylene, pbenanthrene and anthracene binding to the six fractions were determined by fluorescence quenching titration. The Kdo~ values obtained for the polycyclic aromatic hydrocarbons （PAHs） binding to the hydrophobic fractions were larger than those to the hydrophilic fractions. Nonlinear Stem-Volmer plots were observed when binding phenanthrene and anthracene to some hydrophilic fraction samples, suggesting saturation of polar interaction binding sites. A significant correlation of logKdo~ values with molecular weights and molar absorptivities at 280 nm was observed, while atomic ratio of C/t-I was found to be a poor indicator for aromaticity. Other structural descriptors such as paraffinic carbon and polarity influenced the DOM-fraction ability to bind PAHs. Different interaction mechanisms underlying binding of the different fractions to the PAHs were also discussed.展开更多
Humic substances(HS),which are defined as a series of highly acidic,relatively high-molecular-weight,and yellow to black colored substances formed during the decay and transformation of plant and microbial remains,ubi...Humic substances(HS),which are defined as a series of highly acidic,relatively high-molecular-weight,and yellow to black colored substances formed during the decay and transformation of plant and microbial remains,ubiquitously occur in nature.Humic substances represent the largest stable organic carbon pool in terrestrial environments and are the central characteristic of the soil.However,the validity of the HS concept and the justification of their extraction procedure have been recently debated.Here,we argue that the traditional humic paradigm is still relevant.Humic substances are distinctive and complex because the extracted HS formed during the humification are chemically distinct from their precursors and are heterogeneous among soils.By reviewing the concept,formation pathways,and stabilization of HS,we propose that the key question facing soil scientists is whether HS are soil microbial residues or unique synthesized compounds.Without revealing the distinctiveness of HS,it is impossible to address this question,as the structure,composition,and reactivity of HS are still poorly known owing to the heterogeneity and geographical variability of HS and the limits of the currently available analytical techniques.In our view,the distinctiveness of HS is fundamental to the soil,and thus further studies should be focused on revealing the distinctiveness of HS and explaining why HS hold this distinctiveness.展开更多
Experimental and theoretical analysis were made on the natural humic acid removal and the membrane fouling of ultrafiltration （UF） with in-line coagulation. The results showed dissolved organic carbon （DOC） and UV...Experimental and theoretical analysis were made on the natural humic acid removal and the membrane fouling of ultrafiltration （UF） with in-line coagulation. The results showed dissolved organic carbon （DOC） and UV254 removals by the UF with in-line coagulation at pH 7 were increased from 28% to 53% and 40% to 78% in comparison with direct UF treatment respectively. At the same time, the analysis of high performance liquid chromatography showed that UF with coagulation had significant improvement of removal of humic acid with molecular weights less than 6000 Da in particular. Compared to direct UF, the in-line coagulation UF also kept more constant permeate flux and very slight increase oftransmembrane pressure during a filtration circle. Two typical membrane fouling models were used by inducing two coefficients Kc and Kp corresponding to cake filtration model and pore narrowing model respectively. It was found that membrane fouling by pore-narrowing effect was effectively alleviated and that by cake-filtration was much decreased by in-line coagulation. Under the condition of coagulation prior to ultrafiltration at pH 7, the cake layer formed on the membrane surface became thicker, but the membrane filtration resistance was lower than that at pH 5 with the extension of operation time.展开更多
Humic acid(HA) is a readily available and low-cost material that is used to enhance crop production and reduce nitrogen(N) loss. However, there is little consensus on the efficacy of different HA components. In the cu...Humic acid(HA) is a readily available and low-cost material that is used to enhance crop production and reduce nitrogen(N) loss. However, there is little consensus on the efficacy of different HA components. In the current study, a soil column experiment was conducted using the ^(15)N tracer technique in Dezhou City, Shandong Province, China, to compare the effects of urea with and without the addition of weathered coal-derived HA components on maize yield and the fate of fertilizerderived N(fertilizer N). The HA components were incorporated into urea by blending different HA components into molten urea to obtain the three different types of HA-enhanced urea(HAU). At harvest, the aboveground dry biomass of plants grown with HAU was enhanced by 11.50–21.33% when compared to that of plants grown with U. More significantly, the grain yields under the HAU treatments were 5.58–18.67% higher than the yield under the urea treatment. These higher yields were due to an increase in the number of kernels per plant rather than the weight of individual kernels. The uptake of fertilizer N under the HAU treatments was also higher than that under the urea treatment by 11.49–29.46%, while the unaccounted N loss decreased by 12.37–30.05%. More fertilizer-derived N was retained in the 0–30 cm soil layer under the HAU treatments than that under the urea treatment, while less N was retained in the 30–90 cm soil layer. The total residual amount of fertilizer N in the soil column, however, did not differ significantly between the treatments. Of the three HAU treatments investigated, the one with an HA fraction derived from extraction with pH values ranging from 6 to 7, resulted in the best improvement in all assessment targets. This is likely due to the abundance of the COO/C–N=O group in this HA component.展开更多
Sorption and desorption of perfluorooctane sulfonate （PFOS） on humic acid at different temperatures were studied. It was found that the sorption process could be modeled with power kinetic equation very well, sugges...Sorption and desorption of perfluorooctane sulfonate （PFOS） on humic acid at different temperatures were studied. It was found that the sorption process could be modeled with power kinetic equation very well, suggesting that diflusion predominated the sorption of PFOS on the humic acid. The sorption capacity was doubled when the temperature increased from 5 to 35°C, and thermodynamics parameters △G0 was calculated to be –7.11 to –5.04 kJ/mol, △H0 was 14.2 kJ/mol, and △S 0 was 69.5 J/（mol·K）, indicating that the sorption was a spontaneous, endothermic, and entropy driven process. Desorption hysteresis occurred at all studied temperatures which suggested that humic acid may be an important sink of PFOS in the environment.展开更多
Bentonite has been extensively studied because of its strong sorption ability and low permeability.In this work,the Na-bentonite from Gaomiaozi County (China) has been characterized by XRD,FTIR and acid-base titration...Bentonite has been extensively studied because of its strong sorption ability and low permeability.In this work,the Na-bentonite from Gaomiaozi County (China) has been characterized by XRD,FTIR and acid-base titration.The sorption of Eu(III) on Na-bentonite in the absence/presence of humic acid (HA) was studied at T = 25 ± 2 °C and in 0.01 mol/L NaClO4 solution.The effects of pH,HA,contact time and initial Eu(III) concentrations were also investigated.The results indicate that the sorption of Eu(III) on Na-bentonite was dependent on pH values.The presence of HA had little effect on Eu(III) sorption at low pH values,but decreased Eu(III) sorption at high pH values.X-ray absorption fine structure spectroscopy (XAFS) was applied to characterize the local structural environment of the adsorbed Eu(III) on bare Na-bentonite and HA-bentonite hybrids.The re- sults indicate that Eu(III) was bound to O atoms at a distance of about 2.39 at pH 4.15.The results are crucial for the evalua- tion of the sorption and migration of other trivalent lanthanides and actinides in bentonite as backfill materials.展开更多
Tylosin（TYL） and sulfamethazine（SMT） are ionizable and polar antimicrobial compounds,which have seeped into the environment in substantial amounts via fertilizing land with manure or sewage. Sorption of TYL and SM...Tylosin（TYL） and sulfamethazine（SMT） are ionizable and polar antimicrobial compounds,which have seeped into the environment in substantial amounts via fertilizing land with manure or sewage. Sorption of TYL and SMT onto humic acid（HA） may affect their environmental fate. In this study, the sorption of TYL and SMT on HA at different conditions（pH, ionic strength） was investigated. All sorption isotherms fitted well to the Henry and Freundlich models and they were highly nonlinear with values of n between 0.5 and 0.8, which suggested that the HA had high heterogeneity. The sorption of TYL and SMT on HA decreased with increasing p H（2.0–7.5）, implying that the primary sorption mechanism could be due to cation exchange interactions between TYL~＋/SMT~＋ species and the functional groups of HA.Increasing ionic strength resulted in a considerable reduction in the K_d values of TYL and SMT,hinting that interactions between H bonds and π–π EDA might be an important factor in the sorption of TYL and SMT on HA. Results of Fourier transform infrared（FT-IR） and ~13C-nuclear magnetic resonance（NMR） analysis further demonstrated that carboxyl groups and O-alkyl structures in the HA could interact with TYL and SMT via ionic interactions and H bonds,respectively. Overall, this work gives new insights into the mechanisms of sorption of TYL and SMT on HA and hence aids us in assessing the environmental risk of TYL and SMT under diverse conditions.展开更多
Insights from the adverse effect of humic acid （HA） on arsenate removal with hydrous ferric oxide （HFO） coprecipitation can further our understanding of the fate of As（V） in water treatment process. The motivati...Insights from the adverse effect of humic acid （HA） on arsenate removal with hydrous ferric oxide （HFO） coprecipitation can further our understanding of the fate of As（V） in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As（V） on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering （SERS）, extended X-ray absorption fine structure （EXAFS） spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared （ATR-FTIR） measurement, and charge distribution multisite complexation （CD- MUSIC） modeling. The As（V） removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As（V） mass concentration. The SERS analysis excluded the HA-As（V） complex formation. The EXAFS results indicate that As（V） formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26--3.31 ,~. The in situ ATR-FTIR measurements show that As（V） replaces surface hydroxyl groups and forms inner- sphere complex. High concentrations of HA may physically block the surface sites and inhibit the As（V） access. The adsorption of As（V） and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As（V） and HA reasonably well.展开更多
Two humic acids （HAs） were isolated from contaminated river sediments present under comparative conditions in the Pearl River Basin, China. YFHA （the HA extracted at an open pyrite mining area in Yunfu） exhibited ...Two humic acids （HAs） were isolated from contaminated river sediments present under comparative conditions in the Pearl River Basin, China. YFHA （the HA extracted at an open pyrite mining area in Yunfu） exhibited a lower absorption intensity for certain bands in the Fourier transform infrared spectra, a lower E 4 /E 6 value （the UV absorbances at 465 nm （E 4 ） and 665 nm （E 6 ））, a lower apparent molecular weight, a lower polarity and a lower oxygen functionality in comparison with GZHA （the HA isolated at an urban living area in Guangzhou）. All these differences indicated a higher degree of humification of YFHA than GZHA. Overall, the enrichment patterns of permanent heavy metals in the studied HAs were similar to those in corresponding sediments. In particular, YFHA exhibited high enrichment of trace element Tl, a characteristic concomitant from the mining of the pyrite minerals. The adsorption isotherms of two HAs for goethite and pyrolusite, two representative geological materials, conformed to the Langmuir equation. Based on the qualitative relationships between the Langmuir constants of the adsorption isotherms and the chemical characteristics of HAs, the main mechanism of HA adsorption on these materials was suggested to be hydrophobic interaction. This study highlighted the promising use of HA as a peculiar bio-indicator of uncommon trace metal contaminations. The HA adsorption mechanism on representative geological materials further provided a theoretical basis for the study on the unusual metal behavior in complex environmental settings.展开更多
Cyclodextrin-modified graphene oxide nanosheets(denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spect...Cyclodextrin-modified graphene oxide nanosheets(denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and potentiometric acid-base titration. The characterization results indicated that CD was successfully grafted onto GO surfaces by forming a chemical bond. Mutual effects on the simultaneous removal of hexavalent uranium and humic acid by CD/GO from aqueous solution were investigated. The results indicated that U(VI) and humic acid(HA) sorption on CD/GO were greatly affected by pH and ionic strength. The presence of HA enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH, whereas the presence of U(VI) enhanced HA sorption. The surface adsorbed HA acted as a "bridge" between U(VI) and CD/GO, and formed strong inner-sphere surface complexes with U(VI). Sorption isotherms of U(VI) or HA on CD/GO could be well fitted by the Langmuir model. This work highlights that CD/GO can be used as a promising material in the enrichment of U(VI) and HA from wastewater in U(VI) and humic substances obtained by environmental pollution cleanup.展开更多
For phosphorus （P） recovery from wastewater, the effect of humic substances （HS） on the precipitation of calcium phosphate was studied. Batch experiments of calcium phosphate precipitation were undertaken with syn...For phosphorus （P） recovery from wastewater, the effect of humic substances （HS） on the precipitation of calcium phosphate was studied. Batch experiments of calcium phosphate precipitation were undertaken with synthetic water that contained 20 mg/L phosphate （as P） and 20 mg/L HS （as dissolved organic carbon, DOC） at a constant pH value in the range of 8.0-10.0. The concentration variations of phosphate, calcium （Ca） and HS were measured in the precipitation process; the crystalline state and compositions of the precipitates were analysed by powder X-ray diffraction （XRD） and chemical methods, respectively. It showed that at solution pH 8.0, the precipitation rate and removal efficiency of phosphate were greatly reduced by HS, but at solution pH ≥9.0, the effect of HS was very small. The Ca consumption for the precipitation of phosphate increased when HS was added; HS was also removed from solution with the precipitation of calcium phosphate. At solution pH 8.0 and HS concentrations ≤3.5 mg/L, and at pH ≥ 9.0 and HS concentrations ≤ 10 mg/L, the final precipitates were proved to be hydroxyapatite （HAP） by XRD. The increases of solution pH value and initial Ca/P ratio helped reduce the influence of HS on the precipitation of phosphate.展开更多
Cadmium (Cd) and arsenic (As) are two of the most toxic elements.However,the chemical behaviors of these two elements are different,making it challenging to utilize a single adsorbent with high adsorption capacity for...Cadmium (Cd) and arsenic (As) are two of the most toxic elements.However,the chemical behaviors of these two elements are different,making it challenging to utilize a single adsorbent with high adsorption capacity for both Cd(Ⅱ) and As(Ⅴ) removal.To solve this problem,we synthesized HA/Fe-Mn oxides-loaded biochar (HFMB),a novel ternary material,to perform this task,wherein scanning electron microscopy (SEM) combined with EDS (SEM-EDS) was used to characterize its morphological and physicochemical properties.The maximum adsorption capacity of HFMB was 67.11 mg/g for Cd(Ⅱ) and 35.59 mg/g for As(Ⅴ),which is much higher compared to pristine biochar (11.06 mg/g,0 mg/g for Cd(Ⅱ) and As(Ⅴ),respectively).The adsorption characteristics were investigated by adsorption kinetics and the effects of the ionic strength and pH of solutions.X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR) revealed that chelation and deposition were the adsorption mechanisms that bound Cd(Ⅱ) to HFMB,while ligand exchange was the adsorption mechanism that bound As(Ⅴ).展开更多
The changes in humic substances （HS） is fundamental in detecting soil carbon sequestration mechanisms in natural and cultivated environments. Based on a long-term trial, the amounts of water dissolved substances （...The changes in humic substances （HS） is fundamental in detecting soil carbon sequestration mechanisms in natural and cultivated environments. Based on a long-term trial, the amounts of water dissolved substances （WSS）, humic acid （HA）, fulvic acid （FA） and humin （HU） were determined to explore the impact of long-term fertilization on HS. Increases in the amounts of WSS, HA, FA and HU were significant different among the treatments with manure. A significant correlation was found between the increased soil organic carbon （SOC） and HS （R^2=0.98, P〈0.01）. The change in the E4/E6 ratio was significantly correlated with the increased SOC （R2=0.88, P〈0.01）, HA （R^2=0.91, P〈0.01）, FA （R^2=0.91, P〈0.01） and HU （R^2=0.88, P〈0.01）. The cluster was mainly divided into two parts as manure fertilization and inorganic fertilization, based on the increases in HA, FA and HU. These results suggest that long term fertilization with manure favours carbon sequestration in HS and is mainly stabilized as HU, while the HA becomes more aliphatic. We conclude that increases in SOC can be linked to changes in the molecular characteristics of HS fractions under long term fertilization.展开更多
[Objective] The paper aimed to study highly efficient utilization of biogas slurry and the effect of highly efficient biogas slurry on vegetables,so as to provide basis for wide and effective application of biogas slu...[Objective] The paper aimed to study highly efficient utilization of biogas slurry and the effect of highly efficient biogas slurry on vegetables,so as to provide basis for wide and effective application of biogas slurry.[Method] Using secondary aerobic fermentation technology,a small amount of humic acid was added to biogas slurry to enhance the biological activity of biogas slurry.Through greenhouse experiment,the effect of highly efficient nutrient solution of biogas slurry on yield and quality of green pepper,tomato and cucumber was studied.[Result] Compared with control and traditional application of biogas slurry,application of highly efficient nutrient solution of biogas slurry increased the yield of green pepper,tomato and cucumber,and the increase extents were 12.4%,47.4%,19.9% and 2.7%,15.9%,9.1%,respectively.Compared with traditional application of biogas slurry,application of highly efficient nutrient solution of biogas slurry significantly increased Vc content of green pepper and cucumber with the increase extent of 16.8% and 43.8%,respectively.[Conclusion] Application of highly efficient nutrient solution of biogas slurry can effectively promote the yield of green pepper,tomato and cucumber and change the qualities of vegetables,and significantly enhance the biological activity of biogas slurry.展开更多
文摘Twenty-three progressive extractions were performed to study individual humic acids (HAs) and humin fractions from a typical black soil (Mollisol) in Heilongjiang Province, China using elemental analysis and spectroscopic techniques. After 23 HA extractions the residue was separated into high and low organic carbon humin fractions. HA yield was the highest for the first extraction and then gradually decreased with further extractions. Organic carbon (OC) of the humin fractions accounted for 58% of total OC …
基金the National Basic Research Program (973) of China (No.2004CB418502,2003CB415002)the National Natural Science Foundation of China (No.29977002).
文摘The humic acids (HAs) isolated from the sediments of the various rivers,lakes,and reservoirs in China were studied using elemental analyzer,fourier transform infrared (FT-IR),and CP/MAS 13C nuclear magnetic resonance (NMR) spectroscopy.The results showed that the HAs were characterized by some common chemical and physicochemical properties,but they also pose some differences in the C-containing functional groups.The C/N,C/H,O/C,and O/H ratios differ widely for the various HAs,showing that the elemental comp...
基金supported by the National Natural Science Foundation of China (41171226)the Program for New Century Excellent Talents in University (NCET-12-0479)the Foundation for Youths Teacher by Northwest A&F University
文摘Revegetation is a traditional practice widely used for soil protection. We evaluated the effect of natural revegetation succession on soil chemical properties and carbon fractions （particulate organic carbon （POC）, humus carbon （HS-C）, humic acid carbon （HA-C） and fulvic acid carbon （FA-C）） on the Loess Plateau of China. The vegetation types, in order from the shortest to the longest enclosure duration, were： （a） abandoned overgrazed grassland （AbG3; 3 years）; （b） Hierochloe odorata Beauv. （HiO7; 7 years）; （c） Thymus mongoficus Ronnm （ThM15; 15 years）; （d） Artemisia sacrorum Ledeb （AtS25; 25 years）; （e） Stipa bungeana Trin Ledeb （StB36; 36 years） and （f） Stipa grandis P. Smirn （StG56; 56 years）. The results showed that the concentrations of soil organic carbon, total nitrogen and available phosphorus increased with the increase of restoration time except for ThM15. The concen- tration of NH4-N increased in the medium stage （for ThM15 and AtS25） and decreased in the later stage （for StB36 and StG56） of vegetation restoration. However, NO3-N concentration significantly increased in the later stage （for StB36 and StG56）. Carbon fractions had a similar increasing trend during natural vegetation restoration. The con- centrations of POC, HS-C, FA-C and HA-C accounted for 24.5%-49.1%, 10.6%-15.2%, 5.8%-9.1% and 4.6%-6.1% of total carbon, respectively. For AbG3, the relative changes of POC, HS-C and FA-C were significantly higher than that of total carbon during the process of revegetation restoration. The higher relative increases in POC, HS-C and FA-C confirmed that soil carbon induced by vegetation restoration was sequestrated by higher physical and chemical protection. The increases of soil C fractions could also result in higher ecological function in semiarid grassland ecosystems.
基金supported by the National Basic Research Program (973) of China (No. 2008CB418200)the National Knowledge Innovation Program of Chinese Academy of Sciences (No. KZCX2-yw-102)the National Natural Science Foundation of China (No.40525011, 40632011)
文摘Six hydrophobic and hydrophilic fractions were isolated using XAD-8 and XAD-4 resins, and were extensively characterized. Partition coefficients of perylene, pbenanthrene and anthracene binding to the six fractions were determined by fluorescence quenching titration. The Kdo~ values obtained for the polycyclic aromatic hydrocarbons （PAHs） binding to the hydrophobic fractions were larger than those to the hydrophilic fractions. Nonlinear Stem-Volmer plots were observed when binding phenanthrene and anthracene to some hydrophilic fraction samples, suggesting saturation of polar interaction binding sites. A significant correlation of logKdo~ values with molecular weights and molar absorptivities at 280 nm was observed, while atomic ratio of C/t-I was found to be a poor indicator for aromaticity. Other structural descriptors such as paraffinic carbon and polarity influenced the DOM-fraction ability to bind PAHs. Different interaction mechanisms underlying binding of the different fractions to the PAHs were also discussed.
基金supported by the National Natural Science Foundation of China(Nos.41571231 and 41201221)the National Key Research and Development Program of China(No.2016YFD0200304)+3 种基金the Scientific Instrument and Equipment Development Project of Chinese Academy Sciences(CAS)(No.YJKYYQ20170058)the Natural Science Foundation of Jiangsu Province,China(No.BK2012496)the Youth Innovation Promotion Association,CAS(No.2017362)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.19KJB180010)。
文摘Humic substances(HS),which are defined as a series of highly acidic,relatively high-molecular-weight,and yellow to black colored substances formed during the decay and transformation of plant and microbial remains,ubiquitously occur in nature.Humic substances represent the largest stable organic carbon pool in terrestrial environments and are the central characteristic of the soil.However,the validity of the HS concept and the justification of their extraction procedure have been recently debated.Here,we argue that the traditional humic paradigm is still relevant.Humic substances are distinctive and complex because the extracted HS formed during the humification are chemically distinct from their precursors and are heterogeneous among soils.By reviewing the concept,formation pathways,and stabilization of HS,we propose that the key question facing soil scientists is whether HS are soil microbial residues or unique synthesized compounds.Without revealing the distinctiveness of HS,it is impossible to address this question,as the structure,composition,and reactivity of HS are still poorly known owing to the heterogeneity and geographical variability of HS and the limits of the currently available analytical techniques.In our view,the distinctiveness of HS is fundamental to the soil,and thus further studies should be focused on revealing the distinctiveness of HS and explaining why HS hold this distinctiveness.
基金The National Natural Science Foundation of China (No. 50138020)
文摘Experimental and theoretical analysis were made on the natural humic acid removal and the membrane fouling of ultrafiltration （UF） with in-line coagulation. The results showed dissolved organic carbon （DOC） and UV254 removals by the UF with in-line coagulation at pH 7 were increased from 28% to 53% and 40% to 78% in comparison with direct UF treatment respectively. At the same time, the analysis of high performance liquid chromatography showed that UF with coagulation had significant improvement of removal of humic acid with molecular weights less than 6000 Da in particular. Compared to direct UF, the in-line coagulation UF also kept more constant permeate flux and very slight increase oftransmembrane pressure during a filtration circle. Two typical membrane fouling models were used by inducing two coefficients Kc and Kp corresponding to cake filtration model and pore narrowing model respectively. It was found that membrane fouling by pore-narrowing effect was effectively alleviated and that by cake-filtration was much decreased by in-line coagulation. Under the condition of coagulation prior to ultrafiltration at pH 7, the cake layer formed on the membrane surface became thicker, but the membrane filtration resistance was lower than that at pH 5 with the extension of operation time.
基金supported by the National Natural Science Foundation of China (31601827)the National Key Research and Development Program of China (2016YFD0200402)
文摘Humic acid(HA) is a readily available and low-cost material that is used to enhance crop production and reduce nitrogen(N) loss. However, there is little consensus on the efficacy of different HA components. In the current study, a soil column experiment was conducted using the ^(15)N tracer technique in Dezhou City, Shandong Province, China, to compare the effects of urea with and without the addition of weathered coal-derived HA components on maize yield and the fate of fertilizerderived N(fertilizer N). The HA components were incorporated into urea by blending different HA components into molten urea to obtain the three different types of HA-enhanced urea(HAU). At harvest, the aboveground dry biomass of plants grown with HAU was enhanced by 11.50–21.33% when compared to that of plants grown with U. More significantly, the grain yields under the HAU treatments were 5.58–18.67% higher than the yield under the urea treatment. These higher yields were due to an increase in the number of kernels per plant rather than the weight of individual kernels. The uptake of fertilizer N under the HAU treatments was also higher than that under the urea treatment by 11.49–29.46%, while the unaccounted N loss decreased by 12.37–30.05%. More fertilizer-derived N was retained in the 0–30 cm soil layer under the HAU treatments than that under the urea treatment, while less N was retained in the 30–90 cm soil layer. The total residual amount of fertilizer N in the soil column, however, did not differ significantly between the treatments. Of the three HAU treatments investigated, the one with an HA fraction derived from extraction with pH values ranging from 6 to 7, resulted in the best improvement in all assessment targets. This is likely due to the abundance of the COO/C–N=O group in this HA component.
基金supported by the National Natural Science Foundation of China (No. 20477050, 20621703)
文摘Sorption and desorption of perfluorooctane sulfonate （PFOS） on humic acid at different temperatures were studied. It was found that the sorption process could be modeled with power kinetic equation very well, suggesting that diflusion predominated the sorption of PFOS on the humic acid. The sorption capacity was doubled when the temperature increased from 5 to 35°C, and thermodynamics parameters △G0 was calculated to be –7.11 to –5.04 kJ/mol, △H0 was 14.2 kJ/mol, and △S 0 was 69.5 J/（mol·K）, indicating that the sorption was a spontaneous, endothermic, and entropy driven process. Desorption hysteresis occurred at all studied temperatures which suggested that humic acid may be an important sink of PFOS in the environment.
基金supported by the National Natural Science Foundation of China (20971126, 20907055 & 20677058)973 project from Ministry of Science and Technology of ChinaSpecial Foundation of High-level Waste Disposal (2007-840)
文摘Bentonite has been extensively studied because of its strong sorption ability and low permeability.In this work,the Na-bentonite from Gaomiaozi County (China) has been characterized by XRD,FTIR and acid-base titration.The sorption of Eu(III) on Na-bentonite in the absence/presence of humic acid (HA) was studied at T = 25 ± 2 °C and in 0.01 mol/L NaClO4 solution.The effects of pH,HA,contact time and initial Eu(III) concentrations were also investigated.The results indicate that the sorption of Eu(III) on Na-bentonite was dependent on pH values.The presence of HA had little effect on Eu(III) sorption at low pH values,but decreased Eu(III) sorption at high pH values.X-ray absorption fine structure spectroscopy (XAFS) was applied to characterize the local structural environment of the adsorbed Eu(III) on bare Na-bentonite and HA-bentonite hybrids.The re- sults indicate that Eu(III) was bound to O atoms at a distance of about 2.39 at pH 4.15.The results are crucial for the evalua- tion of the sorption and migration of other trivalent lanthanides and actinides in bentonite as backfill materials.
基金supported by the National Natural Science Foundation of China (Nos. 41503095, 41173104)the Natural Science Foundation of Universities of Anhui Province (No. KJ2015A016)+1 种基金the Ph D Fund of Anhui University of Science and Technology(No. ZY540)the Key Science Foundation for Young Teachers of Anhui University of Science and Technology (No. QN201507)
文摘Tylosin（TYL） and sulfamethazine（SMT） are ionizable and polar antimicrobial compounds,which have seeped into the environment in substantial amounts via fertilizing land with manure or sewage. Sorption of TYL and SMT onto humic acid（HA） may affect their environmental fate. In this study, the sorption of TYL and SMT on HA at different conditions（pH, ionic strength） was investigated. All sorption isotherms fitted well to the Henry and Freundlich models and they were highly nonlinear with values of n between 0.5 and 0.8, which suggested that the HA had high heterogeneity. The sorption of TYL and SMT on HA decreased with increasing p H（2.0–7.5）, implying that the primary sorption mechanism could be due to cation exchange interactions between TYL~＋/SMT~＋ species and the functional groups of HA.Increasing ionic strength resulted in a considerable reduction in the K_d values of TYL and SMT,hinting that interactions between H bonds and π–π EDA might be an important factor in the sorption of TYL and SMT on HA. Results of Fourier transform infrared（FT-IR） and ~13C-nuclear magnetic resonance（NMR） analysis further demonstrated that carboxyl groups and O-alkyl structures in the HA could interact with TYL and SMT via ionic interactions and H bonds,respectively. Overall, this work gives new insights into the mechanisms of sorption of TYL and SMT on HA and hence aids us in assessing the environmental risk of TYL and SMT under diverse conditions.
基金supported by the National Natural Science Foundation of China (No. 41373123, 41023005, 21321004)Research Center for EcoEnvironmental Sciences, Chinese Academy of Sciences (No. YSW2013A01)
文摘Insights from the adverse effect of humic acid （HA） on arsenate removal with hydrous ferric oxide （HFO） coprecipitation can further our understanding of the fate of As（V） in water treatment process. The motivation of our study is to explore the competitive adsorption mechanisms of humic acid and As（V） on HFO on the molecular scale. Multiple complementary techniques were used including macroscopic adsorption experiments, surface enhanced Raman scattering （SERS）, extended X-ray absorption fine structure （EXAFS） spectroscopy, flow-cell attenuated total reflectance Fourier transform infrared （ATR-FTIR） measurement, and charge distribution multisite complexation （CD- MUSIC） modeling. The As（V） removal efficiency was reduced from over 95% to about 10% with the increasing HA concentration to 25 times of As（V） mass concentration. The SERS analysis excluded the HA-As（V） complex formation. The EXAFS results indicate that As（V） formed bidentate binuclear surface complexes in the presence of HA as evidenced by an As-Fe distance of 3.26--3.31 ,~. The in situ ATR-FTIR measurements show that As（V） replaces surface hydroxyl groups and forms inner- sphere complex. High concentrations of HA may physically block the surface sites and inhibit the As（V） access. The adsorption of As（V） and HA decreased the point of zero charge of HFO from 7.8 to 5.8 and 6.3, respectively. The CD-MUSIC model described the zeta potential curves and adsorption edges of As（V） and HA reasonably well.
基金supported by the United Foundation of National Natural Science Foundation of China and Guang-dong Provincial Government(No.U0633001)the National Natural Science Foundation of China(No.40930743)
文摘Two humic acids （HAs） were isolated from contaminated river sediments present under comparative conditions in the Pearl River Basin, China. YFHA （the HA extracted at an open pyrite mining area in Yunfu） exhibited a lower absorption intensity for certain bands in the Fourier transform infrared spectra, a lower E 4 /E 6 value （the UV absorbances at 465 nm （E 4 ） and 665 nm （E 6 ））, a lower apparent molecular weight, a lower polarity and a lower oxygen functionality in comparison with GZHA （the HA isolated at an urban living area in Guangzhou）. All these differences indicated a higher degree of humification of YFHA than GZHA. Overall, the enrichment patterns of permanent heavy metals in the studied HAs were similar to those in corresponding sediments. In particular, YFHA exhibited high enrichment of trace element Tl, a characteristic concomitant from the mining of the pyrite minerals. The adsorption isotherms of two HAs for goethite and pyrolusite, two representative geological materials, conformed to the Langmuir equation. Based on the qualitative relationships between the Langmuir constants of the adsorption isotherms and the chemical characteristics of HAs, the main mechanism of HA adsorption on these materials was suggested to be hydrophobic interaction. This study highlighted the promising use of HA as a peculiar bio-indicator of uncommon trace metal contaminations. The HA adsorption mechanism on representative geological materials further provided a theoretical basis for the study on the unusual metal behavior in complex environmental settings.
基金supported by the National Natural Science Foundation of China(91326202,21375148,21207136,21225730)the Hefei Center for Physical Science and Technology(2012FXZY005)
文摘Cyclodextrin-modified graphene oxide nanosheets(denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and potentiometric acid-base titration. The characterization results indicated that CD was successfully grafted onto GO surfaces by forming a chemical bond. Mutual effects on the simultaneous removal of hexavalent uranium and humic acid by CD/GO from aqueous solution were investigated. The results indicated that U(VI) and humic acid(HA) sorption on CD/GO were greatly affected by pH and ionic strength. The presence of HA enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH, whereas the presence of U(VI) enhanced HA sorption. The surface adsorbed HA acted as a "bridge" between U(VI) and CD/GO, and formed strong inner-sphere surface complexes with U(VI). Sorption isotherms of U(VI) or HA on CD/GO could be well fitted by the Langmuir model. This work highlights that CD/GO can be used as a promising material in the enrichment of U(VI) and HA from wastewater in U(VI) and humic substances obtained by environmental pollution cleanup.
基金The German Research Foundation (DFG-Graduiertenkolleg 366) Grant Program for the High-Level Returned Scholars fromAbroad, Ministry of Personnel of China (No. 2004-2005)
文摘For phosphorus （P） recovery from wastewater, the effect of humic substances （HS） on the precipitation of calcium phosphate was studied. Batch experiments of calcium phosphate precipitation were undertaken with synthetic water that contained 20 mg/L phosphate （as P） and 20 mg/L HS （as dissolved organic carbon, DOC） at a constant pH value in the range of 8.0-10.0. The concentration variations of phosphate, calcium （Ca） and HS were measured in the precipitation process; the crystalline state and compositions of the precipitates were analysed by powder X-ray diffraction （XRD） and chemical methods, respectively. It showed that at solution pH 8.0, the precipitation rate and removal efficiency of phosphate were greatly reduced by HS, but at solution pH ≥9.0, the effect of HS was very small. The Ca consumption for the precipitation of phosphate increased when HS was added; HS was also removed from solution with the precipitation of calcium phosphate. At solution pH 8.0 and HS concentrations ≤3.5 mg/L, and at pH ≥ 9.0 and HS concentrations ≤ 10 mg/L, the final precipitates were proved to be hydroxyapatite （HAP） by XRD. The increases of solution pH value and initial Ca/P ratio helped reduce the influence of HS on the precipitation of phosphate.
基金supported by the National Key Research and Development Project of China(No.2016YFD0800706)the Science and Technology Project of Fujian Province of China(No.2018Y0080)the Science and Technology Project of Xiamen(No.3502Z20172026)
文摘Cadmium (Cd) and arsenic (As) are two of the most toxic elements.However,the chemical behaviors of these two elements are different,making it challenging to utilize a single adsorbent with high adsorption capacity for both Cd(Ⅱ) and As(Ⅴ) removal.To solve this problem,we synthesized HA/Fe-Mn oxides-loaded biochar (HFMB),a novel ternary material,to perform this task,wherein scanning electron microscopy (SEM) combined with EDS (SEM-EDS) was used to characterize its morphological and physicochemical properties.The maximum adsorption capacity of HFMB was 67.11 mg/g for Cd(Ⅱ) and 35.59 mg/g for As(Ⅴ),which is much higher compared to pristine biochar (11.06 mg/g,0 mg/g for Cd(Ⅱ) and As(Ⅴ),respectively).The adsorption characteristics were investigated by adsorption kinetics and the effects of the ionic strength and pH of solutions.X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FT-IR) revealed that chelation and deposition were the adsorption mechanisms that bound Cd(Ⅱ) to HFMB,while ligand exchange was the adsorption mechanism that bound As(Ⅴ).
基金supported by the National Natural Science Foundation of China (30873470)the National Special Research Fund for Non-Profit Sector (Agriculture) (201203030)the grant from Qingdao Agricultural University, China (631214)
文摘The changes in humic substances （HS） is fundamental in detecting soil carbon sequestration mechanisms in natural and cultivated environments. Based on a long-term trial, the amounts of water dissolved substances （WSS）, humic acid （HA）, fulvic acid （FA） and humin （HU） were determined to explore the impact of long-term fertilization on HS. Increases in the amounts of WSS, HA, FA and HU were significant different among the treatments with manure. A significant correlation was found between the increased soil organic carbon （SOC） and HS （R^2=0.98, P〈0.01）. The change in the E4/E6 ratio was significantly correlated with the increased SOC （R2=0.88, P〈0.01）, HA （R^2=0.91, P〈0.01）, FA （R^2=0.91, P〈0.01） and HU （R^2=0.88, P〈0.01）. The cluster was mainly divided into two parts as manure fertilization and inorganic fertilization, based on the increases in HA, FA and HU. These results suggest that long term fertilization with manure favours carbon sequestration in HS and is mainly stabilized as HU, while the HA becomes more aliphatic. We conclude that increases in SOC can be linked to changes in the molecular characteristics of HS fractions under long term fertilization.
基金Supported by"Eleventh Five-Year"National Technology Support Program(2008BADC4B17)~~
文摘[Objective] The paper aimed to study highly efficient utilization of biogas slurry and the effect of highly efficient biogas slurry on vegetables,so as to provide basis for wide and effective application of biogas slurry.[Method] Using secondary aerobic fermentation technology,a small amount of humic acid was added to biogas slurry to enhance the biological activity of biogas slurry.Through greenhouse experiment,the effect of highly efficient nutrient solution of biogas slurry on yield and quality of green pepper,tomato and cucumber was studied.[Result] Compared with control and traditional application of biogas slurry,application of highly efficient nutrient solution of biogas slurry increased the yield of green pepper,tomato and cucumber,and the increase extents were 12.4%,47.4%,19.9% and 2.7%,15.9%,9.1%,respectively.Compared with traditional application of biogas slurry,application of highly efficient nutrient solution of biogas slurry significantly increased Vc content of green pepper and cucumber with the increase extent of 16.8% and 43.8%,respectively.[Conclusion] Application of highly efficient nutrient solution of biogas slurry can effectively promote the yield of green pepper,tomato and cucumber and change the qualities of vegetables,and significantly enhance the biological activity of biogas slurry.
