Compost effect on soil humic acid: A NMR study

The humic acid (HA) fraction of a food and vegetable residues compost (CM) was taken as indicator to trace the fate of CM organic matter in four years CM amended soil. (1)H and (13)C NMR spectroscopy were used to investigate the nature of the HA isolates from CM, control soil (S(4)) and amended soil. The result indicated a significant structural difference between CM HA and S(4) HA, and supported the presence of both HA fractions in soil at the end of the amendment trials. However, the nature and content of CM HA in soil did not fully explain the increase of soil cation exchange capacity (CEC) after amendment. All CM humic fractions (i.e., fulvic acid, humic acid and humin) were found to contribute to the change of the soil organic matter composition. It is concluded that although CM HA is a suitable indicator of the survival of compost organic matter in soil during amendment, all three humic fractions should be monitored and analyzed to fully understand changes in the composition and properties of amended soil.     

The effect of humic acid in chronic deoxynivalenol intoxication

Environmental Science and Pollution Research - The most common mycotoxin found in European foodstuffs, especially unprocessed grains, is deoxynivalenol (DON), which inhibits proteosynthesis and...     

天然沸石去除腐殖酸和氨氮的研究

采用改性的浙江缙云天然斜发沸石,进行去除氨氮和腐殖酸的研究。腐殖酸对氨氮的去除有影响,含量越高。影响也越大。沸石主要去除大分子量的腐殖酸,对小分子量的腐殖酸去除效果较差。由于大分子腐殖酸会干扰氨氮的去除,去除大分子的腐殖酸有助于提高沸石去除氨氮的效果。     

Sorption of cyromazine on humic acid: Effects of pH,ionic strength and foreign ions

Cyromazine (CY) is a triazine pesticide used as an insect growth inhibitor for fly control in cattle manure, field crops, vegetables, and fruits. Sorption of CY onto humic acid (HA) may affect its environmental fate. In this study, HA was used to investigate the sorption of CY at different solution chemistry conditions (pH, ionic strength) and in the presence of foreign ions and norfloxacin. All sorption isotherms fitted well with the Freundlich and Langmuir models. The sorption reached a maximum at initial pH 4.0 over the initial pH range of 3.0–7.0, implying that the primary sorption mechanism was cation exchange interaction between CY⁺ species and the negatively charged functional groups of HA. Increasing Ca²⁺ concentration resulted in a considerable reduction in the K _d values of CY, hinting that Ca²⁺ had probably competed with CY⁺ for the cation exchange sites on the surfaces of HA. The sorption of CY on HA in different ionic media followed the order of NH₄Cl ≈ KCl > K₂SO₄ > ZnCl₂ ≈ CaCl₂ at pH 5.0. Spectroscopic evidence demonstrated that the amino groups and triazine ring of CY was responsible for sorption onto HA, while the carboxyl group and the O-alkyl structure of HA participated in adsorbing CY.     

Effect of pH on the aggregation of a gray humic acid in colloidal and solid states

The potential of triethylenetetramine (TETA) to inhibit the oxidation of three pyrrhotites, Garson, McCreedy and Po-97 has been studied systematically and confirmed by comparing the release of Fe and SO4(2-) from samples with and without coating treatment. Each sample, original or coated by TETA, was exposed to oxygen, 1 x 10(-3) M FeCl3, and Acidithiobacillus ferrooxidans, respectively, for specific oxidation periods. Both abiotic and biotic oxidation of samples treated by this passivating agent has been reduced significantly in this study. Under the aerobic condition, lower concentrations of ferric, total Fe or SO4(2-) were obtained from the coated samples than those from the uncoated samples. In the presence of 1 x 10(-3) M FeCl3 at 30 degrees C, TETA was able to reduce oxidation rates of Garson, McCreedy and Po-97 by 83%, 79%, and 81% (based on Fe release), respectively. A higher pH, lower Eh, and lower concentrations of total Fe and SO4(2-) were also observed in the biotic oxidation of coated Garson by Acidithiobacillus ferrooxidans. The protection of pyrrhotite surface from oxidant attack by TETA barrier and the alkaline property of this coating agent can be used to interpret the inhibition of oxidation.     

pH值、离子强度和重金属离子对腐殖酸紫外谱图的影响

研究pH值、溶液离子强度和金属离子对腐殖酸紫外光谱的影响,分析腐殖酸的结构特征,探讨E3/E4与pH值和溶液离子强度的关系。结果表明,腐殖酸的紫外光谱吸收带,随pH值增大主要发生蓝移。但随溶液离子强度增大,pH值对腐殖酸紫外吸收带的影响逐渐降低直至不影响。随溶液离子强度增大,腐殖酸的紫外光谱吸收带都发生红移、吸收强度增大。且腐殖酸的E3/E4值与溶液离子强度具有显著的正相关性。腐殖酸的紫外光谱中的吸收带,随投加Cu2+或Cd2+浓度增大而发生红移。     

用微观作用力解析无机离子对腐殖酸的膜污染行为影响

基于Na+、Ca2+离子在天然水体中的普遍存在及对超滤膜有机污染行为的影响,本研究主要考察了不同离子条件下腐殖酸(HA)对PVDF超滤膜污染行为的影响机理。使用原子力显微镜结合自制的膜材料及污染物探针定量测定了不同离子条件下PVDF-HA及HA-HA之间的相互作用力,同时进行了相应的膜污染实验及定量研究腐殖酸的去除效果。结果表明,PVDF-HA及HA-HA之间的相互作用力大小与膜污染速率及污染幅度呈正相关关系。一价Na+离子通过电荷屏蔽可降低HA表面的带电量,对HA膜污染行为及PVDF-HA及HA-HA之间作用力的影响并不明显。二价Ca2+离子通过电荷中和作用大幅度降低了HA表面的有效带电量,使得PVDF-HA及HA-HA之间的粘附力增大,加剧了膜污染速率。而过多的Ca2+离子会加剧HA之间的聚合,降低了HA进入膜孔内的机率,虽然会短暂的增加腐殖酸的去除效率但无法从根本减轻膜污染。     

The double-edged sword of humic substances: contrasting their effect on respiratory stress in eastern rainbow fish exposed to low pH

High amounts of humic substances (HS) are commonly found in natural acidic waterways and have been suggested to offer some protection against low pH. This study investigated the ability of HS to decrease respiratory stress in eastern rainbowfish (Melanotaenia splendida splendida) exposed to decreases in pH (range of 7–3.5) in soft and hard water. Repeated measures ANOVA revealed a significant difference in respiration (time taken for ten operculum movements) between pH and HS treatments, with a significant interaction between pH and HS present in 5/6 trials. Respiratory stress was shown to increase with increasing acidity, but significantly decreased in treatments with HS (10 and 20 mg/L) compared to those without. The fish exposed to pH treatments without HS also displayed increased hyperactivity, larger operculum movements and increased mucous production. Increased morbidity was shown in HS treatments at pH 3.5 (soft water) and at pH 4 (hard water) compared to treatment without HS. This indicates that HS is helpful in ameliorating the effects of decreased pH on respiration at sublethal pH levels; however, as pH decreases further, it seems that HS increases the toxicity (morbidity) of the low pH.     

Influence of ionic strength and pH on the limitation of latex microsphere deposition sites on iron-oxide coated sand by humic acid

This study, for the first time, investigates and quantifies the influence of slight changes in solution pH and ionic strength (IS) on colloidal microsphere deposition site coverage by Suwannee River Humic Acid (SRHA) in a column matrix packed with saturated iron-oxide coated sand.Triple pulse experimental (TPE) results show adsorbed SRHA enhances microsphere mobility more at higher pH and lower IS and covers more sites than at higher IS and lower pH. Random sequential adsorption (RSA) modelling of experimental data suggests 1 μg of adsorbed SRHA occupied 9.28 ± 0.03 × 10⁹ sites at pH7.6 and IS of 1.6 mMol but covered 2.75 ± 0.2 × 10⁹ sites at pH6.3 and IS of 20 mMol. Experimental responses are suspected to arise from molecular conformation changes whereby SRHA extends more at higher pH and lower ionic strength but is more compact at lower pH and higher IS. Results suggest effects of pH and IS on regulating SRHA conformation were additive.     

Binding of Pb(II) in the system humic acid/goethite at acidic pH

The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.     

Binding of Pb(II) in the system humic acid/goethite at acidic pH

The study of Pb(II) binding to the system humic acid/goethite in acidic medium is reported in the present paper. From a macroscopic point of view, we have constructed the experimental sorption isotherms (using atomic absorption spectroscopy) and compared them with the prediction of the additivity rule. It is found that this system presents positive deviations, that is, the amount sorbed is about an order of magnitude higher than predicted. Apart from this, microscopic and structural aspects have also been studied using in situ and ex situ infrared spectroscopy. These results suggest that the presence of Pb(II) increases the amount of humic acid bound to the oxide. It is proposed that proton displacement due to the interaction between humic substances and the oxide, along with the formation of ternary complexes with the Pb(II) cation bridging the oxide and the humic substances (Type A complexes), cause the deviation from additivity.     

The effect of humic acid on uptake/adsorption of copper by a marine bacterium and two marine ciliates

The effect of humic acid (HA) on Cu uptake by a bacterium and two bacterivorus ciliates was investigated. The presence of HA resulted in a statistically significant (p<0.001) decrease in Cu associated with bacteria that were exposed to 67 microg Cu L(-1). Complexation of Cu appears to lower the availability of Cu with respect to bacterial cell surface binding and uptake. For ciliates, 10 mg HA L(-1) significantly reduced uptake of Cu by Uronema, but did not reduce uptake of Cu by Pleuronema. Uronema exposed to 67 microg Cu L(-1) accumulated 54% less Cu when 10 mg HA L(-1) was present (0.50 pg ciliate(-1) vs 0.23 pg ciliate(-1)). Uronema feeding on V. natriegens, took up less than half as much Cu as unfed Uronema when exposed to Cu without HA (0.41 pg Cu fed ciliate(-1) vs 0.86 pg Cu unfed ciliate(-1), but only 40% less when exposed to Cu and HA (0.31 pg Cu fed ciliate(-1) vs 0.51 pg Cu unfed ciliate(-1)). The lower % reduction attributable to fed ciliates in the presence of HA suggests that some of the Cu associated with HA is available through trophic processes.     

An investigation of inorganic antimony species and antimony associated with soil humic acid molar mass fractions in contaminated soils

The presence of antimony compounds is often suspected in the soil of apple orchards contaminated with lead arsenate pesticide and in the soil of shooting ranges. Nitric acid (1M) extractable Sb from the shooting range (8300 microg kg(-1)) and the apple orchard (69 microg kg(-1)) had considerably higher surface Sb levels than the control site (<1.5 microg kg(-1)), and Sb was confined to the top approximately 30 cm soil layer. Sb(V) was the principal species in the shooting range and the apple orchard surface soils. Size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS) analysis of humic acids isolated from the two contaminated soils demonstrated that Sb has complexed to humic acid molar mass fractions. The results also indicate that humic acids have the ability to arrest the mobility of Sb through soils and would be beneficial in converting Sb(III) to a less toxic species, Sb(V), in contaminated areas.     

Effect of humic substances on the Fenton treatment of wastewater at acidic and neutral pH

This paper describes results of treatability studies of the effect of humic substances (humate, HS, at the concentration 500-5000 mg l-1) on the Fenton (Fe2+/H2O2) treatment of industrial wastewater at pH 3.5 and 7.0. Without humate, the removal of all contaminants was significantly higher at pH 3.5 than at pH 7. At pH 7.0, the removal of all compounds in the presence of HS (3000 mg l-1) was comparable to that at pH 3.5 without HS. At pH 3.5, humate had no effect on the removal of arsenic, thiocyanate and cyanide, but the removal of all organic compounds (phenol, 2,4-dimethylphenol, benzene, toluene, o-xylene, m- & p-xylene and dichloromethane) was significantly inhibited. Mechanisms of the processes are discussed. It is suggested that, in the presence of HS, acidification of the treated wastewater may not only be unnecessary but it can even hinder the degradation of organic pollutants.     

一维饱和多孔介质中胡敏酸的运移研究

研究了胡敏酸在不同多孔介质中的运移特征.结果表明:(1)CXTFIT.2.1软件对多孔介质中胡敏酸运移的拟合效果随多孔介质不同而有较大的差异,其对石英砂和河沙中胡敏酸的运移过程拟合较好,对3种土壤(风沙土、黄绵土和黑垆土)中胡敏酸的运移过程拟合较差.(2)胡敏酸溶液在多孔介质中的运移行为与不同多孔介质有关,在石英砂和河沙中运移迅速,而在土壤中运移缓慢;胡敏酸的快速运移对应较低的阻滞因子和吸附系数,而缓慢运移对应较高的阻滞因子和吸附系数.对于石英砂和河沙,胡敏酸的运移在石英砂中较快,在河沙中较慢;对于3种土壤(风沙土、黄绵土和黑垆土),胡敏酸在风沙土中运移最快,在黑垆土中运移最慢.     

腐殖酸和铁对阿特拉津光降解影响的研究

为考察除草剂在水体中的自净性能,对模拟太阳光(λ> 290 nm)下腐殖酸和铁元素对阿特拉津的光化学降解进行了研究。结果表明,单独辐照阿特拉津几乎不降解。在分别加入3、5和10 mg/L的腐殖酸时,阿特拉津的降解率分别为34.36 %、40.74%和15.66 %;在Fe(Ⅲ)投加量从0.01 mmol/L增加到0.2 mmol/L时,阿特拉津的降解率从24.36 %增加到34.97 %。而在当腐殖酸与铁共存时,阿特拉津降解率则进一步提高。紫外可见光谱和荧光光谱均表明,腐殖酸-铁络合物的形成及其光化学作用,促进了阿特拉津的降解。     

腐植酸对多环芳烃在污染土壤中淋出及截留分解的效果研究

多环芳烃是固废拆解地一类污染较严重的有毒有机物质,用腐植酸作表面活性剂淋洗污染土壤起到较好的增溶及截留分解污染物的作用,达到修复污染土壤的目的。实验结果表明,随着腐植酸加入量的增加,菲、萘、荧蒽、芘和∑PAHs的淋出量显著提高,在污染红壤中最大淋出率分别为52.9%、70.1%、30.5%、46.1%和42.8%,在污染水稻土中最大淋出率分别为51.8%、67.3%、35.0%、38.3%和35.5%,同时多环芳烃的截留分解率也相对较高,而污染红壤和水稻土的总修复率分别达到56.3%和49.8%。     

Effect of humic acid on water chemistry, bioavailability and toxicity of aluminium in the freshwater snail, Lymnaea stagnalis, at neutral pH

The influence of humic acid on the water chemistry of environmentally relevant concentrations of Al at neutral pH was studied, together with its effect on the bioavailability and toxicity of Al in Lymnaea stagnalis. Humic acid significantly reduced the loss of Al from the water and increased the fraction of filterable Al, although this was a relatively small fraction of total Al. Filterable Al concentration in the presence or absence of humic acid was independent of initial Al concentration. Humic acid only partly reduced toxicity, as observed by a reduction in behavioural suppression, and had no effect on the level of Al accumulated in tissues. These results suggest that humic acid maintains Al in a colloidal form that is bioavailable to L. stagnalis. However, these colloidal Al-humic acid species were less toxic since behavioural toxicity was reduced. Humic acid may play an important role in limiting the toxicity of Al to freshwater organisms.     

Accumulation, transformation, and release of inorganic arsenic by the freshwater cyanobacterium Microcystis aeruginosa

Arsenic (As) as a major hazardous metalloid was affected by phytoplankton in many aquatic environments. The toxic dominant algae Microcystis aeruginosa was exposed to different concentrations of inorganic arsenic (arsenate or arsenite) for 15 days in BG11 culture media. Arsenic accumulation, toxicity, and speciation in M. aeruginos as well as the changes of As species in media were examined. M. aeruginosa has a general well tolerance to arsenate and a definite sensitivity to arsenite. Additionally, arsenate actively elevated As methylation by the algae but arsenite definitely inhibited it. Interestingly, the uptake of arsenite was more pronounced than that of arsenate, and it was correlated to the toxicity. Arsenate was the predominant species in both cells and their growth media after 15 days of exposure to arsenate or arsenite. However, the amount of the methylated As species in cells was limited and insignificantly affected by the external As concentrations. Upon uptake of the inorganic arsenic, significant quantities of arsenate as well as small amounts of arsenite, DMA, and MMA were produced by the algae and, in turn, released back into the growth media. Bio-oxidation was the first and primary process and methylation was the minor process for arsenite exposures, while bioreduction and the subsequent methylation were the primary metabolisms for arsenate exposures. Arsenic bioaccumulation and transformation by M. aeruginosa in aquatic environment should be paid more attention during a period of eutrophication.     

The reactions of paraquat and divalent metal ions with humic acid: Factors influencing stoichiometry 2

Abstract

Laurentide humic acid has been titrated with paraquat and with selected divalent metal ions. In some cases, the humic acid was spiked with one cation before titration with another one. Several equivalence points were determined for the binding of the divalent cations, including paraquat. Three equivalence points agreed well with values predicted from the acidic properties of the humic acid. Eight independent experiments gave nine replicate values for an equivalence point that corresponds to 79.2 mole % of the total pairs of carboxyl groups. It is postulated that this represents a large molecular weight or structural fraction of the humic acid. The remaining 20.8 mole % can either bind one divalent cation to two carboxylate anions or bind one divalent cation to one carboxylate anion, with another anion providing for charge balance. Aggregation ‐ disaggregation and dissolution ‐precipitation phenomena may determine which case prevails, and they in turn are sensitive to the chemical compositions of samples. It should be possible to develop analytical chemical methods for characterizing the stoichiometric properties of humic acid samples.