The influence of organic matter on sorption and fate of glyphosate in soil - Comparing different soils and humic substances

Soil organic matter (SOM) is generally believed not to influence the sorption of glyphosate in soil. To get a closer look on the dynamics between glyphosate and SOM, we used three approaches: I. Sorption studies with seven purified soil humic fractions showed that these could sorb glyphosate and that the aromatic content, possibly phenolic groups, seems to aid the sorption. II. Sorption studies with six whole soils and with SOM removed showed that several soil parameters including SOM are responsible for the strong sorption of glyphosate in soils. III. After an 80 day fate experiment, ∼40% of the added glyphosate was associated with the humic and fulvic acid fractions in the sandy soils, while this was the case for only ∼10% of the added glyphosate in the clayey soils. Glyphosate sorbed to humic substances in the natural soils seemed to be easier desorbed than glyphosate sorbed to amorphous Fe/Al-oxides.     

溶液中阴离子和腐殖酸对UV/H2O2降解2,4-二氯酚的影响

研究了UV/H2O2工艺对2,4-二氯酚(2,4-DCP)的去除效果和水中阴离子、腐殖酸对该工艺降解2,4-DCP的影响.结果表明:UV/H2O2工艺可以有效地去除水中2,4-DCP,光降解过程符合一级反应动力学模型;在H2O2投加量为8 mg/L、1个30 W低压汞灯照射下,2,4-DCP在蒸馏水和自来水中反应速率常数分别为0.023 2、0.016 2 min-1;NO-3、Cl-、HCO-3对2,4-DCP光降解有抑制作用,当3种阴离子摩尔浓度为0.5、10.0、20.0 mmol/L时,对2,4-DCP光降解的抑制程度为HCO-3＞NO-3＞Cl-;腐殖酸在低浓度时,促进光降解反应进行,在高浓度时,2,4-DCP的光降解受到抑制.自来水中的反应速率常数低于蒸馏水中的反应速率常数是由于水中多种阴离子和腐殖酸影响的结果.     

Enhanced multi-metal extraction with EDDS of deficient and excess dosages under the influence of dissolved and soil organic matter

This study investigated the influence of dissolved and soil organic matter on metal extraction from an artificially contaminated soil. With high concentration of DOM, the extraction of Cu, Zn and Pb was enhanced by forming additional metal-EDDS complexes under EDDS deficiency. However, the enhancement of metal extraction under EDDS excess was probably due to the soil structure being disrupted owing to humic acid enhanced Al and Fe dissolution, which induced more metals dissolving from the soils. Fulvic acid was found to enhance metal extraction to a greater extent compared with humic acid because of its high content of the carboxylic functional group. Cu extraction from the soil with high organic matter content using EDDS was the lowest due to the high binding affinity of Cu to SOM, whereas Zn extraction became the highest because of a preference for EDDS to extract Zn due to the high stability constant of ZnEDDS.     

Influences of redox transformation, metal complexation and aggregation of fulvic acid and humic acid on Cr(VI) and As(V) removal by zero-valent iron

This study investigated the removal kinetics and mechanisms of Cr(VI) and As(V) by Fe(0) in the presence of fulvic acid (FA) and humic acid (HA) by means of batch experiments. The focus was on the involvements of FA and HA in redox reactions, metal complexation, and iron corrosion product aggregation in the removal of Cr(VI) and As(V) removal by Fe(0). Synthetic groundwater was used as the background electrolyte to simulate typical groundwater. The results showed faster Cr(VI) removal in the presence of HA compared to FA. Fluorescence spectroscopy revealed that no redox reaction occurred in the FA and HA. The results of the speciation modeling indicate that the free Fe(II) concentration was higher in the presence of HA, resulting in a higher removal rate of Cr(VI). However, the removal of As(V) was inhibited in the HA solution. Speciation modeling showed that the concentration of dissolved metal-natural organic matter (metal-NOM) complexes significantly affected the aggregation of the iron corrosion products which in turn affected the removal of As(V). The aggregation was found to be induced by gel-bridging of metal-NOM with the iron corrosion products. The effects of metal-NOM on the aggregation of the iron corrosion products were further confirmed by TEM studies. Larger sizes of iron corrosion products were formed in the FA solution compared to HA solution. This study can shed light on understanding the relationships between the properties of NOM (especially the content of metal-binding sites) and the removal of Cr(VI) and As(V) by Fe(0).     

Effects of humic acids derived from lignite and cattle manure on antioxidant enzymatic activities of barley root

To investigate the effects of humic acids (HAs) on the ability of plants to defend themselves against oxidative stress, barley was hydroponically cultured in the absence and presence of HAs, and the antioxidant enzymatic activities (catalase, superoxide dismutase, ascorbate and glutathione peroxidases) of root tissue were evaluated. Auxin-like structures in HAs, which were extracted from an oxidation product of lignite (LHA) and compost derived from cattle manure (CHA), were identified by pyrolysis-gas chromatography/mass spectrometry (GC/MS) with tetramethylammonium hydroxide. The LHA, which had the lower molecular weight, was more effective in promoting the growth of barley root than CHA. However, the amounts of auxin-like structures in the CHA were much higher than those for LHA. The antioxidant enzymatic activities were initially decreased in the presence of LHA and CHA at the first day after refreshing the culture solution, but were significantly increased on the second day. The CHA sample, which contained relatively high levels of phenolic acids that contained auxin-like structures, was effective in increasing four types of enzymatic activities, while the activities of catalase and ascorbate peroxidase were increased in the presence of LHA, which contains naphthalene derivatives. These results indicate that using HAs as a supplement can be effective in enhancing antioxidation enzymatic activities, while the appearance of the effects is retarded because of the decomposition and release of auxin-like compounds from HAs by organic acids from the plant roots.     

Mobility and efficacy of 2,4-D herbicide from slow-release delivery systems based on organo-zeolite and organo-bentonite complexes

This research aimed to develop slow-release formulations (SRFs) of 2,4-dichlorophenoxyacetic acid (2,4-D) using zeolite and bentonite minerals modified with cetyltrimethylammonium (CTMA) surfactant. Adsorption–desorption, greenhouse bioassay and column experiments were carried out to assess the potential of the SRFs to control weeds while reducing the herbicide leaching losses to deep layers of soil. The results showed that only 6.5 mmol 2,4-D kg^?1 was retained by Na-bent, and the herbicide was not adsorbed by Na-zeol at all. The surface modification with CTMA surfactant, however, improved the 2,4-D adsorption capacity of the zeolite and bentonite up to 207.5 and 415.8 mmol kg^?1, respectively. The synthesized organo-minerals slowly released the retained 2,4-D discharging 22 to 64% of the adsorbed 2,4-D to the solution phase within 7 days. The SRFs significantly (P = 0.05) reduced the herbicide mobility within the soil columns keeping a great portion of the herbicide active ingredient in the upper 5 cm soil layer. The SRFs were significantly (P = 0.05) as effective as the free technical herbicide in weed control without harming the ryegrass as the main plant. Therefore, the synthesized SRFs could be considered as useful tools for weed control in sustainable agriculture.     

生物可降解螯合剂[S,S]-乙二胺二琥珀酸和乳酸乙酯提取土壤中重金属的研究

研究了生物可降解的有机螯合剂[S,S]-乙二胺二琥珀酸([S,S]-EDDS,简写为EDDS)和乳酸乙酯(EL)对重金属污染土壤中重金属的提取效率,并用X射线衍射(XRD)和红外光谱(FT-IR)分析了螯合剂提取对土壤理化性质的影响.结果表明:EDDS对土壤中的Cd、Cu、Pb和Zn有较高的提取率,效果比EL好;EDDS和EL混合提取的重金属提取率增加,但相比单独使用EDDS没有超过10%.FT-IR分析表明,提取前后FT-IR谱图中特征吸收频率没有显著改变,但强度有所改变.XRD分析表明,提取前后土壤晶格结构发生明显的变化,螯合剂提取改变了土壤微观结构.     

Effect of some heavy metals and soil humic substances on the phytochelatin production in wild plants from silver mine areas of Guanajuato, Mexico

Phytochelatins (PCs) were determined in the wild plants, focusing on their relationship with the levels of heavy metals and humic substances (HS) in soil. Ricinus communis and Tithonia diversifolia were collected from several sites in Guanajuato city (Mexico), which had long been the silver and gold mining center. The analysis of PCs in root extracts was carried out by liquid chromatography (derivatization with monobromobimane). Total Ag, Cd, Cu and Pb in plant roots and in soil samples, as well as soil HS were determined. The association of metals with HS in soils was evaluated by size exclusion chromatography (SEC) with UV and ICP-MS detection. The results obtained revealed the induction of PCs in R. communis but not in T. diversifolia. The levels of Cd and Pb in plant roots presented strong positive correlation with PC-2 (r = 0.9395, p = 0.005; r = 0.9573, p = 0.003, respectively), indicating that these two metals promote PCs induction in R. communis. On the other hand, the inverse correlation was found between soil HS and metal levels in roots of R. communis (Cu > Pb > Cd > Ag), in agreement with the decreasing affinity of these metals to HS. Importantly, the inverse correlation between soil HS and plant PC-2 was observed (r = −0.7825, p = 0.066). These results suggest that metals strongly bound to HS could be less bioavailable to plants, which in turn would limit their role in the induction of PCs. Indeed, the SEC elution profiles showed Pb but not Cd association with HS and the correlation between metal in soil and PC-2 in plant was statistically significant only for Cd (r = 0.7857, p = 0.064). Based on these results it is proposed that the role of heavy metals in PCs induction would depend on their uptake by R. communis, which apparently is controlled by the association of metals with soil HS. This work provides further evidence on the role of environmental conditions in the accumulation of heavy metals and phytochelatin production in plants.     

Distribution of Al-, Fe- and Mn-pools and their correlation in soils from two acid deposition small catchments in Hunan, China

Distribution of Al-, Fe- and Mn-pools was investigated in five forest soil profiles (consisting of four horizons) in each of two Hunan catchments (BLT and LKS) where acid deposition has been considered critical. Al- and Fe-pools were higher in BLT than those in LKS, but Mn-pools much lower in BLT. Mn-pools vary from topsoils to bottom soils, but there are different trends for different Mn speciation. Al- and Fe-pools, except amorphous Fe_ox, were positively correlated to contents of soil organic matter (OM) showed by the loss on ignition in the two catchments. Accumulation of Al- and Fe-pools may occur in the area where soil organic matter was enriched (e.g. in top soil and rhizosphere soil). However, no direct correlation is observed between Mn and OM. Acidic atmospheric deposition may affect transforming among speciations of Al-, Fe- and Mn-pools and leaching of soil Al, Fe and Mn through formation of soluble organo-metal dissolved Al which was potentially toxic, increased. There were significant correlations between Al-pools complexes or change of oxidation–reduction conditions. Mn_ex (exchangeable Mn) and Mn_ox (amorphous and organic Mn) were highly linearly correlation with soil pH values at LKS but at BLT. Under acid deposition, the availability of the nutrient Fe increased with the amount of dissolved Al, which was potentially toxic, in the two catchments. There are no significant correlations between Al_ex (exchangeable Al) and Mn_ex, Fe_ex (exchangeable Fe) and Mn_ex in this work, indicating potentially toxic Mn increase seldom accompanying with Al increase in the two catchments.     

Effect of biosolid incorporation to mollisol soils on Cr, Cu, Ni, Pb, and Zn fractionation, and relationship with their bioavailability

Biosolid application to soil may be a supply of nutrients and micronutrients but it may also accumulate toxic compounds which would be absorbed by crops and through them be incorporated to the trophic chain.

The present study deals with the effect of biosolid application on Cr, Cu, Pb, Ni, and Zn in agricultural soils. The procedure used is sequential extraction so that the availability of those metals may be estimated and related to their bioavailability as determined through two indicator plants grown in greenhouse: ryegrass (Lolium perenne L.) and red clover (Trifolium pratense). Results showed that biosolid application to soil increased total Cu and Zn content. Sequential extraction showed that the more labile Zn fractions increased after biosolid application to soil. This was confirmed when assessing the total content of this metal in shoot and root of the plants under study, since a higher content was found in plant tissues, while no significant differences were found for Cu, Cr, Ni, and Pb.     

Effect of microbial activity, soil water content and added copper on the temporal distribution patterns of HCB and DDT among different soil organic matter fractions

Temporal changes in the distribution of exogenous HCB and DDT among different soil organic matter fractions were studied under sterile and non-sterile conditions, different soil water contents, and different concentrations of added Cu(2+). The residence time was 311days. Soil organic matter was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions by a methyl isobutyl ketone (MIBK) method. Results revealed that there is a mass transfer tendency of DDT and HCB from FA, HA and BHA to IR and lipid fractions with increasing residence time. Microbial activity accelerated the mass transfer, while the addition of Cu(2+) slowed it down. The HCB and DDT transfer rate decreased as the soil moisture increased from 1.9% to 60%, but increased when soil moisture increased further to 90%. A two-compartment first order kinetic model was used to describe the mass transfer from FA, HA and BHA.     

Wild fire impact on copper, zinc, lead and cadmium distribution in soil and relation with abundance in selected plants of Lamiaceae family from Vidlic Mountain (Serbia)

Fire has been considered as an improving factor in soil quality, but only if it is controlled. Severe wild fire occurred in the summer 2007 on the Vidlic Mountain (Serbia) overspreading a huge area of meadows and forests.Main soil characteristics and content of heavy metals (Cu, Pb, Cd, Zn) in different fractions obtained after sequential extraction of soil from post-fire areas and from fire non disturbed areas were studied. In four plant species of Lamiaceae family (Ajuga genevensis L., Lamium galeobdolon (L.) L., Teucrium chamaedrys L., Acinos alpinus (L.) Moench.), that grow in typical habitats of the mountain, distribution of heavy metals in aerial parts and roots was investigated too.For all samples from post-fire area cation exchange capacity and soil organic matter content are increased while rH is decreased. Fire caused slightly increased bioavailability of the observed metals but more significant rise happened in metal amounts bound to oxides and organics. The plants showed variable behavior. T. chamaedrys collected on the post-fire area contained elevated concentrations of all analyzed metals. A. alpinus showed higher phytoaccumulation for Zn and Cd, while the other two plant species for Pb and Cd in the post-fire areas.