Oxidation of chlorophenols in soil at natural pH by catalyzed hydrogen peroxide: the effect of soil organic matter.

This investigation reports on the effects of soil organic matter (SOM) during the oxidation of chlorophenols with Fe2+-catalyzed H2O2 (Fenton oxidation) system. The soil pH was 7.1 and was not altered. Sorption experiments of soil pre-treated under various oxidation conditions were performed. Concentrations of organic matter in the liquid phase and soil before and after oxidation were analyzed. The results were correlated to the observation in batch Fenton oxidation tests. They showed that the oxidation of chlorophenols at natural soil pH depended on the dose of H2O2 and Fe2+. The soil organic content did not vary significantly after various Fenton treatments, while the sorption of chlorophenols was 10-25% less by the oxidation. The concentration of chlorophenols in the liquid phase exhibited a "decrease and rebound" phenomenon in the batch Fenton oxidation tests. It appeared that the oxidation of SOM resulted in the release of sorbed chlorophenols which were then oxidized by the excess H2O2. An "oxidation-desorption-oxidation" scheme was proposed to describe one of the interaction mechanisms among the oxidant, SOM, and chlorophenols during oxidation.     

The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants

The experiments were done to investigate the effect of soil pH and organic matter content on EDTA-extractable heavy metal contents in soils and heavy metal concentrations in rice straw and grains. EDTA-extractable Cr contents in soils and concentrations in rice tissues were negatively correlated with soil pH, but positively correlated with organic matter content. The combination of soil pH and organic matter content would produce the more precise regression models for estimation of EDTA-Cu, Pb and Zn contents in soils, demonstrating the distinct effect of the two factors on the availability of these heavy metals in soils. Soil pH greatly affected heavy metal concentrations in rice plants. Furthermore, inclusion of other soil properties in the stepwise regression analysis improved the regression models for predicting straw Fe and grain Zn concentrations, indicating that other soil properties should be taken into consideration for precise predicting of heavy metal concentrations in rice plants.     

pH及Zn2+对土壤和铁、铝氧化物吸附苄嘧磺隆的影响

用平衡吸附法研究了3种供试样品(广州赤红壤、铝氧化物、针铁矿)对苄嘧磺隆的等温吸附,同时研究了pH及Zn2 对供试样品吸附苄嘧磺隆的影响.结果表明,在实验所用的苄嘧磺隆的浓度范围内,供试样品对苄嘧磺隆的吸附量各不相同;供试样品吸附苄嘧磺隆的量随溶液pH及Zn2 浓度的改变而变化,且影响不尽相同,这主要与供试样品的组成有关.     

Evaluation of the effect of small organic acids on phytoextraction of Cu and Pb from soil with tobacco Nicotiana tabacum

Phytoremediation, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. However its use is limited by the time required for plant growth, the nutrient supply and, moreover, by the limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction, but they have also revealed several negative side-effects. The objective of this study was to investigate the use of three natural low molecular weight organic acids (NLMWOA) (citric, oxalic, and tartaric acid) as an alternative to synthetic chelators. Slurry-, column-, toxicity- and phytoextraction experiments were performed. For the phytoextraction experiment the three NLMWOA were applied to a copper- and a lead-contaminated soil respectively. A significant increase in copper uptake was visible only in the citric acid treatment (67 mg kg-1) in comparison to the EDTA treatment (42 mg kg-1). The NLMWOA application showed no enhanced effect concerning the lead phytoextraction. A possible explanation for this lack of significance could be the rate of the degradation of NLMWOA. This rate might well be too high for these heavy metals with low mobility and bioavailability such as lead. The amounts of NLMWOA applied to the soil were very high (62.5 mmol kg-1 of soil) and the effect was too little. In this respect EDTA, which was applied in very small amounts (0.125 mmol kg-1) was more efficient. Thus making NLMWOA unsuitable to enhance phytoextraction of heavy metals from soil.     

天然有机物对零价铁去除水体中砷的影响研究

在研究零价铁对水体中砷去除动力学的基础上,着重探讨了天然有机物腐殖酸对零价铁除砷的影响.并对零价铁的腐蚀产物进行了分析.结果表明,水体中的砷可以通过在零价铁腐蚀产物上的吸附得到快速去除.腐殖酸显著降低了砷的去除率,这归因于腐殖酸与零价铁腐蚀产生的铁离子形成络合物,阻止了Fe(OH)3(或Fe(OH)2)沉淀的产生.腐殖酸浓度越高.砷的去除率越低.1.00 mg腐殖酸最多可以络合约0.75 mg铁离子.当铁离子与腐殖酸的络合达到饱和后,零价铁进一步腐蚀产生的铁离子可形成Fe(OH)3(或Fe(OH)2)沉淀,这些沉淀物可吸附水体中的腐殖酸和砷,从而加速砷的去除.冷冻干燥后的零价铁腐蚀产物的结构以无定型为主,含有少量的结晶化合物,包括γ-Fe2O3、γ-FeO(OH)和Fe3O4等.腐殖酸的存在可进一步增加腐蚀产物中的无定型成分.光电能谱(XPS)分析结果显示,吸附在腐蚀产物上的砷为5价,没有发现5价砷被还原成3价砷.在应用零价铁修复砷污染水体时,应考虑腐殖酸的影响.     

蹄角粉及其水解多肽对污染土壤中Cu2+形态调控效应

以含氮12%左右的屠宰场废弃蹄角为原料,经过超细粉碎打破蹄角晶体结构和在极端环境下人工水解为游离巯基多肽将其作为肥料对植物的生长效应和对土壤中Cu2+的钝化效应进行研究。结果表明：在清洁土壤种植小白菜实验中,其单株最高生物量为水解多肽组合（17.81 g）,比市售复混肥生物量（15.52 g）高2.29 g,且最高相对叶绿素为50.03,直接用蹄角粉处理小白菜也可达到单株生物量 17.72 g,这表明蹄角粉及其水解多肽对植物的生长具有明显的促进效应,是一种优质有机肥;钝化效应研究发现,在总铜含量为80、100、300 mg·kg-1的污染土壤中,蹄角粉及其水解多肽均有钝化效应,经过45 d的钝化处理,蹄角粉效果最佳,对3种污染土壤的有效铜含量降低率分别为50.20%、47.21%、42.30%,比水解多肽处理组分别高29.97%、11.70%、7.9%。钝化与种植结合实验表明,小白菜总铜含量符合GB 5009.13-2017标准限值要求。说明蹄角粉及其水解多肽既有肥料效应,又有钝化效应,可用于铜污染土壤的钝化修复。     

有机配体对纳米零价铁还原硝基苯的影响与机理

通过FeSO4·7H2O与NaBH4反应,采用液相还原法制备纳米级零价铁(NZVI),并用XRD,SEM对其性能进行表征。研究了纳米零价铁还原硝基苯(NB)的动力学规律及柠檬酸、草酸、柠檬酸钠、草酸钠、乙二胺四乙酸二钠(EDTA二钠盐)几种有机小分子对其还原效率的影响,并对其机理进行了初步探讨。结果表明,纳米零价铁去除硝基苯反应符合准一级动力学方程,并且当硝基苯浓度一定时,增加NZVI投加量,去除率会显著增大;当NZVI浓度一定时,硝基苯浓度越低,去除率越高;柠檬酸和EDTA二钠盐在较低浓度时抑制还原反应进行,而在3 mmol/L左右时,具有促进还原反应进行的作用,而草酸、柠檬酸钠和草酸钠则为抑制作用。     

Effects of pH, Fe, and Cd on the uptake of Fe2+ and Cd2+ by rice

The rhizosphere plays an important role in altering cadmium (Cd) solubility in paddy soils and Cd accumulation in rice. However, more studies are needed to elucidate the mechanism controlling rice Cd solubility and bioavailability under different rhizosphere conditions to explain the discrepancy of previous studies. A rice culture with nutrient solution and vermiculite was conducted to assess the effects of pH, Eh, and iron (Fe) concentration on Cd, Fe fractions on the vermiculite/root surface and their uptake by rice. The solution pH was set from 4.5 to 7.5, with additions of Fe (30 and 50 mg L^?1) and Cd (0.5 and 0.9 mg L^?1). At pH 5.5, the Eh in the rice rhizosphere was higher whereas transpiration, Cd²⁺, and Fe²⁺ adsorption on the vermiculite/root surface and accumulation in rice were lower than the other pH treatments. Cadmium addition had no impact on pH and Eh in rice rhizosphere while Fe addition decreased pH and increased Eh significantly. Compared with control, Fe addition resulted in the decrease of rhizosphere Cd, Fe solubility and bioavailability. Higher redox potential in the rice rhizosphere resulted in the decline of transpiration, Cd, and Fe accumulation in the rice tissues, suggesting that the transfer of two elements from soil to rice was depressed when the rhizosphere was more oxidized.     

Fe3+和Cu2+对饮用水氯消毒副产物三卤甲烷形成的影响

为了研究水中存在Br-的情况下,Fe3+和Cu2+对三卤甲烷(THMs)的生成及CHCl3、CHBrCl2、CHBr2Cl、CHBr3 4种消毒副产物相对分布的影响,以腐殖酸模拟氯消毒过程中的前体物进行实验。结果表明,在pH为6、7和9 3种条件下,Fe3+抑制了THMs的生成,pH=6时只有CHCl3生成量随着Fe3+浓度的增加逐渐减少,其余3种消毒副产物均在增加,pH=7时4种消毒副产物浓度均减小并在Fe3+浓度为2 mg/L时生成量最低,pH=9时的生成趋势与pH=6时类似。Cu2+能促进THMs的生成,在pH为6、7和9时,当加入0.5 mg/L Cu2+时,THMs总量分别增加了16.7%、22.6%和2.5%,随着pH增加,THMs总量增加。在3种pH环境中,Cu2+对THMs生成的影响大于Fe3+,在偏酸性环境中,Fe3+影响THMs生成,产生的致癌风险高,当金属离子浓度为2.5 mg/L时,致癌风险相差最高为15%,在中性和偏碱性环境中,Cu2+影响THMs生成,产生的致癌风险高。     

The effect of nitrogen form on rhizosphere soil pH and zinc phytoextraction by Thlaspi caerulescens

The phytoextraction of Zn may be improved by applying N fertilizers to increase the biomass and Zn content of shoots. Rhizosphere-pH change from uptake of different N forms will affect Zn phyto-availability in the rhizosphere and Zn phytoextraction. This glasshouse study examined the effect of N form on Zn phytoextraction by Thlaspi caerulescens (Prayon). The plants were grown in a Zn-contaminated soil (total Zn 250 mg kg-1 soil; pHwater 5.7) and supplied with (NH4)2SO4, Ca(NO3)2 or urea [(NH2)2CO]. The form was maintained by applying the nitrification inhibitor dicyandiamide. A biodegradable chelator ethylenediaminedisuccinic acid (EDDS) was included for comparison. The addition of N doubled the shoot biomass. The highest shoot Zn content occurred in the Ca(NO3)2 treatment and was associated with the highest rhizosphere pH. The lowest shoot dry weight occurred in the EDDS treatment. The Zn concentration in the shoots increased as the rhizosphere pH increased. A significant correlation occurred between Ca and Zn concentrations in the shoots. This study demonstrated that Ca(NO3)2 is a more effective treatment than , urea or EDDS for enhancing Zn phytoextraction in a mildly acidic soil.     

The effects of particle size, organic matter content, crop residues and dissolved organic matter on the sorption kinetics of atrazine and isoproturon by clay soil

Reliable predictions of the fate and behaviour of pesticides in soils is dependent on the use of accurate ‘equilibrium’ sorption constants and/or rate coefficients. However, the sensitivity of these parameters to changes in the physicochemical characteristics of soil solids and interstitial solutions remains poorly understood. Here, we investigate the effects of soil organic matter content, particle size distribution, dissolved organic matter and the presence of crop residues (wheat straw and ash) on the sorption of the herbicides atrazine and isoproturon by a clay soil. Sorption K_d's derived from batch ‘equilibrium’ studies for both atrazine and isoproturon by <2 mm clay soil were approximately 3.5 L/kg. The similarity of K_oc's for isoproturon sorption by the <2 mm clay soil and <2 mm clay soil oxidised with hydrogen peroxide suggested that the sorption of this herbicide was strongly influenced by soil organic matter. By contrast, K_oc's for atrazine sorption by oxidised soil were three times greater than those for <2 mm soil, indicating that the soil mineral components might have affected sorption of this herbicide. No significant differences between the sorption of either herbicide by <2 mm clay soil and (i) <250 μm clay soil, (ii) clay soil mixed with wheat straw or ash at ratios similar to those observed under field conditions, (iii) <2 mm clay soil in the presence of dissolved organic matter as opposed to organic free water, were observed.     

Fate and transport of monoterpenes through soils. Part II: calculation of the effect of soil temperature, water saturation and organic carbon content

This theoretical study was performed to investigate the influence of soil temperature, soil water content and soil organic carbon fraction on the mobility of monoterpenes (C10HnOn') applied as pesticides to a top soil layer. This mobility was expressed as the amount volatilized and leached from the contaminated soil layer after a certain amount of time. For this, (slightly modified) published analytical solutions to a one dimensional, homogeneous medium, diffusion/advection/biodegradation mass balance equation were used. The required input-parameters were determined in a preceding study. Because the monoterpenes studied differ widely in the values for their physico-chemical properties, the relative importance of the various determinants also differed widely. Increasing soil water saturation reduced monoterpene vaporization and leaching losses although a modest increase was usually observed at high soil water contents. Organic matter served as the major retention domain, reducing volatilization and leaching losses. Increasing temperature resulted in higher volatilization and leaching losses. Monoterpene mobility was influenced by vertical water flow. Volatilization losses could be reduced by adding a clean soil layer on top of the contaminated soil. Detailed insight into the specific behaviour of different monoterpenes was obtained by discussing intermediate calculation results; the transport retardation factors and effective soil diffusion coefficients. One insight was that the air-water interface compartment is probably not an important partitioning domain for monoterpenes in most circumstances. The results further indicated that biodegradation is an important process for monoterpenes in soil.     

Influence of soil pH on the fractionation of Cr, Cu and Zn in solid phases from a landfill site

The spatial variability of soil pH for engineered Weathered Oxford Clay is described using 35 samples collected from the base of a new cell in an existing landfill. Soil pH variability influences the reactivity of Cr, Cu and Zn in the site. The reactivity of these metals as natural components was determined using a sequential extraction method. The total concentration of Cr, Cu and Zn and the mineralogical composition were also determined. The results showed that due to the presence of a layer rich in pyrite in the base, a natural acidification may occur which can produce a soil pH as low as 2.7. The spatial variability of soil pH in this area has been described with an anisotropical variogram model and the estimation of its values at unsampled locations was carried out using the ordinary kriging algorithm. From the spatial modelling of the soil pH, it was found that the metals in the soil solid phases follow a similar distribution.     

油菜秸秆髓芯对水中铜离子吸附作用及其机理

使用单因素实验,分别考察不同溶液pH、油菜秸秆髓芯加入量、溶液初始Cu2+浓度和吸附时间4个因素对油菜秸秆髓芯吸附水中Cu2+影响作用.采用BBD实验设计分析和优化其吸附条件,并得到最佳吸附条件组合.使用吸附等温方程和动力学方程对其吸附Cu2+过程进行评价,运用红外光谱技术对吸附Cu2+前后油菜秸秆髓芯进行分析,初步推断油菜秸秆髓芯吸附水中Cu2+的机理.最佳吸附条件参数组合:在温度为25℃条件下、初始Cu2+浓度为31 mg/L、溶液pH为5.0和油菜秸秆髓芯加入量为1.17 g/L条件组合下吸附120 min,在此组合条件下油菜秸秆髓芯对水中Cu2+最大去除率达到96.86%.吸附等温方程表明,其吸附Cu2+行为更符合Langmuir方程;动力学方程显示,其吸附Cu2+行为符合二次动力学方程.红外光谱显示,油菜秸秆髓芯中的—C=O、酰胺II基团参与Cu2+的络合吸附.油菜秸秆髓芯对水中Cu2+呈现出良好的吸附性能,为油菜秸秆髓芯作为Cu2+ 吸附剂提供了应用基础与理论依据.     

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.     

Chemical and microbiological qualities of The East River (Dongjiang) water,with particular reference to drinking water supply in Hong Kong

Currently, about 80% of drinking water in Hong Kong is abstracted from The East River (Dongjiang) that is located in the mainland side of China. Literature records and monitoring results of 2000-2001 confirmed that the lower section of the Dongjiang had been contaminated by organic and inorganic pollutants. Statistical analyses showed that the increases of total cadmium, copper and zinc in the surface layer of sediment of Hong Kong reservoirs from 1994 to 2001 were positively correlated (significant at p<0.05) with those in the surface layer of sediments of the lower Dongjiang. Recent microbiological survey revealed that pathogens such as Salmonella spp., Vibro spp., Giardia lamblia and Cryptosporidium parvum appeared occasionally in water samples of the Dongjiang and Hong Kong reservoirs. While analytical results found that currently most of the heavy metals, trace organics and microbes were removed by the drinking water treatment plants in Hong Kong, the long-term health risk of drinking water contamination should not be overlooked. The Water Supplies Department of Hong Kong is recommended to intensify its water quality monitoring program to cover pathogenic bacteria and parasites in watercourses and reservoirs.     

The complexation of Cu(II) by anthropogenic fulvic acids extracted from composted urban and livestock wastes

Abstract

The fulvic acid (fua) fractions of two samples of composted solid wastes [urban (urfua) and livestock (lsfua) wastes], commercialized to be used in agriculture as organic correctives or fertilizers, were analyzed for their affinity towards Cu(II) at pH=6. Molecular fluorescence spectroscopy (synchronous mode) was used to monitor the quenching caused by the complexation upon addition of Cu(II) to fua. Spectral data were preprocessed by a chemometric self‐modeling mixture analysis method (SIMPLISMA) to detect the number of different types of fluorescent binding sites that exist in each fua, their spectra and the corresponding quenching profiles [fluorescence intensity as function of the total Cu(II) concentration]. From the analysis of the quenching profiles, the amount of binding sites (Cl) and the corresponding conditional stability constants (K') were calculated. Both fua samples have approximately Cl = 0.21 mmol/g and the logarithms of K’ are 4.21(3) and 4.51(8), respectively for urfua and lsfua. The differences detected between these fua samples and those extracted from natural soils can be attributed mainly to the relatively small humification extent of the present anthropogenic fua samples.     

不同pH值条件下Fe3+、Cu2+和Zn2+对厨余垃圾两相厌氧消化水解酸化过程的影响

通过间歇实验研究了在pH=7和不调节pH两种情况下添加不同浓度的Fe3 、Cu2 和Zn2 对厌氧消化水解酸化阶段有机酸组分和含量的影响.结果表明,pH=7时,添加50 mg/L Fe3 和30 mg/L Cu2 ,有利于厨余垃圾水解酸化过程的进行,反应生成的VFA(挥发性脂肪酸)含量增加.不调节pH时,添加100 mg/L以下的Fe3 和Cu2 对VFA含量也有所促进,但乳酸含量也增加.在2种pH条件下添加Zn2 对反应的促进或抑制作用均不明显.     

Effects of pH, organic acids, and inorganic ions on lead desorption from soils

The desorption characteristics of lead in two variable charge soils (one developed from Arenaceous rock (RAR) and the other derived from Quaternary red earths (REQ)) were studied, and the effects of pH value, organic acid, and competitive ions were examined. Desorption of Pb(2+) decreased from nearly 100.0 to 20.0% within pH 1.0-4.0 in both soils, and then the decrease diminished at pH > 4.0. Organic ligands at relatively low concentrations (< or =10(-3) mol L(-1)) slightly inhibited Pb(2+) desorption, but enhanced Pb(2+) desorption at higher concentrations. In this study, citric acid or acetic acid at higher concentrations (>10(-3) mol L(-1)) had the greatest improvement of Pb(2+) desorption, followed by malic acid; and the smallest was oxalic acid. Desorption of the adsorbed Pb(2+) increased greatly with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Pb(2+) desorption more than Zn(2+) at the same loading.     

Effects of pH,initial Pb2+ concentration,and polyculture on lead remediation by three duckweed species

Various geographical duckweed isolates have been developed for phytoremediation of lead. The Pb²⁺ removal efficiency of Lemna aequinoctialis, Landoltia punctata, and Spirodela polyrhiza was investigated in monoculture and polyculture at different levels of pH and initial Pb²⁺ concentrations. L. aequinoctialis was not sensitive to the tested pH but significantly affected by initial Pb²⁺ concentration, whereas synergistic effect of pH and initial Pb²⁺ concentration on removal efficiency of L. punctata and S. polyrhiza was found. Although the majority of polycultures showed median removal efficiency as compared to respective monocultures, some of the polycultures achieved higher Pb²⁺ removal efficiencies and can promote population to remove Pb²⁺. Besides, the three duckweed strains could be potential candidates for Pb²⁺ remediation as compared to previous reports. Conclusively, this study provides useful references for future large-scale duckweed phytoremediation.