Sorption-desorption behavior of PCP on soil organic matter and clay minerals

Pentachlorophenol (PCP) contamination is a severe environmental problem due to its widespread occurrence, toxicity and recalcitrance. In order to gain a better understanding of the fate of PCP in soils, the role of the soil organic matter (SOM) and clay minerals in the PCP sorption-desorption was studied on two bulk field soils, two subsoils (i.e., SOM or clay-removed soil) and two artificial soils. The two field soils used were a silty loam from New Mexico (NM) containing 10% clay and a sandy-clay-loam from Colombia (CO) South America comprised of 18% clay minerals. The bulk CO soil containing kaolinite sorbed significantly less PCP than the NM soil. All soils depicted an apparent hysteresis during sorption. The CO bulk and subsoils desorbed 14-20% and 15-26% of the sorbed PCP respectively whereas the NM bulk and subsoils desorbed only 4-12% and 5-16%, respectively. Experiments conducted with pure clay and artificial soils indicated that the expandable clay minerals were key sorbent material. Additional studies to investigate the interaction between SOM and clay minerals are needed to fully understand sorptive phenomena.     

Potential contributions of clay minerals and organic matter to pentachlorophenol retention in soils

Sorption of pentachlorophenol (PCP) by pure minerals and humic acids were measured to obtain additional perspective on the potential contributions of both clay minerals and soil organic matter (SOM) to contaminants retention in soils. Four types of common soil minerals and two kinds of humic acids (HAs) were tested. The sorption affinity for PCP conformed to an order of HAs > K-montmorillonite > Ca-montmorillonite > goethite > kaolinite. Such a difference in sorption capacity could be attributed to the crucial control of HAs. Clay minerals also had their contribution, especially K-montmorillonite, which played an important, if not dominant, role in the controlling process of PCP sorption. By removing 80% (on average) of the organic carbon from the soils with H(2)O(2), the sorption decreased by an average of 50%. The sorption reversibility had been greatly favored as well. Considering the uncharged mineral fractions in soil before and after H(2)O(2)-treated, the main variation in sorption behavior of the soil might thus be related to the removed organic carbon and the reduced pH. This testified rightly the interactive effect of SOM and clay minerals on PCP sorption as a function of pH.     

Effect of organic fertilizers derived dissolved organic matter on pesticide sorption and leaching

Incorporation of organic fertilizers/amendments has been, and continues to be, a popular strategy for golf course turfgrass management. Dissolved organic matter (DOM) derived from these organic materials may, however, facilitate organic chemical movement through soils. A batch equilibrium technique was used to evaluate the effects of organic fertilizer-derived DOM on sorption of three organic chemicals (2,4-D, naphthalene and chlorpyrifos) in USGA (United States Golf Association) sand, a mixed soil (70% USGA sand and 30% native soil) and a silt loam soil (Typic Fragiochrept). DOM was extracted from two commercial organic fertilizers. Column leaching experiments were also performed using USGA sand. Sorption experiments showed that sorption capacity was significantly reduced with increasing DOM concentration in solution for all three chemicals. Column experimental results were consistent with batch equilibrium data. These results suggest that organic fertilizer-derived DOM might lead to enhanced transport of applied chemicals in turf soils.     

Cosorption study of organic pollutants and dissolved organic matter in a soil

In this study we have evaluated the effects of dissolved organic matter (DOM) on sorption of imidacloprid, 3,4-dichloroaniline (3,4-DCA) and 4-bromoaniline (4-BA) on a typical calcareous soil (Luvic Xerosol) from south-eastern Spain. Two different types of DOM were used, that is to say, dissolved natural organic matter extracts from a commercial peat (DNOM) and a high-purity tannic acid (TA) solution. The experiments were carried out in a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results indicated that the presence of both DNOM and TA, over a concentration range of 15-100 mg L(-1), produced an increase in the amount of 3,4-DCA and 4-BA sorbed and a decrease in the amount of imidacloprid retained on the soil studied. A modified distribution coefficient, K(doc), has been proposed as a safer parameter for soil sorption predictions of organic pollutants and it could be of help to model the fate of these in the environment.     

Environmental fate of amitrole: influence of dissolved organic matter

In this study the environmental fate of amitrole in terrestrial and aquatic model ecosystems was investigated. Under aerobic conditions mineralization of amitrole is the main degradation pathway. The experiments revealed that the leaching behaviour is low in the presence or the absence of dissolved organic matter (DOM) despite the high water solubility due to a strong binding of amitrole to soil constituents. Under anaerobic conditions the addition of DOM increases the transport of amitrole in soil columns. The tests with water/sediment model ecosystems showed that the mineralization of amitrole is lower in comparison to aerobic soil experiments. Up to 80.6% of the applied 14C-labelled amitrole transfer into the sediment and about 1/3 of this amount formed bound residues, which are not extractable.     

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.     

Chemical characteristics of chromophoric dissolved organic matter in rainwater

Proton nuclear magnetic resonance (¹H-NMR), UV absorbance and excitation-emission matrix (EEM) fluorescence spectroscopy were used to define the chemical characteristics of chromophoric dissolved organic matter (CDOM) in whole and C₁₈ extracted rainwater. The average total recovery of fluorescence determined from the sum of extract and filtrate fractions relative to the whole was 86% suggesting that 14% of fluorescent CDOM in rainwater is comprised of very hydrophobic material that cannot be eluted from the column. Half the fluorescence of rainwater was recovered in the filtrate fraction which is important because it suggests that 50% of the chromophoric material present in precipitation is relatively hydrophilic. The average spectral slope coefficient was smaller in extracted samples (16.3 ± 9.0 μm^?1) relative to whole samples (18.9 ± 2.8 μm^?1) suggesting that the extracted material contains larger molecular weight material. Approximately one-third of the total dissolved organic carbon (DOC) in rainwater exists in the extract fraction suggesting that a large percentage of the uncharacterized DOC in rainwater can be accounted for by these hydrophobic macromolecular species. The fluorescence of extracted samples is strongly correlated with total NMR integration and is most sensitive to aromatic protons suggesting that molecules in this region are the most important in controlling the optical properties of rainwater. The lower removal efficiency of CDOM in rainwater relative to surface waters or the water-soluble fraction of aerosols during solid phase extraction (SPE) suggests that rainwater contains significantly more hydrophilic chromophoric compounds which are compositionally different than found in these other aquatic matrices.     

Column- and catchment-scale transport of cadmium: effect of dissolved organic matter

In the Ellen catchment on the Pinjarra Plain, NE of Perth in Western Australia, cadmium from fertilisers is starting to leach from soils. About 70% of surface soils in the Ellen catchment are sandy and often on top of a shallow ephemeral water table. Adsorption of Cd in the sandy soils of the Ellen catchment was studied by batch adsorption and by leaching small columns of soil. Adsorption of Cd increases linearly with increasing soil organic matter content and exponentially with increasing pH. Cadmium is significantly mobilised in the sandy soils by dissolved organic matter.The capacity of most of the sandy soils in the Ellen catchment to adsorb phosphate from fertiliser has been saturated. Resulting concentrations in Ellen Brook average 500 μg L⁻¹ P. Cadmium is adsorbed more strongly in the sandy soils than phosphate and is just starting to leach into Ellen Brook. From a comparison of Cd/P ratios in water, soils and fertiliser, cadmium concentrations in Ellen Brook are estimated to be at 10–30% of their maximum for complete breakthrough from soils. Present concentrations of Cd in Ellen Brook average 0.1 μg L⁻¹ and are estimated to approach the maximum for complete breakthrough in 100 yr. Maximum Cd concentrations in Ellen Brook could range from 0.6 to 2 μg L⁻¹, depending on rates of input with fertiliser and future increases in agricultural land use in the catchment.Breakthrough curves, resulting from leaching Cd through small columns of sandy soil, indicate that adsorption significantly increases the effective hydrodynamic dispersion of Cd. Longitudinal dispersivities, measured at pore-water velocities of 0.7–14 m day⁻¹, were 5 cm for Cd and 0.1–0.2 cm for chloride. The much greater dispersion of Cd in the sandy soils than of chloride is shown not to be caused by non-equilibrium adsorption.     

水体溶解性有机物的化学分级表征：原理与方法

综述了水体溶解性有机物（DOM）的化学分级表征法即树脂吸附分级法（RA）的研究与进展，同时基于该方法存在的一些问题结合我国典型水质体系，从树脂的选择、净化、分级的定义、水样过柱流速、水样树脂体积比的确定等方面进行了研究探讨，给出了完整的实验参数和操作方法。     

Association of benzo(a)pyrene with dissolved organic matter: Prediction of Kdom from structural and chemical properties of the organic matter

The affinity of dissolved organic matter (DOM) for binding a polycyclic aromatic hydrocarbon, benzo(a)pyrene (BaP), was measured for 11 surface and ground waters and a commercial humic acid. The hydrophobic-acid (HbA) and hydrophobic-neutral (HbN) compositions of the DOM, solution absorptivity at 270nm (ABS₂₇₀), and DOM molar volumes were determined. Waters enriched in HbA material had a larger molar volume and higher aromatic content (as indicated by the ABS₂₇₀). There was a good correlation between the size and HbA content of the DOM from the different sources and the K_dom for binding BaP. An excellent predictive relationship (r² = 0.9) was demonstrated between the ABS₂₇₀ of a water and the K_dom for binding BaP. Based on these results, it is suggested that binding of BaP to DOM depends not only on the hydrophobicity of DOM, but also on the existence of an open structure within the DOM to provide access of the aqueous solute to hydrophobic domains within the DOM.     

Analysis of adsorption processes of dissolved organic matter (DOM) on ferrihydrite using surrogate organic compounds

Environmental Science and Pollution Research - Ferrihydrite (Fh) has been recently used in water treatment for removing dissolved organic matter (DOM), but its governing interactions with...     

Microbial degradation of dissolved organic matter (DOM) and its influence on phenanthrene-DOM interactions

Microbial degradation-induced changes in the characteristics of dissolved organic matter (DOM), and the subsequent effects on phenanthrene-DOM interactions were investigated based on the microbial incubation of DOM collected from four different sources for 28 d. Partially biodegraded DOM presented higher specific UV absorbance (SUVA), lower protein-like fluorescence, higher humic-like fluorescence, lower aliphatic carbon fraction, and higher hydrophobic neutral fractions compared to the original DOM. Microbial changes in DOM led to an increase in the isotherm nonlinearity as well as the extent of phenanthrene binding. A negative relationship between SUVA and the Freundlich n values was established for the original and the biodegraded DOM, suggesting that aromatic condensed structures may play important roles in providing nonlinear strong binding sites irrespective of microbial degradation. In contrast, there were two separate slopes of the correlations between the percentage of hydrophobic acid (HoA) fraction and the n values for the original and the biodegraded DOM with a higher slope exhibited for the latter, implying that the microbial utilization of oxygen-containing structures in the HoA fractions may contribute to enhancing the associated isotherm nonlinearity.     

Investigating interactions of phenanthrene with dissolved organic matter: limitations of Stern-Volmer plot

Although linear binding isotherms of hydrophobic organic chemicals (HOCs) with dissolved organic matter (DOM) are widely reported, several studies showed nonlinear HOC-DOM interactions. This study pointed out that fluorescence static quenching modeling (FSQM), which often uses a Stern-Volmer type plot to process the data from fluorescence quenching experiments, is conceptually different from the classic Stern-Volmer equation. We also emphasized that although linear Stern-Volmer plots are generally observed in literature, it does not necessarily indicate a linear HOC-DOM interaction. According to both mathematical simulation and laboratory sorption experiments in this study, nonlinear interactions could be concealed by the use of Stern-Volmer plot. Moreover, this study tested the two assumptions for applying FSQM to process binding data. Our results showed that binding coefficient (K(DOC)) for phenanthrene is neither independent of free solute concentration, nor DOM concentration, which is a critical limitation for using FSQM in a form of Stern-Volmer equation to examine HOC-DOM interactions. Therefore, the true characteristics of HOC-DOM interactions need to be examined using different ways of experimental design and data processing.     

Spatial variation of organochlorine pesticides and dissolved organic matter in urban closed lakes

Abstract

Closed lakes located in urban parks act as sinks of organochlorine pesticides (OCPs), which have been used, for decades, as insecticides, herbicides and fungicides. The closed lakes from Bucharest, Romania, are periodically managed to prevent eutrophication and accumulation of pollutants. However, it is not known if these practices reduce or enhance the legacy pollution with OCPs. The aim of this study was to explore the spatial variation of OCPs in closed lakes. The total concentration of OCPs in water and sediments ranged between 0.0176 and 37.1?µg/L, and between 122 to 1,890?ng/g, respectively. The concentrations of OCPs were compared with the consensus-based sediment quality guidelines (SQGs) in order to evaluate the ecological risks of sediments. The highest potential adverse effects were associated with γ-HCH exposure. Periodical draining and dredging of lakes lead to the resuspension of contaminants, increasing pesticide bioavailability and accumulation in sediments. In addition, we observed that fluorescent dissolved organic matter (DOM) might influence the OCPs cycle. The quantity and character of fluorescent DOM can provide further insight into OCPs degradation. Also, this study may help urban planners to determine the state of urban waters and to find the best solution for water management.     

Effect of short-term sunlight irradiation on absorbance spectra of chromophoric organic matter dissolved in coastal and riverine water

Samples of riverine and coastal, filtered (filter pore size 0.2 μm) water were exposed to short-term sunlight irradiation which reduced their absorbance in the UV and visible regions. Absorbance losses in coastal chromophoric dissolved organic matter (CDOM) were up to 10-fold smaller than those in riverine CDOM. Accompanying changes of absorbance spectra shapes (increased slope parameter) were, probably, a result of decrease of the mean molecular size of light absorbing organic matter. The potential of coastal CDOM to photodegradation was smaller and was exhausted during the course of a day-long experiment. A distinctive feature of spectral changes after sunlight exposure was a maximum absorbance decrease which appeared at 300 nm in riverine and at 280 nm in coastal water. That selective absorbance loss has been ascribed in both cases to the disappearance of chromophores of terrestrial origin which, in coastal water, had a lower mean molecular size (due to flocculation and/or prior photodegradation) but, nevertheless, retained their molecular properties.     

矿化垃圾反应床处理垃圾渗滤液出水中的水溶性有机物

以矿化垃圾反应床处理垃圾渗滤液出水(以下简称尾水)为研究对象,采用国际上最常用的树脂联用法,对其进行梯度分离表征.研究结果表明,憎水性腐殖质对尾水COD和溶解性有机碳(DOC)的贡献分别为42.55%和45.12%,准亲水性物质对尾水中COD和DOC的贡献分别为34.89%和37.14%,憎水性腐殖质和准亲水性物质是尾水中水溶性有机物(DOM)的重要组成部分.近紫外区域吸光度分析发现,尾水中含有大量带共轭双键或苯环的有机物质,这些物质从尾水中去除后,尾水在近紫外区域的吸光度明显下降.分子量分布显示.尾水中DOM的分子量主要集中在2 000 u以下.元素分析和红外光谱结果显示,胡敏酸(HA)和富里酸(FA)带有苯环结构,存在醇羟基或酚羟基及羧酸官能团;准亲水性物质含有较多的羧酸官能团,另外存在一定置的羟基官能团,同时还可能含有三键和双键的结构.     

Sources of fluorescent dissolved organic matter in high salinity seawater (Bohai Bay, China)

Fluorescent dissolved organic matter (FDOM) identified in coastal waters within a large salinity range had been widely reported in previous studies, which stated that conservative mixing of terrestrially derived and river-transported FDOM by clear seawaters could account for the relatively low FDOM fluorescence signals in high salinity seawaters. This study aimed at testing the conservative mixing model in high salinity seawaters in a shallow bay (Bohai Bay, China) with low river flow in a dry season. The water showed high salinities varying in a narrow range (30.52???2.07), and salinity effects on fluorescence quantum yields therefore less likely introduced complications to fluorescence data analyses. By applying a parallel factor analysis to fluorescence excitation emission matrices of the water samples, we identified a tyrosine-like FDOM component, a tryptophan-like FDOM component, and two humic substances-like FDOM components. Based on a theoretical analysis, we found that dissolved organic carbon concentrations and suspended solid concentrations of the bulk-water samples as well as the maximum fluorescence signals of each identified FDOM component showed spatial distributions that could not be accounted for by the conservative mixing model. Marine autochthonous processes including microbial activities and FDOM releasing from resuspended sediment were likely to be invoked.     

Effect of ozone pretreatment on characteristics of dissolved organic matter formed in aerobic and anaerobic digestion of waste-activated sludge

Environmental Science and Pollution Research - The characteristics of dissolved organic matter (DOM) formed in aerobic and anaerobic digestion of waste-activated sludge (WAS) after ozone...     

The effects of dissolved organic matter and pH on sampling rates for polar organic chemical integrative samplers (POCIS)

The effect of solution pH and levels of dissolved organic matter (DOM) on the sampling rates for model pharmaceuticals and personal care products (PPCPs) and endocrine disrupting substance (EDS) by polar organic chemical integrative samplers (POCIS) was investigated in laboratory experiments. A commercially available POCIS configuration containing neutral Oasis HLB (hydrophilic-lipophilic balance) resin (i.e. pharmaceutical POCIS) and two POCIS configurations prepared in-house containing MAX and MCX anion and cation exchange resins, respectively were tested for uptake of 21 model PPCPs and EDS, including acidic, phenolic, basic and neutral compounds. Laboratory experiments were conducted with dechlorinated tap water over a pH range of 3, 7 and 9. The effects of DOM were studied using natural water from an oligotrophic lake in Ontario, Canada (i.e. Plastic Lake) spiked with different amounts of DOM (the concentration of dissolved organic carbon ranged from 3 to 5 mg L⁻¹ in uptake experiments). In experiments with the commercial (HLB) POCIS, the MCX-POCIS and the MAX-POCIS, the sampling rates generally increased with pH for basic compounds and declined with pH for acidic compounds. However, the sampling rates were relatively constant across the pH range for phenols with high pKa values (i.e. bisphenol A, estrone, estradiol, triclosan) and for the neutral pharmaceutical, carbamazepine. Thus, uptake was greatest when the amount of the neutral species in solution was maximized relative to the ionized species. Although the solution pH affected the uptake of some model ionic compounds, the effect was by less than a factor of 3. There was no significant effect of DOM on sampling rates from Plastic Lake. However, uptake rates in different aqueous matrixes declined in the order of deionized water > Plastic Lake water > dechlorinated tap water, so other parameters must affect uptake into POCIS, although this influence will be minor. MAX-POCIS and MCX-POCIS showed little advantage over the commercial POCIS configuration for monitoring in natural waters.     

O3/ H2O2法对生化出水中不同种类有机物的去除效果研究

采用XAD-8/XAD-4吸附树脂联用技术将城市污水生化出水中有机物分为疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物,研究了O3/H2O2法对这4类有机物的去除效果.结果表明:(1)O3/H2O2法对生化出水中有机物的去除效果明显好于O3法、H2O2法.反应60 min时,O3/H2O2法对溶解有机碳(DOC)和254 nm波长处的单位比色皿光程下的紫外吸光度(UV254)的去除率分别达到49%和82%.(2)生化出水经O3/H2O2处理后,一部分疏水性有机物(疏水酸和非酸疏水物质)在反应过程中转化为亲水性有机物(弱疏水物质和亲水物质).(3)生化出水中71%的三卤甲烷生成势(THMFP)由疏水酸和亲水物质产生,特别是疏水酸,其产生的THMFP占总量的48%.反应60 min时,O3/H2O2法对疏水酸、非酸疏水物质、弱疏水物质和亲水物质产生的THMFP的去除率分别为64%、100%、88%和18%.