城市污水二级出水中溶解性有机物特性分析

分别采用凝胶色谱、亲疏水性组分分离、荧光色谱等方法,研究了城市污水处理厂二级出水中溶解性有机物的分子量分布、亲疏水组分含量以及荧光光谱特性。结果表明,二级出水中疏水性组分较亲水性组分多,疏水性组分约占总有机物的64.3%,而亲水性组分占35.7%左右;二级出水及其不同亲/疏水组分中溶解性有机物分子量分布基本集中在4.5 kDa以下,其中弱疏水性组分和亲水性组分中主要为分子量小于1.5 kDa的有机物;二级出水溶解性有机物中含有腐殖酸类、富里酸类以及蛋白质类物质,其中含量以腐殖酸类为主。     

Comparison of structural features of water-soluble organic matter from atmospheric aerosols with those of aquatic humic substances

Elemental analysis, Fourier transform infrared coupled to attenuated total reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning-¹³C-nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopies were used to compare the chemical features of water-soluble organic compounds (WSOC) from atmospheric aerosols with those of aquatic humic and fulvic acids. The influence of different meteorological conditions on the structural composition of aerosol WSOC was also evaluated. Prior to the structural characterisation, the WSOC samples were separated into hydrophobic acids and hydrophilic acids fractions by using a XAD-8/XAD-4 isolation procedure. Results showed that WSOC hydrophobic acids are mostly aliphatic (40–62% of total NMR peak area), followed by oxygenated alkyls (15–21%) and carboxylic acid (5.4–13.4%) functional groups. Moreover, the aromatic content of aerosol WSOC samples collected between autumn and winter seasons is higher (∼18–19%) than that of samples collected during warmer periods (∼6–10%). The presence of aromatic signals typical of lignin-derived structures in samples collected during low-temperature conditions highlights the major contribution of wood burning processes in domestic fireplaces into the bulk chemical properties of WSOC from aerosols. According to our investigations, aerosol WSOC hydrophobic acids and aquatic fulvic and humic acids hold similar carbon functional groups; however, they differ in terms of the relative carbon distribution. Elemental analysis indicates that H and N contents of WSOC hydrophobic acids samples surpass those of aquatic fulvic and humic acids. In general, the obtained results suggest that WSOC hydrophobic acids have a higher aliphatic character and a lower degree of oxidation than those of standard fulvic and humic acids. The study here reported suggests that aquatic fulvic and humic acids may not be good models for WSOC from airborne particulate matter.     

Influence of temperature and origin of dissolved organic matter on the partitioning behavior of polycyclic aromatic hydrocarbons

Background, aim, and scope  

The behavior of polycyclic aromatic hydrocarbons (PAHs) is affected by dissolved organic matter (DOM) present in pore water of soils and sediments. Since partitioning to DOM reduces the bioavailable or freely dissolved PAH concentration in pore water, it is important to assess the effect of environmental variables on the magnitude of dissolved organic matter to water partition coefficients (K _DOC). The objective of this study was to apply passive samplers to measure freely dissolved PAHs allowing depletion from the aqueous phase. The method was applied to determine K _DOC at different temperatures for a selection of PAHs with natural DOM of very different origin.     

Organic compounds adsorption onto activated carbon: the effect of association between dissolved humic substances and pesticides

The quantitative determination of pesticide binding to dissolved humic substances is relevant to both water treatment operation using activated carbon adsorption process and the application of transport models that predict the environmental distribution patterns of a given hydrophobic contaminant. In this study and in a first set of experiments, the extent of binding between (i) three pesticides of environmental concern, aldicarb, lindane and pentachlorophenol, and (ii) dissolved commercial humic acid and soil extracted fulvic acid, was determined using dialysis experiments and water solubility enhancement tests. In a second set of experiments, the influence of dissolved humic substances or pesticide on the retention of the other co-adsorbate onto activated carbon was investigated in binary systems. It was found that association was negligible for aldicarb and that the pesticide sorption onto activated carbon was not affected by humic acid (8.5 mg liter(-1) DOC). The association constants K for lindane and pentachlorophenol were identical in the presence of fulvic acid (logK=4.1) but lower than that observed with humic acid. In the presence of humic acid, binding affinity for pentachlorophenol (logK=4.6) was higher than the one observed for lindane (logK=4.4), despite its much higher water solubility. This observation suggests that the aromatic character of the pentachlorophenol molecule contributes to association interactions with humic acid. From co-adsorption experiments onto activated carbon it was found that fulvic acid (7.7 mg litre(-1) DOC) slightly enhances sorption kinetics of pentachlorophenol. Lindane (1 mg litre(-1)) does not affect sorption kinetics for fulvic acid but markedly enhances both the sorption kinetics and adsorptive capacity for humic acid. Activated carbon retention of dissolved humic substances or pesticide appears to be enhanced by the association potential that exists between these co-adsorbates in some binary systems.     

Copper binding by peat fulvic and humic acids extracted from two horizons of an ombrotrophic peat bog

We studied the binding of Cu(II) to humic acids and fulvic acids extracted from two horizons of an ombrotrophic peat bog by metal titration experiments at pH 4.5, 5.0, 5.5, and 6.0 and 0.1 M KNO3 ionic strength. Free metal ion concentrations in solution were measured using an ion selective electrode. The amounts of base required to maintain constant pH conditions were recorded and used to calculate H+/Cu2+ exchange ratios. The amount of Cu(II) bound to the humic fractions was greater than the amount bound to the fulvic fractions and only at the highest concentrations of metal ion the amount of Cu(II) sorbed by both fractions became equal. The proton to metal ion exchange ratios are similar for all humic substances, with values ranging from 1.0 to 2.0, and decreasing with increased pH. The amount of Cu(II) bound is practically independent of the horizon from which the sample was extracted. The results indicate that the humic substances show similar cation binding behaviour, despite the differences in chemical composition. The copper binding data are quantitatively described with the NICA-Donnan model, which allows to characterize only the carboxylic type binding sites. The values of the binding constants are higher for the humic acids than for the fulvic acids.     

The fate of dissolved organic carbon (DOC) in the wastewater treatment process and its importance in the removal of wastewater contaminants

Goal, Scope and Background Dissolved organic carbon (DOC) constitutes a parameter of organic pollution for waters and wastewaters, which is not so often studied, and it is not yet regulated by directives. The term ‘DOC’ is used for the fraction of organics that pass through a 0.45 μm pores’ size membrane. The type of wastewater plays an important role in the quality of DOC and it has been shown that DOC may contain aquatic humic substances, hydrophobic bases, hydrophobic neutrals, hydrophilic acids, hydrophilic bases and hydrophilic neutrals. The quality of the DOC is expected to affect its fate in a wastewater treatment plant (WWTP), since a considerable fraction of DOC is not biodegradable, and it may be released in the aquatic environment together with the treated effluent. In the present study, the occurrence of DOC during the wastewater treatment process is investigated and its removal rates during primary, secondary and overall treatment are being estimated. Furthermore, a correlation is being attempted between DOC and the concentrations of selected Persistent Organic Pollutants (POPs) and Heavy Metals (HMs) in the dissolved phase of wastewaters, to examine whether there are common sources for these pollution parameters in WWTPs. Also, DOC is being correlated with the partition coefficients of the above-mentioned pollutants in wastewater, in order to examine the effect of ‘solubility enhancement’ in WWTPs and to evaluate the result of this phenomenon in the efficiency of a WWTP to remove organic pollutants. Methods For the purposes of this study, 24-h composite wastewater samples were collected from the influent (raw wastewater, RW), the effluent of primary sedimentation tank (primary sedimentation effluent, PSE) and the effluent of secondary sedimentation tank (secondary sedimentation effluent, SSE). Samples were analyzed for the presence of 26 POPs (7 PCBs and 19 organochlorine pesticides), 8 HMs and DOC. Results and Discussion Mean concentrations of DOC in RW and PSE were at similar levels (∼ 70 mg l⁻¹), suggesting that primary treatment has a minor effect on the DOC content of wastewater. DOC concentrations in SSE were significantly lower (∼ 19 mg l⁻¹) as a result of the degradation of organic compounds in the biological reactor. Calculated removals of DOC were 0.8% in the primary treatment, 63% in the secondary treatment, and 69% in the overall treatment, exhibiting large differences from other organic pollution parameters, such as BOD and COD. The overall DOC removal was found to be independent from the DOC concentration in raw wastewater. Poor correlation was also observed between the DOC content and the concentrations of wastewater contaminants, such as persistent organic pollutants (POPs) and heavy metals (HMs), probably suggesting that their occurrence in WWTPs is due to different sources. A good negative linear relationship was revealed between DOC concentrations and the logarithms of the distribution coefficients (K _d) of various POPs and HMs between the solid and the liquid phases of wastewater. This relationship suggests that DOC facilitates hydrophobic pollutants to remain in the dissolved phase thus causing lower removal percentages during the treatment process. Conclusion DOC was measured at three stages of a municipal WWTP that receives mainly domestic wastewater and urban runoff. DOC concentrations in untreated and primarily treated wastewater were almost equal, and only after the secondary sedimentation there was a decrease. Concentrations and removal rates of DOC were in the same levels as in other WWTPs that receive municipal wastewater. The origin of DOC was found to be different to the one of POPs and of HMs, as no correlation was observed between the concentrations of DOC and the concentrations of these pollutants. On the contrary, DOC was found to have significant negative correlation with the K _d of all pollutants examined, suggesting that it plays an important role in the partitioning of those pollutants between the dissolved and the sorbed phase of wastewaters. This effect of DOC on partitioning can affect the ability of WWTPs to remove toxic pollutants, and that way it facilitates the discharge of those chemicals in the aquatic ecosystems together with the treated effluent. Recommendation By the results of this work it is shown that the presence of DOC in wastewaters can significantly affect the partition of hazardous pollutants between the dissolved and the sorbed phase. It is therefore of importance that this parameter is controlled more in wastewaters, since it can cause a decrease in the efficiency of WWTPs to remove quantitatively persistent pollutants.     

Evidence for a charge-transfer interaction between dissolved humic materials and organic molecules: I. Study of the binding interaction between humic materials and chloranil

Recent evidence indicates that organic environmental contaminants associate with or bind to dissolved humic materials. Binding constants for many systems have been determined, but little is known about the nature of these interactions. Using UV difference spectroscopy we have established the electron donating ability of humic materials and introduced a simple, direct method for measuring binding constants. Chloranil (tetrachlorobenzoquinone), a well known electron acceptor, was combined with Aldrich humic materials (2.7 mg C/l) giving rise to a shift in the chloranil 290 nm band. Spectra of several such solutions with differing chloranil concentrations when analyzed versus a chloranil reference contained a negative peak at this wavelength due to the binding interaction. The concentration of bound chloranil could be directly determined by measurement of the negative peak. The binding constant (K_doc) for the chloranil-humic system was determined to be 1.2 × 10⁵. Binding continued to occur over a period of several weeks, indicating that studies which measured binding constants for relatively short periods of time may have generated binding constants which were lower than those applicable to the environment. A charge transfer mechanism can be postulated for the chloranil-humic system as well as for similar systems.     

Effect of soil and sediment composition on acetochlor sorption and desorption

Background, aim, and scope  Herbicide fate and its transport in soils and sediments greatly depend upon sorption–desorption processes. Quantitative determination of herbicide sorption–desorption is therefore essential for both the understanding of transport and the sorption equilibrium in the soil/sediment–water system; and it is also an important parameter for predicting herbicide fate using mathematical simulation models. The total soil/sediment organic carbon content and its qualitative characteristics are the most important factors affecting sorption–desorption of herbicides in soil or sediment. Since the acetochlor is one of the most frequently used herbicides in Slovakia to control annual grasses and certain annual broad-leaved weeds in maize and potatoes, and posses various negative health effects on human beings, our aim in this study was to investigate acetochlor sorption and desorption in various soil/sediment samples from Slovakia. The main soil/sediment characteristics governing acetochlor sorption–desorption were also identified. Materials and methods  The sorption–desorption of acetochlor, using the batch equilibration method, was studied on eight surface soils, one subsurface soil and five sediments collected from the Laborec River and three water reservoirs. Soils and sediments were characterized by commonly used methods for their total organic carbon content, distribution of humus components, pH, grain-size distribution, and smectite content, and for calcium carbonate content. The effect of soil/sediment characteristics on acetochlor sorption–desorption was examined by simple correlation analysis. Results  Sorption of acetochlor was expressed as the distribution coefficient (K _d). K _d values slightly decreased as the initial acetochlor concentration increased. These values indicated that acetochlor was moderately sorbed by soils and sediments. Highly significant correlations between the K _d values and the organic carbon content were observed at both initial concentrations. However, sorption of acetochlor was most closely correlated to the humic acid carbon, and less to the fulvic acid carbon. The total organic carbon content was found to also significantly influence acetochlor desorption. Discussion  Since the strong linear relationship between the K _d values of acetochlor and the organic carbon content was already released, the corresponding K _oc values were calculated. Considerable variation in the K _oc values suggested that other soil/sediment parameters besides the total soil organic carbon content could be involved in acetochlor sorption. This was revealed by a significant correlation between the K _oc values and the ratio of humic acid carbon to fulvic acid carbon (C_HA/C_FA). Conclusions  When comparing acetochlor sorption in a range of soils and sediments, different K _d values which are strongly correlated to the total organic carbon content were found. Concerning the humus fractions, the humic acid carbon content was strongly correlated to the K _d values, and it is therefore a better predictor of the acetochlor sorption than the total organic carbon content. Variation in the K _oc values was attributed to the differences in distribution of humus components between soils and sediments. Desorption of acetochlor was significantly influenced by total organic carbon content, with a greater organic carbon content reducing desorption. Recommendations and perspectives  This study examined the sorption–desorption processes of acetochlor in soils and sediments. The obtained sorption data are important for qualitative assessment of acetochlor mobility in natural solids, but further studies must be carried out to understand its environmental fate and transport more thoroughly. Although, the total organic carbon content, the humus fractions of the organic matter and the C_HA/C_FA ratio were sufficient predictors of the acetochlor sorption–desorption. Further investigations of the structural and chemical characteristics of humic substances derived from different origins are necessary to more preciously explain differences in acetochlor sorption in the soils and sediments observed in this study.     

Comparison of photochemical behavior of various humic substances in water: III. Spectroscopic properties of humic substances

Spectral absorption coefficients and fluorescence quantum efficiencies were determined for humic substances from a variety of sources. Specific absorption coefficients k_h, for humic substances at wavelengths λ from 300 to 500 nm can be closely described by the relation Ae^B(450-λ), where A and B are constants. When the k_h values are in units of liter (mg organic carbon)^?1meter^?1 and wavelength λ is in nanometers, mean values of A and B for aquatic humus in the 12 water bodies studied were 0.6±0.3 and 0.014±0.001, respectively. Spectral absorption coefficients of dissolved organic matter in blackwater rivers, of the “yellow substance” in the sea, and of fulvic acids extracted from soils are very similar. Fluorescence quantum yields of humic substances were low and more variable than the absorption coefficients, ranging from 0.0005 to 0.012 with excitation at 350 nm (average of 0.0045±0.0038 for 6 waters). Fluorescence spectra for the humic substances were remarkably similar with maximum emission at 430 to 470 nm. Results of this study can be used to compute photolysis rates of pollutants as a function of depth in natural water bodies.     

The effect of pH, ion strength and reactant content on the complexation of Cu2+ by various natural organic ligands from water and soil in Hong Kong

The complexation constants for copper associated with different natural organic ligands, including dissolved organic carbon (DOC) extracted from water, water soluble organic carbon (WSOC), fulvic acid (FA) and humic acid (HA) from soil, were determined and then compared based on discrete single site model. Both ion-selective electrode (ISE) and anodic stripping voltammetry were used to determine the content of free copper ions, while the relative number of complexation sites was estimated using a fluorescence quenching (FQ) at the same time. ISE proved to be the most applicable technique when the concentration of copper was above 10(-7) moll(-1). The logk values for two WSOC sample sites (Song Ziyuan and Xin Niangtan) were 4.64 and 4.66; higher than both the DOC and HA values yet lower than the FA values, which were unusually high due to unavoidable pollution from the cation exchange resin used during the purification process. Binding affinities between the copper ions and the organic ligands obtained from streams in Yong Wei (DOC) and Song Ziyuan (WSOC) were influenced by pH, ion strength, and reactant concentration. Values for logk increased with increases in pH (ion strength of 0.1 N). At pH 4, the logk values decreased with increases in the supporting electrolyte concentration and total copper ion additions.     

Carbaryl, 2,4-D,and Triclopyr Adsorption in Thatch-Soil Ecosystems

Thatch development in intensively managed turf sites may cause environmental concerns for greater sorption or leaching of applied chemicals in terrestrial ecosystems. To determine the adsorption potential of Carbaryl (1-Napthyl N-methylcarbamate), 2,4-D (2,4-dichloro-phenoxyacetic acid), and Triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) in turf ecosystems, composite thatch and underlying soil samples from three- and six-year-old stands of cool-season Southshore creeping bentgrass (Agrostis palustris Huds.) and warm-season Meyer zoysiagrass (Zoysia japonica Steud.) were collected. The samples were processed and analyzed for total organic carbon (C_Org); extractable (C_Ext), humic (C_HA) and fulvic acid (C_FA); anthrone reactive nonhumic carbon (ARC) fractions; and C_HA and C_FA associated iron (Fe) contents. Pesticide adsorption capacity (K _f ) and intensity (1/n), organic carbon partition coefficient (K _OC ) and Gibbs free energy change (Δ G) were calculated for thatch materials and the underlying soils using a modified batch/flow technique. Both bentgrass (BT) and zoysiagrass thatch (ZT) contained a greater concentration of C_Ext, C_FA, C_HA, and ARC than the respective soils (BS and ZS). The C_Ext, C_FA, C_HA, and ARC concentration was higher in BT compared with ZT. The BT contained a greater concentration of bound Fe in both C_FA and C_HA fractions than in BS, whereas ZT had more bound Fe in C_HA fraction than in ZS. On average, the BT had a greater concentration of bound Fe in C_Ext, C_FA, and C_HA fractions than in the ZT. Among the pesticides, Carbaryl had higher K _f and 1/n values than 2,4-D and Triclopyr for both thatch and soil. Although the K _OC and Δ G values of Carbaryl were higher in both BT and ZT than in the underlying soils, the K _OC and Δ G values of 2,4-D were significantly higher in BS and ZS than in the overlying thatch materials. The 2,4-D and Triclopyr had higher leaching indices (LI) than Carbaryl for both BT and ZT materials than the respective soils. The Carbaryl, however, had a higher LI for soils than for thatch materials. Averaged across thatch materials and soils, C_Org accounted for 96, 85, and 84% variations in Carbaryl, 2,4-D, and Triclopyr adsorption, respectively. Among the C_Org fractions, lignin followed by C_FA and C_HA accounted for greater adsorption of pesticides, especially Carbaryl. The concentration of C_HA and C_FA bound Fe did not correlate with K _f and 1/n values of pesticides.     

DOC removal paradigms in highly humic aquatic ecosystems

Background, aim, and scope  Dissolved humic substances (HS) usually comprise 50–80% of the dissolved organic carbon (DOC) in aquatic ecosystems. From a trophic and biogeochemical perspective, HS has been considered to be highly refractory and is supposed to accumulate in the water. The upsurge of the microbial loop paradigm and the studies on HS photo-degradation into labile DOC gave rise to the belief that microbial processing of DOC should sustain aquatic food webs in humic waters. However, this has not been extensively supported by the literature, since most HS and their photo-products are often oxidized by microbes through respiration in most nutrient-poor humic waters. Here, we review basic concepts, classical studies, and recent data on bacterial and photo-degradation of DOC, comparing the rates of these processes in highly humic ecosystems and other aquatic ecosystems. Materials and methods  We based our review on classical and recent findings from the fields of biogeochemistry and microbial ecology, highlighting some odd results from highly humic Brazilian tropical lagoons, which can reach up to 160 mg C L⁻¹. Results and discussion  Highly humic tropical lagoons showed proportionally lower bacterial production rates and higher bacterial respiration rates (i.e., lower bacterial growth efficiency) than other lakes. Zooplankton showed similar δ¹³C to microalgae but not to humic DOC in these highly humic lagoons. Thus, the data reviewed here do not support the microbial loop as an efficient matter transfer pathway in highly humic ecosystems, where it is supposed to play its major role. In addition, we found that some tropical humic ecosystems presented the highest potential DOC photo-chemical mineralization (PM) rates reported in the literature, exceeding up to threefold the rates reported for temperate humic ecosystems. We propose that these atypically high PM rates are the result of a joint effect of the seasonal dynamics of allochthonous humic DOC input to these ecosystems and the high sunlight incidence throughout the year. The sunlight action on DOC is positive to microbial consumption in these highly humic lagoons, but little support is given to the enhancement of bacterial growth efficiency, since the labile photo-chemical products are mostly respired by microbes in the nutrient-poor humic waters. Conclusions  HS may be an important source of energy for aquatic bacteria in humic waters, but it is probably not as important as a substrate to bacterial growth and to aquatic food webs, since HS consumption is mostly channeled through microbial respiration. This especially seems to be the case of humic-rich, nutrient-poor ecosystems, where the microbial loop was supposed to play its major role. Highly humic ecosystems also present the highest PM rates reported in the literature. Finally, light and bacteria can cooperate in order to enhance total carbon degradation in highly humic aquatic ecosystems but with limited effects on aquatic food webs. Recommendations and perspectives  More detailed studies using C- and N-stable isotope techniques and modeling approaches are needed to better understand the actual importance of HS to carbon cycling in highly humic waters.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Semi-empirical estimation of sorption of hydrophobic pollutants on natural sediments and soils

Methods were developed for estimating the equilibrium sorption behavior of hydrophobic pollutants. At low pollutant concentration (aqueous phase concentration less than half the solubility), sorption isotherms were linear, reversible, and characterized by a partition coefficient, K_p. Partition coefficients normalized to organic carbon, K_OC ($\text{K}{}_{\mathrm{OC}}\text{=}\text{K}{}_{\mathrm{p}}\text{fraction}$ organic carbon), were highly invariant over a set of sediments and soils collected from throughout the nation. Equations for estimating K_OC from water solubility (including crystal energy) and octanol/water partition coefficients were developed. The predictive equations were tested on literature sorption data and found to estimate measured K_OC's generally within a factor of two.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'_W) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb_T) in pure water. Experimental breakthrough volumes (Vb_E) were first determined using purified and deionized water as the matrix for selected compounds having Vb_T < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4–5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb_E curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5–6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb_E in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

铁盐和铝盐混凝对印染废水生化出水中溶解性有机污染物的去除特性

以三氯化铁和硫酸铝为混凝剂,印染废水二级生化出水为研究对象,并利用XAD-8/XAD-4吸附树脂联用技术将印染废水生化出水中溶解性有机物分为疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物,通过小试实验探讨了2种混凝剂对生化出水中各类溶解性有机物的去除效果及特点。实验结果表明,对于该印染废水的生化出水,溶解性有机物的主要成分是疏水性物质,以DOC表征时占总DOC的75%,其中疏水酸约占41%,疏水性物质也是引起色度的主要物质,所占比例以ADMI7.6表征时为89%,其中以非酸疏水物质的贡献最大,达到52%,并且非酸疏水物质中不饱和双键或芳香环有机物的含量较高。在三氯化铁和硫酸铝各自最佳的混凝条件下,均能够有效去除由疏水性物质（疏水酸和非酸疏水物质）引起的色度,但三氯化铁对弱疏水性物质以及亲水物质的去除率高于硫酸铝,这使得三氯化铁对印染废水生化出水中的溶解性有机物的去除效果优于硫酸铝。并且三氯化铁和硫酸铝混凝工艺均能明显降低生化出水的毒性。     

Distribution of PAHs and PCBs to dissolved organic matter: high distribution coefficients with consequences for environmental fate modeling

Dissolved organic carbon/water distribution coefficients (K(DOC)) were measured for a selection of PCBs with octanol/water partition coefficients (K(OW)) ranging from 10(5.6) to 10(7.5). A solid phase dosing and sampling technique was applied to determine K(DOC) to Aldrich humic acid. This technique is in particular suitable for determining the distribution of very hydrophobic chemicals to complex matrices like humic acids. The K(DOC) values were calculated from the experimental data using a linear model. Determined K(DOC)'s were evaluated in relation to octanol/water partition coefficients of the test compounds, and compared to literature data. Measured K(DOC) values were somewhat higher than literature data, which can probably be attributed to the overestimation of freely dissolved aqueous concentration as a result of incomplete phase separation in other studies, and to the unique character of Aldrich humic acid as a "sorbent" or co-solute or to the fact that Aldrich humic acid is not a typical DOC, and other (adsorption) processes can occur. This study reports DOC distribution coefficients that belong to the highest ones ever measured. In addition, the DOC distribution was discussed in relation to current risk assessment modeling.     

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.     

Influence of dissolved humic substances on the leaching of MCPA in a soil column experiment

The influence of dissolved humic substances on the transport of (4-chloro-2-methylphenoxy) acetic acid (MCPA) in a sandy soil with a low organic carbon content was studied in a column experiment. Soil columns were eluted with aqueous solutions containing different fractions of humic substances. More than 70% of the applied compound was found in the leachate in all sandy soil experiments, but distinct differences were obtained depending on the composition of the eluent. The addition of both humic and fulvic acids to the eluent affected the leaching behaviour of MCPA. While the presence of humic acids increased and accelerated the movement of MCPA in the investigated sandy soil, fulvic acids caused the opposite effect: increased retention was observed relative to the control. We concluded that a possible carrier transport or retention strongly depends on the composition of the dissolved organic matter. Thus, changes in the composition of dissolved organic matter may affect MCPA movement into deeper soil layers.     

Partition of Volatile Organic Compounds in Activated Sludge and Wastewater

Abstract

The Henry’s law constant is important in the gas-liquid mass transfer process. Apparent dimensionless Henry’s law constant, or the gas-liquid partition coefficient (K’ _H), for both hydrophilic (methanol, isopropyl alcohol, and acetone) and hydrophobic (toluene and p-xylene) organic compounds in deionized (DI) water, a wastewater with a maximum total dissolved organic carbon (DOC) content of 700 mg/L, and DI water mixed with a maximum activated sludge suspended solid (SS) concentration of 40,000 mg/L were measured using the single equilibrium technique at 293 K.

Experimental results demonstrate that the K’ _H of any of the test volatile organic compounds varied among three situations. First, the K’_H of the hydrophilic compounds in mixed liquor with the maximum SS concentration was 9–21% higher than those in DI water. Second, those for toluene and p-xylene were 77% and 93% lower, respectively, in the mixed liquor with the maximum SS concentration. Third, the K’_H values of all of the test compounds in the wastewater were only 10% lower than those in DI water.

A model was developed to relate K’ _H with wastewater DOC and the SS concentration in the activated sludge using an organic carbon-water partition coefficient and activated sludge-water partition coefficient as model parameters. The model was verified and model parameters for test compounds estimated.