Bioavailability of hydrophobic organic contaminants and quality of organic carbon

U.S. laws require that contaminant bioaccumulation potential be evaluated before dredged material can be recycled. Simple fugacity models, e.g. organic contaminant aqueous partition coefficient (K _oc)-derived theoretical bioaccumulation potential, are commonly used to estimate the partitioning of hydrophobic organic contaminants between sediment organic matter and organism lipid. K _oc-derived models, with or without the addition of a soot carbon term, did not accurately or consistently predict total polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls partitioning of eight sediments from ongoing dredging operations onto C₁₈-coated filter paper. These models also failed to predict the partitioning of individual PAHs from these eight sediments. These data underscore the trade-offs between the ease of using simple models and the uncertainty of predicted partitioning values.     

Controlling various contaminants in wastewater effluent through membranes and engineered wetland

For effective wastewater reclamation and water recovery, the treatment of natural and effluent organic matters (NOM and EfOM), toxic anions, and micropollutants was considered in this work. Two different NOM (humic acid of the Suwannee River, and NOM of US and Youngsan River, Korea), and one EfOM from the Damyang wastewater treatment plant, Korea, were selected for investigating the removal efficiencies of tight nanofiltration (NF) and ultrafiltration (UF) membranes with different properties. Nitrate, bromate, and perchlorate were selected as target toxic anions due to their well known high toxicities. Tri-(2-chloroethyl)-phosphate (TCEP), oxybenzone, and caffeine, due to their different K _ow and pK _a values, were selected as target micropollutants. As expected, the NF membranes provided high removal efficiencies in terms of all the tested contaminants, and the UF membrane provided fairly high removal efficiencies for anions (except for nitrate) and the relatively hydrophobic micropollutant, oxybenzon. Through the wetlands, nitrate was successfully removed. Therefore, a fair process of combining membranes with an engineered wetland could be proposed for sustainable wastewater reclamation and optimum control of contaminats.     

Adsorption and partition of benzo(a)pyrene on sediments with different particle sizes from the Yellow River

Experiments have been carried out to study the sorption of Benzo(a)pyrene(Bap) on sediment particles from the Yellow River using a batch equilibration technique. Effects of particle size on the adsorption and partition of Bap were investigated with the particle content of 3 g/L. Several significant results were obtained from the study. (1) Isotherms of Bap could be fitted with the dual adsorption-partition model under different particle sizes, and the measured value of the adsorption and partition was in agreement with the theoretical value of the dual adsorption-partition model. (2) When the particle diameter was d ? 0.025 mm, the adsorption was predominant in the sorption of Bap, which accounted for 68.7%–82.4% of the sorption. For the particles with the size of 0.007 mm?d<0.025 mm, the adsorption was predominant when the equilibrium concentration of Bap was 0–8.87 μg/L in the water phase; and the partition was predominant when the equilibrium concentration of Bap was higher than 8.87 μg/L in the water phase. When the particle diameter was d<0.007 mm, the partition was predominant. (3) On the point of particle size, the contribution of adsorption to sorption followed the order: “d?0.025 mm”>“0.007 mm ?d<0.025 mm” >“d<0.007 mm”. (4) The partition coefficients of Bap in solids with different particle sizes were linearly correlated with the organic content, and the K _oc of Bap was about 1.26 × 10⁵ (L/kg).     

土壤与沉积物对多环芳烃类有机物的吸附作用

吸附作用是疏水性有机物在土壤和沉积物环境中的重要迁移转化行为之一。多环芳烃是环境中一种重要的疏水性有机污染物。文章着重阐述了多环芳烃类有机物在土壤和沉积物中有机质和粘土矿物吸附机理，指出土壤、沉积物有机质的结构异质性是导致非线形吸附的重要原因；分析了影响多环芳烃吸附过程的诸多因素，并提出该研究领域存在的问题以及今后发展的方向。     

Adsorption of pesticides by salorthids and camborthids of Punjab,Pakistan

This study was conducted to examine adsorption of pesticides bifenthrin, carbosulfan, λ-cyhalothrin, cypermethrin, endosulfan, parathion methyl, monocrotophos and 4-nitrophenol by sandy clay loam (S.C.L) and sandy loam (S.L) soils (with varying organic content). There was no significant difference between the observed soil water partitioning coefficient values (K _d) derived from linear and nonlinear Freundlich isotherms. Adsorption of pesticides on S.C.L soils was higher than those on S.L soils. K _d values showed significant correlations (r ²?=?0.8???0.99 and 0.65???0.97) with soil organic carbon content (OC) and weak correlations (r ²?=?0.2???0.29 and 0.1???0.18) with clay contents of S.C.L and S.L soil at p?≤?0.05, respectively for all pesticides (except monocrotophos). Observed K _oc values (soil-water partitioning constants based on the organic C fraction of the soil) were in accordance with the literature values of Wauchope and Tomlin with a maximum deviation of less than 0.5 log units. Ten Quantitative Property-Property Relationships (QPPR) among water solubility, n-octanol water coefficient (K _ow) and K _oc were proposed for studied pesticides except monocrotophos. The models were considered acceptable when predicted-observed difference for log?K _ow and log?K _oc were ≤?0.3 and ≤?0.5?log units, respectively, during the validation procedure. This work indicates that the log?K _oc derived from the log K_ow, from some of existing relationships, may be a fair predictor where observed values (i.e., K _d and K _oc) are not available. Furthermore, predicted leaching potential by groundwater ubiquity scores (GUS) equation was solved by using observed K _oc values and literature reported half lives of pesticides. GUS ranked the mobility of nonvolatile compounds i.e., bifenthrin, λ-cyhalothrin, cypermethrin and endosulfan extremely low; methyl parathion very low; 4-nitrophenol low; carbofuran and monocrotophos very high in S.C.L and S.L soils, respectively. Results discussed in this paper provide background to prioritize pesticides or chemical groups that should be evaluated under field conditions with regard to their leaching potential to groundwater in arid climates.     

基于TLSER和QSPR关系预测PAHs和PCBs的LDPE膜-空气分配系数

有机污染物在被动采样材料与环境介质之间的平衡分配系数(K_P),是测定环境中有机污染物浓度的重要参数,但K_P值大部分都需要经过繁琐的实验测定获取,无法逐个测定数量繁多的污染物,因此需开发一种预测K_P值的方法。为此,搜集整理了一些多环芳香烃(PAHs)和多氯联苯(PCBs)的低密度聚乙烯(LDPE)-空气分配系数(K_PA)的实测值,基于理论线性溶解能(TLSER)和定量结构性质关系(QSPR),利用逐步多元线性回归(MLR)分别构建了预测K_PA值的模型。模型的决定系数R2adj分别为0.927和0.956,交叉验证系数Q2LOO分别为0.915和0.946,外部系数Q2ext分别为0.913和0.960。结果表明,2种模型具有良好的拟合优度、稳健性和预测能力,并解释了模型的机理。所构建的2种模型均可用来预测应用域内有机污染物的LDPE膜-空气分配系数。     

Abiotic association of phthalic acid esters with humic acid of a sludge landfill

The abiotic association between phthalic acid esters (PAEs) and humic substances (HS) in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with ¹⁴C-labeling was used to study the abiotic association of two abundant PAEs (diethyl phthalate and di-n-butyl phthalate) with humic acid (HA) isolated from a sludge landfill with different stabilization times and different molecular weights. Elemental analysis and Fourier Transform Infrared Spectrophotometer (FTIR) suggested that high K _A value of HA was related to the high aromatic content and large molecular weight of HA. The results indicated that the association strength of PAEs with HA depended on both the properties of the PAEs and the characteristics of HA. The K _A values of the association were strongly dependent on solution pH, and decreased dramatically as the pH was increased from 3.0 to 9.0. The results suggested that nonspecific hydrophobic interaction between PAEs and HA was the main contributor to the association of the PAEs with HA. The interactive hydrogen-bonds between the HA and the PAEs molecules may also be involved in the association.     

Metal partitioning in sediment pore water from the Ondo coastal region,Nigeria

Distribution and equilibrium partitioning of metals (Cd, Cu, Cr, Fe, Ni, Pb, Mn, and Zn) between pore water and surface sediments at the Ilaje coast of Ondo State, Nigeria, were studied. The Ilaje River can be one of the interesting research locations because of its economic nature and history of oil pollution. Seasonal variations were observed to investigate possible variations in the availability of metals for organisms throughout the year. The concentrations in both sediments and pore water during the dry and wet seasons were as follows: Cu?>?Fe???Mn?>?Pb?>?Ni?>?Cr?>?Cd?>?Zn. The pore water–sediment partition coefficient (K _p) showed that Zn and Cd were highly mobile while Fe and Cu have restricted mobility. Dissolved organic carbon (DOC) in pore water had a strong influence on mobility and bioavailability of all the metals (p?K _oc), increased levels of Fe and Cu were linked to lithological origin. Concentrations of Pb and Ni were associated with petroleum-related sources. The significance of the field-based techniques for ecotoxicological purposes is discussed.     

Freshwaters: which NOM matters?

One of the difficulties encountered in the study of natural organic matter (NOM) in aquatic environments concerns terminology: a large number of different names and acronyms are used. In fact, this diversity merely reflects the variety of approaches applied to the study of NOM, leading to the definition and measurement of different operationally-defined fractions. As a result, the choice of the ‘best’ method to use and of the ‘best’ fraction to work on in a particular case is far from straightforward. This has as a consequence that often very simple methods for NOM characterisation are used in applied environmental studies and surveys. This study includes, first, a review of the most widely applied terminology, as described in over 500 articles, and, second, a first attempt at assessing how the panoply of methods available is really used in applied environmental studies.     

Influence of body size on the uptake,depuration, and bioaccumulation of polychlorinated biphenyl congeners by Baltic Sea blue mussels,Mytilus edulis

The present study was designed to examine the influence of body size on the bioaccumulation of polychlorinated biphenyl (PCB) congeners by Baltic Sea blue mussels, Mytilus edulis L. This was done, firstly, by establishing the relationship (as a power function: PCB tissue conc = a tissue dry wt^b) between tissue concentration and body weight for seven PCB congeners (International Union of Pure and Applied Chemistry No. 52, 101, 105, 118, 138, 153, and 180) in field sampled mussels; and, secondly, by assessing the influence of body weight on the uptake clearance coefficients, the depuration rate coefficients and the calculated bioaccumulation factors (BAFs) of three ¹⁴C-labelled PCB congeners (IUPAC No. 31, 49, 153) in mechanistic kinetic experiments. Both the background tissue concentrations of PCB 138, PCB 153 and PCB 180 and the predicted BAF values in the kinetic experiments correlated negatively with body weight (b=-0.17 and-0.31, respectively). Of the two kinetic rate coefficients examined, only the uptake clearance rate showed weight dependency (b=-0.32, i.e. negative correlation with body weight), whereas depuration rates were unaffectd by body weight. Uptake clearance rates and BAFs adjusted for body weight increased with the octanol/water partition coefficient (K_ow) of the congener, whereas depuration rates dectreased with K_ow. These observations suggest that size-dependent bioaccumulation of hydrophobic organic contaminants (HOCs) in suspension-feeding bivalves is driven by size-related differences in uptake rate, although several other mechanisms may also affect bioaccumulation in natural mussel beds (e.g. sizerelated differences in lipid content, production, and contaminant exposure). From an ecotoxicological perspective size-dependent bioaccumulation implies not only that variability due to body size differences has to be dealt with in experimental designs, but also that several ecological factors such as size-specific predation and shifts in population structure may affect HOC cycling by dense populations of bivalve suspensionfeeders.     

Adsorption and movement of carbaryl in soils: A verification of cosolvent theory and comparison of batch equilibrium and soil thin layer chromatography results

Batch equilibrium and soil thin layer chromatography (TLC) techniques were used to investigate the influence of different volume fractions of organic cosolvents (acetone and methanol) on the adsorption and movement of carbaryl in four different types of Indian soils. L-shaped isotherms were obtained for both the cosolvent–water mixtures at all f _s values and were in close agreement with the Freundlich equation. Higher adsorption was observed on F.R.I. soil (FSL) followed by Alampur soil (ASL), Kalai soil (KL), and Bhoran soil (BSL) at all f _s values for both the cosolvent systems as was anticipated from the K and K _D values. The K and K _D values also confirmed that carbaryl adsorption was higher in methanol–water mixture than acetone–water mixture and decreased with increasing f _s values. The frontal R _f values obtained from soil TLC studies were inversely proportional to the K and K _D values for both the cosolvent systems. The higher K and K _D values and lower R _f values in methanol–water mixtures relative to acetone–water mixtures for all the soils indicated that acetone had a greater potential for ground water contamination compared to methanol. The adsorption data were used to evaluate the cosolvent theory for describing adsorption of carbaryl in acetone–water and methanol–water mixtures. The aqueous phase partition coefficients, K _DW (mol g^?1), normalized with respect to f _oc for carbaryl was evaluated by extrapolating f _s → 0.     

Nuclear magnetic resonance studies of interactions between organic pollutants and soil components,a review

This article presents a short overview of selected recent papers using nuclear magnetic resonance (NMR) to investigate interactions between organic pollutants and soil components such as organic matter, clays, whole soils, and sediments. First, we describe solid state cross polarisation magic angle spinning (CP-MAS) experiments as the main tools to investigate covalent bonds. Second, we report NMR approaches allowing us to assess molecule mobility and to characterise non-covalent interactions. Those approaches include correlations between K _oc values and soil organic matter functions determined by CP-MAS, ²H NMR fingerprints, relaxation time measurements, ¹⁹F and ¹H high resolution (HR)-MAS experiments.     

Determination and QSPR analysis of log Kow and log Koc for fluorine containing benzene derivatives

Octanol‐water partition coefficients (Kow) and soil organic carbon sorption coefficients (Koc) were determined for 14 fluorinated benzene derivatives. Quantitative structure‐property relationships were developed using molecular connectivity indices and quantum chemical parameters to analyze the most significant factors influencing these physico‐chemical properties of the compounds. The substitution by F in benzene derivatives has greater influence on Koc than on Kow.     

Feasibility of bubble surface modification for natural organic matter removal from river water using dissolved air flotation

A novel, functionalized bubble surface can be obtained in dissolved air flotation (DAF) by dosing chemicals in the saturator. In this study, different cationic chemicals were used as bubble surface modifiers, and their effects on natural organic matter (NOM) removal from river water were investigated. NOM in the samples was fractionated based on molecular weight and hydrophobicity. The disinfection byproduct formation potentials of each fraction and their removal efficiencies were also evaluated. The results showed that chitosan was the most promising bubble modifier compared with a surfactant and a synthetic polymer. Tiny bubbles in the DAF pump system facilitated the adsorption of chitosan onto microbubble surfaces. The hydrophobic NOM fraction was preferentially removed by chitosan-modified bubbles. Decreasing the recycle water pH from 7.0 to 5.5 improved the removal of hydrophilic NOM with low molecular weight. Likewise, hydrophilic organic compounds gave high dihaloacetic acid yields in raw water. An enhanced reduction of haloacetic acid precursors was obtained with recycle water at pH values of 5.5 and 4.0. The experimental results indicate that NOM fractions may interact with bubbles through different mechanisms. Positive bubble modification provides an alternative approach for DAF to enhance NOM removal.

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Regression models for some solute distribution equilibria in the terrestrial environment

Sorption coefficients (K_p) of several organochlorine insecticides (OCs) in volcanic ash silt from Central Java are presented.

Selected experimental and estimated octanol‐water partition coefficient (P) values are used to study log‐log regressions with K_p data collected from the literature (PAHs, chlorophenols, phenylureas, chloro‐s‐triazines, carbamates and organophosphorus insecticides) and those of the OCs determined in the present study. Leaching distances and bioactivities in soil are correlated with the K_p values of the pesticides, and with the organic matter and the water content of the soil.     

Effects of different sediment fractions on sorption of galaxolide

Sorption isotherms of galaxolide (HHCB) of different fractions from two sediments with different mineral and organic carbon contents were determined to compare HHCB sorption behavior and contribution to the total sorption. The HHCB sorption isotherms that used the batch equilibration method were studied on different sediments of different fractions. The sorption isotherms of 600°C heating fractions were detailed using the linear model, while the other fractions were nonlinear and fitted well with the Freundlich model. The dissolved organic carbon (DOC) removed, NaOH extracted, and 375°C heating fractions showed more nonlinear sorption than the original sediments, which suggested more heterogeneous sorption sites in these fractions. Compared to the original sediments, the 375°C heating fractions had higher carbonnormalized distribution coefficient (K _oc) values, indicating a higher sorption affinity for HHCB. Among the different sediment fractions, the contribution of the 600°C heating fractions to the overall sorption were the lowest (< 20%), while the 375°C heating fractions were the highest (up to 85%).     

Biokinetic modeling of heavy metals in earthworms

Studies concerning bioaccumulation kinetics and bioconcentration factor (BCF) of heavy metals like zinc (Zn), lead (Pb), chromium (Cr), cadmium (Cd), and copper (Cu) in earthworm Eudrilus eugeniae tissues including integument, gizzard, clitellum, and head region were undertaken. Calculated BCF, predicted K _ow, and predicted K _oc showed a significant correlation between heavy metals in different earthworm tissues, in substrate spiked with heavy metals. The regression coefficient (r ²) between heavy metal uptake concentration and exposure time varied between 0.73 and 0.99, indicating significant correlation. The K _oc was a maximum of 13.9016 in case of Cu and integument at an exposure time of 100 days and a minimum of 0.1114 in case of Cr with respect to head at the same exposure time. Earthworms accumulated heavy metals following chronic exposure to municipal solid waste containing heavy metals. BCF and uptake rate kinetics of heavy metals were calculated and showed increased values in head tissue followed by integument.     

可溶性有机质对芘在泥炭和高岭土上吸附和解吸的影响

为掌握可溶性有机质(DOM)对憎水性有机污染物吸附和解吸行为的影响,本研究选取四环多环芳烃——芘作为目标污染物,通过批平衡实验研究了不同分子量组分DOM对芘在泥炭和高岭土上吸附和解吸的影响.结果表明,吸附和解吸数据均可以用Freundlich模型很好地拟合(R²>0.93).DOM的添加抑制了泥炭对芘的吸附,并且分子量越大的DOM产生的抑制效应越明显,主要是由于DOM与芘分子的竞争、增溶作用及泥炭表面微孔的堵塞引起的.与之相反,DOM促进了芘在高岭土上的吸附,DOM分子量越大,促进效应越强,这是由于DOM与芘分子之间通过累积吸附或共吸附增加高岭土对芘的吸附.DOM促进了芘在泥炭和高岭土上的解吸,并且促进效应随分子量的增加而增强.此外,芘在泥炭和高岭土上的解吸均存在迟滞现象,均在低浓度时表现出更明显的效应.DOM_bulk和DOM_(>14000 Da)增加了芘在泥炭上的解吸迟滞现象,但降低了其在高岭土上的解吸迟滞现象.     

几类有机污染物的微塑料/水分配系数的线性溶解能关系模型

水体中的微塑料会吸附其中的有机污染物,影响有机污染物和微塑料的环境归趋和生态毒性。研究微塑料对有机污染物的吸附行为,对于评价有机污染物和微塑料的环境赋存、迁移及生物有效性有重要意义。污染物在微塑料与水之间的平衡分配系数(Kd),是表征微塑料对有机污染物吸附能力的重要参数。实验方法难以逐个测定众多有机污染物的Kd值,有必要发展其预测模型。本研究搜集了有机污染物的线性溶解能关系(LSER)参数及Kd值,构建了可预测有机污染物在聚丙烯微塑料与海水、聚乙烯微塑料与海水、聚乙烯微塑料与淡水之间Kd值的LSER模型。模型具有良好的拟合优度(R2adj介于0.794~0.903)、稳健性(Q2LOO和Q2BOOT分别介于0.763~0.863和0.720~0.804)和预测能力(R2ext和Q2ext分别介于0.886~0.971和0.825~0.954),能够用于预测多氯联苯、多环芳烃、六氯环已烷和氯苯类有机污染物的Kd值。     

Distribution and vertical migration of polycyclic aromatic hydrocarbons in forest soil pits of southeastern Tibet

PAHs could be transported to Tibetan Plateau in accompany with atmospheric circulation. The forest regions were found be an important sink for PAHs, while their distributions and migrations in forest are still uncertain. In this study, soil profile samples were collected in southeastern Tibet and the concentrations, distributions, and migration of PAHs in forest region were investigated. The PAHs levels in the forest soils were at the low end of remote sites, ranged from 27.4 to 120.3 ng g^?1 on a dry weight based. Due to low ambient temperature and high organic carbon content, enrichment of PAHs was found in higher altitude on north side. According to the soil profiles, the vertical distributions of PAHs in organic layers were mainly influenced by pedogenesis, while the vertical distributions in mineral layers were dominated by downward leaching effect. Enrich factor (EF) of PAHs was estimated, and the values in organic layers were positively correlated with the octanol–air partition coefficients (K _OA), but EFs in mineral layers decreased with the K _OA values. PAHs in the surface soils on the north side of forest were relatively stable, while the migration of PAHs on the south sides and other clearing sites was more active. The leaching rates of PAHs in clearing site ranged between 1.42 and 29.3%. The results from this study are valuable on the characterization of PAHs in Tibetan Plateau.