Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r²=0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK_FOC values of 6.02 to 6.42(μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C_e, the BC had higher K_oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C_e=0.05 S_w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

Contribution of black carbon to nonlinearity of sorption and desorption of acetochlor on sediment

In order to investigate the contribution of various black carbon (BC) contents to nonlinearity of sorption and desorption isotherms for acetochlor on sediment, equilibrium sorption and desorption isotherms were determined to measure sorption and desorption of acetochlor in sediment amended with various amounts of BC. In this paper, two types of BC referred to as BC400 and BC500 were prepared at 400°C and 500°C, respectively. Higher preparation temperature facilitated the formation of micropores on BC to enhance its sorption capacity. Increase of the BC content obviously increased the sorption amount and reduced the desorption amount for acetochlor. When the BC500 contents in total organic carbon (TOC) increased from 0 to 60%, Freundlich sorption coefficient (K _f) increased from 4.07 to 35.74, and desorption hysteresis became gradually obvious.When the content of BC in TOC was lower than 23%, the sorption isotherm had a significant linear correlation (p = 50.05). In case of desorption, a significant nonlinear change could be observed when the content of BC was up to 13%. Increase of BC content in the sediment would result in shifting the sorption-desorption isotherms from linearity to nonlinearity, which indicated that contribution of BC to nonlinear adsorption fraction became gradually remarkable.     

土壤和沉积物中非水解有机碳对菲的吸附

采用改进的酸水解方法对土壤和沉积物中的有机质组分进行了分离和提取,用固体13C核磁共振（13CNMR）表征了非水解有机碳（NHC）,同时研究了不同有机质组分对菲的吸附行为,结果表明,菲的吸附等温线都呈现出明显的非线性,能很好地拟合Freundlich方程;而且NHC和碳黑（BC）比其原始和去矿样品的吸附容量都有明显提高.这些结果揭示了NHC和BC主要控制着菲在土壤和沉积物中的吸附行为.沉积物及其NHC对菲的吸附容量要高于土壤及其NHC,这与土壤和沉积物中有机质的不同来源有关.     

沉积物对菲和五氯酚的吸附性能

研究了菲和五氯酚（PCP）在五种沉积物的吸附解吸行为，菲和PCP在各沉积物上的吸附和解吸都是较快的过程。均能在8h内达到平衡，吸附和解吸结果表明，高有机质含量的沉积物对菲和PCP的吸附和持留能力都较强，菲和PCP在各沉积物中的吸附系数跟沉积物的有机质含量呈线性正相关。等温吸附结果表明，低有机质含量的三种沉积物比有机质含量较高的两种沉积物呈更好的线性关系。不同沉积物对菲和PCP的吸附性能差异跟沉积物的有机质含量密切相关。     

土壤和沉积物中有机质对双酚A和17α-乙炔基雌二醇的吸附行为

研究了土壤和沉积物原始样品bulk及其有机质组分(非水解性有机质NHC、碳黑BC和腐殖酸HA)对17α-乙炔基雌二醇(EE2)和双酚A(BPA)的吸附行为.所有的吸附等温线都很好地拟合了Freundlich模型,除HA和bulk外,所有的吸附等温线都为显著的非线性(n值为0.46—0.76).对于EE2和BPA的吸附非线性因子n值都存在这样的关系:HA>NHC>BC.EE2以有机碳归一化的Freundlich吸附能力(lgKOC)有BC>NHC>bulk>HA的关系,说明有机质成熟度越高,对EE2或者BPA的吸附能力越高.在土壤和沉积物有机质SOM(NHC、BC和HA)对吸附BPA和EE2的贡献上,NHC、BC和HA对沉积物和土壤对BPA总吸附贡献上要明显弱于它们对EE2的贡献.除了内分泌干扰物(EDCs)的疏水性影响EE2和BPA的吸附能力的差异外,分子大小和带电子苯环数也影响它们的吸附能力差异.     

多环芳烃在全土及其碱提残余物上的吸附行为

以菲和芘为代表性化合物,采用8种有机质含量不同的天然全土样品及其碱提残余物进行吸附实验,并利用不同吸附模型进行数据拟合,藉以探讨有机质含量对土壤吸附行为的影响.结果表明,Freundlich吸附模型的非线性指数n都小于1,显示全土和碱提残余物在多环芳烃的吸附过程中表现出非线性特征.菲和芘的吸附行为随土壤有机质含量不同而变化,碱提残余物的吸附能力强于全土,两者吸附行为的差异主要归因于土壤有机质含量和性状的区别.     

Sorption and desorption of pymetrozine on six Chinese soils

Pymetrozine is a selective insecticide with a unique chemical structure and mode to control hemipteran and homopteran. While pymetrozine has brought great benefits to crop production by killing insects, its residues in soil may have a detrimental effect on environment. Therefore, it is of great importance to investigate its behaviors in soil. In this study, the sorption and desorption of pymetrozine on six Chinese soils were investigated using a batch equilibrium approach to understand its mobile behavior in the soils. Both sorption and desorption isotherms of pymetrozine were in good agreement with the Freundlich model. The sorption coefficient K_F varied between 3.37 and 58.32 mL∙g⁻¹ and the sorption isotherms were nonlinear, with 1/n ranging from 0.57 to 0.91. A regression equation was proposed to predict the sorption of pymetrozine on six different soil samples: log K_F = 4.3708 − 4.5709 × log (pH in 0.01mol·L⁻¹ CaCl₂) + 0.4700 × log OC% + 0.0057 × sand (%) + 0.0022 × CEC(clay), with R² = 0.9982. The organic carbon content of soil positively affected the sorption of pymetrozine, but soil pH had a negative effect on the sorption. Additionally, effects of CaCl₂ concentration, soil to solution ratio and pesticide form were investigated. The sorption was promoted with an increase in soil to solution ratio and a decrease in CaCl₂ concentration. The possible variation of the five formulated products of pymetrozine was also investigated.     

The influences of different organic fractions in refuse on the sorption and bioavailability of dibutyl phthalate

The structure and composition of the organic matter in landfilled refuse might have an influence on the migration and transformation of dibutyl phthalate (DBP). Humic acid (HA) and humin (HU) were separated from aged-refuse to determine the influences of different organic fractions in the refuse on the sorption and bioavailability of DBP. The sorption kinetics and isotherms for the sorption of DBP to HA, HU, and whole refuse were determined. The results showed that the sorption constants (K) and nonlinearities decreased in the order HU?>?whole refuse?>?HA. The HA had lower K values than did the other refuse fractions, and it retarded the biodegradation of DBP over a short degradation period (48?h). Increasing the amount of HA present caused the amount of DBP that was biodegraded to decrease significantly, 81.3% of the DBP sorbed to HA being degraded in the original experiments after 48?h but 21.8% of the DBP being degraded when three times as much HA was used. Similar results were not observed when the amount of HU used was changed. These findings suggest that HA plays an important role in the biodegradation of DBP adsorbed by refuse.     

土壤和沉积物中的聚合有机质对多环芳烃分布和提取的影响

为了研究土壤和沉积物中凝聚型有机碳(碳黑、干酪根)的含量及其对多环芳烃(PAHs)分布和提取的影响,分别用三氟醋酸(TFA)和在375℃下通氧燃烧的方法从珠江三角洲2个污染土壤和5个河口沉积物样品中提取酸非水解有机碳(NHC)和碳黑(BC);用索氏抽提法和不同溶剂的加速溶剂萃取法(包括连续加速萃取法ASESum和标准溶剂萃取法ASESTD)抽提土壤和沉积物中的多环芳烃,并在不同温度梯度(25℃到150℃)下用水为溶剂加速溶剂萃取其水溶态.结果表明,1)NHC是珠江三角洲土壤和沉积物中总有机碳的重要组成部分,NHC碳明显高于BC碳,NHC和BC分别占土壤和沉积物中有机碳的25.6%￣73.8%和4.64%￣17.3%.2)3种有机溶剂(丙酮、甲苯1、甲苯2)连续抽提的PAHs含量是索氏抽提的2.11倍;5种ASE方法(丙酮、甲苯1、甲苯2、ASESum、ASESTD)提取的PAHs含量与NHC含量存在明显的相关性,而且比PAHs含量与BC或无定型有机碳(AOC)含量的相关性更明显.3)在不同温度梯度下水溶态PAHs浓度符合Van’tHoff方程.研究说明除了BC外,非水解有机碳对土壤和沉积物中PAHs的分布和提取具有重要影响.     

Metal immobilization by sludge-derived biochar: roles of mineral oxides and carbonized organic compartment

Pyrolyzing sludge into biochar is a potentially promising recycling/disposal solution for municipal wastewater sludge, and the sludge-derived biochar (SDBC) presents an excellent sorbent for metal immobilization. As SDBC is composed of both mineral oxides and carbonized organic compartment, this study therefore compared the sorption behaviour of Pb and Zn on SDBC to those of individual and mixture of activated carbon (AC) and amorphous aluminium oxide (Al₂O₃). Batch experiments were conducted at 25 and 45 °C, and the metal-loaded sorbents were artificially aged in the atmosphere for 1–60 days followed by additional sorption experiments. The Pb sorption was generally higher than Zn sorption, and the co-presence of Pb reduced Zn sorption on each studied sorbent. Higher sorption capacities were observed at 45 °C than 25 °C for SDBC and AC, while the opposite was shown for Al₂O₃, indicating the significance of temperature-dependent diffusion processes in SDBC and AC. Nevertheless, metal sorption was more selective on Al₂O₃ that showed a greater affinity towards Pb over Zn under competition, correlating with the reducible fraction of sequential extraction. Furthermore, significant amounts of Pb and Zn were additionally sorbed on SDBC following 30-day ageing. The X-ray diffraction revealed the formation of metal-phosphate precipitates, while the X-ray photoelectron spectroscopy showed a larger quantity of metal–oxygen bonding after 30-day ageing of metal-loaded SDBC. The results may imply favourable long-term transformation and additional sorption capacity of SDBC. In conclusion, SDBC resembles the sorption characteristics of both organic and mineral sorbents in different aspects, presenting an appropriate material for metal immobilization during soil amendment.     

Sorption of 1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane (DDT) by clays and organoclays

This study focused on the sorption isotherms of 1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane (p,p'-DDT) and 1,1-dichloro-2,2-bis(p-chlorophenyl) ethylene (p,p'-DDE) on different original clays (i.e., zeolite, montmorillonite and attapulgite) and organoclay complexes. Sorption of organic pollutants was determined using gas chromatographic (GC) techniques to investigate the sorption behavior, and characterize the effect of, different organic cations. The original clays only sorbed low amounts of p,p'-DDT and p,p'-DDE, and the sorptive curves can be classified as L-shaped. Organoclays exhibited higher amounts of p,p'-DDT and p,p'-DDE sorption. The p,p'-DDT and p,p'-DDE sorption increased with increasing total organic carbon (OC) content of the organoclays. For hexadecyltrimethylammonium (HDTMA)-modified organoclays, the dominant adsorptive medium showed the partitioning sorption of hydrophobic-hydrophobic interaction, indicating no competitive sorption. The sorptive curves can be classified as C-shaped of constant partition (CP). However, benzyltrimethylammonium (BTMA)-modified organoclays exhibited competitive sorption. The sorption isotherm curves can be classified as S-shaped. The sorptive capacity of the HDTMA-modified organoclays for p,p'-DDT were higher than those for p,p'-DDE, but the BTMA-modified organoclays showed a reverse trend. This can be attributed to the different structures and shapes of organic cations, giving different sorptive mechanisms. The p,p'-DDT and p,p'-DDE sorption onto HDTMA-modified organoclays were caused by chemical interaction, with the BTMA modified organoclays occuring due to physical sorption.     

A comparative study of modified and unmodified maize tassels for removal of selected trace metals in contaminated water

Powdered maize tassels were studied and found to exhibit metal sorption properties due to the availability of functional groups. The tassels have a high amount of soluble organic substances that can dissolve in aqueous media, contributing to secondary pollution during a water treatment process. A chelating agent was chemically attached on the maize tassels with a view to increase the sorption capacity, minimize leaching, and enhance the tassels’ stability. Thermogravimetric analysis confirmed that modification improved their thermal stability to withstand temperatures above 600°C as well as reduced the “secondary pollution”. The modified sorbent was employed for the sorption of lead, copper, and cadmium ions in both the model solutions and the real samples. The contact time and pH were optimized after which Langmuir and Freundlich isotherms were applied to the data. The sorption capacities for Cu²⁺, Cd²⁺, and Pb²⁺ improved from 3.4, 0.8, and 1.7?g?kg^?1, respectively, to 6.3, 2.6, and 2.6?g?kg^?1 in the same order. The sorbent was shown to remove up to 95% of the metals in less than 10 min. This study has a potential application for the remediation of polluted waters.     

久效磷在海洋沉积物上的吸附行为

研究了久效磷在海洋沉积物上的吸附行为，发现其吸附行为主要受沉积物有机质的影响，沉积物有机质的分配作用对久效磷的吸附起主要作用，在实验浓度范围内，吸附行为很好地服从线性吸附等温式，因而其吸附行为较为简单，海水的离子强度对其吸附行为影响很大，海水中分配系数明显高于淡水，温度对其吸附行为也起一定的作用，分配系数随着温度的升高略微减小。     

Sorption of phenanthrene to biochar modified by base

Biochar (BC) is a potential material for removal of polycyclic aromatic hydrocarbons from soil and water, and base modification is a promising method for improving its sorption ability. In this study, we synthesized a series of base-modified biochars, and evaluated their sorption of phenanthrene. Original biochars were produced by pyrolysis of three feedstocks (rice straw, wood and bamboo) at five temperatures (300°C, 350°C, 400°C, 500°C and 700°C). Base-modified biochars were further obtained by washing of biochars with base solution. The base soluble carbon (SC) was extracted from the supernatant, which were only obtained from biochars pyrolyzed at low temperatures (<500°C) and the content was decreased with the increase of pyrolysis temperature. The SC content between different feedstocks followed the trend of rice straw>wood>bamboo when same pyrolysis conditions were applied. It was found that base modification improved the sorption of phenanthrene on biochars that SC could be extracted from (extractable-BCs). However, base treatment but had limited effects for biochars that no SC could be extracted from. It suggested that base modification improved the sorption of phenanthrene to extractable-BCs by removing the SC and thus increasing the surface area and hydrophobicity. Therefore, base modification was suggested to be used in modifying extractable-BCs.

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Sorption of tetracycline to sediments and soils: assessing the roles of pH,the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL^- and L^2-). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

Detection of organic contamination in sediments by double-shoot pyrolysis–GC/MS

Pyrolysis coupled with gas chromatography–mass spectrometry (Py–GC–MS) has been previously proved to be an appropriate tool for the screening of organic contaminants in sediments. In this work the double-shoot pyrolysis technique has been applied to assess the contamination degree of sediment samples from Castro Marim Natural Park (South Portugal) and the Ria of Huelva (SW Spain). Compounds released both by thermodesorption at sub-pyrolysis temperatures (250–280°C) and subsequent pyrolysis (300–500°C) revealed information on the origin of the sedimentary organic matter and the occurrence of organic contamination in the sediments. Thermal desorption was found to be effective in releasing organic contaminants from spiked samples. However, in real sediments samples, higher pyrolysis temperatures (>300°C) were necessary to detect the occurrence of organic contaminants. Particularly polycyclic aromatic hydrocarbons (PAHs) and linear alkylbenzenes (LABs) were detected in variable proportions in most sediment samples.     

Identification of Anthropogenic Organic Contamination Associated with the Sediments of a Hypereutropic Tropical Lake, Venezuela

The concentrations of organic carbon (Corg), inorganic carbon (Cinorg), organic nitrogen (Norg) and total aromatic (Arom_T) were determined in 25 samples of bottom sediments from the Lake Valencia, Venezuela, as a contribution to the knowledge about pollution by organic compounds in tropical lakes. Results demonstrate that the Corg and Norg concentrations do not show the pollution indexes by themselves. This is a consequence of the masking effect of naturally derived organic matter from the decay of algae and organisms in the water column and terrestrial plants, which are transported to the lake. Nevertheless, the Arom_T concentrations and the normalised Arom_T (normalized to organic carbon) make it possible to detect organic matter of anthropogenic origin, in the Arom_T levels are about nine times higher than those natural. The variation in the band intensity of the IRFT spectra for some functional groups present in the saturate and aromatic hydrocarbon fractions gives an indication of anthropogenic contribution for some zones of the lake. With the ¹H NMR spectra it was not possible to differentiate a natural source from an anthropogenic one in the lake. Naturally occurring organic compounds (eicosane, pentacosane, and hexacosane) were detected with GC technique in the saturated hydrocarbon fraction. The presence of an unresolved complex mixture (UCM) in the GC chromatograms indicates pollution by branched and cyclic hydrocarbons. These compounds are probably produced by the incomplete combustion of oil products. Potentially toxic organic compounds such as anthracene, phenanthrene and chrysene were found in the aromatic hydrocarbon fraction, which despite presenting low concentrations (ppb order) accumulate in the lake sediments along with the natural source organic matter. The main access paths of organic pollutants to the lake are the rivers which cross the two urban and industrial areas (Maracay and Valencia cities). The mixture of polluted sediments with bottom natural sediments and the autochthonous contribution of organic matter mitigate the pollution levels progressively towards the center of the lake.     

批量平衡法研究芳香族酮类化合物在东北黑土中的吸附

本文用批量平衡法研究－系列芳香族酮类化合物在东北黑土中的吸附,采用Ｆｒｅ－ｎｕｎｄｌｉｃｈ吸附等温方程求得土壤吸附常数（ｋｆ）,研究表明：１２种芳香族酮类化合物的吸附等温线有线性和非线性两种形式,对化合物的土壤有机碳吸附常数（ｌｇＫｏｃ）进行定量结构－性质（ＱＳＰＲ）分析,发现芳香族酮类化合物的土壤有机碳吸附常数与正辛醇／水分配系数相关不显著,土壤有机碳吸附常数与分子极化率（ａ）有较好的相关性,这     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

Origin and Distribution of Suspended Organic Matter As Inferred From Carbon Isotope Composition in A Mediterranean Semi-Enclosed Marine System

Abstract

The origin and distribution of suspended organic matter, the trophic features and the stable carbon isotopic composition of particulate organic carbon (POC) were studied monthly in a Western Mediterranean semi-enclosed basin. Sampling stations were selected as a function of wind-exposure and the degree of vegetation cover and then compared with an adjacent unvegetated site. the predominant vegetation was seagrass (Posidonia oceanica and Cymodocea nodosa) and Caulerpa prolifera. Water samples were analyzed for total suspended matter (inorganic and organic fractions), photosynthetic pigments (chlorophyll-a and phaeopigments), dissolved organic carbon, particulate organic carbon and their isotopic composition. Temperature and salinity were also measured at the same sampling sites within range of Mediterranean limits. the suspended organic matter concentration was 1.77 ± 1.55 mg l^?1; the chlorophyll-a concentration was low (0.35 ± 0.24 μg l^?1); the disolved organic carbon concentration was 2,140 ± 2,010 μg l^?1; the particulate organic carbon concentration was 212 ± 106 μg l^?1 and the isotopic composition was 18.77 ± 2.51%_°. There were significant temporal differences except for phaeopigments, POC and its POC isotopic composition, and there were no spatial differences other than for δ¹³C. This picture highlighted a general seasonal trend and trophical features similar to adjacent sea.

Spatial differences in δ¹³C showed that the source of suspended organic matter was different between stations as that between sources and wind-hydrodynamic constraints. In