Surfactive stabilization of multi-walled carbon nanotube dispersions with dissolved humic substances

Soil humic substances (HS) stabilize carbon nanotube (CNT) dispersions, a mechanism we hypothesized arose from the surfactive nature of HS. Experiments dispersing multi-walled CNT in solutions of dissolved Aldrich humic acid (HA) or water-extractable Catlin soil HS demonstrated enhanced stability at 150 and 300 mg L⁻¹ added Aldrich HA and Catlin HS, respectively, corresponding with decreased CNT mean particle diameter (MPD) and polydispersivity (PD) of 250 nm and 0.3 for Aldrich HA and 450 nm and 0.35 for Catlin HS. Analogous trends in MPD and PD were observed with addition of the surfactants Brij 35, Triton X-405, and SDS, corresponding to surfactant sorption maximum. NEXAFS characterization showed that Aldrich HA contained highly surfactive domains while Catlin soil possessed a mostly carbohydrate-based structure. This work demonstrates that the chemical structure of humic materials in natural waters is directly linked to their surfactive ability to disperse CNT released into the environment.     

Influence of dissolved humic substances on the mass transfer of organic compounds across the air-water interface

The effect of dissolved humic substances (DHS) on the rate of water-gas exchange of two volatile organic compounds was studied under various conditions of agitation intensity, solution pH and ionic strength. Mass-transfer coefficients were determined from the rate of depletion of model compounds from an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution (dynamic system). Under these conditions, the overall transfer rate is controlled by the mass-transfer resistance on the water side of the water-gas interface. The experimental results show that the presence of DHS hinders the transport of the organic molecules from the water into the gas phase under all investigated conditions. Mass-transfer coefficients were significantly reduced even by low, environmentally relevant concentrations of DHS. The retardation effect increased with increasing DHS concentration. The magnitude of the retardation effect on water-gas exchange was compared for Suwannee River fulvic and humic acids, a commercially available leonardite humic acid and two synthetic surfactants. The observed results are in accordance with the concept of hydrodynamic effects. Surface pressure forces due to surface film formation change the hydrodynamic characteristics of water motion at the water-air interface and thus impede surface renewal.     

Relationships between colored dissolved organic matter and dissolved organic carbon in different coastal gradients of the Baltic Sea

Due to high terrestrial runoff, the Baltic Sea is rich in dissolved organic carbon (DOC), the light-absorbing fraction of which is referred to as colored dissolved organic matter (CDOM). Inputs of DOC and CDOM are predicted to increase with climate change, affecting coastal ecosystems. We found that the relationships between DOC, CDOM, salinity, and Secchi depth all differed between the two coastal areas studied; the W Gulf of Bothnia with high terrestrial input and the NW Baltic Proper with relatively little terrestrial input. The CDOM:DOC ratio was higher in the Gulf of Bothnia, where CDOM had a greater influence on the Secchi depth, which is used as an indicator of eutrophication and hence important for Baltic Sea management. Based on the results of this study, we recommend regular CDOM measurements in monitoring programmes, to increase the value of concurrent Secchi depth measurements.     

Optimal conditions for chlorothalonil and dissolved organic carbon in horizontal subsurface flow constructed wetlands

The most efficient system of horizontal subsurface flow constructed wetlands (HSSFCW) for removing dissolved organic carbon (DOC) in the presence of chlorothalonil pesticide (CLT) present in synthetic domestic wastewater was determined using the macrophyte Phragmites australis. Two concentrations of CLT (85 and 385 μg L^?1) and one concentration of glucose (20 mg L^?1) were evaluated in four pilot scale horizontal surface flow constructed wetlands coupled with two sizes of silica gravel, igneous gravel, fine chalky gravel (3.18–6.35 mm), coarse gravel (12.70–25.40 mm) and two water surface heights (20 and 40 cm). For a month, wetlands were acclimated with domestic wastewater. Some groups of bacteria were also identified in the biofilm attached to the gravel. In each treatment periodic samplings were conducted in the influent and effluent. Chlorothalonil was quantified by gas chromatography (GC-ECD m), DOC by an organic carbon analyzer and bacterial groups using conventional microbiology in accordance with Standard Methods. The largest removals of DOC (85.82%–85.31%) were found when using fine gravel (3.18–6.35 mm) and the lower layer of water (20 cm). The bacterial groups quantified in the biofilm were total heterotrophic, revivable heterotrophic, Pseudomonas and total coliforms. The results of this study indicate that fine grain gravel (3.18–6.35 mm) and both water levels (20 to 40 cm) can be used in the removal of organic matter and for the treatment of agricultural effluents contaminated with organo-chloride pesticides like CLT in HSSFCW.     

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.     

A comparative characterization of dissolved organic matter by means of original aqueous samples and isolated humic substances

The aim of our study is to test the use of less time-consuming spectroscopic methods applied on original water samples in order to obtain information about DOM composition without any sample preparation. These results were directly compared with results from a conventional isolation and characterization procedure of dissolved humic substances (fulvic acids – FA) isolated from the same water sample. FAs were characterized by UV-, fluorescence-, FTIR spectroscopy and elemental composition. UV absorbance and fluorescence behavior of FAs and original water samples follow the same pattern. A lower UV absorbance and a lower humification index (derived from the synchronous fluorescence spectra) of about 15% is typical for water samples compared to the FAs. We computed linear relationships between properties of the original water sample (UV-, synchronous fluorescence spectra) and the isolated FA (IR absorption, C/N ratio). The application of synchronous fluorescence and UV spectroscopy of aqueous samples has been proved to result in similar information about DOM composition as the characterization of isolated humic substances concerning the content of aromatic structures and the degree of humification.     

滇池流域不同土壤类型和土地利用方式的土壤中溶解性有机碳的流失特性研究

采集滇池流域不同土壤类型、不同土地利用方式下的土壤样品,进行土壤中溶解性有机碳(DOC)的静态解吸实验,通过测定不同时间下溶入水相的COD量,探究不同土壤类型及土地利用方式下DOC的流失特性,从而揭示不同土地利用方式对滇池流域面源污染的影响.结果表明,同一土地利用方式的不同类型土壤中DOC的溶出平衡时间为壤土＞粘土＞粘壤土,其中退耕区(粘壤土＞粘土＞壤土)、大棚(粘土＞粘壤土=壤土)土壤不符合该规律,溶出平衡时间基本为1.5～2.5h;不同的土壤类型和土地利用方式下,DOC的溶出率为1.00％～2.75％,同一土地利用方式的不同类型土壤中DOC的溶出率存在一定差别,这是由于不同类型的土壤中砂粒、粉粒、粘粒的含量有所差异.     

Influence of sorption to dissolved humic substances on transformation reactions of hydrophobic organic compounds in water. Part II: hydrolysis reactions

The effect of dissolved humic acid (HA) on two types of hydrolysis reactions was investigated: (I) dehydrochlorination of gamma-hexachlorocyclohexane (HCH) and 1,1,2,2-tetrachloroethane (TeCA) as a reaction involving hydroxide ions (OH(-)) and (II) hydrolysis of 1-octyl acetate (OA) which is catalyzed by H(+) at the applied pH value (pH 4.5). The rate of TeCA hydrolysis was not affected by addition of 2 g l(-1) of HA at pH 10 (k' = 0.33 h(-1)) but HCH hydrolysis was significantly inhibited (k' = 4.6 x 10(-3) h(-1) without HA and 2.8 x 10(-3)h(-1) at 2 g l(-1) HA). HCH is sorbed by 51% whereas TeCA sorption is insignificant at this HA concentration. Sorbed HCH molecules are effectively protected due to electrostatic repulsion of OH(-) by the net negative charge of the HA molecules. In contrast, OA hydrolysis at pH 4.5 (k' = 1.6 x 10(-5) h(-1)) was drastically accelerated after addition of 2 g l(-1) HA (k' = 1.1 x 10(-3) h(-1)). The ratio of the pseudo-first-order rate constants of the sorbed and the freely dissolved ester fraction is about 70. H(+) accumulation in the microenvironment of the negatively charged HA molecules was suggested to contribute to the higher reaction rate for the sorbed fraction in case of this H(+)-catalyzed reaction. Analogous effects from anionic surfactants are known as micellar catalysis.     

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.     

The binding of three PCB congeners to dissolved organic carbon in freshwaters

The binding of three polychlorinated biphenyl (PCB) congeners to natural levels of dissolved organic carbon (DOC) was measured in 12 lakes and streams using Sep-Pak C₁₈ columns. The association coefficients calculated on the basis of DOC (i.e. K_DOC mL/g C), varied by over an order of magnitude among the different freshwaters and ranged between 2.05 × 10² and 8.86 × 10³ mL/g C for PCB 52 and 1.03 × 10⁴ and 1.70 × 10⁵ mL/g C for PCB 153. In general, there were no significant correlations (p > 0.05) between the K_DOC values and various chemical parameters in the study lakes and streams.

A relationship was derived between the fraction of bound PCB and the octanol-water partition coefficient. While this relationship explained almost 50% of the variation in the observed data, it is apparent that other factors influence K_DOC values and that in natural freshwaters, only a small fraction of the DOC is involved in the binding of PCBs and other hydrophobic pollutants.     

Seasonal variability of formaldehyde production from photolysis of rainwater dissolved organic carbon

Photochemical production of formaldehyde (HCHO) was measured in rainwater from 13 precipitation events in Wilmington, North Carolina, USA under conditions of simulated sunlight. HCHO concentrations increased in all samples irradiated with no changes observed in dark controls. HCHO photoproduction rates were strongly correlated with dissolved organic carbon (DOC) suggesting HCHO was derived from direct or indirect photolysis of rainwater DOC. The higher photoproduction rates (0.03–2.9 μM h^?1) relative to those reported for surface waters suggests that rainwater DOC is more photolabile in terms of HCHO production than surface waters. HCHO photoproduction rates were higher in growing season (1.0 ± 1.0 μM h^?1) compared to non-growing season (0.08 ± 0.05 μM h^?1) even when rates were normalized for DOC (6.8 ± 3.6 μM h^?1 mM C^?1 versus 1.8 ± 1.0 μM h^?1 mM C^?1). The higher growing season rate may be related to seasonal differences in the composition of DOC as evidenced by differences in fluorescence per unit carbon of rainwater samples. Irradiation of C18 extracts of rainwater also produced HCHO, but at lower rates compared to corresponding whole rain samples, suggesting that hydrophyllic components of rainwater play a role in HCHO photoproduction. Our results indicate that photolysis of rainwater DOC produces significant amounts of HCHO, and possibly other low molecular weight organic compounds, likely increasing its reactivity and bioavailability.     

不同垃圾渗滤液组合处理工艺中DOM的变化特征

为了快速表征垃圾渗滤液处理过程中有机物的特性变化,分别采用紫外光谱和三维荧光光谱对2种垃圾渗滤液处理工艺不同单元溶解性有机物(DOM)的变化进行了系统分析。结果表明,二级RO和厌氧+好氧+MBR+NF+RO工艺对渗滤液COD和NH3-N的去除率分别为98.7%、99.0%和98.8%、98.6%。随着处理过程的进行,2个处理工艺中DOM的SUVA254、E253/E203分别由0.74、0.33和0.46、0.12下降至0.015、0.014和0.010、0.012,有机物的芳香性和不饱和性下降,脂肪链芳香烃化合物开始增加。不同处理阶段渗透液DOM三维荧光光谱表明,随着处理过程的进行,类富里酸和类蛋白物质的含量逐渐下降,芳构化程度开始降低。其中二级RO系统对渗滤液中类富里酸物质的去除效果较好,而厌氧-好氧-MBR-NF-RO工艺中,类酪氨酸物质主要通过微生物降解去除,NF和RO膜对类富里酸和类腐殖酸物质的截留效果较好。     

Effect of dissolved organic carbon on the environmental distribution of nonpolar organic compounds

The effect of dissolved organic carbon on the process of pollutant sorption to aquatic sediments was studied using sediments from the Boonton Reservoir/Rockaway River system in northern New Jersey. Addition of DOC to the aqueous phase reduced the sorption of DDT to sediments, but had no effect on the sorption of Lindane. The effect of the DOC is to increase the amount of DDT in the soluble phase and enable transport of the compound throughout an aquatic system. The apparent influence of DOC on the equilibrium distribution of organic compounds is illustrated by modifying an existing environmental model.     

The influence of organic matter on sorption and fate of glyphosate in soil - Comparing different soils and humic substances

Soil organic matter (SOM) is generally believed not to influence the sorption of glyphosate in soil. To get a closer look on the dynamics between glyphosate and SOM, we used three approaches: I. Sorption studies with seven purified soil humic fractions showed that these could sorb glyphosate and that the aromatic content, possibly phenolic groups, seems to aid the sorption. II. Sorption studies with six whole soils and with SOM removed showed that several soil parameters including SOM are responsible for the strong sorption of glyphosate in soils. III. After an 80 day fate experiment, ∼40% of the added glyphosate was associated with the humic and fulvic acid fractions in the sandy soils, while this was the case for only ∼10% of the added glyphosate in the clayey soils. Glyphosate sorbed to humic substances in the natural soils seemed to be easier desorbed than glyphosate sorbed to amorphous Fe/Al-oxides.     

Chlorothalonil binding to aquatic humic substances assessed from gas purge studies

Abstract

Fate of the fungicide chlorothalonil (TCIN) binding to dissolved organic acid fractions was quantified using gas‐purge desorption studies. Binding studies were conducted to measure the dissolved organic carbon partition constant (K_DOC) with aquatic fulvic and humic acid fractions purified from cranberry bog water. Desorption studies at DOC concentrations up to 50 mg L^‐1 resulted in mean log K_DOC values of 4.63 (s.d.=0.5, n=8) and 4.81 (s.d.=0.7, n=7) for fulvic and humic acids, respectively. These values deviated from reported K_OC (organic carbon) values by 0.5 to 1.5 orders of magnitude. The relationship between K_OC and K_DOC did not conform to accepted ratios of 10: 1 to 3: 1, although these studies were conducted with the strong hydrophobic fraction of DOC. Binding was rapid suggesting hydrophobic partitioning or weak Van Der Waals forces as binding mechanisms. The strong binding potential for TCIN to aquatic humic substances corresponds to increased solubility in the aqueous system. Sorption to DOC suggests a possible transport mechanism which may result in elevated concentrations of TCIN in cranberry bog systems.     

Study on dissolved organic carbon in precipitation in Northern China

Dissolved organic carbon (DOC) was measured in 483 precipitation samples collected at 10 sites in Northern China from December 2007 to November 2008. The annual volume-weighted mean (VWM) concentrations and wet deposition fluxes of DOC for 10 sites ranged from 2.4 to 3.9 mg C/L and 1.4 to 2.7 g C m^?2 yr^?1, respectively. The proportion of DOC to total organic carbon (TOC) was 79% on average, suggesting that a significant fraction of TOC was present as insoluble particulate organic carbon. Due to intensive domestic coal use for house heating and smaller dilution of scavenged organic carbon, higher VWM concentrations of DOC were observed during winter and spring than during summer and autumn. When precipitation events were classified via air mass back-trajectories, the mixed trajectories from SE and NW always corresponded to significantly higher DOC than those from SE or NW alone, coinciding with the centre of a low pressure system moved eastward and the wind direction changed from southeast to northwest. The results also showed that each site had a similar seasonal variation for DOC wet deposition flux. The largest flux occurred during the rainy season, and the lowest flux appeared during winter months. The product of the TC/DOC ratio and the DOC flux yielded an average TC wet deposition flux of 3.2 g C m^?2 yr^?1 in Northern China, accounting for 8.6% and 22% of the carbon sink magnitude (37 g C m^?2 yr^?1) in terrestrial ecosystems and anthropogenic carbon emissions (14 g C m^?2 yr^?1), respectively. This indicates that atmospheric wet deposition of TC is a significant carbon flux that cannot be neglected in regional models of the carbon cycle, and should be considered along with dry deposition in the removal mechanism for carbon from regional atmosphere.     

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.     

活性炭多维电极法去除水中腐殖酸过程与宏观动力学研究

采用活性炭多维电极法去除水中溶解态腐殖酸。实验结果表明 ,与活性炭单纯吸附法相比 ,活性炭多维电极法可显著提高对溶解态腐殖酸的去除率 ;在连续运行条件下 ,延长水力停留时间、升高槽电压、溶液偏碱性有利于腐殖酸的去除 ;高效液相色谱分析结果表明 ,电极的氧化还原作用可使有机物分子量变小或矿化 ,因而处理系统有可能延长活性炭的使用寿命     

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5mg L(-1). These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.